Method for producing inorganic fluoride luminescent material

Abstract

A method of producing an inorganic fluoride luminescent material that uses a non-aqueous solution is provided.　This production method of an inorganic fluoride luminescent material involves: a step for either preparing a first non-aqueous solution that contains a first ion, a second ion and a first non-aqueous hydrogen fluoride-containing solution and a second non-aqueous solution that contains a third ion and a second non-aqueous hydrogen fluoride-containing solution, or preparing a third non-aqueous solution that contains the first ion, the second ion, the third ion and a third non-aqueous hydrogen fluoride-containing solution; and a step for either mixing the first non-aqueous solution, the second non-aqueous solution and a non-aqueous organic solution, or mixing the third non-aqueous solution and the non-aqueous organic solution, to obtain an inorganic fluoride luminescent material that contains a first element M1 and / or ammonium, a second element M2 and a third element M3.　

Description

[Technical Field]

[0001] The present invention relates to a method for producing an inorganic fluoride luminescent material. [Background technology]

[0002] Fluoride crystals have excellent transparency. Inorganic fluoride luminescent materials obtained by adding rare earth metal elements to fluoride crystals are used as laser media for fiber lasers and fiber amplifiers, and as phosphors that convert the wavelength of excitation light from a light source. Phosphors are used in combination with light-emitting elements that emit light on the short wavelength side, corresponding to ultraviolet light to visible light, in light-emitting devices for lighting, automotive applications, LCD backlights, and the like.

[0003] Examples of laser media for fiber lasers and fiber amplifiers include LiYF4 (hereinafter also referred to as "YLF"), LiLuF4, BaY2F8, and KY3F, which are doped with at least one rare earth metal element selected from the group consisting of Tm, Ho, Pr, Er, and Yb. 10 fluoride crystals such as those mentioned above, ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF) glass fibers with ZrF4 as the main component, and AlF3-based glass fibers (AlF3-BaF2-SrF2-CaF2-MgF2-YF3) with AlF3 as the main component.

[0004] As a phosphor, a fluoride phosphor that emits red light can be used. For example, Patent Document 1 discloses that K2SiF6:Mn 4+ A method for obtaining an inorganic fluoride phosphor having a composition represented by the formula: [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-224536 Summary of the Invention [Problem to be solved by the invention]

[0006] The optical properties of inorganic fluoride luminescent materials depend on the hydroxide ions (OH - ) or water (HO). For example, as described in Patent Document 1, inorganic fluoride phosphors produced using an aqueous solution are affected by the moisture (hydroxide ions (OH) - ) or water) may affect the optical properties. Therefore, an object of the present invention is to provide a method for producing an inorganic fluoride luminescent material using a non-aqueous solution without using an aqueous solution. [Means for solving the problem]

[0007] The present invention includes the following aspects. In one aspect of the present invention, a first non-aqueous solution including at least one first ion containing at least one selected from the group consisting of a first element M1 and an ammonium ion, at least one second ion containing a second element M2 other than the first element M1, and a first non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass or more and 100% by mass or less, and a second non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass or more and 100% by mass or less, or a second non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass or more and 100% by mass or less, is prepared. Alternatively, a second non-aqueous solution including at least one first ion containing at least one selected from the group consisting of a first element M1 and an ammonium ion, The aforementionedA method for producing an inorganic fluoride luminescent material includes preparing a third non-aqueous solution containing at least one type of second ion containing a second element M2 other than a first element M1, a third ion containing a third element M3 other than the first element M1 and the second element M2, and a third non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass or more and 100% by mass or less; and mixing the first non-aqueous solution, the second non-aqueous solution, and a non-aqueous organic liquid having a hydrogen fluoride content of less than 20% by mass, or mixing the third non-aqueous solution and a non-aqueous organic liquid having a hydrogen fluoride content of less than 20% by mass, to obtain an inorganic fluoride luminescent material containing the first element M1 and / or ammonium, the second element M2, and the third element M3. [Effects of the Invention]

[0008] According to the above-described embodiment, it is possible to provide a production method that can obtain an inorganic fluoride luminescent material using a non-aqueous solution without using an aqueous solution. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a flowchart showing a first example of a method for producing an inorganic fluoride luminescent material. [Figure 2] 10 is a flowchart showing a second example of a method for producing an inorganic fluoride luminescent material. [Figure 3] FIG. 1 is a schematic cross-sectional view showing an example of a light-emitting device using an inorganic fluoride fluorescent material. [Figure 4] 1 is a diagram showing infrared reflection spectra of an inorganic fluoride phosphor according to Example 1 and an inorganic fluoride phosphor according to Comparative Example 1. FIG. [Figure 5] 1 is a diagram showing ultraviolet-visible reflection spectra of an inorganic fluoride phosphor according to Example 1 and an inorganic fluoride phosphor according to Comparative Example 1. FIG. [Figure 6] 1 is a diagram showing the excitation spectra of an inorganic fluoride phosphor according to Example 1 and an inorganic fluoride phosphor according to Comparative Example 1. FIG. [Figure 7]1 is a diagram showing the emission spectra of an inorganic fluoride phosphor according to Example 1 and an inorganic fluoride phosphor according to Comparative Example 1. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, a method for producing an inorganic fluoride luminescent material according to the present disclosure will be described based on embodiments. However, the embodiments shown below are merely examples for embodying the technical concept of the present invention, and the present invention is not limited to the method for producing the inorganic fluoride luminescent material described below. The relationship between color names and chromaticity coordinates, the relationship between light wavelength ranges and monochromatic light color names, etc., conforms to JIS Z8110. In this specification, light emission is not limited to light emission having a wavelength in the wavelength range of visible light, but also includes light emission having a wavelength range outside the wavelength range of visible light.

[0011] Method for producing inorganic fluoride luminescent material A method for producing an inorganic fluoride luminescent material includes: preparing a first non-aqueous solution containing at least one first ion containing at least one selected from the group consisting of a first element M1 and ammonium; at least one second ion containing a second element M2 other than the first element M1; and a first non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass or more and 100% by mass or less; preparing a second non-aqueous solution containing a third ion containing a third element M3 other than the first element M1 and the second element M2; and a second non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass or more and 100% by mass or less; and mixing the first non-aqueous solution, the second non-aqueous solution, and a non-aqueous organic liquid having a hydrogen fluoride content of less than 20% by mass to obtain an inorganic fluoride luminescent material containing the first element M1 and / or ammonium, the second element M2, and the third element M3.

[0012] A method for producing an inorganic fluoride luminescent material includes preparing a third non-aqueous solution including at least one first ion containing at least one selected from the group consisting of a first element M1 and ammonium, at least one second ion containing a second element M2 other than the first element M1, a third ion containing a third element M3 other than the first element M1 and the second element M2, and a second non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass or more and 100% by mass or less, and mixing the third non-aqueous solution with a non-aqueous organic liquid having a hydrogen fluoride content of less than 20% by mass to obtain an inorganic fluoride luminescent material containing the first element M1 and / or ammonium, the second element M2, and the third element M3.

[0013] In the method for producing an inorganic fluoride luminescent material, a non-aqueous solution is used instead of an aqueous solution, thereby making it possible to obtain an inorganic fluoride luminescent material whose optical properties are not affected by moisture in the production process.

[0014] 1 is a flowchart showing a first example of a method for producing an inorganic fluoride luminescent material. The method for producing an inorganic fluoride luminescent material includes preparing a first non-aqueous solution (S101), preparing a second non-aqueous solution (S102), and mixing the first non-aqueous solution, the second non-aqueous solution, and a non-aqueous organic liquid containing less than 20% by mass of hydrogen fluoride to obtain an inorganic fluoride luminescent material containing a first element M1 and / or ammonium, a second element M2, and a third element M3 (S103). The method for producing an inorganic fluoride luminescent material may also include post-treatments (S104) of the obtained inorganic fluoride luminescent material, such as separation, washing, and drying.

[0015] 2 is a flowchart showing a second example of a method for producing an inorganic fluoride luminescent material. The method for producing an inorganic fluoride luminescent material includes preparing a third non-aqueous solution (S201), and mixing the third non-aqueous solution with a non-aqueous organic liquid containing less than 20% by mass of hydrogen fluoride to obtain an inorganic fluoride luminescent material containing a first element M1 and / or ammonium, a second element M2, and a third element M3 (S202). The method for producing an inorganic fluoride luminescent material may also include post-treatments (S203) such as separation, washing, and drying of the obtained inorganic fluoride luminescent material.

[0016] 1. Preparation of Non-aqueous Solution The first non-aqueous solution contains at least one first ion containing at least one selected from the group consisting of a first element M1 and ammonium, at least one second ion containing a second element M2 other than the first element, and a first non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content ranging from 20% to 100% by mass. The compound containing the first element M1 or ammonium and the compound containing the second element M2 are dissolved in the first non-aqueous hydrogen fluoride-containing liquid to become the first ion and the second ion, which together with the first non-aqueous hydrogen fluoride-containing liquid form the first non-aqueous solution.

