WO2014192515A1 - Fluorescent material and method for producing same - Google Patents

Fluorescent material and method for producing same Download PDF

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Publication number
WO2014192515A1
WO2014192515A1 PCT/JP2014/062396 JP2014062396W WO2014192515A1 WO 2014192515 A1 WO2014192515 A1 WO 2014192515A1 JP 2014062396 W JP2014062396 W JP 2014062396W WO 2014192515 A1 WO2014192515 A1 WO 2014192515A1
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heat treatment
phosphor material
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zirconium
metal element
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PCT/JP2014/062396
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French (fr)
Japanese (ja)
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中島　靖
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第一稀元素化学工業株式会社
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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
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus
    • C09K11/71—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus also containing alkaline earth metals

Definitions

  • the present invention relates to a phosphor material and a manufacturing method thereof.
  • the “phosphor material” in this specification means “a material used for an application utilizing photoluminescence (that is, a phenomenon in which visible light is emitted by ultraviolet irradiation)”.
  • a phosphor material that emits visible light (generally, light having a wavelength of 380 nm or more and less than 830 nm) by ultraviolet irradiation is used for lighting devices, backlights for liquid crystal display devices, and the like.
  • Patent Documents 1 to 3 Many known phosphor materials contain rare earth elements as light emitting elements (for example, Patent Documents 1 to 3). However, rare earth elements have problems such as a small reserve, a limited production country such as China, and a high cost for separation and purification. Therefore, a phosphor material using an element other than a rare earth element as a light emitting element is required.
  • the oxide-based material is excellent in stability, 3.6MgO ⁇ 4CaF 2 ⁇ which a light emitting element and Mn 4+ as a red phosphor GeO 2 : 0.01Mn (for example, Patent Document 4) is known.
  • a green phosphor ZnGa 2 O 4 : Mn (for example, Patent Document 5) using Mn 2+ as a light emitting element is known.
  • ZnO having an oxygen defect as a light emission center for example, Patent Document 6 is known. It has also been shown that faujasite-type zeolite containing Ag ions becomes an orange to green phosphor (for example, Patent Document 7).
  • the above oxide materials also have the following problems.
  • ZnGa 2 O 4: Ga 2 O 3 is the main component of Mn is reserves as with any rare earth element There are few and it is very expensive as a raw material. Ag in zeolite containing Ag ions is also an expensive raw material.
  • An object of the present invention is to provide a phosphor material using an element other than a rare earth element as a light-emitting element, which is an inexpensive phosphor material and has high emission efficiency. Moreover, it aims at providing the manufacturing method.
  • the present invention has found that an oxide-based phosphor material having a specific composition can achieve the above object, and has completed the present invention.
  • this invention relates to the following phosphor material and its manufacturing method.
  • H 1-x Zr 2 P 3 O 12- (x / 2) (1) [Wherein x is 0.005 or more and less than 0.4. ]
  • a phosphor material characterized by the following: 2. (M n + y H 1-ny ) 1-x Zr 2 P 3 O 12- (x / 2) (2) [In the formula, M represents a metal element, and n represents an average valence of the metal element M. Moreover, x is 0.005 or more and less than 0.4, and y is 0.01 or more and less than 0.90 / n. ]
  • a phosphor material characterized by the following: 3.
  • Item 4. The method according to Item 3, which is a method for manufacturing the phosphor material according to Item 1. 5.
  • M represents a metal element, n represents an average valence of the metal element M, and R represents H, H 3 O, or NH 4.
  • y is the number of moles of the metal element M, and y is 0.01 or more and less than 0.90 / n.), and the starting material B is heat-treated at 400 to 850 ° C. in a reducing atmosphere.
  • the phosphor material of the present invention is roughly classified into the phosphor material of the first aspect (not including the metal element M) and the phosphor material of the second aspect (including the metal element M). Can do.
  • the phosphor material of the first aspect is H 1-x Zr 2 P 3 O 12- (x / 2) (1) [Wherein x is 0.005 or more and less than 0.4. ] It is represented by.
  • the phosphor material of the second aspect is (M n + y H 1-ny ) 1-x Zr 2 P 3 O 12- (x / 2) (2)
  • M represents a metal element
  • n represents an average valence of the metal element M.
  • x is 0.005 or more and less than 0.4
  • y is 0.01 or more and less than 0.90 / n.
  • It is represented by.
  • the phosphor material of the first embodiment and the second embodiment is a zirconium phosphate-based phosphor material using an element other than a rare earth element as a light emitting element, and visible light (light having a wavelength of 380 nm or more and less than 830 nm) by ultraviolet irradiation. Is emitted. Specifically, for example, fluorescence (395 nm) is obtained by irradiating excitation light (254 nm).
  • the phosphor material of the present invention can be widely used for phosphor materials such as lighting devices and backlights for liquid crystal display devices.
  • x is 0.005 or more and less than 0.4, x is preferably 0.01 or more and 0.35 or less, and is 0.01 or more and 0.2 or less. More preferred.
  • the range of x is defined as 0.005 or more and less than 0.4.
  • N represents the average valence of the metal element M (details will be described later).
  • M is composed of a trivalent metal element (0.3 mol) and a tetravalent metal element (0.7 mol)
  • Y is 0.01 or more and less than 0.90 / n.
  • y is preferably 0.1 or more and 0.45 or less.
  • the range of y is defined as 0.01 or more and less than 0.90 / n.
  • the metal element M examples include, but are not limited to, alkali metals (Li, Na, K, Rb, Cs, etc.), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), titanium group (Ti , Zr, Hf), vanadium group (V, Nb, Ta), chromium group (Cr, Mo, W), manganese group (Mn, Tc, Re), iron group (Fe, Co, Ni), platinum group (Pd , Pt, etc.), copper group (Cu, Ag, Au), zinc group (Zn, Cd, Hg), boron group (Al, In, etc.), carbon group (Sn, Pb), and the like.
  • These metal elements M can be used alone or in combination of two or more.
  • the metal element M at least one of an alkali metal and an alkaline earth metal is preferable.
  • the phosphor material of the second aspect has pores depending on the embodiment, and the inorganic acid salt and / or organic acid salt of the metal element M is adsorbed on the surface of the phosphor material and / or the pores. You may do it.
  • inorganic acid salts include forms such as nitrates, sulfates, and carbonates.
  • forms, such as an oxalate and acetate, are mentioned as organic acid salt.
  • the method for producing the phosphor material of the present invention is not limited as long as the phosphor materials of the first aspect and the second aspect described above are obtained, respectively, but are produced by the following production method. It is preferable.
  • the phosphor material according to the first aspect is obtained by using a starting material A represented by RZr 2 P 3 O 12 (where R represents H, H 3 O or NH 4 ) in a reducing atmosphere at 400 to 850 ° C. It is preferable to manufacture by the manufacturing method characterized by heat-treating.
  • the phosphor material of the second aspect is M n + y R 1-ny Zr 2 P 3 O 12 (where M represents a metal element, n represents an average valence of the metal element M, R represents H, H 3 O or NH 4 where y is the number of moles of the metal element M, and y is 0.01 or more and less than 0.90 / n). It is preferably produced by a production method characterized by heat treatment at 400 to 850 ° C.
  • the starting material A is crystalline zirconium phosphate represented by RZr 2 P 3 O 12 (where R represents H, H 3 O or NH 4 ), and in particular, zirconium ammonium phosphate (NH 4 Zr 2 P 3 O 12 ) is preferably used as the starting material A.
  • HZr 2 P 3 O 12 is obtained by heat-treating zirconium ammonium phosphate (NH 4 Zr 2 P 3 O 12 ), and by contacting HZr 2 P 3 O 12 with water, (H 3 O ) Zr 2 P 3 O 12 is produced. Details of the generation will be described later.
  • zirconium phosphate ammonium (NH 4 Zr 2 P 3 O 12), zirconium compounds, chemical synthesis using a carboxylic acid compound and phosphoric acid compound, a raw material mixture containing at least one ammonium compounds and ammine compound It is preferable to use those prepared by the method (direct crystal precipitation method). Further, as NH 4 Zr 2 P 3 O 12 prepared by the direct crystal precipitation method, for example, those prepared according to the description in JP-A-60-239313 or commercially available products can be used.
  • a phosphoric acid compound or an aqueous solution thereof is added to a mixed solution containing a zirconium compound and a carboxylic acid compound.
  • the zirconium compound is preferably a zirconium compound that is water-soluble or water-soluble by an acid.
  • zirconium halides such as zirconium oxychloride, zirconium hydroxide chloride, zirconium tetrachloride and zirconium bromide; zirconium salts of mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate; organic acids such as zirconyl acetate and zirconyl formate
  • Zirconium salts such as ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, and zirconium ammonium citrate can be used.
  • zirconium compounds at least one of zirconium oxychloride and zirconium sulfate is preferable.
  • an aliphatic polycarboxylic acid and a salt thereof that are water-soluble or water-soluble by an acid and have two or more carboxyl groups (—COOH) are preferable.
  • aliphatic dibasic acids and salts thereof such as oxalic acid, sodium oxalate, sodium hydrogen oxalate, ammonium oxalate, ammonium hydrogen oxalate, lithium oxalate, maleic acid, malonic acid, succinic acid and salts thereof;
  • Examples thereof include aliphatic oxyacids such as citric acid, ammonium citrate, tartaric acid and malic acid, and salts thereof.
  • oxalic acid and at least one of its sodium salt and ammonium salt are preferable.
  • the phosphoric acid compound is preferably water-soluble or water-soluble by acid.
