WO2015093430A1 - Method for producing fluorescent substance - Google Patents

Method for producing fluorescent substance Download PDF

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WO2015093430A1
WO2015093430A1 PCT/JP2014/083114 JP2014083114W WO2015093430A1 WO 2015093430 A1 WO2015093430 A1 WO 2015093430A1 JP 2014083114 W JP2014083114 W JP 2014083114W WO 2015093430 A1 WO2015093430 A1 WO 2015093430A1
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reaction solution
phosphor
solid compound
moles
reaction
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PCT/JP2014/083114
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French (fr)
Japanese (ja)
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秀幸 江本
伊藤　和弘
基 田中
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電気化学工業株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
    • C09K11/615—Halogenides
    • C09K11/616—Halogenides with alkali or alkaline earth metals

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  • the present invention relates to a method for producing a phosphor that emits red light when excited by blue light. More specifically, the general formula: A 2 MF 6 : Mn 4+ (the element A is an alkali metal element containing at least K, and the element M is selected from Si, Ge, Sn, Ti, Zr and Hf containing at least Si.
  • the present invention relates to a production method capable of obtaining a composite fluoride phosphor represented by one or more metal elements) in a safe and high yield, and capable of obtaining a phosphor having high external quantum efficiency and excellent luminous efficiency.
  • a blue LED chip as a light source, a green phosphor that emits green when receiving blue, and a red phosphor that emits red when receiving blue are combined.
  • a method using an additive mixing principle is widely used.
  • red phosphors As red phosphors, nitride phosphors such as CaAlSiN 3 : Eu and (Sr, Ca) AlSiN 3 : Eu and sulfide phosphors such as (Ca, Sr) S: Eu are well known.
  • Fluoride phosphors have attracted attention as red phosphors having a very sharp fluorescence spectrum and a high brightness while being deep red (Non-patent Documents 1 and 2).
  • This phosphor has a structure in which Mn 4+ is substituted and dissolved in a part of a tetravalent element M site, and exhibits a fluorescence spectrum in which a plurality of line-like light emission are combined by electronic transition of Mn 4+ .
  • Patent Document 1 discloses an A 2 [MF 6 ] crystal serving as a phosphor base and Mn serving as an emission center.
  • a production method is disclosed in which K 2 MnF 6 crystals are prepared, dissolved in hydrofluoric acid, and evaporated to dryness.
  • Patent Document 2 discloses a method for producing a single metal such as silicon by immersing it in a mixed solution of hydrofluoric acid and potassium permanganate.
  • Patent Documents 3 and 4 disclose a method for producing a reaction solution in which a part of the constituent elements of the fluoride phosphor is dissolved and adding the remaining constituent elements in the form of a reaction solution or a solid state compound. Has been.
  • Patent Document 1 requires a reaction apparatus excellent in heat resistance and corrosion resistance to evaporate hydrofluoric acid, and a facility for excluding hydrogen fluoride gas harmful to the human body generated by the evaporation. Therefore, expensive production facilities are required for mass production.
  • the manufacturing method described in Patent Document 2 is manufactured because it is difficult to control the amount of manganese in the manufactured phosphor, and thus the characteristics of the manufactured phosphor are non-uniform, and unreacted silicon remains during manufacturing. The luminous intensity of the phosphor is insufficient, and the productivity of the phosphor is low due to the slow deposition reaction rate of the phosphor.
  • Patent Document 3 and Patent Document 4 it is difficult to control the particle size of the phosphors deposited, and sufficient light emission characteristics cannot be obtained.
  • the present inventors added a compound of a specific element of the phosphor constituent elements in a solid state to a reaction solution in which the raw material of the phosphor is dissolved in hydrofluoric acid at a blending ratio different from the element composition of the phosphor
  • a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ can be produced in a safe and high yield by reacting within a predetermined temperature range and at a predetermined composition ratio, and the external quantum efficiency is high.
  • the present inventors have found that a high phosphor can be produced and completed the present invention.
  • the present invention relates to a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ (wherein the element A is an alkali metal element containing at least K, and the element M is Si containing at least Si, And one or more metal elements selected from Ge, Sn, Ti, Zr and Hf, F is fluorine, and Mn is manganese.
  • element A, elements M, F and Mn are mixed with the molar ratio of element A to element M ([number of moles of element A in the reaction liquid] / [mol of element M in the reaction liquid).
  • the number]) is dissolved in a range of 0.04 or more and 1.3 or less, and the reaction solution is prepared, and the maximum temperature of the reaction solution is kept at 35 ° C. or less while the element A is solid in the reaction solution.
  • the molar ratio of the element A in the solid compound to the element A in the reaction solution ([number of moles of element A in the solid compound] / [number of moles of element A in the reaction solution]) is 1 or more. It aims at providing the manufacturing method of the fluorescent substance including the process of adding and making these react so that it may become 50 or less range.
  • the solid compound of element A is preferably a hydrogen fluoride salt of element A.
  • the element A is preferably potassium (K), and the element M is preferably silicon (Si).
  • a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ can be produced in a safe and high yield, and has a high external quantum efficiency.
  • a phosphor can be obtained.
  • Example 1 The X-ray-diffraction pattern of the fluorescent substance obtained in Example 1 is shown. The excitation and the fluorescence spectrum of the fluorescent substance obtained in Example 1 are shown.
  • the present invention is a method for producing a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ .
  • the element A is an alkali metal element containing at least K. Specifically, in addition to K, Na and Li may be used. When an alkali metal element other than K is included, the K content is preferably large from the viewpoint of chemical stability, and preferably K alone.
  • the element M is at least one metal element selected from Si, Ge, Sn, Ti, Zr and Hf containing at least Si, and preferably Si alone having excellent chemical stability.
  • the excitation band of the phosphor of the present invention is influenced by the constituent elements, but is greatly influenced by the type of the element M in particular.
  • reaction solution in which element A, elements M, F, and Mn are dissolved at a specific composition ratio and a solid compound of element A are prepared as starting materials.
  • reaction solution is prepared by dissolving a raw material compound that supplies element A, element M, Mn, and F in a solvent made of hydrofluoric acid.
  • concentration of hydrogen fluoride in hydrofluoric acid as the solvent the more Mn impurities unrelated to the phosphor can be reduced.
  • concentration is too high, the vapor pressure increases and the handling risk increases. More than 70 mass% is preferable.
  • the element A source examples include fluoride, hydrogen fluoride, nitrate, carbonate, acetate, and chloride of element A.
  • the element M source it is preferable to use an oxide, hydroxide, or carbonate of the element M instead of the element M alone because of its stability.
  • K 2 MnF 6 or KMnO 4 can be used, but K 2 MnF 6 is preferably used. K 2 MnF 6 is preferable because F and K (corresponding to the element A) constituting the phosphor can be simultaneously supplied in addition to Mn.
  • the compounding amount of the raw material compound is adjusted so that the molar ratio of element A to element M in the reaction solution is in the range of 0.04 to 1.3.
  • Solid compound of element A fluoride, hydrogen fluoride, nitrate, carbonate, acetate, and chloride of element A can be used. Among these, those that do not generate heat when dissolved in a hydrofluoric acid reaction solution are preferred, and hydrofluoric acid salts are preferred.
  • the solid compound may be in a granular form such as a powder or a granule, or in a bulk form obtained by pressure-molding these granular substances. The difference in form affects the dissolution and the precipitation reaction of the phosphor when added to the reaction solution, and affects the particle size and distribution of the obtained phosphor. If the solid compound of element A is added to the reaction solution in a fine state, the particle size of the obtained phosphor becomes fine, and if added in a large bulk state, the particle size of the obtained phosphor becomes large.