[0017] 1st element M1 The first element M1 may be at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements. Specifically, the first element M1 may be at least one element selected from the group consisting of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, and Ra. The first element M1 may be one element or two or more elements selected from the group consisting of alkali metal elements and alkaline earth metal elements. For example, when the target inorganic fluoride luminescent material is K2SiF6 containing a third element M3 that contributes to luminescence, K can be selected as the first element M1. When the target inorganic fluoride luminescent material is LiYF4 containing a third element M3 that contributes to luminescence, Li can be selected as the first element M1. For example, when the target inorganic fluoride luminescent material is ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF), Ba and Na can be selected as the first element M1. When the target inorganic fluoride luminescent material is an AlF3-based glass fiber (AlF3-BaF2-SrF2-CaF2-MgF2-YF3), Ba, Sr, Ca and Mg can be selected as the first element M1.

[0018] First ion The first ion may be a cation of the first element M1 or ammonium. Specifically, the first ion may be Li + , Na + , K. + , Rb + , Cs + , Fr + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ and NH4 +The first ion may be one or more cations selected from the group consisting of the first element M1 and / or ammonium. When the target inorganic fluoride luminescent material is an inorganic fluoride phosphor having a composition represented by formula (I) described later, the first ion is preferably at least one cation selected from the group consisting of alkali metal elements and ammonium, and Li + , Na + , K. + , Rb + , Cs + and NH4 + It is preferable that the first ion is at least one type of cation selected from the group consisting of: Examples of raw materials for the first element M1 or ammonium that become the first ion include compounds containing the first element M1 or ammonium, such as fluorides, fluoride hydrides, chlorides, bromides, iodides, acetates, and carbonates containing alkali metal elements, alkaline earth metal elements, or ammonium ions. When the raw material for the first element M1 or ammonium is a fluoride containing the first element M1 or ammonium, it may contain a second element M2 in addition to the first element M1 and fluorine.

[0019] The lower limit of the first ion concentration is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. The upper limit of the first ion concentration is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. When the first ion concentration is within the range of 1% by mass or more and 20% by mass or less, the yield of the obtained inorganic fluoride luminescent material tends to be improved. The first ion may be one type of ion selected from the group consisting of the first element M1 and ammonium, or may contain two or more types of ions selected from the group consisting of the first element M1 and ammonium. When two or more types of first ions are contained, the concentration of the first ion is the total concentration of the two or more types of first ions.

[0020] 2nd element M2 The second element M2 is an element other than the first element M1, and the second element M2 may be at least one element selected from the group consisting of non-luminescent transition metal elements, Group 12 elements, Group 13 elements, Group 14 elements, and Group 15 elements. In this specification, the term "non-luminescent transition metal element" refers to a transition metal element that does not contribute to luminescence in an inorganic fluoride luminescent material. The non-luminescent transition metal element in this specification primarily constitutes the host crystal of the inorganic fluoride luminescent material and does not contribute to luminescence. Examples of non-luminescent transition metal elements include at least one element selected from the group consisting of Sc, Ti, Y, Zr, Nb, La, Gd, Hf, and Ta. Examples of Group 12 elements include at least one element selected from the group consisting of Zn, Cd, and Hg. Examples of Group 13 elements include at least one element selected from the group consisting of Al, Ga, In, and Tl. Examples of Group 14 elements include at least one element selected from the group consisting of Si, Ge, Sn, and Pb. The Group 15 element may be at least one element selected from the group consisting of As, Sb, and Bi. The second element M2 may be one or more elements selected from the group consisting of non-luminescent transition metal elements, Group 12 elements, Group 13 elements, Group 14 elements, and Group 15 elements. The second element M2 is preferably at least one element selected from the group consisting of Sc, Ti, Y, Zr, Nb, La, Gd, Hf, Ta, Zn, Cd, Hg, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, and Bi. When the desired inorganic fluoride luminescent material is K2SiF6 containing a third element M3 that contributes to luminescence, Si can be selected as the second element M2. When the desired inorganic fluoride luminescent material is LiYF4 containing a third element M3 that contributes to luminescence, Y can be selected as the second element M2. When the inorganic fluoride luminescent material is ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF), Zr, La, and Al can be selected as the second element M2. When the inorganic fluoride luminescent material is AlF3-based glass fiber (AlF3-BaF2-SrF2-CaF2-MgF2-YF3), Al and Y can be selected as the second element M2.In this specification, "non-luminescent" refers not only to not emitting light due to light having a wavelength in the wavelength range of visible light, but also to not emitting light due to light having a wavelength outside the wavelength range of visible light.

[0021] Second ion The second ion may be a cation consisting of the second element M2 or a first complex ion containing the second element and fluorine. Specifically, the cation consisting of the second element M2 may be Sc 3+ , Ti 3+ , Ti 4+ , Y 3+ , Zr 4+ , Nb 4+ , Nb 5+ , La 3+ , Gd 3+ , Hf 4+ , Ta 4+ , Ta 5+ , Zn 2+ , Cd 2+ , Hg + , Hg 2+ , Al 3+ , Ga 3+ , In 3+ , Tl + , Tl 3+ , Si 4+ , Ge 2+ , Ge 4+ , Sn 2+ , Sn 4+ , Pb 2+ , Pb 4+ , As 3+ , As 5+ , Sb 3+ , Sb 5+ and Bi 3+and at least one cation selected from the group consisting of: When the target inorganic fluoride luminescent material is an inorganic fluoride phosphor having a composition represented by formula (I) described below, the second ion is preferably an ion of at least one element selected from the group consisting of non-luminescent transition metal elements, Group 13 elements, Group 14 elements, and Group 15 elements. Examples of raw materials for the second element M2 that become the second ion include compounds containing the second element M2, such as fluorides, fluorine hydrides, chlorides, bromides, iodides, acetates, carbonates, and sulfates, containing at least one second element M2 selected from the group consisting of non-luminescent transition metal elements, Group 12 elements, Group 13 elements, Group 14 elements, and Group 15 elements. When the raw material for the second element M2 is a fluoride containing the second element M2, it may contain the first element M1 or ammonium in addition to the second element M2 and fluorine.

[0022] The second ion is preferably a first complex ion containing a second element M2 and fluorine. The first complex ion is preferably a first complex ion containing at least one second element M2 selected from the group consisting of non-luminescent transition metal elements, Group 13 elements, Group 14 elements, and Group 15 elements. The first complex ion is preferably a complex ion containing at least one second element M2 selected from the group consisting of Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, Y, La, Nb, Ta, Bi, and Gd. When the first ion is a first complex ion, it is more preferably a first fluoride complex ion containing the second element M2 and fluorine. The first fluoride complex ion containing the second element M2 is preferably a first fluoride complex anion bonded to the second element M2 with two or more fluorine atoms as the central atom. When the second ion is a first fluoride complex ion containing the second element M2 and fluorine, for example, YF4 - , SiF6 2- , AlF6 3-Examples of raw materials that can be used to form the first fluoride complex ion include tetrafluoroyttrium salts, hexafluorosilicic acid or hexafluorosilicates, hexafluorogermanium salts, hexafluorostannates, hexafluorotitanates, hexafluorozirconates, hexafluoroaluminates, and hexafluorogallates.

[0023] The lower limit of the second ion concentration is preferably 0.50% by mass or more, more preferably 0.75% by mass or more, and even more preferably 1% by mass or more. The upper limit of the second ion concentration is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. When the concentration of the second ion consisting of the second element is within the range of 0.50% by mass or more and 20% by mass or less, the yield of the obtained inorganic fluoride luminescent material tends to be improved. The second ion may be one type of ion consisting of one type of second element M2, or two or more types of ions consisting of two or more types of second elements M2. When two or more types of second ions are contained, the concentration of the second ion is the sum of the concentrations of the two or more types of second ions.

[0024] The lower limit of the concentration of the first complex ion containing the second element M2 is preferably 2% by mass or more, more preferably 4% by mass or more, and even more preferably 6% by mass or more. The upper limit of the concentration of the first complex ion in the first non-aqueous solution is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less. When the concentration of the first complex ion containing the second element M2 in the first non-aqueous solution is in the range of 2% by mass or more and 45% by mass or less, the yield of the obtained inorganic fluoride luminescent material tends to be improved.