  • alkali metal and ammonium salts of orthophosphoric acid such as phosphoric acid, monobasic sodium phosphate, dibasic ammonium phosphate, and tribasic sodium phosphate; at least one P—O—P such as metaphosphoric acid and pyrophosphoric acid
  • P—O—P such as metaphosphoric acid and pyrophosphoric acid
  • alkali metal salts and ammonium salts of condensed phosphoric acid having a bond At least one ammonium salt of phosphoric acid and orthophosphoric acid is preferable.
  • ammonium compound a compound that is water-soluble or water-soluble by an acid is preferable.
  • the ammonium compound include inorganic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium hydrogen carbonate; and organic ammonium compounds such as tetrapropylammonium hydroxide and tetraethylammonium hydroxide.
  • inorganic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium hydrogen carbonate
  • organic ammonium compounds such as tetrapropylammonium hydroxide and tetraethylammonium hydroxide.
  • at least 1 sort (s) of the above-mentioned zirconium compound, carboxylic acid compound, and phosphoric acid compound is an ammonium containing compound, they can also be considered and used as an ammonium ion source.
  • ammonium compound among the above, at least one of ammonium phosphate, aqueous ammonia, ammonium chloride, and ammonium oxalate is more preferable.
  • the ratio of the zirconium compound (as Zr), the carboxylic acid compound (as C 2 O 4 ), and the phosphoric acid compound (as PO 4 ) in the raw material mixed solution is A (28, 3, 69), B (63, 6, 31), C (44, 43, 13) and D (1, 97, 2) are within a region surrounded by a straight line, and Zr is It is desirable to adjust so that the ammonium compound is about 0.2 to 100 mol per mol.
  • the form of the raw material mixed solution in which each component is uniformly dissolved or dispersed may be either a solution or a slurry containing undissolved excess raw material.
  • the concentration of the raw material mixture is preferably adjusted to a concentration at which Zr is 0.01 to 25% by mass, particularly 0.1 to 10% by mass.
  • a dilute solution having a Zr of less than 0.01% by mass may be economically disadvantageous because it takes a long time to crystallize the target product.
  • Zr exceeds 25% by mass carboxylate, phosphate and the like are precipitated as crystals, which may make it difficult to filter and wash the crystalline zirconium phosphate as a product.
  • the pH of the raw material mixture is not limited, but is preferably 10 or less, more preferably 0.5 to 7. When the pH exceeds 10, crystalline zirconium phosphate having a low crystallinity tends to be generated.
  • pH adjusters used for adjusting the pH of the raw material mixture include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; ammonium and alkali such as ammonium hydroxide, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide and sodium carbonate. Examples are metal hydroxides and carbonates.
  • reaction temperature of the raw material mixture (in the present invention, the reaction of each component and the crystallization reaction of crystalline zirconium phosphate by aging are collectively referred to as reaction) is preferably 50 ° C. or higher. If the reaction temperature is less than 50 ° C., it takes a long time to crystallize the target product, which may be economically disadvantageous.
  • the upper limit of the reaction temperature is not limited, but may be about 200 ° C. from the viewpoint of economy and the like.
  • the reaction time varies depending on the type of raw material (that is, the reactivity of the raw material); the mixing ratio of the raw material; the concentration, temperature and pH of the raw material mixture; the desired crystallinity of the reaction product, etc. It is preferable that it is a grade.
  • the produced NH 4 Zr 2 P 3 O 12 is subjected to solid-liquid separation by known means such as filtration, decantation, and centrifugation, washed, and then dehydrated and dried according to a conventional method.
  • a drying method in addition to heat drying or air drying, a method of removing adsorbed water with a drying agent such as phosphorus pentoxide, calcium chloride, silica gel, or the like can be applied.
  • the obtained NH 4 Zr 2 P 3 O 12 is put into various ceramic crucibles such as alumina or platinum crucible and heat-treated at about 500 to about 700 ° C. for about 1 hour to about 5 hours, so that HZr 2 It can be changed to P 3 O 12 .
  • HZr 2 P 3 O 12 generally has a chemically and thermally stable three-dimensional network structure, and partially contains ammonium ions, hydrogen ions, H 2 O molecules having a small molecular diameter, and the like. It has a zeolitic tunnel structure contained in the microscopic pores of the network structure.
  • These crystalline zirconium phosphates are represented by the general formula shown at the beginning: RZr 2 P 3 O 12 (where R represents H, H 3 O or NH 4 ), and can be used as the starting material A. it can.
  • the starting material B which is a material for producing the phosphor material of the second aspect, can be prepared using the starting material A.
  • the starting material B can be prepared by preparing a mixed solution containing the starting material A and the metal element M, and heat-treating the mixed solution or one obtained by evaporating and drying the mixed solution.
  • the metal element M examples include, but are not limited to, alkali metals (Li, Na, K, Rb, Cs, etc.), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), titanium group (Ti , Zr, Hf), vanadium group (V, Nb, Ta), chromium group (Cr, Mo, W), manganese group (Mn, Tc, Re), iron group (Fe, Co, Ni), platinum group (Pd , Pt, etc.), copper group (Cu, Ag, Au), zinc group (Zn, Cd, Hg), boron group (Al, In, etc.), carbon group (Sn, Pb), and the like.
  • These metal elements M can be used alone or in combination of two or more.
  • the metal element M at least one of an alkali metal and an alkaline earth metal is preferable.
  • the solvent of the mixed solution is not limited as long as the cation of the metal element M can exist stably, and water is optimal from the economical and environmental aspects. Further, it may be acidic (for example, hydrochloric acid, sulfuric acid, nitric acid or an aqueous solution thereof) or alkaline (for example, aqueous ammonia).
  • acidic for example, hydrochloric acid, sulfuric acid, nitric acid or an aqueous solution thereof
  • alkaline for example, aqueous ammonia
  • the metal element M can be introduced into the crystalline zirconium phosphate.
  • the metal element M can be adsorbed on the surface and / or pores of crystalline zirconium phosphate in the form of inorganic acid salt or organic acid salt. Therefore, as a result, even when the ratio exceeds 1 / n, the fluorescence characteristic is expressed.
  • the above mixed solution can also be prepared by mixing a solution having a metal ion concentration of the metal element M of 500 ppm by weight or less (particularly 250 ppm by weight or less) with crystalline zirconium phosphate.
  • a solution having a metal ion concentration of the metal element M of 500 ppm by weight or less (particularly 250 ppm by weight or less) with crystalline zirconium phosphate By the method of the present invention, even when the metal element M has a small metal ion content, the metal ions can be effectively adsorbed.
  • the lower limit value of the metal ion concentration of the metal element M is not particularly limited, but is usually about 10 ppm by weight.
  • the heat treatment conditions for the heat treatment of the mixed solution or the evaporated and dried product thereof are that crystalline zirconium phosphate is changed to HZr 2 P 3 O 12 by heat treatment, and ion substitution between H in the molecule and the metal element M is performed. There is no limitation as long as the conditions are satisfied.
  • the heat treatment condition is preferably about 600 to 800 ° C., more preferably about 650 to 750 ° C.
  • the heat treatment atmosphere at this time is not particularly limited, and can be performed in the air. After the heat treatment, for example, the starting material B (M n + y R 1-ny Zr 2 P 3 O 12 ) can be obtained through washing and drying in pure water.
  • the phosphor material of the first aspect and the phosphor material of the second aspect are obtained by heat-treating the starting material A and the starting material B, respectively, in a reducing atmosphere at 400 to 850 ° C.
  • the heat treatment temperature may be 400 to 850 ° C, and 600 to 800 ° C is particularly preferable.
  • the range of x in the general formula of the phosphor material may not be 0.005 or more and less than 0.4, which is not preferable.
  • the heat treatment time can be appropriately set according to the heat treatment temperature, but generally a short time is required when the heat treatment is performed at a high temperature, and a long time is required when the heat treatment is performed at a low temperature.
  • the heat treatment can be performed under normal pressure, but can also be performed under pressure.
  • the pressure in the case of carrying out under pressure is not limited, but generally it is preferably about 0.1 to 40 MPa.
  • the reducing atmosphere is not limited.
  • a reducing gas containing at least one of hydrogen and carbon monoxide can be used.
  • the present invention is characterized in that heat treatment is performed in a reducing atmosphere, and a phosphor material having desired fluorescence characteristics cannot be obtained even if heat treatment is performed in an air atmosphere or an oxidizing atmosphere.
  • the volatile metal element M does not flow out of the autoclave, so that the peripheral equipment is not eroded and no special material equipment is required. It will be advantageous.
  • the phosphor material of the present invention is a zirconium phosphate-based phosphor material using an element other than a rare earth element as a light-emitting element, and emits visible light (light having a wavelength of 380 nm or more and less than 830 nm) by ultraviolet irradiation. Specifically, for example, fluorescence (395 nm) is obtained by irradiating excitation light (254 nm).
  • the phosphor material of the present invention can be widely used for phosphor materials such as lighting devices and backlights for liquid crystal display devices.
  • Preferred zirconium compound (as Zr), carboxylic acid compound (as C 2 O 4 ), and phosphoric acid compound (as PO 4 ) in the raw material mixture when preparing NH 4 Zr 2 P 3 O 12 by direct crystal precipitation method It is a molar ratio triangular component figure which shows a ratio (area
  • FIG. (1) relates to Experimental Example 2, and shows the results of thermogravimetric analysis (TG) -differential thermal analysis (DTA) of NH 4 Zr 2 P 3 O 12 (the pyrolysis product is HZr 2 P 3 O 12).