  • the solid compound of element A is prepared in such an amount that the element A in the solid compound has a specific molar ratio with respect to the element A in the reaction solution in order to deposit a high-purity phosphor in a high yield. To do. That is, if the amount of element A in the solid compound is too small relative to element A in the reaction solution, the external quantum efficiency of the obtained phosphor tends to be low, and if it is too large, the characteristics of the obtained phosphor vary. There is a tendency to grow. Therefore, the molar ratio of the element A in the solid compound to the element A in the reaction solution ([number of moles of element A in the solid compound] / [number of moles of element A in the reaction solution]) is 1 or more and 50. Adjust to the following range.
  • reaction between the reaction solution and the solid compound of element A is performed at a constant temperature or lower.
  • the temperature of the reaction solution rises.
  • Mn dissolved in the reaction liquid becomes a compound other than the fluoride phosphor, and this compound becomes an impurity. Since these impurities are colored, when they coexist with the phosphor, the fluorescence emission is inhibited.
  • the maximum reaction liquid temperature in the reaction step is maintained at 35 ° C. or lower.
  • ⁇ Post-processing> it is preferable to perform a washing step and a classification step on the phosphor produced in the above reaction step as a post-treatment.
  • the phosphor is recovered by solid-liquid separation by filtration or the like, and washed with an organic solvent such as methanol, ethanol, or acetone. If the phosphor is washed with water, a part of the phosphor is hydrolyzed to produce a brown manganese compound, which may deteriorate the characteristics of the phosphor. For this reason, it is necessary to use an organic solvent in the cleaning process.
  • the concentration of hydrofluoric acid used for washing is preferably 15% by mass or more from the viewpoint of suppressing hydrolysis of the fluoride phosphor. After the cleaning process, it is preferable to dry the phosphor and evaporate the cleaning liquid completely. Moreover, by classifying using a sieve having an opening of a predetermined size, variation in the particle size of the phosphor can be suppressed and adjusted within a certain range.
  • Table 1 shows the starting materials used in the production methods of Examples and Comparative Examples, the composition ratio of specific elements, the maximum temperature of the reaction solution, and various evaluation results.
  • the composition ratio [number of moles of K in the solid compound] / [number of moles of K in the reaction liquid] is the mole of K contained in the K 2 MnF 6 and KHF 2 raw materials dissolved in the reaction liquid. It was calculated from the number and the number of moles of K contained in the KHF 2 raw material added as a solid compound.
  • the composition ratio [number of moles of K in the reaction solution] / [number of moles of Si in the reaction solution] is the number of moles of K contained in the K 2 MnF 6 and KHF 2 raw materials dissolved in the reaction solution, It was calculated from the number of moles of Si contained in the SiO 2 raw material dissolved in the reaction solution.
  • the maximum temperature (° C.) of the reaction solution was measured using a sheath type thermocouple (K type) coated with a fluororesin.
  • the yield (unit:%), crystal phase (X-ray diffraction), external quantum efficiency at an excitation wavelength of 455 nm, and emission peak wavelength in the production methods of the phosphors of Examples and Comparative Examples were measured as follows.
  • the yield is a ratio of the mass of the phosphor actually obtained with respect to the theoretical mass when it is assumed that Si and Mn of the SiO 2 and K 2 MnF 6 raw materials are all K 2 SiF 6 : Mn.
  • a preferred yield is 60% or more, and a more preferred yield is 70% or more.
  • the crystal phase is a crystal phase determined by an X-ray diffraction pattern, and is measured and evaluated with an X-ray diffractometer (Ultima IV manufactured by Rigaku Corporation). A CuK ⁇ tube was used for this measurement. Specifically, it was determined whether or not the same pattern as the K 2 SiF 6 crystal and the same pattern as the KHF 2 crystal.
  • the external quantum efficiency is obtained by measuring the excitation / fluorescence spectrum of a phosphor with a spectrofluorometer (F-7000, manufactured by Hitachi High-Technologies Corporation).
  • the excitation wavelength of the fluorescence spectrum was 455 nm
  • the monitor fluorescence wavelength of the excitation spectrum was 632 nm
  • the total luminous flux emission spectrum was measured using an integrating sphere for the phosphor.
  • Kazuaki Okubo et al. Quantum efficiency measurement of NBS standard phosphor, Journal of the Illuminating Society of Japan, 1999, Vol. 83, No. 2, p. 87-93.
  • As the excitation light a spectral xenon lamp light source was used.
  • a preferable external quantum efficiency is 0.35 or more
  • a more preferable external quantum efficiency is 0.45 or more.
  • the emission peak wavelength was obtained by performing excitation / fluorescence spectrum measurement of the phosphor using a spectrofluorimeter (F-7000, manufactured by Hitachi High-Technologies Corporation).
  • the excitation wavelength of the fluorescence spectrum was 455 nm, and the monitor wavelength of the excitation spectrum was 632 nm.
  • Example 1 Preparation process> 1.
  • Reaction liquid K 2 MnF 6 powder was produced by the method described in Non-Patent Document 1. Specifically, 800 ml of 40% strength by weight hydrofluoric acid was placed in a 1 liter fluororesin beaker, 260 g of KHF 2 powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) and potassium permanganate powder (Wako Pure). 12 g of Yaku Kogyo Co., Ltd., reagent grade 1) was dissolved. While stirring this hydrofluoric acid reaction liquid with a magnetic stirrer, 8 ml of 30% hydrogen peroxide (special grade reagent) was added dropwise little by little.
  • Solid compound Separately from the reaction solution 76.56 g of KHF 2 powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) was prepared as a solid compound.
  • the K present in the solid compound is 0.980 mol. Therefore, the composition ratio of K in the solid compound to K in the reaction solution described above [number of moles of K in the solid compound] / [reaction solution] The number of moles of K] was 1.89.
  • the X-ray diffraction pattern of the phosphor obtained by the phosphor manufacturing method of Example 1 was measured with an X-ray diffractometer (manufactured by Rigaku Corporation, Ultimate IV). A CuK ⁇ tube was used for the measurement. The measurement results are shown in FIG. It was confirmed that the phosphor manufactured by the phosphor manufacturing method of Example 1 has the same pattern as the K 2 SiF 6 crystal and does not contain other crystal phases.
  • the excitation / fluorescence spectrum of this phosphor was measured with a spectrofluorometer (manufactured by Hitachi High-Technologies Corporation, F-7000). The measurement results are shown in FIG. In this measurement, the excitation wavelength of the fluorescence spectrum was 455 nm, and the monitor fluorescence wavelength of the excitation spectrum was 632 nm.
  • This phosphor was confirmed to have two excitation bands of ultraviolet light near a peak wavelength of 350 nm and blue light near a peak wavelength of 450 nm, and to have a plurality of narrow-band emissions in the red region of 600 to 700 nm.
  • the external quantum efficiency was 0.512. The external quantum efficiency was measured using the method described above.
  • Examples 2 to 4 and Comparative Examples 1 to 3 > In Examples 2 to 4 and Comparative Examples 1 to 3, the amounts of SiO 2 powder, K 2 MnF 6 powder, and KHF 2 powder in the reaction solution and solid compound were set to the values shown in Table 1, and the same method as in Example 1 was used. Manufactured by.
  • Comparative Example 4 Although Comparative Example 4 was not described in Table 1, it was exactly the same as Example 1 except that KHF 2 powder added in the solid state was changed to KF powder (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.). Manufactured with. The amount of KF added was 56.9 g so as to have the same number of moles as the solid KHF 2 powder added in Example 1. When KF powder was added, the temperature of the reaction solution rose to 60 ° C. due to the heat of dissolution of KF. After completion of the reaction, the mixture was allowed to cool to room temperature, and the precipitate was collected in the same manner as in Example 1.