[0025] The first nonaqueous hydrogen fluoride-containing liquid contained in the first nonaqueous solution can be the same as the second nonaqueous hydrogen fluoride-containing liquid or the third nonaqueous hydrogen fluoride-containing liquid described below, and will therefore be described collectively. The first nonaqueous hydrogen fluoride-containing liquid, the second nonaqueous hydrogen fluoride-containing liquid, and the third nonaqueous hydrogen fluoride-containing liquid (hereinafter also referred to as "nonaqueous hydrogen fluoride-containing liquids") have a hydrogen fluoride content ranging from 20% to 100% by mass. The first nonaqueous hydrogen fluoride-containing liquid may contain an amount of hydrogen fluoride sufficient to dissolve a compound containing a first element M1 or ammonium and a compound containing a second element M2, thereby forming first ions and second ions. The second nonaqueous hydrogen fluoride-containing liquid may contain an amount of hydrogen fluoride sufficient to dissolve a compound containing a third element M3 described below, thereby forming third ions. The third non-aqueous hydrogen fluoride-containing liquid may contain hydrogen fluoride in an amount sufficient to dissolve a compound containing a first element M1 or ammonium, a compound containing a second element M2, and a compound containing a third element M3, thereby forming first ions, second ions, and third ions. The hydrogen fluoride content in the non-aqueous hydrogen fluoride-containing liquid, in which the compound containing the first element M1 or ammonium, the compound containing the second element M2, and the compound containing the third element M3 can be dissolved to form the first ions, second ions, and third ions, is in the range of 20% to 100% by mass. The non-aqueous hydrogen fluoride-containing liquid may be 100% by mass of liquid hydrogen fluoride under standard conditions (25°C, 1 atmosphere). The hydrogen fluoride content in the non-aqueous hydrogen fluoride-containing liquid may be in the range of 20% to 30% by mass, or may be in the range of 60% to 80% by mass.

[0026] In addition to hydrogen fluoride, the non-aqueous hydrogen fluoride-containing liquid may contain a compound that is liquid under standard conditions (25°C, 1 atmosphere) and has a boiling point of 120°C or higher. The non-aqueous hydrogen fluoride-containing liquid may contain at least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds, amines, ureas, amides, carbamic acids, trialkylphosphines, ethers, esters, alcohols, and quaternary ammonium salts. The compound contained in the non-aqueous hydrogen fluoride-containing liquid may be at least one compound selected from the group consisting of nitrogen-containing heterocyclic compounds, amines, ureas, amides, carbamic acids, trialkylphosphines, ethers, esters, alcohols, and quaternary ammonium salts. An example of a commercially available non-aqueous hydrogen fluoride-containing liquid is Olah's reagent, which is a pyridine-HF complex containing 70% by mass of hydrogen fluoride and pyridine. Another example of a non-aqueous hydrogen fluoride-containing liquid is a triethylamine-HF complex containing 28% by mass of hydrogen fluoride and triethylamine. Other examples of non-aqueous hydrogen fluoride-containing liquids include a urea-HF complex containing 65-75% by mass of hydrogen fluoride and urea, and a DMPU-HF complex containing 65% by mass of hydrogen fluoride and N,N'-dimethylpropylene urea. Components contained in the non-aqueous hydrogen fluoride-containing liquid (e.g., pyridine) can be detected by nuclear magnetic resonance (proton NMR) by dissolving the resulting inorganic fluoride luminescent material in a deuterated solvent.

[0027] Examples of the nitrogen-containing heterocyclic compounds include alicyclic compounds having a ring selected from pyrrolidine and piperidine, and heterocyclic aromatic compounds having a ring selected from pyrrole, pyrazole, imidazole, isoxazole, thiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, indole, benzimidazole, benzoxazole, benzothiazole, benzotriazole, purine, quinoline, isoquinoline, quinoxaline, quinazoline, acridine, and phenanthroline. The nitrogen-containing heterocyclic compounds may contain fluorine, chlorine, or bromine.

[0028] Examples of the nitrogen-containing heterocyclic compound include imidazole, and examples of the fluorine-containing compound include imidazolium salts represented by the following formula (1).

[0029] [ka]

[0030] In formula (1), R1 and R3 each independently represent an alkyl group having 1 to 4 carbon atoms; 2、 R 4、 and R5 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In addition, some or all of R1 to R5 may be bonded to each other to form a ring. Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. R 2、 R 4、 and R5 may be a hydrogen atom, a methyl group, or an ethyl group, or may be a hydrogen atom. In formula (1), q is a number from 1 to 4 and does not necessarily have to be an integer. The number of q can be calculated from the elemental analysis value of the compound.

[0031] Specific examples of the compound represented by formula (1) include 1,3-dimethylimidazolium salt, 1,3,4-trimethylimidazolium salt, and 1-ethyl-3-methylimidazolium salt. 1-Ethyl-3-methylimidazolium salt is a salt that melts at room temperature. In addition, in formula (1), some or all of R1 to R5 may be bonded to each other to form a ring. Specific examples include 1,3-dimethylbenzimidazolium salt and 1-ethyl-3-methylbenzimidazolium salt.

[0032] Among the nitrogen-containing heterocyclic compounds containing fluorine, chlorine or bromine, the nitrogen-containing heterocyclic compounds mainly containing chlorine or bromine include 2-trichloromethylpyrrole, 2-tribromomethylpyrrole, 4-chloro-3-trichloromethylpyrazole, 4-chloro-3,5-bis[trichloromethyl]pyrazole, 4-chloro-3-tribromomethylpyrazole, 4-chloro-3,5-bis[tribromomethyl]pyrazole, 1-methyl-3-trichloromethylpyrazole-4-carboxylate, 1,2-bis[trichloromethyl]imidazole, 1,3 -Bis[trichloromethyl]imidazole, 1,5-bis[trichloromethyl]imidazole, 2,5-bis[trichloromethyl]imidazole, 4,5-bis[trichloromethyl]imidazole, 1,2,5-tris[trichloromethyl]imidazole, 2,3,4-tris[trichloromethyl]imidazole, 1,2-bis[tribromomethyl]imidazole, 1,3-bis[tribromomethyl]imidazole, 1,5-bis[tribromomethyl]imidazole, 2,5-bis[tribromomethyl]imidazole, 4,5-bis[tribromomethyl]imidazole ]imidazole, 1,2,5-tris[tribromomethyl]imidazole, 2,3,4-tris[tribromomethyl]imidazole, 2-trichloromethylpyridine, 3-trichloromethylpyridine, 4-trichloromethylpyridine, 2,3-2,5-bis[trichloromethyl]pyridine, 2,6-bis[trichloromethyl]pyridine, 3,5-bis[trichloromethyl]pyridine, 2-tribromomethylpyridine, 3-tribromomethylpyridine, 4-tribromomethylpyridine, 2,3-2,5-bis[tribromomethyl]pyridine, 2,6-bis Bis[tribromomethyl]pyridine, 3,5-bis[tribromomethyl]pyridine, 3-trichloromethylpyridazine, 3-tribromomethylpyridazine, 4-trichloromethylpyridazine, 4-tribromomethylpyridazine, 2,4-bis[trichloromethyl]pyrimidine, 2,6-bis[trichloromethyl]pyrimidine, 2,4-bis[tribromomethyl]pyrimidine, 2,6-bis[tribromomethyl]pyrimidine, 2,4-dichloro-5-trichloromethylpyrimidine, 2-trichloromethylpyrazine, 2-tribromomethylpyrazine, 1,3,5-Trisbis[trichloromethyl]triazine, 1,3,5-trisbis[tribromomethyl]triazine, 4-trichloromethylindole, 5-trichloromethylindole, 4-tribromomethylindole, 5-tribromomethylindole, 2-trichloromethylbenzimidazole, 2-tribromomethylbenzimidazole, 5-trichloromethyl-1H-benzotriazole, 5-tribromomethyl-1H-benzotriazole, 6-trichloromethylpurine, 6-tribromomethylpurine, 3-trichloromethylquinoline, 4-trichloromethylquinoline, 3-tribromomethylquinoline, 4-tribromomethyl Examples of the bromomethyl quinolone include 3-trichloromethylisoquinoline, 3-tribromomethylisoquinoline, 4-trichloromethylchinoline, 4-tribromomethylchinoline, 2-trichloromethylquinoxaline, 2-tribromomethylquinoxaline, 5-trichloromethylquinoxaline, 5-tribromomethylquinoxaline, 9-trichloromethylacridine, 9-tribromomethylacridine, 4-trichloromethyl-1,10-phenanthroline, 4-tribromomethyl-1,10-phenanthroline, 5-trichloromethyl-1,10-phenanthroline, and 5-tribromomethyl-1,10-phenanthroline.

[0033] Among the oxygen- and nitrogen-containing heterocyclic compounds containing fluorine, chlorine, or bromine, examples of the oxygen- and nitrogen-containing heterocyclic compounds containing chlorine or bromine include 3,5-bis[trichloromethyl]isoxazole, 3,5-bis[tribromomethyl]isoxazole, 2-trichloromethylbenzoxazole, and 2-tribromomethylbenzoxazole.