  • TG thermogravimetric analysis
  • DTA thermodifferential thermal analysis
  • Experimental Example 1 (phosphor material of the first aspect) HZr 2 P 3 obtained by heat-treating NH 4 Zr 2 P 3 O 12 prepared by the direct crystal precipitation method at 575 ° C. for 5 hours in the atmosphere as crystalline zirconium phosphate (sample 1) used in Experimental Example 1 the O 12 was prepared.
  • Sample 1 was placed in an alumina boat and subjected to a reduction heat treatment for 2 hours at 350 to 900 ° C. (12 kinds of temperatures shown in Table 1) in a 3 mass% H 2 (N 2 balance) gas stream.
  • Table 1 shows the relative fluorescence intensity value and chemical composition at 395 nm with excitation light of 254 nm in each reduction heat treatment product.
  • the relative fluorescence intensity value was measured using an absolute PL electron yield measuring device (Quantaurus-QY, C11347-01) manufactured by Hamamatsu Photonics Co., Ltd.
  • the reduction heat-treated product at 350 ° C. maintained the H 1.00 Zr 2 P 3 O 12.000 composition before the reduction heat treatment.
  • the chemical composition of the heat-treated reduction product at 400 to 850 ° C. was a chemical composition in which hydrogen and oxygen escaped from zirconium phosphate. The amount of hydrogen and oxygen released from the zirconium phosphate increased as the reduction heat treatment temperature increased.
  • the cell volume of the reduced heat treatment was smaller than the cell volume of the atmospheric heat treatment. This supports the phenomenon that hydrogen and oxygen escaped from zirconium phosphate by the reduction heat treatment, as can be seen from the chemical composition results shown in Table 1.
  • FIG. 2 shows the fluorescence spectrum and excitation spectrum of the reduced heat-treated product at 700 ° C. that showed the highest relative fluorescence intensity value. Moreover, the internal quantum yield of this heat-reduced product was 41%, the absorption rate was 43%, and the external quantum yield was 18%. Further, the fluorescence lifetime of this reduced heat-treated product was measured with a small fluorescence lifetime measuring device (Quantaurus-Tau, C11267-01) manufactured by Hamamatsu Photonics Co., Ltd., and found to be 6.4 ns.
  • a small fluorescence lifetime measuring device Quantantaurus-Tau, C11267-01
  • Experimental Example 2 (phosphor material of the first aspect) As crystalline zirconium phosphate (sample 2) used in Experimental Example 2, NH 4 Zr 2 P 3 O 12 prepared by a direct crystal precipitation method was prepared.
  • Sample 2 was placed in an alumina boat and subjected to reduction heat treatment for 2 hours at 400 to 900 ° C. (same as twelve temperatures shown in Table 1) in a 3% by mass H 2 (N 2 balance) gas stream. Further, heat treatment was performed for 2 hours at 400 to 900 ° C. (same as twelve kinds of temperatures shown in Table 1) in an air atmosphere.
  • thermogravimetric analysis of Sample 2 measured at a heating rate of 10 ⁇ min ⁇ 1 in an air stream of 20 ml ⁇ min ⁇ 1 shown in FIG. (TG) —As is clear from the results of differential thermal analysis (DTA), Sample 2: NH 4 Zr 2 P 3 O 12 is temporarily changed to HZr 2 P 3 O 12 by heat treatment at 350 ° C. or higher for 2 hours. Further, this is considered to be due to the change to H 1-X Zr 2 P 3 O 12- (X / 2) .
  • Experimental Example 3 (phosphor material of the first aspect) (H 3 O) Zr 2 P 3 O 12 was prepared as crystalline zirconium phosphate (sample 3) used in Experimental Example 3. Specifically, be immersed 3 days HZr 2 P 3 O 12 where the NH 4 Zr 2 P 3 O 12 prepared from direct crystallization method was obtained by heat treatment for 5 hours at 575 ° C. in air into pure water (H 3 O) Zr 2 P 3 O 12 was obtained.
  • Sample 3 was placed in an alumina boat and subjected to a reduction heat treatment for 2 hours at 400 to 900 ° C. (same as twelve temperatures shown in Table 1) in a 3% by mass H 2 (N 2 balance) gas stream. Further, heat treatment was performed for 2 hours at 400 to 900 ° C. (same as twelve kinds of temperatures shown in Table 1) in an air atmosphere.
  • Experimental Example 4 (phosphor material of the second aspect) HZr 2 P 3 obtained by heat-treating NH 4 Zr 2 P 3 O 12 prepared by the direct crystal precipitation method at 575 ° C. for 5 hours in the atmosphere as crystalline zirconium phosphate (sample 4) used in Experimental Example 4 the O 12 was prepared.
  • Li y R 1-y Zr 2 P 3 O 12 (y: less than 0.90) and Sr y R 1-2y Zr 2 P 3 O 12 (y: less than 0.45) were put in an alumina boat, respectively.
  • Reductive heat treatment was performed for 2 hours at 400 to 900 ° C. (same as 11 kinds of temperatures shown in Table 1) in a 3 mass% H 2 (N 2 balance) gas stream.
  • the relative fluorescence intensity values at 395 nm with excitation light of 254 nm of all the heat-treated products were all 0.10 or more.
  • Li y R 1-y Zr 2 P 3 O 12 (y: 0.90 or more) and Sr y R 1-2y Zr 2 P 3 O 12 (y: 0.45 or more) were each used as an alumina boat. Then, reduction heat treatment was performed for 2 hours at 400 to 900 ° C. (the same as 11 kinds of temperatures shown in Table 1) in a gas flow of 3 mass% H 2 (N 2 balance). The relative fluorescence intensity values at 395 nm with excitation light of 254 nm of each heat-treated product were all 0.05 or less.

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Abstract

The present invention provides an oxide-based fluorescent material which uses an element other than a rare earth element as a light-emitting element, uses inexpensive raw materials, and exhibits high luminous efficiency. More specifically, the present invention provides a fluorescent material characterized by being represented by the formula H1-xZr2P3O12-(x/2) (1) [in the formula, x is at least 0.005 but lower than 0.4], and a fluorescent material characterized by being represented by the formula (Mn+ yH1-ny)1-xZr2P3O12-(x/2) (2) [in the formula, M denotes a metallic element and n denotes the average valency of the metallic element M. In addition, x is at least 0.005 but lower than 0.4, and y is at least 0.01 but lower than 0.90/n].

Description

蛍光体材料及びその製造方法Phosphor material and method for producing the same
　本発明は、蛍光体材料及びその製造方法に関する。 The present invention relates to a phosphor material and a manufacturing method thereof.
　なお、本明細書における「蛍光体（phosphor）材料」とは、「フォトルミネセンス（photoluminescence、即ち紫外線照射によって可視光を発光する現象）を利用する用途に用いられる材料」を意味する。 In addition, the “phosphor material” in this specification means “a material used for an application utilizing photoluminescence (that is, a phenomenon in which visible light is emitted by ultraviolet irradiation)”.
　紫外線照射によって可視光（一般に波長が３８０ｎｍ以上８３０ｎｍ未満の光）を発光する蛍光体材料は、照明装置、液晶表示装置用バックライト等に使用されている。 A phosphor material that emits visible light (generally, light having a wavelength of 380 nm or more and less than 830 nm) by ultraviolet irradiation is used for lighting devices, backlights for liquid crystal display devices, and the like.
　従来の蛍光体材料には、発光元素として希土類元素を含有するものが多く知られている（例えば、特許文献１～３）。しかしながら、希土類元素は、埋蔵量が少ないこと、産出国が中国などに限定されていること、分離精製コストが高いこと等の問題がある。そこで、発光元素として希土類元素以外の元素を用いた蛍光体材料が求められている。 Many known phosphor materials contain rare earth elements as light emitting elements (for example, Patent Documents 1 to 3). However, rare earth elements have problems such as a small reserve, a limited production country such as China, and a high cost for separation and purification. Therefore, a phosphor material using an element other than a rare earth element as a light emitting element is required.
　発光元素として希土類元素以外の元素を用いた蛍光体材料の中で、安定性の優れている酸化物系材料としては、赤色蛍光体としてはＭｎ４＋を発光元素とした３．６ＭｇＯ・４ＣａＦ２・ＧｅＯ２：０．０１Ｍｎ（例えば、特許文献４）が知られている。緑色蛍光体としてはＭｎ２＋を発光元素としたＺｎＧａ２Ｏ４：Ｍｎ（例えば、特許文献５）が知られている。緑色及び青色蛍光体としては、酸素欠陥を発光中心としたＺｎＯ（例えば、特許文献６）が知られている。また、Ａｇイオンを含有するフォージャサイト型ゼオライトが橙色～緑色蛍光体になることも示されている（例えば、特許文献７）。 Among the fluorescent materials using an element other than a rare earth element as an emission element, the oxide-based material is excellent in stability, 3.6MgO · 4CaF 2 · which a light emitting element and Mn 4+ as a red phosphor GeO 2 : 0.01Mn (for example, Patent Document 4) is known. As a green phosphor, ZnGa 2 O 4 : Mn (for example, Patent Document 5) using Mn 2+ as a light emitting element is known. As the green and blue phosphors, ZnO having an oxygen defect as a light emission center (for example, Patent Document 6) is known. It has also been shown that faujasite-type zeolite containing Ag ions becomes an orange to green phosphor (for example, Patent Document 7).