  • KF powder special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.
  • the yield of the phosphor in Comparative Example 4 was 75%, the crystal phase recognized by X-ray diffraction measurement was only the K 2 SiF 6 phase, and the average particle size was 13 ⁇ m. However, as a result of the quantum efficiency measurement, the absorptance was 0.752 and the external quantum efficiency was 0.340. It was confirmed that the external quantum efficiency of the obtained phosphor was remarkably lowered by exceeding 35 ° C. in the reaction step in which the phosphor was deposited.

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Abstract

　The present invention pertains to a method for producing a fluorescent substance, the method making it possible to produce a composite fluoride-based fluorescent substance represented by the general formula: A2MF6:Mn4+ (in the formula, element A is an alkali metal element including at least K; element M is a metal element of one or more selected from Si, Ge, Sn, Ti, Zr, and Hf, including at least Si; F is fluorine; and Mn is manganese) safely and at high yield, and also making it possible to obtain a fluorescent substance having high external quantum efficiency. The present invention is characterized in including: a step for preparing a reaction solution by dissolving element A, element M, F, and Mn in a solvent comprising hydrofluoric acid so that the molar ratio of element A to element M ([number of mols of element A in reaction solution]/[number of mols of element M in reaction solution]) is within a range of 0.04-1.3; and a step for adding a solid compound of element A to the reaction solution so that the molar ratio of element A in the solid compound to element A in the reaction solution ([number of mols of element A in solid compound]/[number of mols of element A in reaction solution]) is within a range of 1-50 while maintaining the maximum temperature of the reaction solution at 35°C or below, and causing a reaction.

Description

蛍光体の製造方法Method for manufacturing phosphor
　本発明は、青色光で励起された際に赤色発光する蛍光体の製造方法に関する。より詳しくは、一般式：Ａ２ＭＦ６：Ｍｎ４＋（元素Ａは少なくともＫを含有するアルカリ金属元素であり、元素Ｍは少なくともＳｉを含有するＳｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ及びＨｆから選ばれる一種以上の金属元素）で表される複合フッ化物蛍光体を安全かつ高収率で得ることができ、しかも外部量子効率が高く発光効率に優れた蛍光体を得ることができる製造方法に関する。 The present invention relates to a method for producing a phosphor that emits red light when excited by blue light. More specifically, the general formula: A 2 MF 6 : Mn 4+ (the element A is an alkali metal element containing at least K, and the element M is selected from Si, Ge, Sn, Ti, Zr and Hf containing at least Si. The present invention relates to a production method capable of obtaining a composite fluoride phosphor represented by one or more metal elements) in a safe and high yield, and capable of obtaining a phosphor having high external quantum efficiency and excellent luminous efficiency.
　照明及びディスプレイ用の白色光を得るために、光源としての青色ＬＥＤチップと、青色を受けて緑色を発光する緑色蛍光体と、青色を受けて赤色を発光する赤色蛍光体とを組み合わせて光の加法混合原理を利用する方式のものが広く普及している。 In order to obtain white light for illumination and display, a blue LED chip as a light source, a green phosphor that emits green when receiving blue, and a red phosphor that emits red when receiving blue are combined. A method using an additive mixing principle is widely used.
　赤色蛍光体として、ＣａＡｌＳｉＮ３：Ｅｕや（Ｓｒ，Ｃａ）ＡｌＳｉＮ３：Ｅｕなどの窒化物蛍光体や、（Ｃａ，Ｓｒ）Ｓ：Ｅｕなどの硫化物蛍光体などがよく知られているが、一般式：Ａ２［ＭＦ６］：Ｍｎ４＋（元素Ａは、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ、ＮＨ４など、元素ＭはＧｅ、Ｓｉ、Ｓｎ、Ｔｉ、Ｚｒなど）で表される複合フッ化物蛍光体は、蛍光スペクトルが非常にシャープであり、深い赤色でありながら輝度が高い赤色蛍光体として注目されている（非特許文献１及び２）。この蛍光体は、４価の元素Ｍサイトの一部にＭｎ４＋が置換固溶した構造を有し、Ｍｎ４＋の電子遷移により、複数のライン状発光が組み合わさった蛍光スペクトルを示す。 As red phosphors, nitride phosphors such as CaAlSiN 3 : Eu and (Sr, Ca) AlSiN 3 : Eu and sulfide phosphors such as (Ca, Sr) S: Eu are well known. General formula: A 2 [MF 6 ]: Mn 4+ (element A is Li, Na, K, Rb, Cs, NH 4, etc., element M is Ge, Si, Sn, Ti, Zr, etc.) Fluoride phosphors have attracted attention as red phosphors having a very sharp fluorescence spectrum and a high brightness while being deep red (Non-patent Documents 1 and 2). This phosphor has a structure in which Mn 4+ is substituted and dissolved in a part of a tetravalent element M site, and exhibits a fluorescence spectrum in which a plurality of line-like light emission are combined by electronic transition of Mn 4+ .
　このＡ２［ＭＦ６］：Ｍｎ４＋で表される複合フッ化物蛍光体の製造方法として、特許文献１には、蛍光体の母体となるＡ２［ＭＦ６］結晶と発光中心となるＭｎを含むＫ２ＭｎＦ６結晶を用意し、それらの結晶をフッ化水素酸中に溶解し、蒸発乾固させる製造方法が開示されている。
　また、特許文献２には、ケイ素などの単体金属をフッ化水素酸と過マンガン酸カリウムの混合液に浸漬して製造する方法が開示されている。
　さらに、特許文献３、４には、フッ化物蛍光体の構成元素の一部を溶解した反応液に、残りの構成元素を反応液又は固体状態の化合物の形態で添加して製造する方法が開示されている。 As a method for producing a composite fluoride phosphor represented by A 2 [MF 6 ]: Mn 4+ , Patent Document 1 discloses an A 2 [MF 6 ] crystal serving as a phosphor base and Mn serving as an emission center. A production method is disclosed in which K 2 MnF 6 crystals are prepared, dissolved in hydrofluoric acid, and evaporated to dryness.
Patent Document 2 discloses a method for producing a single metal such as silicon by immersing it in a mixed solution of hydrofluoric acid and potassium permanganate.
Further, Patent Documents 3 and 4 disclose a method for producing a reaction solution in which a part of the constituent elements of the fluoride phosphor is dissolved and adding the remaining constituent elements in the form of a reaction solution or a solid state compound. Has been.
　しかし、特許文献１記載の製造方法は、フッ化水素酸を蒸発させるために耐熱性・耐食性に優れた反応装置と、蒸発に伴い発生する人体に有害なフッ化水素ガスの除外設備とが必要となり、量産化する場合には高額な製造設備が必要となる。
　また、特許文献２記載の製造方法は、製造された蛍光体のマンガン量の制御が困難であるため製造された蛍光体の特性が不均一であり、製造時の未反応ケイ素が残存するため製造された蛍光体の発光強度が不十分であり、なおかつ、蛍光体の析出反応速度が遅いために生産性が低い。
　さらに、特許文献３及び特許文献４記載の製造方法は、析出する蛍光体の粒子サイズの制御が困難であり、十分な発光特性が得られない。 However, the production method described in Patent Document 1 requires a reaction apparatus excellent in heat resistance and corrosion resistance to evaporate hydrofluoric acid, and a facility for excluding hydrogen fluoride gas harmful to the human body generated by the evaporation. Therefore, expensive production facilities are required for mass production.