[0034] Among the sulfur- and nitrogen-containing heterocyclic compounds containing fluorine, chlorine, or bromine, examples of the sulfur- and nitrogen-containing heterocyclic compounds containing chlorine or bromine include 4,5-bis[trichloromethyl]thiazole, 4,5-bis[tribromomethyl]thiazole, 5-trichloromethyl-thiadiazole, 5-tribromomethyl-thiadiazole, 2-trichloromethylbenzothiazole, and 2-tribromomethylbenzothiazole.

[0035] Examples of amines include methylamine, ethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, n-propylamine, isopropylamine, n-butylamine, dibutylamine, tributylamine, diethylenetriamine, monoethanolamine, triethanolamine, 1,2-propylenediamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, o-toluidine, p-nitrotoluene, N-(2-aminoethyl)ethanolamine, aniline, piperazine, and triethylenetetramine.

[0036] Examples of ureas include urea, 1,1,3,3-tetramethylurea, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, 1,3-di(n-propyl)-2-imidazolidinone, 1,3-di(n-butyl)-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, N,N'-dimethylpropylurea, N,N'-diethylpropylurea, N,N'-di(n-propyl)propylurea, and N,N'-di(n-butyl)propylurea.

[0037] Examples of amides include N,N'-dimethylformamide, N,N'-diethylformamide, N,N'-dimethylacetamide, and 1-methyl-2-pyrrolidone.

[0038] Examples of carbamic acids include carbamic acid and ethyl carbamate.

[0039] Examples of trialkylphosphines include hexamethylphosphoramide.

[0040] Examples of ethers include n-butyl ether, n-hexyl ether, anisole, phenetole, butylphenyl ether, amylphenyl ether, methoxytoluene, benzyl methyl ether, diphenyl ether, dibenzyl ether, 1,2-diethoxyethane, 1,2-dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.

[0041] Examples of esters include n-butyl acetate, n-pentyl acetate, isopentyl acetate, cyclohexyl acetate, benzyl acetate, butyl propionate, isopentyl propionate, methyl benzoate, dimethyl phthalate, and γ-butyrolactone.

[0042] The alcohols are alcohols having a hydrocarbon group with 4 or more carbon atoms, such as 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, butanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexanol, 2-methyl-2-pentanol, 1-heptanol, 2-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, and 1-dodecanol.

[0043] The quaternary ammonium salt includes a quaternary ammonium salt represented by the following formula (2).

[0044] [ka]

[0045] In formula (2), R6 represents an alkyl group having 1 to 4 carbon atoms, R7 represents a methoxymethyl group, a methoxyethyl group, or an ethoxymethyl group, and q represents a number from 1 to 4.

[0046] The quaternary ammonium salt represented by formula (2) is composed of a quaternary ammonium cation and a fluorohydrogenate anion. Examples of R6 in the quaternary ammonium cation include linear or branched alkyl groups having 1 to 4 carbon atoms. Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl groups. Examples of R7 in the quaternary ammonium cation include methoxymethyl, methoxyethyl, and ethoxymethyl groups. Examples of the fluorohydrogenate anion include F(HF) where q is a number between 1 and 4. q - Examples of the fluorohydrogenate anion include the fluorohydrogenate anion represented by the following formula: q does not necessarily have to be an integer, and is preferably a number of 1.5 or more and 3 or less, and more preferably a number of 2 or more and 2.5 or less.

[0047] Specific examples include N-methoxymethyl-N-methylpyrrolidinium fluorohydrogenate, N-methoxymethyl-N-ethylpyrrolidinium fluorohydrogenate, N-methoxymethyl-Nn-propylpyrrolidinium fluorohydrogenate, N-methoxymethyl-N-iso-propylpyrrolidinium fluorohydrogenate, N-methoxymethyl-Nn-butylpyrrolidinium fluorohydrogenate, N-methoxymethyl-N-iso-butylpyrrolidinium fluorohydrogenate, N-methoxymethyl-N-tert-butylpyrrolidinium fluorohydrogenate, N-methoxyethyl-N-methylpyrrolidinium fluorohydrogenate, N-methoxyethyl-N-ethylpyrrolidinium fluorohydrogenate, N-methoxyethyl-Nn-propylpyrrolidinium fluorohydrogenate, and N-methoxyethyl-N-iso-propylpyrrolidinium. Examples of the fluorohydrogenate include N-methoxyethyl-Nn-butylpyrrolidinium fluorohydrogenate, N-methoxyethyl-N-iso-butylpyrrolidinium fluorohydrogenate, N-methoxyethyl-N-tert-butylpyrrolidinium fluorohydrogenate, N-ethoxymethyl-N-methylpyrrolidinium fluorohydrogenate, N-ethoxymethyl-N-ethylpyrrolidinium fluorohydrogenate, N-ethoxymethyl-Nn-propylpyrrolidinium fluorohydrogenate, N-ethoxymethyl-N-iso-propylpyrrolidinium fluorohydrogenate, N-ethoxymethyl-Nn-butylpyrrolidinium fluorohydrogenate, N-ethoxymethyl-N-iso-butylpyrrolidinium fluorohydrogenate, and N-ethoxymethyl-N-tert-butylpyrrolidinium fluorohydrogenate.

[0048] Preparation of the second non-aqueous solution The second non-aqueous solution contains third ions including a third element M3 other than the first element M1 and the second element M2, and a second non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content of 20% by mass to 100% by mass. The second non-aqueous solution may contain the first element M1 or a first ion including the first element M1, as long as it contains third ions including the third element M3. The lower limit of the third ion concentration in the second non-aqueous solution is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. The upper limit of the third ion concentration in the second non-aqueous solution is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. When the third ion concentration in the second non-aqueous solution is 1% by mass or more to 20% by mass or less, the yield of the resulting inorganic fluoride luminescent material tends to be improved. The compound containing the third element M3 is dissolved in the second non-aqueous hydrogen fluoride-containing liquid, becomes a third ion, and forms a second non-aqueous solution together with the second non-aqueous hydrogen fluoride-containing liquid.

[0049] Third element M3 The third element M3 is preferably at least one element selected from luminescent transition metal elements. In this specification, the luminescent transition metal element refers to a transition metal element that is added to the host crystal structure of the inorganic fluoride luminescent material and contributes to luminescence. For example, in the case of a phosphor, an activator element added to the host crystal excites electrons by absorbing the energy of electromagnetic waves such as X-rays, ultraviolet rays, and visible light, and releases energy when the electrons return to the ground state, thereby contributing to luminescence.

[0050] The luminescent transition metal element in the third element M3 may be at least one third element selected from the group consisting of Mn, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu. The third element M3 may be one element or two or more elements selected from the luminescent transition metal elements. For example, when the target inorganic fluoride luminescent material is an inorganic fluoride phosphor having a composition represented by formula (I) described below, the third element M3 is an activator element, and Mn can be selected. For example, when the target inorganic fluoride luminescent material is LiYF4, Pr can be selected as the third element M3 to be added. For example, when the target inorganic fluoride luminescent material is ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF) or AlF3-based glass fiber (AlF3-BaF2-SrF2-CaF2-MgF2-YF3), the third element M3 to be added can be at least one element selected from the group consisting of Pr, Nd, Ho, Er, Dy, Tm, and Yb.

[0051] Third ion The third ion may be a cation consisting of the third element M3 or a second complex ion containing the third element M3. Specifically, the cation consisting of the third element M3 may be Mn 2+ , Mn 4+ , Mn 5+ , Mn 6+ , Mn 7+ , Ce 3+ , Ce 4+ , Pr 3+ , Pr 4+ , Nd 2+ , Nd 3+ , Pm 3+ , Sm 2+ ,EU 2+ ,EU 3+ , Tb 3+ , Tb 4+ , Dy 2+ , Dy 3+ , Ho 3+ , Er 3+ , Tm 2+ , Tm 3+ , Yb 2+ , Yb 3+ , and Lu3+ Examples of raw materials for the third element M3 that becomes the third ion include compounds containing the third element M3, such as fluorides, fluorine hydrides, chlorides, bromides, iodides, acetates, carbonates, and sulfates, containing at least one third element M3 selected from the group consisting of luminescent transition metal elements. When the raw material for the third element M3 is a fluoride containing the third element M3, it may contain the first element M1 or ammonium in addition to the third element M3 and fluorine.

[0052] The third ion is preferably a second complex ion containing at least one third element M3 selected from the group consisting of luminescent transition metal elements and fluorine, and more preferably a second fluoride complex ion containing the third element M3. When the target inorganic fluoride luminescent material is an inorganic fluoride phosphor having a composition represented by formula (I) described below, the second complex ion is preferably a complex ion containing Mn, and more preferably a second fluoride complex ion containing Mn (MnF6 2- ) is more preferable. Examples of raw materials that become the second fluoride complex ions include hexafluoromanganic acid and hexafluoromanganate.