　しかしながら、上記酸化物系材料にも次のような問題がある。例えば、３．６ＭｇＯ・４ＣａＦ２・ＧｅＯ２：０．０１Ｍｎの主成分であるＧｅＯ２，ＺｎＧａ２Ｏ４：Ｍｎの主成分であるＧａ２Ｏ３は、いずれも希土類元素と同様に埋蔵量が少なく、原料として極めて高価である。また、Ａｇイオンを含有するゼオライト中のＡｇも高価な原料である。更に、３．６ＭｇＯ・４ＣａＦ２・ＧｅＯ２：０．０１Ｍｎ，ＺｎＧａ２Ｏ４：Ｍｎ，ＺｎＧａ２Ｏ４：ＺｎＯ，Ａｇイオンを含有するゼオライトのいずれも、発光元素として希土類元素を用いた蛍光体材料と比べて発光輝度が低い。 However, the above oxide materials also have the following problems. For example, 3.6MgO · 4CaF 2 · GeO 2 : GeO 2 which is a main component of 0.01Mn, ZnGa 2 O 4: Ga 2 O 3 is the main component of Mn is reserves as with any rare earth element There are few and it is very expensive as a raw material. Ag in zeolite containing Ag ions is also an expensive raw material. Furthermore, 3.6MgO · 4CaF 2 · GeO 2 : 0.01Mn, ZnGa 2 O 4: Mn, ZnGa 2 O 4: ZnO, none of the zeolite containing Ag ions, phosphor with a rare earth element as a light emitting element Luminous brightness is low compared to materials.
　よって、発光元素として希土類元素以外の元素を用いた蛍光体材料であって、原料が安価であり且つ発光効率が高い酸化物系の蛍光体材料の開発が望まれている。 Therefore, it is desired to develop a phosphor material using an element other than a rare earth element as a light emitting element, which is an inexpensive raw material and has high luminous efficiency.
特表２０００－５１６２９６号公報Special Table 2000-516296 特開２００５－４８１０７号公報JP 2005-48107 A 特開２００８－６９２９０号公報JP 2008-69290 A 特開２００８－２０２０４４号公報JP 2008-202044 A 特開２０００－８０３６３号公報JP 2000-80363 A 特開２００６－２３３０４７号公報JP 2006-233047 A 特開２０１２－５２１０２号公報JP 2012-52102 A
　本発明は、発光元素として希土類元素以外の元素を用いた蛍光体材料であって、原料が安価であり且つ発光効率が高い酸化物系の蛍光体材料を提供することを目的とする。また、その製造方法を提供することを目的とする。 An object of the present invention is to provide a phosphor material using an element other than a rare earth element as a light-emitting element, which is an inexpensive phosphor material and has high emission efficiency. Moreover, it aims at providing the manufacturing method.
　本発明は、上記目的を達成すべく鋭意研究を重ねた結果、特定の組成からなる酸化物系の蛍光体材料が上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present invention has found that an oxide-based phosphor material having a specific composition can achieve the above object, and has completed the present invention.
　即ち、本発明は、下記の蛍光体材料及びその製造方法に関する。
１．Ｈ１－ｘＺｒ２Ｐ３Ｏ１２－（ｘ／２）　（１）
〔式中、ｘは０．００５以上０．４未満である。〕
で表されることを特徴とする蛍光体材料。
２．（Ｍｎ＋ ｙＨ１－ｎｙ）１－ｘＺｒ２Ｐ３Ｏ１２－（ｘ／２）　（２）
〔式中、Ｍは金属元素を示し、ｎは金属元素Ｍの平均価数を示す。また、ｘは０．００５以上０．４未満であり、ｙは０．０１以上０．９０／ｎ未満である。〕
で表されることを特徴とする蛍光体材料。
３．ＲＺｒ２Ｐ３Ｏ１２（但し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。）で表される出発原料Ａを還元性雰囲気中４００～８５０℃で熱処理することを特徴とする蛍光体材料の製造方法。
４．上記項１に記載の蛍光体材料の製造方法である、上記項３に記載の製造方法。
５．Ｍｎ＋ ｙＲ１－ｎｙＺｒ２Ｐ３Ｏ１２（但し、Ｍは金属元素を示し、ｎは金属元素Ｍの平均価数を示し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。また、ｙは金属元素Ｍのモル数であり、ｙは０．０１以上０．９０／ｎ未満である。）で表される出発原料Ｂを還元性雰囲気中４００～８５０℃で熱処理することを特徴とする蛍光体材料の製造方法。
６．上記項２に記載の蛍光体材料の製造方法である、上記項５に記載の製造方法。 That is, this invention relates to the following phosphor material and its manufacturing method.
1. H 1-x Zr 2 P 3 O 12- (x / 2) (1)
[Wherein x is 0.005 or more and less than 0.4. ]
A phosphor material characterized by the following:
2. (M n + y H 1-ny ) 1-x Zr 2 P 3 O 12- (x / 2) (2)
[In the formula, M represents a metal element, and n represents an average valence of the metal element M. Moreover, x is 0.005 or more and less than 0.4, and y is 0.01 or more and less than 0.90 / n. ]
A phosphor material characterized by the following:
3. A phosphor material characterized by heat-treating a starting material A represented by RZr 2 P 3 O 12 (wherein R represents H, H 3 O or NH 4 ) in a reducing atmosphere at 400 to 850 ° C. Manufacturing method.
4). Item 4. The method according to Item 3, which is a method for manufacturing the phosphor material according to Item 1.
5. M n + y R 1-ny Zr 2 P 3 O 12 (M represents a metal element, n represents an average valence of the metal element M, and R represents H, H 3 O, or NH 4. ) y is the number of moles of the metal element M, and y is 0.01 or more and less than 0.90 / n.), and the starting material B is heat-treated at 400 to 850 ° C. in a reducing atmosphere. A method for manufacturing a phosphor material.
6). Item 6. The method according to Item 5, which is a method for manufacturing the phosphor material according to Item 2.
　以下、本発明の蛍光体材料及びその製造方法について詳細に説明する。 Hereinafter, the phosphor material of the present invention and the manufacturing method thereof will be described in detail.
　本発明の蛍光体材料
　本発明の蛍光体材料は、第一態様の蛍光体材料（金属元素Ｍを含まない）と第二態様の蛍光体材料（金属元素Ｍを含む）とに大別することができる。 The phosphor material of the present invention The phosphor material of the present invention is roughly classified into the phosphor material of the first aspect (not including the metal element M) and the phosphor material of the second aspect (including the metal element M). Can do.
　第一態様の蛍光体材料は、Ｈ１－ｘＺｒ２Ｐ３Ｏ１２－（ｘ／２）　（１）
〔式中、ｘは０．００５以上０．４未満である。〕
で表されることを特徴とする。 The phosphor material of the first aspect is H 1-x Zr 2 P 3 O 12- (x / 2) (1)
[Wherein x is 0.005 or more and less than 0.4. ]
It is represented by.
　また、第二態様の蛍光体材料は、（Ｍｎ＋ ｙＨ１－ｎｙ）１－ｘＺｒ２Ｐ３Ｏ１２－（ｘ／２）　（２）
〔式中、Ｍは金属元素を示し、ｎは金属元素Ｍの平均価数を示す。また、ｘは０．００５以上０．４未満であり、ｙは０．０１以上０．９０／ｎ未満である。〕
で表されることを特徴とする。 The phosphor material of the second aspect is (M n + y H 1-ny ) 1-x Zr 2 P 3 O 12- (x / 2) (2)
[In the formula, M represents a metal element, and n represents an average valence of the metal element M. Moreover, x is 0.005 or more and less than 0.4, and y is 0.01 or more and less than 0.90 / n. ]
It is represented by.
　第一態様及び第二態様の蛍光体材料は、発光元素として希土類元素以外の元素を用いたリン酸ジルコニウム系の蛍光体材料であり、紫外線照射によって可視光（波長が３８０ｎｍ以上８３０ｎｍ未満の光）を発光する。具体的には、例えば、励起光（２５４ｎｍ）を照射することにより、蛍光（３９５ｎｍ）が得られる。 The phosphor material of the first embodiment and the second embodiment is a zirconium phosphate-based phosphor material using an element other than a rare earth element as a light emitting element, and visible light (light having a wavelength of 380 nm or more and less than 830 nm) by ultraviolet irradiation. Is emitted. Specifically, for example, fluorescence (395 nm) is obtained by irradiating excitation light (254 nm).
　それにより、本発明の蛍光体材料は、照明装置、液晶表示装置用バックライト等をはじめとする蛍光体材料の用途に幅広く利用することができる。 Thereby, the phosphor material of the present invention can be widely used for phosphor materials such as lighting devices and backlights for liquid crystal display devices.
　第一態様の蛍光体材料において、ｘは０．００５以上０．４未満であり、ｘは０．０１以上０．３５以下であることが好ましく、０．０１以上０．２以下であることがより好ましい。なお、ｘが０．００５未満の場合には、得られる蛍光強度が弱くなり、０．４以上の場合にも蛍光強度が低下する。そのため、本発明ではｘの範囲は０．００５以上０．４未満と規定している。 In the phosphor material of the first aspect, x is 0.005 or more and less than 0.4, x is preferably 0.01 or more and 0.35 or less, and is 0.01 or more and 0.2 or less. More preferred. In addition, when x is less than 0.005, the obtained fluorescence intensity becomes weak, and when it is 0.4 or more, the fluorescence intensity decreases. Therefore, in the present invention, the range of x is defined as 0.005 or more and less than 0.4.
　第二態様の蛍光体材料において、ｘの範囲の説明は上記と同じである。 In the phosphor material of the second aspect, the description of the range of x is the same as described above.