In addition, the manufacturing method described in Patent Document 2 is manufactured because it is difficult to control the amount of manganese in the manufactured phosphor, and thus the characteristics of the manufactured phosphor are non-uniform, and unreacted silicon remains during manufacturing. The luminous intensity of the phosphor is insufficient, and the productivity of the phosphor is low due to the slow deposition reaction rate of the phosphor.
Furthermore, in the production methods described in Patent Document 3 and Patent Document 4, it is difficult to control the particle size of the phosphors deposited, and sufficient light emission characteristics cannot be obtained.
米国特許出願公開第２００６／０１６９９９８号明細書US Patent Application Publication No. 2006/0169998 国際公開２００９／１１９４８６号パンフレットInternational Publication No. 2009/119486 Pamphlet 特開２０１０－２０９３１１号公報JP 2010-209111 A 特開２０１２－２２４５３６号公報JP 2012-224536 A
　本発明者らは、蛍光体の原料を蛍光体の元素組成とは異なる配合比でフッ化水素酸に溶解させた反応液に、蛍光体構成元素のうちの特定元素の化合物を固体状態で添加し、所定の温度範囲内及び所定の組成比で反応させることにより、一般式：Ａ２ＭＦ６：Ｍｎ４＋で表される蛍光体を安全かつ高い収率で製造でき、しかも、外部量子効率が高い蛍光体を製造できることを見出し、本発明を完成させた。 The present inventors added a compound of a specific element of the phosphor constituent elements in a solid state to a reaction solution in which the raw material of the phosphor is dissolved in hydrofluoric acid at a blending ratio different from the element composition of the phosphor In addition, a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ can be produced in a safe and high yield by reacting within a predetermined temperature range and at a predetermined composition ratio, and the external quantum efficiency is high. The present inventors have found that a high phosphor can be produced and completed the present invention.
　すなわち、本発明は、一般式：Ａ２ＭＦ６：Ｍｎ４＋で表される蛍光体（式中、元素Ａは少なくともＫを含有するアルカリ金属元素であり、元素Ｍは少なくともＳｉを含有するＳｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ及びＨｆから選ばれる一種以上の金属元素であり、Ｆはフッ素であり、Ｍｎはマンガンである）の製造方法であって、
フッ化水素酸からなる溶媒に、元素Ａ、元素Ｍ、Ｆ及びＭｎを、元素Ｍに対する元素Ａのモル比（［反応液中の元素Ａのモル数］／［反応液中の元素Ｍのモル数］）が０．０４以上１．３以下の範囲となるように溶解させて反応液を調製する工程、及び
反応液の最高温度を３５℃以下に保ちながら、反応液に、元素Ａの固体状化合物を、反応液中の元素Ａに対する固体状化合物中の元素Ａのモル比（［固体状化合物中の元素Ａのモル数］／［反応液中の元素Ａのモル数］）が１以上５０以下の範囲となるように添加してこれらを反応させる工程
を含む蛍光体の製造方法を提供することを目的とする。 That is, the present invention relates to a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ (wherein the element A is an alkali metal element containing at least K, and the element M is Si containing at least Si, And one or more metal elements selected from Ge, Sn, Ti, Zr and Hf, F is fluorine, and Mn is manganese.
In a solvent composed of hydrofluoric acid, element A, elements M, F and Mn are mixed with the molar ratio of element A to element M ([number of moles of element A in the reaction liquid] / [mol of element M in the reaction liquid). The number]) is dissolved in a range of 0.04 or more and 1.3 or less, and the reaction solution is prepared, and the maximum temperature of the reaction solution is kept at 35 ° C. or less while the element A is solid in the reaction solution. The molar ratio of the element A in the solid compound to the element A in the reaction solution ([number of moles of element A in the solid compound] / [number of moles of element A in the reaction solution]) is 1 or more. It aims at providing the manufacturing method of the fluorescent substance including the process of adding and making these react so that it may become 50 or less range.
　元素Ａの固体状化合物は、元素Ａのフッ化水素塩であることが好ましい。
　また、元素Ａはカリウム（Ｋ）であることが好ましく、元素Ｍはケイ素（Ｓｉ）であることが好ましい。 The solid compound of element A is preferably a hydrogen fluoride salt of element A.
The element A is preferably potassium (K), and the element M is preferably silicon (Si).
　本発明の蛍光体の製造方法によれば、一般式：Ａ２ＭＦ６：Ｍｎ４＋で表される蛍光体を、安全かつ高い収率で製造することができ、なおかつ、高い外部量子効率を有する蛍光体を得ることができる。 According to the method for producing a phosphor of the present invention, a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ can be produced in a safe and high yield, and has a high external quantum efficiency. A phosphor can be obtained.
実施例１で得た蛍光体のＸ線回折パターンを示す。The X-ray-diffraction pattern of the fluorescent substance obtained in Example 1 is shown. 実施例１で得た蛍光体の励起・蛍光スペクトルを示す。The excitation and the fluorescence spectrum of the fluorescent substance obtained in Example 1 are shown.
　本発明は、一般式：Ａ２ＭＦ６：Ｍｎ４＋で表される蛍光体の製造方法である。
　元素Ａは、少なくともＫを含有するアルカリ金属元素であり、具体的にはＫの他に、ＮａやＬｉであってもよい。Ｋ以外のアルカリ金属元素を含む場合、化学的安定性の観点からＫ含有量は多い方がよく、好ましくはＫ単独である。 The present invention is a method for producing a phosphor represented by the general formula: A 2 MF 6 : Mn 4+ .
The element A is an alkali metal element containing at least K. Specifically, in addition to K, Na and Li may be used. When an alkali metal element other than K is included, the K content is preferably large from the viewpoint of chemical stability, and preferably K alone.
　元素Ｍは、少なくともＳｉを含有するＳｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ及びＨｆから選ばれる一種以上の金属元素であり、好ましくは化学的安定性に優れるＳｉ単独である。本発明の蛍光体の励起帯は、構成元素の影響を受けるが、特に元素Ｍの種類によって大きく影響される。 The element M is at least one metal element selected from Si, Ge, Sn, Ti, Zr and Hf containing at least Si, and preferably Si alone having excellent chemical stability. The excitation band of the phosphor of the present invention is influenced by the constituent elements, but is greatly influenced by the type of the element M in particular.
　本発明の蛍光体の製造方法では、出発原料として、元素Ａ、元素Ｍ、Ｆ及びＭｎを特定の組成比率となるように溶解させた反応液と、元素Ａの固体状化合物とを準備する。 In the phosphor manufacturing method of the present invention, a reaction solution in which element A, elements M, F, and Mn are dissolved at a specific composition ratio and a solid compound of element A are prepared as starting materials.
＜反応液＞
　反応液は、フッ化水素酸からなる溶媒に、元素Ａ、元素Ｍ、Ｍｎ、Ｆを供給する原料化合物を溶解することによって調製する。
　溶媒としてのフッ化水素酸のフッ化水素濃度は、高いほど蛍光体とは無関係なＭｎ不純物を低減できるが、高すぎると蒸気圧が高くなって取扱いの危険性が大きくなるため、５０質量％以上７０質量％以下が好ましい。 <Reaction solution>
The reaction solution is prepared by dissolving a raw material compound that supplies element A, element M, Mn, and F in a solvent made of hydrofluoric acid.
The higher the concentration of hydrogen fluoride in hydrofluoric acid as the solvent, the more Mn impurities unrelated to the phosphor can be reduced. However, if the concentration is too high, the vapor pressure increases and the handling risk increases. More than 70 mass% is preferable.