[0053] The lower limit of the third ion concentration is preferably 1% by mass or more, more preferably 1.5% by mass or more, and even more preferably 2% by mass or more. The upper limit of the third ion concentration is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less. When the concentration of the third ion consisting of the third element is within the range of 1% by mass or more and 30% by mass or less, the yield of the obtained inorganic fluoride luminescent material tends to be improved. The third ion may be one type of ion consisting of one type of third element M3, or two or more types of ions consisting of two or more types of third elements M3. When two or more types of third ions are contained, the concentration of the third ion is the total concentration of the two or more types of third ions.

[0054] The lower limit of the concentration of the second complex ion containing the third element M3 is usually 2% by mass or more, preferably 4% by mass or more, and more preferably 6% by mass or more. The upper limit of the concentration of the second complex ion in the second non-aqueous solution is usually 50% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass or less. When the concentration of the second complex ion containing the third element is 36% by mass or more, the yield of the obtained inorganic fluoride luminescent material tends to be improved.

[0055] Preparation of the third non-aqueous solution The third non-aqueous solution contains at least one first ion containing at least one selected from the group consisting of a first element M1 and ammonium; The aforementioned The liquid includes at least one type of second ion containing a second element M2 other than a first element M1, a third ion containing a third element M3 other than the first element M1 and the second element M2, and a third non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content in the range of 20 mass % or more and 100 mass % or less. The terms "first element M1" and "ammonium," "first ion," "second element M2," "second ion," "third element M3," and "third ion" refer to the ions or elements contained in the first or second non-aqueous solution. The first, second, and third ion concentrations in the third non-aqueous solution can be within the same ranges as those described above. The third non-aqueous hydrogen fluoride-containing liquid can be the same as the first or second non-aqueous hydrogen fluoride-containing liquid. The second ion can be a first complex ion containing the second element M2 and fluorine, preferably a first fluoride complex ion containing the second element M2. The concentration of the first complex ion can be within the same range as that contained in the first non-aqueous solution. The third ion can be a second complex ion containing the third element M3 and fluorine, preferably a second fluoride complex ion containing the third element M3. The concentration of the second complex ion can be in the same range as the concentration contained in the second non-aqueous solution. The compound containing the first element M1 or ammonium, the compound containing the second element M2, and the compound containing the third element M2 are dissolved in the third non-aqueous hydrogen fluoride-containing liquid to become the first ion, the second ion, and the third ion, which together with the third non-aqueous hydrogen fluoride-containing liquid form the third non-aqueous solution.

[0056] In the first, second or third non-aqueous solution, the first ion may be at least one first element M1 selected from the group consisting of alkali metal elements and at least one cation selected from the group consisting of ammonium; the second ion may be a first complex ion containing fluorine and at least one second element M2 selected from the group consisting of non-luminescent transition metal elements, Group 13 elements, Group 14 elements and Group 15 elements; and the third ion may be a second complex ion containing fluorine and at least one third element M3 selected from luminescent transition metal elements.

[0057] In the first, second or third non-aqueous solution, the first ion may be at least one first element M1 selected from the group consisting of alkali metal elements and at least one cation selected from the group consisting of ammonium, the first complex ion may be a first fluoride complex ion containing fluorine and at least one second element M2 selected from the group consisting of Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, La, Nb, Ta, Bi and Gd, and the third element may be Mn, and the second complex ion may be a second fluoride complex ion containing Mn and fluorine.

[0058] Non-aqueous organic liquid A nonaqueous organic liquid containing less than 20% by mass of hydrogen fluoride is prepared as a liquid medium to be mixed with the first, second, or third nonaqueous solution. Hereinafter, a nonaqueous organic liquid containing less than 20% by mass of hydrogen fluoride is also referred to as a "nonaqueous organic liquid." A mixture of the first, second, and nonaqueous organic liquids, and a mixture of the third nonaqueous solution and nonaqueous organic liquid are also referred to as a nonaqueous liquid mixture. The hydrogen fluoride content in the nonaqueous organic liquid may be an amount sufficient to obtain an inorganic fluoride luminescent material in the nonaqueous liquid mixture. Specifically, the hydrogen fluoride content in the nonaqueous organic liquid may be an amount sufficient to precipitate the inorganic fluoride luminescent material in the nonaqueous liquid mixture. The hydrogen fluoride content in the nonaqueous organic liquid sufficient to precipitate the inorganic fluoride luminescent material in the nonaqueous liquid mixture is less than 20% by mass. The hydrogen fluoride content in the non-aqueous organic liquid may be less than 20% by mass, and may be 10% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less. The hydrogen fluoride content may be 0% by mass, meaning the non-aqueous organic liquid is substantially free of hydrogen fluoride. A non-aqueous organic liquid substantially free of hydrogen fluoride refers to a non-aqueous organic liquid having a fluorine content of less than 1% by mass. The non-aqueous organic liquid preferably contains at least one selected from the group consisting of nitriles, ketones, amines, amides, nitrogen-containing heterocyclic compounds, fluorocompounds, ethers, esters, alcohols, and mixtures thereof. The non-aqueous organic liquid may be at least one selected from the group consisting of nitriles, ketones, amines, amides, nitrogen-containing heterocyclic compounds, fluorocompounds, ethers, esters, alcohols, and mixtures thereof.

[0059] Examples of nitriles include acetonitrile, propionitrile, benzonitrile, acrylonitrile, and methacrylonitrile.

[0060] Examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, etc. Examples of ketone compounds having a hydroxyl group (alcohol) as a functional group include diacetone alcohol, etc.

[0061] Examples of fluoro compounds include 1,1,2,2-tetrafluoroethylene, 2,2,3,3-tetrafluoropropyl ether, perfluorocarbon, hydrochlorofluorocarbon, hydrofluorocarbon, and hydrofluoroether.

[0062] Examples of the amines, amides, nitrogen-containing heterocyclic compounds, ethers, esters, and alcohols include the compounds exemplified above as compounds used in the non-aqueous hydrogen fluoride-containing liquid. The amines, amides, nitrogen-containing heterocyclic compounds, ethers, esters, and alcohols may be the same or different compounds as those used in the non-aqueous hydrogen fluoride-containing liquid.

[0063] mixture The prepared first and second nonaqueous solutions or the third nonaqueous solution can be brought into contact with a nonaqueous organic liquid having a hydrogen fluoride content of less than 20% by mass and mixed. The first and second nonaqueous solutions may be brought into contact with the nonaqueous organic liquid by separately adding dropwise the second nonaqueous solution and the nonaqueous organic liquid to the first nonaqueous solution, followed by mixing. The first and second nonaqueous solutions may be brought into contact with the second nonaqueous solution, followed by mixing. The first and second nonaqueous solutions may be brought into contact with the nonaqueous organic liquid by separately adding dropwise the first and second nonaqueous solutions to the nonaqueous organic liquid, followed by mixing. The first and second nonaqueous solutions may be mixed to form the third nonaqueous solution. The third nonaqueous solution may be brought into contact with the nonaqueous organic liquid by either adding dropwise the nonaqueous organic liquid to the third nonaqueous solution or adding dropwise the third nonaqueous solution to the nonaqueous organic liquid. When the non-aqueous organic liquid is added dropwise to the total amount of the first non-aqueous solution and the second non-aqueous solution or the third non-aqueous solution to mix, the amount of the non-aqueous organic liquid added per minute may be in the range of 0.083% by volume to 100% by volume, or may be in the range of 4% by volume to 25% by volume, or may be in the range of 8% by volume to 12% by volume.

[0064] The first non-aqueous solution, the second non-aqueous solution, and the non-aqueous organic liquid, or the third non-aqueous solution and the non-aqueous organic liquid, may be mixed using a batch reactor to obtain a non-aqueous liquid mixture. When the first non-aqueous solution, the second non-aqueous solution, or the third non-aqueous solution is mixed dropwise into the non-aqueous organic liquid, the total amount of the first non-aqueous solution and the second non-aqueous solution, or the amount of the third non-aqueous solution, added dropwise per minute may be in the range of 0.083 to 100% by volume of the non-aqueous organic liquid. When a batch reactor is used, depending on the concentrations of the first ion, the second ion, and the third ion, the volume ratio of the non-aqueous organic liquid to the total amount of the first non-aqueous solution and the second non-aqueous solution, or the amount of the third non-aqueous solution, is preferably 9:1 to 1:9, more preferably 6:4 to 4:6.