　ｎは金属元素Ｍ（詳細は後述）の平均価数を示す。例えば、１モルのＭが、３価の金属元素（０．３モル）と４価の金属元素（０．７モル）とで構成されている場合には、平均価数は（３×０．３＋４×０．７）／（０．３＋０．７）＝３．７である。 N represents the average valence of the metal element M (details will be described later). For example, when 1 mol of M is composed of a trivalent metal element (0.3 mol) and a tetravalent metal element (0.7 mol), the average valence is (3 × 0. 3 + 4 × 0.7) / (0.3 + 0.7) = 3.7.
　ｙは０．０１以上０．９０／ｎ未満である。ｙは０．１以上０．４５以下であることが好ましい。なお、ｙが０．０１未満の場合には、得られる蛍光強度が弱くなり、０．９０／ｎ以上の場合にも蛍光強度が低下する。そのため、本発明ではｙの範囲は０．０１以上０．９０／ｎ未満と規定している。 Y is 0.01 or more and less than 0.90 / n. y is preferably 0.1 or more and 0.45 or less. In addition, when y is less than 0.01, the obtained fluorescence intensity becomes weak, and when 0.90 / n or more, the fluorescence intensity decreases. Therefore, in the present invention, the range of y is defined as 0.01 or more and less than 0.90 / n.
　金属元素Ｍは、限定的ではないが、例えば、アルカリ金属（Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ等）、アルカリ土類金属（Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｒａ）、チタン族（Ｔｉ、Ｚｒ、Ｈｆ）、バナジウム族（Ｖ、Ｎｂ、Ｔａ）、クロム族（Ｃｒ、Ｍｏ、Ｗ）、マンガン族（Ｍｎ、Ｔｃ、Ｒｅ）、鉄族（Ｆｅ、Ｃｏ、Ｎｉ）、白金族（Ｐｄ、Ｐｔ等）、銅族（Ｃｕ、Ａｇ、Ａｕ）、亜鉛族（Ｚｎ、Ｃｄ、Ｈｇ）、ホウ素族（Ａｌ、Ｉｎ等）、炭素族（Ｓｎ、Ｐｂ）等が挙げられる。これらの金属元素Ｍは単独又は２種以上を組み合わせて使用することができる。これらの中でも、金属元素Ｍとして、アルカリ金属及びアルカリ土類金属の少なくとも１種が好ましい。 Examples of the metal element M include, but are not limited to, alkali metals (Li, Na, K, Rb, Cs, etc.), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), titanium group (Ti , Zr, Hf), vanadium group (V, Nb, Ta), chromium group (Cr, Mo, W), manganese group (Mn, Tc, Re), iron group (Fe, Co, Ni), platinum group (Pd , Pt, etc.), copper group (Cu, Ag, Au), zinc group (Zn, Cd, Hg), boron group (Al, In, etc.), carbon group (Sn, Pb), and the like. These metal elements M can be used alone or in combination of two or more. Among these, as the metal element M, at least one of an alkali metal and an alkaline earth metal is preferable.
　なお、第二態様の蛍光体材料は、実施形態によっては細孔を有しており、蛍光体材料の表面及び／又は前記細孔に金属元素Ｍの無機酸塩及び／又は有機酸塩が吸着していてもよい。無機酸塩としては、例えば、硝酸塩、硫酸塩、炭酸塩等の形態が挙げられる。また、有機酸塩としては、シュウ酸塩、酢酸塩等の形態が挙げられる。 Note that the phosphor material of the second aspect has pores depending on the embodiment, and the inorganic acid salt and / or organic acid salt of the metal element M is adsorbed on the surface of the phosphor material and / or the pores. You may do it. Examples of inorganic acid salts include forms such as nitrates, sulfates, and carbonates. Moreover, forms, such as an oxalate and acetate, are mentioned as organic acid salt.
　本発明の蛍光体材料の製造方法
　本発明の蛍光体材料の製造方法は、上記説明した第一態様及び第二態様の蛍光体材料がそれぞれ得られる限り限定されないが、下記の製造方法により製造することが好ましい。 Method for Producing Phosphor Material of the Present Invention The method for producing the phosphor material of the present invention is not limited as long as the phosphor materials of the first aspect and the second aspect described above are obtained, respectively, but are produced by the following production method. It is preferable.
　即ち、第一態様の蛍光体材料は、ＲＺｒ２Ｐ３Ｏ１２（但し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。）で表される出発原料Ａを還元性雰囲気中４００～８５０℃で熱処理することを特徴とする製造方法により製造することが好ましい。 That is, the phosphor material according to the first aspect is obtained by using a starting material A represented by RZr 2 P 3 O 12 (where R represents H, H 3 O or NH 4 ) in a reducing atmosphere at 400 to 850 ° C. It is preferable to manufacture by the manufacturing method characterized by heat-treating.
　また、第二態様の蛍光体材料は、Ｍｎ＋ ｙＲ１－ｎｙＺｒ２Ｐ３Ｏ１２（但し、Ｍは金属元素を示し、ｎは金属元素Ｍの平均価数を示し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。また、ｙは金属元素Ｍのモル数であり、ｙは０．０１以上０．９０／ｎ未満である。）で表される出発原料Ｂを還元性雰囲気中４００～８５０℃で熱処理することを特徴とする製造方法により製造することが好ましい。 Further, the phosphor material of the second aspect is M n + y R 1-ny Zr 2 P 3 O 12 (where M represents a metal element, n represents an average valence of the metal element M, R represents H, H 3 O or NH 4 where y is the number of moles of the metal element M, and y is 0.01 or more and less than 0.90 / n). It is preferably produced by a production method characterized by heat treatment at 400 to 850 ° C.
　先ず、出発原料Ａ及び出発原料Ｂについてそれぞれ説明する。 First, the starting material A and the starting material B will be described.
　出発原料Ａは、ＲＺｒ２Ｐ３Ｏ１２（但し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。）で表される結晶質リン酸ジルコニウムであり、特にリン酸ジルコニウムアンモニウム（ＮＨ４Ｚｒ２Ｐ３Ｏ１２）を出発原料Ａとすることが好ましい。なお、リン酸ジルコニウムアンモニウム（ＮＨ４Ｚｒ２Ｐ３Ｏ１２）を熱処理することにより、ＨＺｒ２Ｐ３Ｏ１２が得られ、ＨＺｒ２Ｐ３Ｏ１２を水と接触させることにより、（Ｈ３Ｏ）Ｚｒ２Ｐ３Ｏ１２が生成する。これらの生成について詳しくは後述する。 The starting material A is crystalline zirconium phosphate represented by RZr 2 P 3 O 12 (where R represents H, H 3 O or NH 4 ), and in particular, zirconium ammonium phosphate (NH 4 Zr 2 P 3 O 12 ) is preferably used as the starting material A. In addition, HZr 2 P 3 O 12 is obtained by heat-treating zirconium ammonium phosphate (NH 4 Zr 2 P 3 O 12 ), and by contacting HZr 2 P 3 O 12 with water, (H 3 O ) Zr 2 P 3 O 12 is produced. Details of the generation will be described later.
　上記リン酸ジルコニウムアンモニウム（ＮＨ４Ｚｒ２Ｐ３Ｏ１２）としては、ジルコニウム化合物、カルボン酸化合物及びリン酸化合物と、アンモニウム化合物及びアンミン化合物の少なくとも１種とを含む原料混合液を用いた化学合成方法（直接結晶析出法）により調製されたものを使用することが好ましい。また、直接結晶析出法より調製されるＮＨ４Ｚｒ２Ｐ３Ｏ１２としては、例えば、特開昭６０－２３９３１３号公報などの記載に準じて調製したもの又は市販品を使用することもできる。 As the zirconium phosphate ammonium (NH 4 Zr 2 P 3 O 12), zirconium compounds, chemical synthesis using a carboxylic acid compound and phosphoric acid compound, a raw material mixture containing at least one ammonium compounds and ammine compound It is preferable to use those prepared by the method (direct crystal precipitation method). Further, as NH 4 Zr 2 P 3 O 12 prepared by the direct crystal precipitation method, for example, those prepared according to the description in JP-A-60-239313 or commercially available products can be used.
　以下、上記ジルコニウム化合物、カルボン酸化合物及びリン酸化合物と、アンモニウム化合物及びアンミン化合物の少なくとも１種とを含む原料混合液を用いた化学合成方法（直接結晶析出法）について説明する。 Hereinafter, a chemical synthesis method (direct crystal precipitation method) using a raw material mixed solution containing the zirconium compound, carboxylic acid compound, and phosphoric acid compound, and at least one of an ammonium compound and an ammine compound will be described.
　当該調製方法では、具体的に、先ず、ジルコニウム化合物及びカルボン酸化合物を含む混合液に対して、リン酸化合物又はその水溶液を加える。 Specifically, in the preparation method, first, a phosphoric acid compound or an aqueous solution thereof is added to a mixed solution containing a zirconium compound and a carboxylic acid compound.