　元素Ａ源としては、例えば、元素Ａのフッ化物、フッ化水素塩、硝酸塩、炭酸塩、酢酸塩、塩化物がある。
　元素Ｍ源としては、その安定性から、元素Ｍ単体でなく、元素Ｍの酸化物、水酸化物、炭酸塩を用いることが好ましい。
　Ｍｎ源としては、Ｋ２ＭｎＦ６やＫＭｎＯ４等を用いることができるが、Ｋ２ＭｎＦ６を用いることが好ましい。Ｋ２ＭｎＦ６であれば、Ｍｎ以外に、蛍光体を構成するＦやＫ（元素Ａに該当）も同時に供給できるため好ましい。 Examples of the element A source include fluoride, hydrogen fluoride, nitrate, carbonate, acetate, and chloride of element A.
As the element M source, it is preferable to use an oxide, hydroxide, or carbonate of the element M instead of the element M alone because of its stability.
As the Mn source, K 2 MnF 6 or KMnO 4 can be used, but K 2 MnF 6 is preferably used. K 2 MnF 6 is preferable because F and K (corresponding to the element A) constituting the phosphor can be simultaneously supplied in addition to Mn.
　反応液における元素Ｍに対する元素Ａのモル比（［反応液中の元素Ａのモル数］／［反応液中の元素Ｍのモル数］）は、あまりに小さいと吸収率が低くなり、外部量子効率が低くなる傾向にあり、あまりに大きいと目的とする蛍光体以外の異相の生成量が増加する傾向がある。そのため、反応液における元素Ｍに対する元素Ａのモル比が０．０４以上１．３以下の範囲となるように原料化合物の配合量を調節する。 If the molar ratio of element A to element M in the reaction solution ([number of moles of element A in the reaction solution] / [number of moles of element M in the reaction solution]) is too small, the absorptance decreases, and the external quantum efficiency Tends to be low, and if it is too large, the amount of foreign phases other than the intended phosphor tends to increase. Therefore, the compounding amount of the raw material compound is adjusted so that the molar ratio of element A to element M in the reaction solution is in the range of 0.04 to 1.3.
＜元素Ａの固体状化合物＞
　元素Ａの固体状化合物としては、具体的には、元素Ａのフッ化物、フッ化水素塩、硝酸塩、炭酸塩、酢酸塩、塩化物を用いることができる。なかでも、フッ化水素酸反応液に溶解した時に発熱しないものが好ましく、フッ化水素塩が好ましい。
　固体状化合物は、粉末、顆粒などの粒状形態、これら粒状のものを加圧成形したバルク状形態であってもよい。これら形態の違いは、反応液に添加した時の溶解及び蛍光体の析出反応に影響し、得られる蛍光体の粒度及びその分布に影響する。元素Ａの固体状化合物を微細な状態で反応液に添加すれば、得られる蛍光体の粒度は細かくなり、大きなバルク状態で添加すれば得られる蛍光体の粒度は大きくなる。 <Solid compound of element A>
Specifically, as the solid compound of element A, fluoride, hydrogen fluoride, nitrate, carbonate, acetate, and chloride of element A can be used. Among these, those that do not generate heat when dissolved in a hydrofluoric acid reaction solution are preferred, and hydrofluoric acid salts are preferred.
The solid compound may be in a granular form such as a powder or a granule, or in a bulk form obtained by pressure-molding these granular substances. The difference in form affects the dissolution and the precipitation reaction of the phosphor when added to the reaction solution, and affects the particle size and distribution of the obtained phosphor. If the solid compound of element A is added to the reaction solution in a fine state, the particle size of the obtained phosphor becomes fine, and if added in a large bulk state, the particle size of the obtained phosphor becomes large.
　元素Ａの固体状化合物は、純度の高い蛍光体を高収率で析出させるために、反応液中の元素Ａに対して、固体状化合物中の元素Ａが特定のモル比となる量を準備する。
　すなわち、固体状化合物中の元素Ａは、反応液中の元素Ａに対してあまりに少ないと得られる蛍光体の外部量子効率が低くなる傾向にあり、あまりに多いと得られる蛍光体の特性のバラツキが大きくなる傾向がある。このため、反応液中の元素Ａに対する固体状化合物中の元素Ａのモル比（［固体状化合物中の元素Ａのモル数］／［反応液中の元素Ａのモル数］）が１以上５０以下の範囲となるように調節する。 The solid compound of element A is prepared in such an amount that the element A in the solid compound has a specific molar ratio with respect to the element A in the reaction solution in order to deposit a high-purity phosphor in a high yield. To do.
That is, if the amount of element A in the solid compound is too small relative to element A in the reaction solution, the external quantum efficiency of the obtained phosphor tends to be low, and if it is too large, the characteristics of the obtained phosphor vary. There is a tendency to grow. Therefore, the molar ratio of the element A in the solid compound to the element A in the reaction solution ([number of moles of element A in the solid compound] / [number of moles of element A in the reaction solution]) is 1 or more and 50. Adjust to the following range.
＜反応液と元素Ａの固体状化合物との反応工程＞
　本発明の蛍光体の製造方法は、反応液と元素Ａの固体状化合物との反応を一定温度以下にて行う。
　反応液に元素Ａの固体状化合物を添加すると、反応液の温度が上昇する。反応液中の温度が上昇すると、反応液中に溶解しているＭｎがフッ化物蛍光体以外の化合物にもなり、この化合物が不純物になる。この不純物は有色のため、蛍光体と共存するとその蛍光発光を阻害する。この不純物を発生させないために、反応工程での反応液最高温度は３５℃以下に維持する。
　元素Ａの固体状化合物が反応液に溶解したときに、局所的に過飽和状態となって蛍光体が析出する。 <Reaction process between reaction solution and solid compound of element A>
In the method for producing the phosphor of the present invention, the reaction between the reaction solution and the solid compound of element A is performed at a constant temperature or lower.
When the solid compound of element A is added to the reaction solution, the temperature of the reaction solution rises. When the temperature in the reaction liquid rises, Mn dissolved in the reaction liquid becomes a compound other than the fluoride phosphor, and this compound becomes an impurity. Since these impurities are colored, when they coexist with the phosphor, the fluorescence emission is inhibited. In order not to generate this impurity, the maximum reaction liquid temperature in the reaction step is maintained at 35 ° C. or lower.
When the solid compound of element A is dissolved in the reaction solution, the phosphor is deposited locally in a supersaturated state.
＜後処理＞
　本発明の蛍光体の製造方法は、後処理として、上記の反応工程で製造された蛍光体に対して洗浄工程、分級工程を行うことが好ましい。
　洗浄を行う場合には、蛍光体をろ過等により固液分離して回収し、メタノール、エタノール、アセトン等の有機溶剤で洗浄する。蛍光体を水で洗浄してしまうと、蛍光体の一部が加水分解して茶色のマンガン化合物が生成し、蛍光体の特性を低下させることがある。このため、洗浄工程では有機溶剤を用いる必要がある。また、有機溶剤での洗浄前に、フッ化水素酸反応液で数回洗浄を行うと、微量生成していた不純物を溶解除去することができる。洗浄に用いるフッ化水素酸の濃度は、フッ化物蛍光体の加水分解抑制の観点から、１５質量％以上が好ましい。洗浄工程後には、蛍光体を乾燥させて洗浄液を完全に蒸発させることが好ましい。
　また、所定の大きさの開口部のある篩を用いて分級することにより、蛍光体の粒度のばらつきを抑制し、一定範囲内に調整できる。 <Post-processing>
In the phosphor production method of the present invention, it is preferable to perform a washing step and a classification step on the phosphor produced in the above reaction step as a post-treatment.