[0065] When a batch reactor is used, the first non-aqueous solution, the second non-aqueous solution, and the non-aqueous organic liquid, or the third non-aqueous solution and the non-aqueous organic liquid, may be mixed by stirring. The method for stirring the non-aqueous liquid mixture may be any method capable of reducing the concentration gradient of each component contained in the non-aqueous solution mixture. Examples of stirring methods include rotating a stirrer at a constant speed, pressurizing the non-aqueous liquid mixture with a pump to generate a flow, and using a mechanical stirrer. The non-aqueous liquid mixture may be stirred continuously or intermittently. When stirring is performed intermittently, the intervals at which stirring is interrupted are not particularly limited. Stirring may be performed for a fixed period of time and then stopped at a fixed period of time, or stirring may be performed at irregular intervals and then stopped at irregular intervals. When stirring is performed intermittently at regular intervals, stirring may be performed for, for example, 1 minute to 30 minutes and then stopped for 1 minute to 30 minutes.

[0066] The first non-aqueous solution, the second non-aqueous solution, and the non-aqueous organic liquid, or the third non-aqueous solution and the non-aqueous organic liquid, may be mixed using a continuous flow reactor using a continuous flow process to obtain a non-aqueous liquid mixture. A reactor using a continuous flow process uses a microchannel to bring the first non-aqueous solution, the second non-aqueous solution, and the non-aqueous organic liquid, or the third non-aqueous solution and the non-aqueous organic liquid, into contact with each other and mix them. The flow rate of the first non-aqueous solution, the second non-aqueous solution, the third non-aqueous solution, and the non-aqueous organic liquid through the microchannel is preferably in the range of 1 mL / min to 1000 mL / min, more preferably in the range of 10 mL / min to 50 mL / min. When a reactor using a continuous flow process is used, the volume ratio of the non-aqueous organic liquid to the total amount of the first non-aqueous solution and the second non-aqueous solution or to the third non-aqueous solution is preferably 1:9 or more and 9:1 or less, and more preferably 6:4 or more and 4:6 or less, although this depends on the first ion concentration, the second ion concentration, and the third ion concentration.

[0067] The mixing of the first non-aqueous solution, the second non-aqueous solution, and the non-aqueous organic liquid, or the third non-aqueous solution and the non-aqueous organic liquid, can be carried out, for example, within a temperature range of 0° C. to 110° C., or alternatively, within a temperature range of 15° C. to 40° C., or within a temperature range of 23° C. to 28° C. The atmosphere in which the non-aqueous liquid mixture is mixed may be, for example, normal air, or an inert gas atmosphere such as nitrogen gas.

[0068] By mixing a first non-aqueous solution, a second non-aqueous solution, and a non-aqueous organic liquid, and a third non-aqueous solution and a non-aqueous organic liquid, an inorganic fluoride luminescent material containing a first element M1 or ammonium, a second element M2, and a third element M3 can be obtained in the resulting non-aqueous liquid mixture. Specifically, the inorganic fluoride luminescent material containing the first element M1 or ammonium, the second element M2, and the third element M3 can be precipitated as a precipitate or the like in the non-aqueous liquid mixture. The obtained inorganic fluoride luminescent material may be subjected to post-treatments such as separation, washing, and drying from the non-aqueous liquid mixture. The washing treatment can be performed using a non-aqueous organic liquid. The drying treatment can be performed using industrially commonly used equipment and methods such as a vacuum dryer, a heating dryer, a conical dryer, or a rotary evaporator. The drying temperature in the heat drying treatment may be any temperature at which the liquid adhering to the inorganic fluoride luminescent material evaporates, and is usually 40° C. or higher, preferably 50° C. or higher, and usually 100° C. or lower, preferably 70° C. or lower. The drying time may be any time at which the liquid adhering to the inorganic fluoride luminescent material evaporates, and is, for example, about 8 hours.

[0069] The inorganic fluoride luminescent material obtained by the production method according to the present disclosure includes, for example, LiYF4 (hereinafter also referred to as "YLF"), LiLuF4, BaY2F8, KY3F, and the like, which contain at least one rare earth element selected from the group consisting of Tm, Ho, Pr, Er, and Yb as a third element M3. 10ZBLAN (ZrF4-BaF2-LaF3-AlF3-NaF) glass fiber mainly composed of ZrF4 containing at least one rare earth element selected from the group consisting of Pr, Nd, Ho, Er, Dy, Tm, and Yb as the third element M3, and AlF3-based glass fiber (AlF3-BaF2-SrF2-CaF2-MgF2-YF3) mainly composed of AlF3 containing the rare earth element as the third element M3. Among the inorganic fluoride luminescent materials obtained by the production method according to the present disclosure, YLF, LiLuF4, BaY2F8, or KY3F 10 The fluoride crystal, ZBLAN glass fiber, and AlF3-based glass fiber having the composition represented by the formula (I) can be used as a laser medium for fiber lasers and fiber amplifiers. The inorganic fluoride luminescent material obtained by the production method according to the present disclosure is produced using a non-aqueous solution, and therefore does not contain hydroxide ions (OH - ) or have optical properties that are less susceptible to water.

[0070] The inorganic fluoride luminescent material obtained by the method of the present disclosure is preferably an inorganic fluoride phosphor having a composition represented by the following formula (I). M1' x [M2 1-z M3' z F y ] (I) (In formula (I), M1' is Li + , Na + , K. + , Rb + , Cs + , Fr + , Be 2+ , Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Ra 2+ and NH4 + M2 is at least one element selected from the group consisting of non-luminescent transition metal elements, Group 13 elements, Group 14 elements, and Group 15 elements; and M3' is Mn 4+ and x is [M2 1-z M3'z F y is the absolute value of the charge of the ion, and y and z satisfy 5 ≦ y ≦ 7 and 0 < z < 0.2, respectively.)

[0071] Since the inorganic fluoride phosphor obtained by the production method according to the present disclosure is produced using a non-aqueous solution, it is not affected by hydroxide ions (OH - ) or water and can maintain excellent luminescence characteristics. Further, by the method of the present disclosure, an inorganic fluoride phosphor produced using a non-aqueous solution is difficult for tetravalent manganese, which is a luminescence center, to be reduced to trivalent manganese by hydroxide ions (OH - ) or water, and the valence of manganese contained in the phosphor can be maintained as tetravalent, so that excellent luminescence characteristics can be maintained.

[0072] In formula (I), M1’ is more preferably Li + , K + [[ID=]19] Na + and NH4 + and is at least one cation selected from the group consisting of, and more preferably K + .

[0073] In formula (I), M2 is preferably at least one element selected from the group consisting of Sc, Ti, Y, Zr, Hf, Ta, Si, Ge, Sn and Pb, more preferably at least one element selected from the group consisting of Si, Ge, Sn, Ti, Zr and Hf, still more preferably at least one element selected from the group consisting of Si, Ge, Ti and Zr, and most preferably Si.

[0074] In formula (I), M3’ is Mn 4+ , and is an activating element that contributes to the luminescence of the inorganic fluoride phosphor having the composition represented by formula (I). In formula (I), the variable z is Mn, which is an activating element in the composition represented by formula (I). 4+represents the molar ratio. In formula (I), the variable z is a number within the range greater than 0 and less than 0.2 (0 < z < 0.2), preferably a number within the range of 0.005 or more and 0.15 or less (0.005 ≤ z ≤ 0.15), more preferably a number within the range of 0.010 or more and 0.100 or less (0.010 ≤ z ≤ 0.100), and even more preferably a number within the range of 0.015 or more and 0.090 or less (0.015 ≤ z ≤ 0.090).

[0075] The inorganic fluoride phosphor having the composition represented by formula (I) is activated by Mn 4+ and absorbs light in the short wavelength region of visible light and emits red light. The excitation light, which is light in the short wavelength region of visible light, is preferably mainly light in the blue region. Specifically, the excitation light irradiated to the inorganic fluoride phosphor having the composition represented by formula (I) preferably has an excitation peak wavelength of the excitation spectrum within the range of 380 nm or more and 485 nm or less. The emission spectrum of the inorganic fluoride phosphor having the composition represented by formula (I) preferably has a peak wavelength within the range of 610 nm or more and 650 nm or less. Also, the numerical value of the full width at half maximum of the emission spectrum of the inorganic fluoride phosphor having the composition represented by formula (I) is preferably small, specifically preferably 10 nm or less. The full width at half maximum refers to the full width at half maximum (Full Width at Half Maximum: FWHM) of the emission peak in the emission spectrum, and refers to the wavelength width of the emission peak showing a value of 50% of the maximum value of the emission peak in the emission spectrum.

[0076] The inorganic fluoride phosphor having the composition represented by formula (I) can be used in a light-emitting device used in, for example, a lighting device, a backlight of a liquid crystal display device, etc. in combination with an excitation light source such as an LED or an LD.

[0077] The excitation light source used in the light-emitting device can be an excitation light source that emits light in the wavelength range of 400 nm to 570 nm. By using an excitation light source in this wavelength range, a light-emitting device with high emission intensity can be provided. The light-emitting element used as the excitation light source of the light-emitting device preferably has an emission peak wavelength in the range of 420 nm to 500 nm, more preferably in the range of 420 nm to 460 nm.