　上記ジルコニウム化合物としては、水溶性又は酸により水可溶性となるジルコニウム化合物が好ましい。例えば、オキシ塩化ジルコニウム、ヒドロオキシ塩化ジルコニウム、四塩化ジルコニウム、臭化ジルコニウム等のハロゲン化ジルコニウム；硫酸ジルコニウム、塩基性硫酸ジルコニウム、硝酸ジルコニウム等の鉱酸のジルコニウム塩；酢酸ジルコニル、ギ酸ジルコニル等の有機酸のジルコニウム塩；炭酸ジルコニウムアンモニウム、硫酸ジルコニウムナトリウム、酢酸ジルコニウムアンモニウム、シュウ酸ジルコニウムナトリウム、クエン酸ジルコニウムアンモニウム等のジルコニウム錯塩等が使用できる。これらのジルコニウム化合物の中では、オキシ塩化ジルコニウム及び硫酸ジルコニウムの少なくとも１種が好ましい。 The zirconium compound is preferably a zirconium compound that is water-soluble or water-soluble by an acid. For example, zirconium halides such as zirconium oxychloride, zirconium hydroxide chloride, zirconium tetrachloride and zirconium bromide; zirconium salts of mineral acids such as zirconium sulfate, basic zirconium sulfate and zirconium nitrate; organic acids such as zirconyl acetate and zirconyl formate Zirconium salts such as ammonium zirconium carbonate, sodium zirconium sulfate, ammonium zirconium acetate, sodium zirconium oxalate, and zirconium ammonium citrate can be used. Among these zirconium compounds, at least one of zirconium oxychloride and zirconium sulfate is preferable.
　カルボン酸化合物としては、水溶性又は酸により水可溶性となり、且つ、カルボキシル基（－ＣＯＯＨ）を２個以上有する脂肪族ポリカルボン酸及びその塩が好ましい。例えば、シュウ酸、シュウ酸ナトリウム、シュウ酸水素ナトリウム、シュウ酸アンモニウム、シュウ酸水素アンモニウム、シュウ酸リチウム、マレイン酸、マロン酸、コハク酸及びこれらの塩類等の脂肪族二塩基酸及びその塩類；クエン酸、クエン酸アンモニウム、酒石酸、リンゴ酸等の脂肪族オキシ酸及びそれらの塩類等が挙げられる。これらの中では、シュウ酸並びにそのナトリウム塩及びアンモニウム塩の少なくとも１種が好ましい。 As the carboxylic acid compound, an aliphatic polycarboxylic acid and a salt thereof that are water-soluble or water-soluble by an acid and have two or more carboxyl groups (—COOH) are preferable. For example, aliphatic dibasic acids and salts thereof such as oxalic acid, sodium oxalate, sodium hydrogen oxalate, ammonium oxalate, ammonium hydrogen oxalate, lithium oxalate, maleic acid, malonic acid, succinic acid and salts thereof; Examples thereof include aliphatic oxyacids such as citric acid, ammonium citrate, tartaric acid and malic acid, and salts thereof. Among these, oxalic acid and at least one of its sodium salt and ammonium salt are preferable.
　リン酸化合物は、水溶性又は酸により水可溶性となるものが好ましい。例えば、リン酸、第一リン酸ナトリウム、第二リン酸アンモニウム、第三リン酸ナトリウム等のオルトリン酸のアルカリ金属塩及びアンモニウム塩；メタリン酸、ピロリン酸等の少なくとも１個のＰ－Ｏ－Ｐ結合を有する縮合リン酸のアルカリ金属塩及びアンモニウム塩等が挙げられる。これらの中では、リン酸及びオルトリン酸のアンモニウム塩の少なくとも１種が好ましい。 The phosphoric acid compound is preferably water-soluble or water-soluble by acid. For example, alkali metal and ammonium salts of orthophosphoric acid such as phosphoric acid, monobasic sodium phosphate, dibasic ammonium phosphate, and tribasic sodium phosphate; at least one P—O—P such as metaphosphoric acid and pyrophosphoric acid Examples thereof include alkali metal salts and ammonium salts of condensed phosphoric acid having a bond. Among these, at least one ammonium salt of phosphoric acid and orthophosphoric acid is preferable.
　次に、得られた混合液に対して、アンモニウム化合物及びアンミン化合物の少なくとも１種を添加する。 Next, at least one of an ammonium compound and an ammine compound is added to the obtained mixed solution.
　アンモニウム化合物としては、水溶性又は酸により水可溶性となる化合物が好ましい。アンモニウム化合物としては、塩化アンモニウム、硫酸アンモニウム、硝酸アンモニウム、炭酸水素アンモニウム等の無機アンモニウム化合物；水酸化テトラプロピルアンモニウム、水酸化テトラエチルアンモニウム等の有機アンモニウム化合物等が挙げられる。なお、前述のジルコニウム化合物、カルボン酸化合物及びリン酸化合物の少なくとも１種がアンモニウム含有化合物である場合には、それらをアンモニウムイオン源ともみなして使用することもできる。 As the ammonium compound, a compound that is water-soluble or water-soluble by an acid is preferable. Examples of the ammonium compound include inorganic ammonium compounds such as ammonium chloride, ammonium sulfate, ammonium nitrate, and ammonium hydrogen carbonate; and organic ammonium compounds such as tetrapropylammonium hydroxide and tetraethylammonium hydroxide. In addition, when at least 1 sort (s) of the above-mentioned zirconium compound, carboxylic acid compound, and phosphoric acid compound is an ammonium containing compound, they can also be considered and used as an ammonium ion source.
　アンモニウム化合物としては、上記の中でもリン酸アンモニウム、アンモニア水、塩化アンモニウム及びシュウ酸アンモニウムの少なくとも１種がより好ましい。 As the ammonium compound, among the above, at least one of ammonium phosphate, aqueous ammonia, ammonium chloride, and ammonium oxalate is more preferable.
　各成分の混合に際しては攪拌を行うことが望ましい。特にリン酸又はその水溶液を添加する際には、部分的にリン酸濃度が高くなる状態をなるべく回避できるように十分に攪拌を行うことが望ましい。 It is desirable to stir when mixing each component. In particular, when adding phosphoric acid or an aqueous solution thereof, it is desirable to sufficiently stir so as to avoid a state in which the phosphoric acid concentration partially increases as much as possible.
　原料混合液は、ジルコニウム化合物（Ｚｒとして）、カルボン酸化合物（Ｃ２Ｏ４として）及びリン酸化合物（ＰＯ４として）の割合が、図１に示すモル比三角成分図において、Ａ（２８、３、６９）、Ｂ（６３、６、３１）、Ｃ（４４、４３、１３）及びＤ（１、９７、２）の各点を結ぶ直線で囲まれた領域内に入り、且つ、Ｚｒが１モル当りアンモニウム化合物が０．２～１００モル程度となるように調節することが望ましい。 The ratio of the zirconium compound (as Zr), the carboxylic acid compound (as C 2 O 4 ), and the phosphoric acid compound (as PO 4 ) in the raw material mixed solution is A (28, 3, 69), B (63, 6, 31), C (44, 43, 13) and D (1, 97, 2) are within a region surrounded by a straight line, and Zr is It is desirable to adjust so that the ammonium compound is about 0.2 to 100 mol per mol.
　原料混合液中の各成分の組成比が上記領域外となる場合には、結晶化速度が遅い、収率が低い、非晶質生成物が混在するする、未反応原料が残存する、所望外の結晶形を含む結晶質となる等の問題点の１又は２以上が生じるおそれがある。 When the composition ratio of each component in the raw material mixture is outside the above range, the crystallization rate is slow, the yield is low, amorphous products are mixed, unreacted raw materials remain, There is a possibility that one or more of the problems such as the crystalline form including the crystalline form may occur.
　各成分を均一に溶解又は分散させた原料混合液の形態は、溶液又は未溶解の過剰原料を含むスラリー状のいずれであってもよい。 The form of the raw material mixed solution in which each component is uniformly dissolved or dispersed may be either a solution or a slurry containing undissolved excess raw material.
　原料混合液の濃度は、Ｚｒが０．０１～２５質量％、特に０．１～１０質量％となる濃度に調整することが好ましい。Ｚｒが０．０１質量％未満の稀薄溶液では、目的生成物の晶出に長時間を要するので経済的に不利になるおそれがある。一方、Ｚｒが２５質量％を上回る場合には、カルボン酸塩、リン酸塩等が結晶として析出するので、生成物たる結晶質リン酸ジルコニウムの濾過及び水洗が困難となるおそれがある。 The concentration of the raw material mixture is preferably adjusted to a concentration at which Zr is 0.01 to 25% by mass, particularly 0.1 to 10% by mass. A dilute solution having a Zr of less than 0.01% by mass may be economically disadvantageous because it takes a long time to crystallize the target product. On the other hand, when Zr exceeds 25% by mass, carboxylate, phosphate and the like are precipitated as crystals, which may make it difficult to filter and wash the crystalline zirconium phosphate as a product.
　上記原料混合液のｐＨは限定的ではないが、１０以下であることが好ましく、特に０．５～７であることがより好ましい。上記ｐＨが１０を超える場合には、結晶化度の低い結晶質リン酸ジルコニウムが生成される傾向がある。原料混合液のｐＨを調整する際に用いるｐＨ調整剤としては、塩酸、硫酸、硝酸等の鉱酸；水酸化アンモニウム、炭酸水素アンモニウム、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等のアンモニウム及びアルカリ金属の水酸化物及び炭酸塩が例示される。 The pH of the raw material mixture is not limited, but is preferably 10 or less, more preferably 0.5 to 7. When the pH exceeds 10, crystalline zirconium phosphate having a low crystallinity tends to be generated. Examples of pH adjusters used for adjusting the pH of the raw material mixture include mineral acids such as hydrochloric acid, sulfuric acid and nitric acid; ammonium and alkali such as ammonium hydroxide, ammonium hydrogen carbonate, sodium hydroxide, potassium hydroxide and sodium carbonate. Examples are metal hydroxides and carbonates.