When washing is performed, the phosphor is recovered by solid-liquid separation by filtration or the like, and washed with an organic solvent such as methanol, ethanol, or acetone. If the phosphor is washed with water, a part of the phosphor is hydrolyzed to produce a brown manganese compound, which may deteriorate the characteristics of the phosphor. For this reason, it is necessary to use an organic solvent in the cleaning process. In addition, when cleaning with a hydrofluoric acid reaction solution is performed several times before cleaning with an organic solvent, impurities generated in a trace amount can be dissolved and removed. The concentration of hydrofluoric acid used for washing is preferably 15% by mass or more from the viewpoint of suppressing hydrolysis of the fluoride phosphor. After the cleaning process, it is preferable to dry the phosphor and evaporate the cleaning liquid completely.
Moreover, by classifying using a sieve having an opening of a predetermined size, variation in the particle size of the phosphor can be suppressed and adjusted within a certain range.
　本発明を以下に示す実施例によってさらに詳しく説明する。表１は、各実施例及び比較例の製造方法に用いた出発原料、特定元素の組成比、反応液の最高温度、及び各種評価結果を示したものである。 The present invention will be described in more detail with reference to the following examples. Table 1 shows the starting materials used in the production methods of Examples and Comparative Examples, the composition ratio of specific elements, the maximum temperature of the reaction solution, and various evaluation results.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１において、組成比［固体状化合物中のＫのモル数］／［反応液中のＫのモル数］は、反応液中に溶解したＫ２ＭｎＦ６及びＫＨＦ２原料に含まれるＫのモル数と、固体状化合物として添加したＫＨＦ２原料に含まれるＫのモル数から算出した。
　また、組成比［反応液中のＫのモル数］／［反応液中のＳｉのモル数］は、反応液中に溶解したＫ２ＭｎＦ６及びＫＨＦ２原料に含まれるＫのモル数と、応液中に溶解したＳｉＯ２原料に含まれるＳｉのモル数から算出した。
　反応液の最高温度（℃）は、フッ素樹脂で被覆したシースタイプの熱電対（Ｋタイプ）を用いて測定した。 In Table 1, the composition ratio [number of moles of K in the solid compound] / [number of moles of K in the reaction liquid] is the mole of K contained in the K 2 MnF 6 and KHF 2 raw materials dissolved in the reaction liquid. It was calculated from the number and the number of moles of K contained in the KHF 2 raw material added as a solid compound.
The composition ratio [number of moles of K in the reaction solution] / [number of moles of Si in the reaction solution] is the number of moles of K contained in the K 2 MnF 6 and KHF 2 raw materials dissolved in the reaction solution, It was calculated from the number of moles of Si contained in the SiO 2 raw material dissolved in the reaction solution.
The maximum temperature (° C.) of the reaction solution was measured using a sheath type thermocouple (K type) coated with a fluororesin.
　実施例及び比較例の蛍光体の製造方法における収率（単位：％）、結晶相（Ｘ線回折）、励起波長４５５ｎｍでの外部量子効率、発光ピーク波長は以下のようにして測定した。 The yield (unit:%), crystal phase (X-ray diffraction), external quantum efficiency at an excitation wavelength of 455 nm, and emission peak wavelength in the production methods of the phosphors of Examples and Comparative Examples were measured as follows.
　収率は、ＳｉＯ２及びＫ２ＭｎＦ６原料のＳｉ及びＭｎが全てＫ２ＳｉＦ６：Ｍｎとなったと仮定した場合の理論質量に対して実際に得られた蛍光体の質量の比率である。好ましい収率は６０％以上であり、より好ましい収率は７０％以上である。 The yield is a ratio of the mass of the phosphor actually obtained with respect to the theoretical mass when it is assumed that Si and Mn of the SiO 2 and K 2 MnF 6 raw materials are all K 2 SiF 6 : Mn. A preferred yield is 60% or more, and a more preferred yield is 70% or more.
　結晶相（Ｘ線回折）は、Ｘ線回折パターンで結晶相を判断したものであり、Ｘ線回折装置（リガク社製Ｕｌｔｉｍａ　ＩＶ）で測定し評価したものである。この測定にはＣｕＫα管球を使用した。具体的にはＫ２ＳｉＦ６結晶と同一パターンか否か、ＫＨＦ２結晶と同一パターンか否かを判断した。 The crystal phase (X-ray diffraction) is a crystal phase determined by an X-ray diffraction pattern, and is measured and evaluated with an X-ray diffractometer (Ultima IV manufactured by Rigaku Corporation). A CuKα tube was used for this measurement. Specifically, it was determined whether or not the same pattern as the K 2 SiF 6 crystal and the same pattern as the KHF 2 crystal.
　外部量子効率は、蛍光体の励起・蛍光スペクトルを分光蛍光光度計（日立ハイテクノロジーズ社製Ｆ－７０００）で測定したものである。蛍光スペクトルの励起波長は４５５ｎｍ、励起スペクトルのモニター蛍光波長は６３２ｎｍであり、蛍光体に対して積分球を用いて全光束発光スペクトル測定を行った。
　この測定にあっては、大久保和明他、ＮＢＳ標準蛍光体の量子効率測定、照明学会誌、平成１１年、第８３巻第２号、ｐ．８７－９３に準拠して行った。励起光には、分光したキセノンランプ光源を分光して使用した。
　好ましい外部量子効率は０．３５以上であり、より好ましい外部量子効率は０．４５以上である。 The external quantum efficiency is obtained by measuring the excitation / fluorescence spectrum of a phosphor with a spectrofluorometer (F-7000, manufactured by Hitachi High-Technologies Corporation). The excitation wavelength of the fluorescence spectrum was 455 nm, the monitor fluorescence wavelength of the excitation spectrum was 632 nm, and the total luminous flux emission spectrum was measured using an integrating sphere for the phosphor.
In this measurement, Kazuaki Okubo et al., Quantum efficiency measurement of NBS standard phosphor, Journal of the Illuminating Society of Japan, 1999, Vol. 83, No. 2, p. 87-93. As the excitation light, a spectral xenon lamp light source was used.
A preferable external quantum efficiency is 0.35 or more, and a more preferable external quantum efficiency is 0.45 or more.
　発光ピーク波長は、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、蛍光体の励起・蛍光スペクトル測定を行って求めた。蛍光スペクトルの励起波長を４５５ｎｍとし、励起スペクトルのモニター波長を６３２ｎｍとした。 The emission peak wavelength was obtained by performing excitation / fluorescence spectrum measurement of the phosphor using a spectrofluorimeter (F-7000, manufactured by Hitachi High-Technologies Corporation). The excitation wavelength of the fluorescence spectrum was 455 nm, and the monitor wavelength of the excitation spectrum was 632 nm.