[0078] As a light-emitting element, nitride semiconductors (In X Al Y Ga 1-X-Y It is preferable to use a semiconductor light-emitting element using a semiconductor light-emitting element having a wavelength of 0≦X, 0≦Y, X+Y≦1. By using a semiconductor light-emitting element as an excitation light source for a light-emitting device, it is possible to obtain a stable light-emitting device that is highly efficient, has high output linearity relative to input, and is resistant to mechanical shock. The half-width of the emission spectrum of the light-emitting element is preferably, for example, 30 nm or less.

[0079] The light emitting device may use, for example, an inorganic fluoride phosphor having a composition represented by formula (I). For example, an inorganic fluoride phosphor having a composition represented by formula (I) may be used as a first phosphor, and a second phosphor having an emission peak wavelength different from that of the first phosphor may be used. As the first phosphor, one type of phosphor may be used alone, or two or more types of phosphors may be used in combination, as long as they have an emission peak wavelength within a desired wavelength range. As the second phosphor, one type of phosphor may be used alone, or two or more types of phosphors may be used in combination, as long as they have an emission peak wavelength within a desired wavelength range.

[0080] An example of a light emitting device will be described with reference to the drawings. Figure 3 is a schematic cross-sectional view showing an example of a light emitting device. This light emitting device is an example of a surface-mounted light emitting device.

[0081] The light emitting device 100 includes a package 40 having a recess formed by lead electrodes 20, 30 and a molded body 42, a light emitting element 10, and a sealing member 50 that covers the light emitting element 10. The light emitting element 10 is disposed in the recess of the package 40 and is electrically connected to a pair of positive and negative lead electrodes 20, 30 provided on the package 40 by conductive wires 60. The sealing member 50 fills the recess, covers the light emitting element 10, and seals the recess. The sealing member 50 includes, for example, a phosphor 70 that converts the wavelength of light from the light emitting element 10 and a resin. The phosphor 70 further includes a first phosphor 71 and a second phosphor 72. The pair of positive and negative lead electrodes 20, 30 are partially exposed on the outer surface of the package 40. The light emitting device 100 emits light when power is supplied from an external source via the lead electrodes 20, 30.

[0082] The sealing member 50 contains a resin and a phosphor 70, and is formed so as to cover the light emitting element 10 placed in the recess of the light emitting device 100. [Example]

[0083] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0084] Example 1 10.0 g of potassium hexafluorosilicate (K2SiF6), which contains K as the first element M1 and Si as the second element M2, was weighed and dissolved in 85 mL of a pyridine-HF complex solution containing 70 mass % hydrogen fluoride and 30 mass % pyridine as a first nonaqueous hydrogen fluoride-containing liquid to prepare a first nonaqueous solution. The first ion in the first nonaqueous solution was K + and the second ion is Si 4+ The first complex ion is the first fluoride complex ion, SiF6, which contains the second element M2 and fluorine. 2- The first ion concentration in 100 mass % of the first nonaqueous solution was 3.43 mass %, the second ion concentration was 1.24 mass %, and the first complex ion concentration was 6.23 mass %. 570 mg of potassium hexafluoromanganate (K2MnF6), containing Mn as the third element M3, was weighed and dissolved in 5 mL of a pyridine-HF complex solution containing 70 mass % hydrogen fluoride and 30 mass % pyridine as a second non-aqueous hydrogen fluoride-containing liquid to prepare a second non-aqueous solution. The first ion in the second non-aqueous solution was K + and the third ion is Mn 4+ The second complex ion is a second fluoride complex ion containing a third element M3 and fluorine, MnF6 2- The first ion concentration in 100 mass % of the first non-aqueous solution was 2.97 mass %, the third ion concentration was 2.09 mass %, and the second complex ion concentration was 6.42 mass %. As a non-aqueous organic liquid, 100 mL of acetonitrile, which does not substantially contain hydrogen fluoride and has a hydrogen fluoride content of substantially 0 mass %, was prepared. A first non-aqueous solution containing K, Si, and fluorine was mixed with a second non-aqueous solution containing K, Mn, and fluorine. The mixture of the first and second non-aqueous solutions was stirred and controlled at a temperature of 23 to 27°C. 100 mL of acetonitrile, a non-aqueous organic liquid, was added dropwise to the mixture over approximately 100 minutes, yielding a precipitate in the non-aqueous liquid mixture. The volume ratio of the non-aqueous organic liquid to the total amount of the first and second non-aqueous solutions was 4.7:5.3. The resulting precipitate was subjected to solid-liquid separation, washed with acetonitrile, then washed with isopropanol, and vacuum dried for 8 hours at 25°C to obtain K2[Si 0.957 Mn 4+ 0.043 An inorganic fluoride phosphor of Example 1 having a composition represented by the formula: [F6] was obtained. The Mn content (mass %) in the inorganic fluoride phosphor of Example 1, measured by the measurement method described below, was 1.07 mass %. When the inorganic fluoride phosphor of Example 1 was dissolved in a deuterated solvent and measured by nuclear magnetic resonance (proton NMR), it is presumed that pyridine, a component contained in the non-aqueous hydrogen fluoride-containing liquid, would be detected from the inorganic fluoride phosphor of Example 1.

[0085] Comparative Example 1 0.99 g of potassium hexafluoromanganate (K2MnF6) and 34.58 g of hexafluorosilicic acid (H2SiF6) were weighed out and dissolved in 100 mL of an HF aqueous solution containing 55 mass % hydrogen fluoride and 45 mass % deionized water, and then 100 mL of deionized water was added to prepare a first aqueous solution. Furthermore, 15.6 g of potassium hydrogen fluoride (KHF2) was weighed out and dissolved in 50 mL of an aqueous HF solution containing 55 mass % of hydrogen fluoride and 45 mass % of deionized water to prepare a second aqueous solution. Next, the second aqueous solution was added dropwise to the first aqueous solution over a period of about 10 minutes while stirring at room temperature to obtain a precipitate. The obtained precipitate was subjected to solid-liquid separation, washed with ethanol, and dried at 110 °C for 8 hours to obtain K2[Si 0.958 Mn 4+ 0.042 F6] was prepared as Comparative Example 1. The Mn content (mass %) in the inorganic fluoride phosphor of Comparative Example 1 measured by the measuring method described below was 1.03 mass %.

[0086] Evaluation and Results 1 Infrared reflectance spectrum The infrared reflectance spectrum of each of the obtained inorganic fluoride phosphors was measured by a diffuse reflectance method using a Fourier transform infrared spectrophotometer (FT / IR-6600, manufactured by JASCO Corporation. Fig. 4 shows the infrared reflectance spectra of the inorganic fluoride phosphor according to Example 1 and the inorganic fluoride phosphor according to Comparative Example 1.

[0087] Evaluation and Results 2 Mn content and internal quantum efficiency The Mn content (mass%) of each of the obtained inorganic fluoride phosphors was measured using a high-frequency inductively coupled plasma (ICP) optical emission spectrometer (PS3500DD-II, manufactured by Hitachi High-Tech Science Corporation). Furthermore, the emission spectrum of each of the obtained inorganic fluoride phosphors excited by excitation light with an emission peak wavelength of 450 nm was measured using a quantum efficiency measurement device (QE-2100, manufactured by Otsuka Electronics Co., Ltd.), and the internal quantum efficiency of the emission of each inorganic fluoride phosphor was measured from the emission spectrum in the range of 600 nm to 650 nm.

[0088] [Table 1]

[0089] The infrared reflectance spectrum of the inorganic fluoride phosphor according to Example 1 produced using the mixture of non-aqueous solutions is 2500 cm -1 From 4000cm -1 In the wave number region of 2500 cm, the decrease in the infrared reflection spectrum is suppressed compared to the infrared reflection spectrum of the inorganic fluoride phosphor according to Comparative Example 1, which was produced using an aqueous solution. -1 From 4000cm -1 The reduction in the infrared reflectance spectrum in the wavenumber region is due to hydroxide ions (OH - ) or indicates the presence of water, and -1 From 4000cm -1 The fact that the reduction in the infrared reflectance spectrum in the wavenumber region is suppressed is due to the hydroxide ions (OH - ) or water is less than that of the inorganic fluoride phosphor of Example 1. - ) and water, and the deterioration of optical properties due to hydroxide ions or water could be suppressed.

[0090] The inorganic fluoride phosphor of Example 1, which was produced using a mixture of non-aqueous solutions, contained less hydroxide ions (OH-) and water, and the tetravalent manganese, which is the luminescent center, remained tetravalent without being reduced to trivalent. Therefore, the inorganic fluoride phosphor of Example 1, which was produced using an aqueous solution, had a higher internal quantum efficiency and superior luminescence properties.