　原料混合液の反応温度（本発明においては、各成分の反応及び熟成による結晶質リン酸ジルコニウムの晶出反応を一括して反応という）は、５０℃以上とすることが好ましい。反応温度が５０℃未満では、目的生成物の晶出に長時間を要するので経済的に不利になるおそれがある。 The reaction temperature of the raw material mixture (in the present invention, the reaction of each component and the crystallization reaction of crystalline zirconium phosphate by aging are collectively referred to as reaction) is preferably 50 ° C. or higher. If the reaction temperature is less than 50 ° C., it takes a long time to crystallize the target product, which may be economically disadvantageous.
　反応温度の上限は限定されないが、経済性等の観点からは２００℃程度とすればよい。反応時間は、原料の種類（即ち原料の反応性）；原料の配合比；原料混合液の濃度、温度及びｐＨ；反応生成物の所望の結晶化度等により異なるが、通常３０分～２０日程度であることが好ましい。 The upper limit of the reaction temperature is not limited, but may be about 200 ° C. from the viewpoint of economy and the like. The reaction time varies depending on the type of raw material (that is, the reactivity of the raw material); the mixing ratio of the raw material; the concentration, temperature and pH of the raw material mixture; the desired crystallinity of the reaction product, etc. It is preferable that it is a grade.
　生成したＮＨ４Ｚｒ２Ｐ３Ｏ１２は、濾過、デカンテーション、遠心分離等の公知の手段によって固液分離し、洗浄した後、常法に従って脱水・乾操する。乾操方法としては、加熱乾操又は風乾の他、五酸化リン、塩化カルシウム、シリカゲル等の乾燥剤により吸着水を除去する方法等が適用できる。また、必要に応じて８００℃以下で加熱処理してもよい。なお、加熱処理温度が８００℃を超える場合には、所望の結晶形が変形して二リン酸ジルコニウム（ＺｒＰ２Ｏ７）等に変換される場合がある。 The produced NH 4 Zr 2 P 3 O 12 is subjected to solid-liquid separation by known means such as filtration, decantation, and centrifugation, washed, and then dehydrated and dried according to a conventional method. As a drying method, in addition to heat drying or air drying, a method of removing adsorbed water with a drying agent such as phosphorus pentoxide, calcium chloride, silica gel, or the like can be applied. Moreover, you may heat-process at 800 degrees C or less as needed. Note that when the heat treatment temperature exceeds 800 ° C., a desired crystal form may be deformed and converted to zirconium diphosphate (ZrP 2 O 7 ) or the like.
　得られたＮＨ４Ｚｒ２Ｐ３Ｏ１２は、アルミナをはじめとする各種セラミックス製坩堝又は白金坩堝に入れて、約５００～約７００℃で約１時間～約５時間熱処理することにより、ＨＺｒ２Ｐ３Ｏ１２に変化させることができる。 The obtained NH 4 Zr 2 P 3 O 12 is put into various ceramic crucibles such as alumina or platinum crucible and heat-treated at about 500 to about 700 ° C. for about 1 hour to about 5 hours, so that HZr 2 It can be changed to P 3 O 12 .
　また、ＨＺｒ２Ｐ３Ｏ１２は、一般的に、化学的及び熱的に安定な三次元網状構造を有しており、アンモニウムイオン、水素イオン、分子径の小さいＨ２Ｏ分子等を部分的に網目構造のミクロな細孔中に含むゼオライト状トンネル構造を備えている。 In addition, HZr 2 P 3 O 12 generally has a chemically and thermally stable three-dimensional network structure, and partially contains ammonium ions, hydrogen ions, H 2 O molecules having a small molecular diameter, and the like. It has a zeolitic tunnel structure contained in the microscopic pores of the network structure.
　ＨＺｒ２Ｐ３Ｏ１２は、大気中に放置すると、大気中の水分とＨＺｒ２Ｐ３Ｏ１２のＨが置換して、Ｈ１－Ｚ（Ｈ３Ｏ）ＺＺｒ２Ｐ３Ｏ１２（Ｚ＝０～１）が得られることが知られており、水と接触させることにより、同様の変化が起こり、最終的には（Ｈ３Ｏ）Ｚｒ２Ｐ３Ｏ１２に変化させることができる。 When HZr 2 P 3 O 12 is left in the atmosphere, moisture in the atmosphere and H in HZr 2 P 3 O 12 are substituted, and H 1 -Z (H 3 O) Z Zr 2 P 3 O 12 (Z = 0 to 1) is known, and the same change occurs upon contact with water, and finally it can be changed to (H 3 O) Zr 2 P 3 O 12 .
　このように、ＮＨ４Ｚｒ２Ｐ３Ｏ１２を熱処理することによりＨＺｒ２Ｐ３Ｏ１２が生成し、ＨＺｒ２Ｐ３Ｏ１２が吸水することによりＨ１－Ｘ（Ｈ３Ｏ）ＺＺｒ２Ｐ３Ｏ１２（Ｚ＝０～１）を経て、最終的には（Ｈ３Ｏ）Ｚｒ２Ｐ３Ｏ１２が生成する。これらの結晶質リン酸ジルコニウムは、冒頭で示した一般式：ＲＺｒ２Ｐ３Ｏ１２（但し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。）で表され、出発原料Ａとして用いることができる。 Thus, NH 4 Zr 2 P 3 O 12 HZr 2 P 3 O 12 is produced by heat-treating, HZr 2 P 3 by O 12 is water H 1-X (H 3 O ) Z Zr 2 Through P 3 O 12 (Z = 0 to 1), (H 3 O) Zr 2 P 3 O 12 is finally produced. These crystalline zirconium phosphates are represented by the general formula shown at the beginning: RZr 2 P 3 O 12 (where R represents H, H 3 O or NH 4 ), and can be used as the starting material A. it can.
　第二態様の蛍光体材料を製造するための原料となる出発原料Ｂは、出発原料Ａを用いて調製することができる。具体的には、出発原料Ａと金属元素Ｍとを含有する混合液を調製し、当該混合液又はそれを蒸発乾固したものを熱処理することにより出発原料Ｂを調製することができる。 The starting material B, which is a material for producing the phosphor material of the second aspect, can be prepared using the starting material A. Specifically, the starting material B can be prepared by preparing a mixed solution containing the starting material A and the metal element M, and heat-treating the mixed solution or one obtained by evaporating and drying the mixed solution.
　金属元素Ｍは、限定的ではないが、例えば、アルカリ金属（Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｃｓ等）、アルカリ土類金属（Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｒａ）、チタン族（Ｔｉ、Ｚｒ、Ｈｆ）、バナジウム族（Ｖ、Ｎｂ、Ｔａ）、クロム族（Ｃｒ、Ｍｏ、Ｗ）、マンガン族（Ｍｎ、Ｔｃ、Ｒｅ）、鉄族（Ｆｅ、Ｃｏ、Ｎｉ）、白金族（Ｐｄ、Ｐｔ等）、銅族（Ｃｕ、Ａｇ、Ａｕ）、亜鉛族（Ｚｎ、Ｃｄ、Ｈｇ）、ホウ素族（Ａｌ、Ｉｎ等）、炭素族（Ｓｎ、Ｐｂ）等が挙げられる。これらの金属元素Ｍは単独又は２種以上を組み合わせて使用することができる。これらの中でも、金属元素Ｍとして、アルカリ金属及びアルカリ土類金属の少なくとも１種が好ましい。 Examples of the metal element M include, but are not limited to, alkali metals (Li, Na, K, Rb, Cs, etc.), alkaline earth metals (Be, Mg, Ca, Sr, Ba, Ra), titanium group (Ti , Zr, Hf), vanadium group (V, Nb, Ta), chromium group (Cr, Mo, W), manganese group (Mn, Tc, Re), iron group (Fe, Co, Ni), platinum group (Pd , Pt, etc.), copper group (Cu, Ag, Au), zinc group (Zn, Cd, Hg), boron group (Al, In, etc.), carbon group (Sn, Pb), and the like. These metal elements M can be used alone or in combination of two or more. Among these, as the metal element M, at least one of an alkali metal and an alkaline earth metal is preferable.
　混合液の溶媒は、金属元素Ｍの陽イオンが安定して存在できればよく、水が経済面及び環境面から最適である。また、酸性（例えば、塩酸、硫酸、硝酸等又はこれらの水溶液）又はアルカリ性（例えば、アンモニア水）のいずれであってもよい。 The solvent of the mixed solution is not limited as long as the cation of the metal element M can exist stably, and water is optimal from the economical and environmental aspects. Further, it may be acidic (for example, hydrochloric acid, sulfuric acid, nitric acid or an aqueous solution thereof) or alkaline (for example, aqueous ammonia).
　結晶質リン酸ジルコニウム（ＲＺｒ２Ｐ３Ｏ１２（但し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。））と金属元素Ｍの配合割合は、結晶質リン酸ジルコニウムに対して金属元素Ｍ（ｎ＝価数）をモル比で換算して、１／０．６ｎ以下が好ましく、１／０．８ｎ以下がより好ましく、１／ｎ以下が最も好ましい。 The compounding ratio of crystalline zirconium phosphate (RZr 2 P 3 O 12 (where R represents H, H 3 O or NH 4 )) and the metal element M is as follows. (N = valence) is converted to a molar ratio, preferably 1 / 0.6n or less, more preferably 1 / 0.8n or less, and most preferably 1 / n or less.