実施例１
＜準備工程＞
１．反応液
　Ｋ２ＭｎＦ６粉末を、非特許文献１に記載されている方法で製造した。具体的には、容量１リットルのフッ素樹脂製ビーカーに濃度４０質量％フッ化水素酸８００ｍｌを入れ、ＫＨＦ２粉末（和光純薬工業社製、特級試薬）２６０ｇ及び過マンガン酸カリウム粉末（和光純薬工業社製、試薬１級）１２ｇを溶解させた。このフッ化水素酸反応液をマグネティックスターラーで撹拌しながら、３０％過酸化水素水（特級試薬）８ｍｌを少しずつ滴下した。過酸化水素水の滴下量が一定量を超えると黄色粒子が析出し始め、反応液の色が紫色から変化し始めた。過酸化水素水を一定量滴下後、しばらく撹拌を続けた後、撹拌を止め、析出粒子を沈殿させた。沈殿後、上澄み液を除去し、メタノールを加え、撹拌・静置し、上澄み液を除去し、さらにメタノールを加えるという操作を、液が中性になるまで繰り返した。その後、ろ過により、析出粒子を回収し、さらに乾燥を行い、メタノールを完全に蒸発除去し、Ｋ２ＭｎＦ６粉末を１９ｇ得た。これらの操作は全て常温で行った。 Example 1
<Preparation process>
1. Reaction liquid K 2 MnF 6 powder was produced by the method described in Non-Patent Document 1. Specifically, 800 ml of 40% strength by weight hydrofluoric acid was placed in a 1 liter fluororesin beaker, 260 g of KHF 2 powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) and potassium permanganate powder (Wako Pure). 12 g of Yaku Kogyo Co., Ltd., reagent grade 1) was dissolved. While stirring this hydrofluoric acid reaction liquid with a magnetic stirrer, 8 ml of 30% hydrogen peroxide (special grade reagent) was added dropwise little by little. When the dropping amount of the hydrogen peroxide solution exceeded a certain amount, yellow particles started to precipitate, and the color of the reaction solution began to change from purple. After a certain amount of hydrogen peroxide solution was dropped, the stirring was continued for a while, and then the stirring was stopped to precipitate the precipitated particles. After the precipitation, the supernatant was removed, methanol was added, and the mixture was stirred and allowed to stand, the supernatant was removed, and methanol was further added until the solution became neutral. Thereafter, the precipitated particles were collected by filtration, further dried, and methanol was completely removed by evaporation to obtain 19 g of K 2 MnF 6 powder. All these operations were performed at room temperature.
　次いで、表１に示す配合量で、濃度５５質量％のフッ化水素酸８４０ｍｌに、ＳｉＯ２粉末（高純度化学研究所製、純度９９％）２８．８ｇを溶解させた。溶解に伴い発熱があったため、室温まで放冷した。十分に放冷した後に、上記のように調製したＫ２ＭｎＦ６粉末７．２ｇ、ＫＨＦ２粉末（和光純薬工業社製、特級試薬）３６ｇを順次溶解させ、反応液を調製した。Ｋ２ＭｎＦ６粉末及びＫＨＦ２粉末は完全に溶解し、その際の溶液温度の上昇はわずかであった。この反応液中に存在するＫは０．５１９ｍｏｌで、Ｓｉは０．４８ｍｏｌであった。この反応液中における組成比［反応液中のＫのモル数］／［反応液中のＳｉのモル数］は１．０８であった。 Next, 28.8 g of SiO 2 powder (manufactured by Kojundo Chemical Laboratory, purity 99%) was dissolved in 840 ml of hydrofluoric acid having a concentration of 55% by mass with the blending amounts shown in Table 1. Since there was an exotherm with dissolution, it was allowed to cool to room temperature. After sufficiently cooling, 7.2 g of K 2 MnF 6 powder and 36 g of KHF 2 powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) prepared as described above were sequentially dissolved to prepare a reaction solution. The K 2 MnF 6 powder and the KHF 2 powder were completely dissolved, and the increase in the solution temperature was slight. K present in the reaction solution was 0.519 mol and Si was 0.48 mol. The composition ratio [number of moles of K in the reaction solution] / [number of moles of Si in the reaction solution] in the reaction solution was 1.08.
２．固形状化合物
　上記反応液とは別に、固形状化合物として、ＫＨＦ２粉末（和光純薬工業社製、特級試薬）７６．５６ｇを準備した。この固形状化合物に存在するＫは０．９８０ｍｏｌであり、このため、前述の反応液中のＫに対する固形状化合物中のＫの組成比［固体状化合物中のＫのモル数］／［反応液中のＫのモル数］は１．８９であった。 2. Solid compound Separately from the reaction solution, 76.56 g of KHF 2 powder (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) was prepared as a solid compound. The K present in the solid compound is 0.980 mol. Therefore, the composition ratio of K in the solid compound to K in the reaction solution described above [number of moles of K in the solid compound] / [reaction solution] The number of moles of K] was 1.89.
＜反応工程＞
　上記の反応液に上記の固形状化合物を少しずつ添加していった。添加に伴い、黄色粉末が生成していることを目視にて確認した。ＫＨＦ２粉末を全量添加後、１０分撹拌し、その後、静置して固形分を沈殿させた。反応液の最高温度は、２８℃であった。
　沈殿確認後、上澄み液を除去し、２０質量％のフッ化水素酸及びメタノールでの洗浄を行い、ろ過により固形部を分離回収し、さらに乾燥処理により、残存メタノールを蒸発除去した。
　乾燥処理後の蛍光体に対し、目開き７５μｍのナイロン製篩を用い、この篩を通過したものだけに分級し、最終的に８７ｇの黄色粉末を得た。 <Reaction process>
The above solid compound was gradually added to the above reaction solution. With the addition, it was visually confirmed that a yellow powder was formed. After adding the entire amount of KHF 2 powder, the mixture was stirred for 10 minutes, and then allowed to stand to precipitate a solid content. The maximum temperature of the reaction solution was 28 ° C.
After confirming the precipitation, the supernatant was removed, washed with 20% by mass of hydrofluoric acid and methanol, the solid part was separated and recovered by filtration, and the residual methanol was evaporated and removed by drying.
The phosphor after the drying treatment was classified using only a nylon sieve having an opening of 75 μm and passed through this sieve, and finally 87 g of yellow powder was obtained.
　ＳｉＯ２及びＫ２ＭｎＦ６原料のＳｉ及びＭｎが全てＫ２ＳｉＦ６：Ｍｎとなったと仮定した場合の理論収量の１０８ｇに対する収率は８１％であった。 The yield based on the theoretical yield of 108 g when assuming that all of Si and Mn in the SiO 2 and K 2 MnF 6 raw materials were K 2 SiF 6 : Mn was 81%.
　実施例１の蛍光体の製造方法で得た蛍光体のＸ線回折パターンをＸ線回折装置（リガク社製、Ｕｌｔｉｍａ　ＩＶ）で測定した。測定にはＣｕＫα管球を使用した。測定結果を図１に示す。
　実施例１の蛍光体の製造方法で製造された蛍光体は、Ｋ２ＳｉＦ６結晶と同一パターンであり、他の結晶相を含んでいないことが確認された。 The X-ray diffraction pattern of the phosphor obtained by the phosphor manufacturing method of Example 1 was measured with an X-ray diffractometer (manufactured by Rigaku Corporation, Ultimate IV). A CuKα tube was used for the measurement. The measurement results are shown in FIG.
It was confirmed that the phosphor manufactured by the phosphor manufacturing method of Example 1 has the same pattern as the K 2 SiF 6 crystal and does not contain other crystal phases.
　この蛍光体の励起・蛍光スペクトルを分光蛍光光度計（日立ハイテクノロジーズ社製、Ｆ－７０００）で測定した。測定結果を図２に示す。この測定における蛍光スペクトルの励起波長は４５５ｎｍ、励起スペクトルのモニター蛍光波長は６３２ｎｍであった。
　この蛍光体は、ピーク波長３５０ｎｍ近傍の紫外光とピーク波長４５０ｎｍ近傍の青色光の二つの励起帯を有し、６００～７００ｎｍの赤色域に複数の狭帯発光を有することが確認された。
　この蛍光体を波長４５５ｎｍの青色光で励起した場合の外部量子効率は、０．５１２であった。外部量子効率の測定方法は前述の方法を用いた。 The excitation / fluorescence spectrum of this phosphor was measured with a spectrofluorometer (manufactured by Hitachi High-Technologies Corporation, F-7000). The measurement results are shown in FIG. In this measurement, the excitation wavelength of the fluorescence spectrum was 455 nm, and the monitor fluorescence wavelength of the excitation spectrum was 632 nm.