[0091] Evaluation and Results 3 UV-Visible Reflectance Spectrum The ultraviolet-visible reflectance spectrum of each of the obtained inorganic fluoride phosphors was measured using an ultraviolet-visible near-infrared spectrophotometer (U-4100, manufactured by Hitachi High-Tech Science Corp.) Fig. 5 shows the ultraviolet-visible reflectance spectra of the inorganic fluoride phosphor according to Example 1 and the inorganic fluoride phosphor according to Comparative Example 1.

[0092] It was confirmed that the ultraviolet-visible reflectance spectrum of the inorganic fluoride phosphor according to Example 1, which was produced using a mixture of non-aqueous solutions, was higher in the wavelength range of 500 nm to 600 nm than the ultraviolet-visible reflectance spectrum of the inorganic fluoride phosphor according to Comparative Example 1, which was produced using an aqueous liquid. In the ultraviolet-visible reflectance spectrum of the inorganic fluoride phosphor according to Example 1, the reduction in reflectance in the wavelength range of 500 nm to 600 nm is due to the presence of Mn, which does not contribute to light emission. 3+ The reason why the reflectance of the ultraviolet-visible reflection spectrum of the inorganic fluoride phosphor according to Example 1 is higher in the wavelength range of 500 nm to 600 nm than that of the inorganic fluoride phosphor according to Comparative Example 1 is that Mn, which does not contribute to light emission, is present. 3+ Mn contributes relatively little to luminescence 4+ From the ultraviolet-visible reflectance spectrum of the inorganic fluoride phosphor according to Example 1, it can be seen that the inorganic fluoride phosphor according to Example 1 contains more Mn, which does not contribute to light emission, than the inorganic fluoride phosphor according to Comparative Example 1. 3+ Mn contributes relatively little to luminescence 4+ It had a high content of fluorine and excellent luminescence properties.

[0093] Evaluation and Results 4 and 5 Excitation and Emission Spectra The excitation spectrum and emission spectrum of each of the obtained fluoride phosphors were measured using a spectrofluorometer (FP-8500DS, manufactured by JASCO Corporation). Fig. 6 shows the excitation spectrum of the inorganic fluoride phosphor according to Example 1 and the inorganic fluoride phosphor according to Comparative Example 1. Fig. 7 shows the emission spectrum of the inorganic fluoride phosphor according to Example 1 and the inorganic fluoride phosphor according to Comparative Example 1.

[0094] It was confirmed that the inorganic fluoride phosphor of Example 1, which was produced using a mixture of non-aqueous solutions, and the inorganic fluoride phosphor of Comparative Example 1, which was produced using an aqueous solution, have excitation spectrum peaks at 350 nm and 450 nm, and have high absorption of excitation light of approximately the same wavelength.

[0095] The inorganic fluoride phosphor according to Example 1, which was produced using a mixture of non-aqueous solutions, and the inorganic fluoride phosphor according to Comparative Example 1, which was produced using an aqueous solution, had almost the same emission spectrum, and both had sharp emission spectra with narrow half-widths. [Industrial Applicability]

[0096] The inorganic fluoride luminescent material obtained by the manufacturing method of the present disclosure can be used as a fiber laser, a laser medium for a fiber amplifier, or a phosphor. In particular, among the inorganic fluoride luminescent materials obtained by the manufacturing method of the present disclosure, the inorganic fluoride phosphor can be suitably used in lighting sources using light-emitting diodes as excitation light sources, light sources for LED displays or liquid crystal backlights, traffic lights, illuminated switches, various sensors, various indicators, small strobes, etc. [Explanation of symbols]

[0097] 10: light emitting element, 20, 30: lead electrode, 40: package, 42: molded body, 50: sealing member, 60: wire, 70: phosphor, 71: first phosphor, 72: second phosphor, 100: light emitting device.

Claims

1. a first non-aqueous solution containing at least one first ion containing at least one selected from the group consisting of a first element M1 and ammonium, at least one second ion containing a second element M2 other than the first element M1, and a first non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content in the range of 20 mass % to 100 mass %; a second non-aqueous solution containing a third ion containing a third element M3 other than the first element M1 and the second element M2, and a second non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content in the range of 20 mass % to 100 mass %, or preparing a third non-aqueous solution containing at least one first ion containing at least one selected from the group consisting of a first element M1 and ammonium, at least one second ion containing a second element M2 other than the first element M1, a third ion containing a third element M3 other than the first element M1 and the second element M2, and a third non-aqueous hydrogen fluoride-containing liquid having a hydrogen fluoride content in the range of 20 mass % to 100 mass %; mixing the first non-aqueous solution, the second non-aqueous solution, and a non-aqueous organic liquid having a hydrogen fluoride content of less than 20% by mass; or a method for producing an inorganic fluoride luminescent material, the method comprising: mixing the third non-aqueous solution with a non-aqueous organic liquid having a hydrogen fluoride content of less than 20 mass %; and obtaining an inorganic fluoride luminescent material containing the first element M1 and / or ammonium, the second element M2, and the third element M3.

2. 2. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the first non-aqueous hydrogen fluoride-containing liquid, the second non-aqueous hydrogen fluoride-containing liquid, or the third non-aqueous hydrogen fluoride-containing liquid contains at least one selected from the group consisting of nitrogen-containing heterocyclic compounds, amines, ureas, amides, carbamic acids, trialkylphosphines, ethers, esters, alcohols, and quaternary ammonium salts.

3. 3. The method for producing an inorganic fluoride luminescent material according to claim 1 or 2, wherein the non-aqueous organic liquid comprises at least one selected from the group consisting of nitriles, ketones, amines, amides, nitrogen-containing heterocyclic compounds, fluoro compounds, ethers, esters, alcohols, and mixtures thereof.

4. 4. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the first element M1 is at least one element selected from the group consisting of alkali metal elements and alkaline earth metal elements.

5. The method for producing an inorganic fluoride luminescent material according to claim 1 , wherein the first ion is a cation formed of the first element M1 or ammonium.

6. 6. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the second element M2 is at least one element selected from the group consisting of non-luminescent transition metal elements, Group 12 elements, Group 13 elements, Group 14 elements, and Group 15 elements.

7. 7. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the second ion is a cation consisting of the second element M2 or a first complex ion containing the second element M2 and fluorine.

8. 7. The method for producing an inorganic fluoride luminescent material according to claim 6, wherein the non-luminescent transition metal element is at least one element selected from the group consisting of Sc, Ti, Y, Zr, Nb, La, Gd, Hf, and Ta.

9. 9. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the third element M3 is at least one element selected from luminescent transition metal elements.

10. 10. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the third ion is a cation composed of the third element M3 or a second complex ion containing the third element M3 and fluorine.

11. 10. The method for producing an inorganic fluoride luminescent material according to claim 9, wherein the luminescent transition metal element is at least one element selected from the group consisting of Mn, Ce, Pr, Nd, Pm, Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

12. the first ion is at least one first element M1 selected from the group consisting of alkali metal elements and at least one cation selected from the group consisting of ammonium, the second ion is a first complex ion containing fluorine and at least one second element M2 selected from the group consisting of non-luminescent transition metal elements, Group 13 elements, Group 14 elements, and Group 15 elements; 12. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the third ion is a second complex ion containing fluorine and at least one third element M3 selected from luminescent transition metal elements.

13. the first complex ion is a first fluoride complex ion containing fluorine and at least one second element M2 selected from the group consisting of Si, Ge, Sn, Ti, Zr, Al, Ga, In, Sc, Hf, La, Nb, Ta, Bi, and Gd, 13. The method for producing an inorganic fluoride luminescent material according to claim 12, wherein the third element is Mn, and the second complex ion is a second fluoride complex ion containing Mn and fluorine.

14. 4. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the obtained inorganic fluoride luminescent material has a composition represented by the following formula (I): M1’ ｘ [M2 １－ｚ M3’ ｚ F ｙ ] (I) (In formula (I), M1′ is Li ＋ , Na ＋ , K. ＋ , Rb ＋ , Cs ＋ and N.H. ４ ＋ M2 is at least one element selected from the group consisting of non-luminescent transition metal elements, Group 13 elements, Group 14 elements, and Group 15 elements; and M3′ is Mn ４＋ and x is [M2 １－ｚ M3' ｚ F ｙ ] is the absolute value of the charge of the ion, and y and z satisfy the ranges 5≦y≦7 and 0<z<0.2, respectively.

15. 15. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the first non-aqueous solution, the second non-aqueous solution, and the non-aqueous organic liquid, or the third non-aqueous solution and the non-aqueous organic liquid, are mixed using a batch reactor.

16. 15. The method for producing an inorganic fluoride luminescent material according to claim 1, wherein the first non-aqueous solution, the second non-aqueous solution, and the non-aqueous organic liquid, or the third non-aqueous solution and the non-aqueous organic liquid, are mixed using a continuous flow reactor.

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