This phosphor was confirmed to have two excitation bands of ultraviolet light near a peak wavelength of 350 nm and blue light near a peak wavelength of 450 nm, and to have a plurality of narrow-band emissions in the red region of 600 to 700 nm.
When this phosphor was excited with blue light having a wavelength of 455 nm, the external quantum efficiency was 0.512. The external quantum efficiency was measured using the method described above.
　発光ピーク波長を、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、蛍光スペクトルの励起波長を４５５ｎｍとして測定したところ、６３２ｎｍにピークがあることを確認した。 When the emission peak wavelength was measured using a spectrofluorimeter (F-7000, manufactured by Hitachi High-Technologies Corporation) with the excitation wavelength of the fluorescence spectrum being 455 nm, it was confirmed that there was a peak at 632 nm.
＜実施例２～４、比較例１～３＞
　実施例２～４、比較例１～３は、反応液及び固形状化合物におけるＳｉＯ２粉末、Ｋ２ＭｎＦ６粉末、ＫＨＦ２粉末の量を表１に示す値とし、実施例１と全く同じ方法により製造した。
　比較例１及び比較例３が示すように、反応液中のＳｉに対するＫのモル比（［反応液中のＫのモル数］／［反応液中のＳｉのモル数］）、及び反応液中のＫに対する固体状化合物中のＫのモル比（［固体状化合物中のＫのモル数］／［反応液中のＫのモル数］）が上方に逸脱すると、Ｋ２ＳｉＦ６：Ｍｎ以外にＫＨＦ２が異相として存在し、外部量子効率が著しく低下した。
　また、比較例２が示すように、反応液中のＫに対する固体状化合物中のＫのモル比（［固体状化合物中のＫのモル数］／［反応液中のＫのモル数］）が下方に逸脱すると、収率が著しく低下した。 <Examples 2 to 4 and Comparative Examples 1 to 3>
In Examples 2 to 4 and Comparative Examples 1 to 3, the amounts of SiO 2 powder, K 2 MnF 6 powder, and KHF 2 powder in the reaction solution and solid compound were set to the values shown in Table 1, and the same method as in Example 1 was used. Manufactured by.
As Comparative Example 1 and Comparative Example 3 show, the molar ratio of K to Si in the reaction solution ([number of moles of K in the reaction solution] / [number of moles of Si in the reaction solution]), and in the reaction solution When the molar ratio of K in the solid compound to K ([number of moles of K in the solid compound] / [number of moles of K in the reaction solution]) deviates upward, in addition to K 2 SiF 6 : Mn KHF 2 was present as a heterogeneous phase and the external quantum efficiency was significantly reduced.
Further, as shown in Comparative Example 2, the molar ratio of K in the solid compound to K in the reaction solution ([number of moles of K in the solid compound] / [number of moles of K in the reaction solution]) When deviating downward, the yield decreased significantly.
＜比較例４＞
　比較例４は、表１には記載しなかったが、固体状態で添加するＫＨＦ２粉末をＫＦ粉末（和光純薬工業社製、特級試薬）に変更したこと以外、実施例１と全く同じ方法で製造した。ＫＦ添加量は、実施例１で添加した固体状のＫＨＦ２粉末と同じモル数となるよう５６．９ｇとした。ＫＦ粉末を添加したところ、ＫＦの溶解熱により反応液の温度が６０℃まで上昇した。反応完了後、常温まで放冷し、実施例１と同様の方法で沈殿物を回収した。
　比較例４における蛍光体の収率は７５％であり、Ｘ線回折測定で認められた結晶相はＫ２ＳｉＦ６相のみであり、平均粒径は１３μｍであった。しかし、量子効率測定を行った結果、吸収率は０．７５２、外部量子効率は０．３４０であった。蛍光体が析出する反応工程で３５℃を超えたことにより、得られた蛍光体の外部量子効率が著しく低くなることが確認された。 <Comparative example 4>
Although Comparative Example 4 was not described in Table 1, it was exactly the same as Example 1 except that KHF 2 powder added in the solid state was changed to KF powder (special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.). Manufactured with. The amount of KF added was 56.9 g so as to have the same number of moles as the solid KHF 2 powder added in Example 1. When KF powder was added, the temperature of the reaction solution rose to 60 ° C. due to the heat of dissolution of KF. After completion of the reaction, the mixture was allowed to cool to room temperature, and the precipitate was collected in the same manner as in Example 1.
The yield of the phosphor in Comparative Example 4 was 75%, the crystal phase recognized by X-ray diffraction measurement was only the K 2 SiF 6 phase, and the average particle size was 13 μm. However, as a result of the quantum efficiency measurement, the absorptance was 0.752 and the external quantum efficiency was 0.340. It was confirmed that the external quantum efficiency of the obtained phosphor was remarkably lowered by exceeding 35 ° C. in the reaction step in which the phosphor was deposited.

Claims (3)

  1. 　一般式：Ａ２ＭＦ６：Ｍｎ４＋で表される蛍光体（式中、元素Ａは少なくともＫを含有するアルカリ金属元素であり、元素Ｍは少なくともＳｉを含有するＳｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ及びＨｆから選ばれる一種以上の金属元素であり、Ｆはフッ素であり、Ｍｎはマンガンである）の製造方法であって、
    フッ化水素酸からなる溶媒に、元素Ａ、元素Ｍ、Ｆ及びＭｎを、元素Ｍに対する元素Ａのモル比（［反応液中の元素Ａのモル数］／［反応液中の元素Ｍのモル数］）が０．０４以上１．３以下の範囲となるように溶解させて反応液を調製する工程、及び
    反応液の最高温度を３５℃以下に保ちながら、反応液に、元素Ａの固体状化合物を、反応液中の元素Ａに対する固体状化合物中の元素Ａのモル比（［固体状化合物中の元素Ａのモル数］／［反応液中の元素Ａのモル数］）が１以上５０以下の範囲となるように添加してこれらを反応させる工程
    を含む蛍光体の製造方法。     A phosphor represented by the general formula: A 2 MF 6 : Mn 4+ (wherein the element A is an alkali metal element containing at least K, and the element M is Si, Ge, Sn, Ti, containing at least Si, One or more metal elements selected from Zr and Hf, F is fluorine, and Mn is manganese).
    In a solvent composed of hydrofluoric acid, element A, elements M, F and Mn are mixed with the molar ratio of element A to element M ([number of moles of element A in the reaction liquid] / [mol of element M in the reaction liquid). The number]) is dissolved in a range of 0.04 or more and 1.3 or less, and the reaction solution is prepared, and the maximum temperature of the reaction solution is kept at 35 ° C. or less while the element A is solid in the reaction solution. The molar ratio of the element A in the solid compound to the element A in the reaction solution ([number of moles of element A in the solid compound] / [number of moles of element A in the reaction solution]) is 1 or more. The manufacturing method of the fluorescent substance including the process of adding and making these react so that it may become 50 or less range.
  2. 　元素Ａの固体状化合物が元素Ａのフッ化水素塩である、請求項１記載の蛍光体の製造方法。 The method for producing a phosphor according to claim 1, wherein the solid compound of element A is a hydrogen fluoride salt of element A.
  3. 　元素Ａがカリウムであり、かつ、元素Ｍがケイ素である、請求項１又は２に記載の蛍光体の製造方法。 The method for producing a phosphor according to claim 1 or 2, wherein the element A is potassium and the element M is silicon.
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