　具体的には、ｎ＝３の金属元素Ｍを用いる場合は、結晶質リン酸ジルコニウム１モルに対して金属元素Ｍを約０．５６モル（１／１．８＝約０．５６）以下に設定することが好ましく。約０．４２モル（１／２．４＝約０．４２）以下に設定することがより好ましく、約０．３３モル（１／３＝約０．３３）以下に設定することが最も好ましい。 Specifically, when the metal element M with n = 3 is used, the metal element M is reduced to about 0.56 mol (1 / 1.8 = about 0.56) or less with respect to 1 mol of crystalline zirconium phosphate. It is preferable to set. More preferably, it is set to about 0.42 mol (1 / 2.4 = about 0.42) or less, and most preferably about 0.33 mol (1/3 = about 0.33) or less.
　かかる比率に設定することにより、結晶質リン酸ジルコニウム内に金属元素Ｍを導入することができる。なお、本発明では、上記比率が１／ｎを超えた場合でも、金属元素Ｍが結晶質リン酸ジルコニウムの表面及び／又は細孔に無機酸塩又は有機酸塩の形態で吸着することもできるため、結果として１／ｎを超えている場合も蛍光特性は発現される。 By setting this ratio, the metal element M can be introduced into the crystalline zirconium phosphate. In the present invention, even when the ratio exceeds 1 / n, the metal element M can be adsorbed on the surface and / or pores of crystalline zirconium phosphate in the form of inorganic acid salt or organic acid salt. Therefore, as a result, even when the ratio exceeds 1 / n, the fluorescence characteristic is expressed.
　上記混合液は、金属元素Ｍの金属イオン濃度が５００重量ｐｐｍ以下（特に２５０重量ｐｐｍ以下）である溶液と結晶質リン酸ジルコニウムとを混合することによっても調製することができる。本発明方法によって、金属元素Ｍの金属イオン含有量が僅かな溶液でもその金属イオンの吸着を効果的に行うことができる。なお、金属元素Ｍの金属イオン濃度の下限値は特に制限されないが、通常は１０重量ｐｐｍ程度とすればよい。 The above mixed solution can also be prepared by mixing a solution having a metal ion concentration of the metal element M of 500 ppm by weight or less (particularly 250 ppm by weight or less) with crystalline zirconium phosphate. By the method of the present invention, even when the metal element M has a small metal ion content, the metal ions can be effectively adsorbed. In addition, the lower limit value of the metal ion concentration of the metal element M is not particularly limited, but is usually about 10 ppm by weight.
　上記混合液又はその蒸発乾固物を熱処理する際の熱処理条件としては、結晶質リン酸ジルコニウムが熱処理によりＨＺｒ２Ｐ３Ｏ１２に変化し、その分子中のＨと金属元素Ｍとのイオン置換が行われる条件であれば限定されない。熱処理条件としては、６００～８００℃程度が好ましく、６５０～７５０℃程度がより好ましい。このときの熱処理雰囲気は特に限定されず、大気中で行うことができる。熱処理後は、例えば、純水中での洗浄、乾燥を経て出発原料Ｂ（Ｍｎ＋ ｙＲ１－ｎｙＺｒ２Ｐ３Ｏ１２）を得ることができる。 The heat treatment conditions for the heat treatment of the mixed solution or the evaporated and dried product thereof are that crystalline zirconium phosphate is changed to HZr 2 P 3 O 12 by heat treatment, and ion substitution between H in the molecule and the metal element M is performed. There is no limitation as long as the conditions are satisfied. The heat treatment condition is preferably about 600 to 800 ° C., more preferably about 650 to 750 ° C. The heat treatment atmosphere at this time is not particularly limited, and can be performed in the air. After the heat treatment, for example, the starting material B (M n + y R 1-ny Zr 2 P 3 O 12 ) can be obtained through washing and drying in pure water.
　出発原料Ａ及び出発原料Ｂをそれぞれ還元性雰囲気中４００～８５０℃で熱処理することにより、第一態様の蛍光体材料及び第二態様の蛍光体材料がそれぞれ得られる。 The phosphor material of the first aspect and the phosphor material of the second aspect are obtained by heat-treating the starting material A and the starting material B, respectively, in a reducing atmosphere at 400 to 850 ° C.
　熱処理温度は４００～８５０℃であればよく、特に６００～８００℃が好ましい。熱処理温度が４００～８５０℃の範囲を外れる場合には、蛍光体材料の一般式中、ｘの範囲が０．００５以上０．４未満とならない場合があるため好ましくない。 The heat treatment temperature may be 400 to 850 ° C, and 600 to 800 ° C is particularly preferable. When the heat treatment temperature is outside the range of 400 to 850 ° C., the range of x in the general formula of the phosphor material may not be 0.005 or more and less than 0.4, which is not preferable.
　熱処理時間は、熱処理温度に応じて適宜設定できるが、一般に高温で熱処理を行う場合には短時間でよく、低温で熱処理を行う場合には長時間を要する。熱処理は、常圧下で行うことができるが、加圧下で実施することもできる。加圧下で実施する場合の圧力は限定されないが、一般に０．１～４０ＭＰａ程度であることが好ましい。 The heat treatment time can be appropriately set according to the heat treatment temperature, but generally a short time is required when the heat treatment is performed at a high temperature, and a long time is required when the heat treatment is performed at a low temperature. The heat treatment can be performed under normal pressure, but can also be performed under pressure. The pressure in the case of carrying out under pressure is not limited, but generally it is preferably about 0.1 to 40 MPa.
　熱処理時は還元性雰囲気を用いる。還元性雰囲気としては限定的ではないが、例えば、水素及び一酸化炭素の少なくとも１種を含む還元性ガスを用いることができる。本発明では、還元性雰囲気中で熱処理を行うのが特徴であり、大気雰囲気又は酸化性雰囲気で熱処理しても所望の蛍光特性を有する蛍光体材料は得られない。 Use a reducing atmosphere during heat treatment. The reducing atmosphere is not limited. For example, a reducing gas containing at least one of hydrogen and carbon monoxide can be used. The present invention is characterized in that heat treatment is performed in a reducing atmosphere, and a phosphor material having desired fluorescence characteristics cannot be obtained even if heat treatment is performed in an air atmosphere or an oxidizing atmosphere.
　上記熱処理をオートクレーブ中で行う場合には、揮発性の金属元素Ｍでもオートクレーブ外へ流出することがないため、周辺設備が侵食されることがなく、特殊な材質の設備等を必要としない点で有利となる。 When the heat treatment is performed in an autoclave, the volatile metal element M does not flow out of the autoclave, so that the peripheral equipment is not eroded and no special material equipment is required. It will be advantageous.
　本発明の蛍光体材料は、発光元素として希土類元素以外の元素を用いたリン酸ジルコニウム系の蛍光体材料であり、紫外線照射によって可視光（波長が３８０ｎｍ以上８３０ｎｍ未満の光）を発光する。具体的には、例えば、励起光（２５４ｎｍ）を照射することにより、蛍光（３９５ｎｍ）が得られる。 The phosphor material of the present invention is a zirconium phosphate-based phosphor material using an element other than a rare earth element as a light-emitting element, and emits visible light (light having a wavelength of 380 nm or more and less than 830 nm) by ultraviolet irradiation. Specifically, for example, fluorescence (395 nm) is obtained by irradiating excitation light (254 nm).
　それにより、本発明の蛍光体材料は、照明装置、液晶表示装置用バックライト等をはじめとする蛍光体材料の用途に幅広く利用することができる。 Thereby, the phosphor material of the present invention can be widely used for phosphor materials such as lighting devices and backlights for liquid crystal display devices.
直接結晶析出法によりＮＨ４Ｚｒ２Ｐ３Ｏ１２を調製する際の原料混合液においてジルコニウム化合物（Ｚｒとして）、カルボン酸化合物（Ｃ２Ｏ４として）及びリン酸化合物（ＰＯ４として）の好ましい割合（領域）を示すモル比三角成分図である。具体的には、Ａ（２８，３，６９）、Ｂ（６３，６，３１）、Ｃ（４４，４３，１３）及びＤ（１，９７，２）の各点を結ぶ直線で囲まれた領域が好ましいことを示す図である。Preferred zirconium compound (as Zr), carboxylic acid compound (as C 2 O 4 ), and phosphoric acid compound (as PO 4 ) in the raw material mixture when preparing NH 4 Zr 2 P 3 O 12 by direct crystal precipitation method It is a molar ratio triangular component figure which shows a ratio (area | region). Specifically, it is surrounded by straight lines connecting points A (28, 3, 69), B (63, 6, 31), C (44, 43, 13) and D (1, 97, 2). It is a figure which shows that an area | region is preferable. 実験例１において、試料：ＨＺｒ２Ｐ３Ｏ１２を３質量％Ｈ２（Ｎ２バランス）ガス気流中７００℃で２時間還元熱処理を行うことにより得られた還元熱処理物の蛍光スペクトル及び励起スペクトルを示す図である。In Experimental Example 1, sample: HZr 2 P 3 O 12 3% by mass H 2 (N 2 balance) Fluorescence spectrum and excitation spectrum of reduction heat treatment product obtained by performing reduction heat treatment at 700 ° C. for 2 hours at 700 ° C. FIG. （１）は、実験例２に関連し、ＮＨ４Ｚｒ２Ｐ３Ｏ１２の熱重量分析（ＴＧ）－示差熱分析（ＤＴＡ）の結果を示す図である（熱分解物はＨＺｒ２Ｐ３Ｏ１２）。（２）は、実験例３に関連し、（Ｈ３Ｏ）Ｚｒ２Ｐ３Ｏ１２のＴＧ－ＤＴＡの結果を示す図である（熱分解物はＨＺｒ２Ｐ３Ｏ１２）。(1) relates to Experimental Example 2, and shows the results of thermogravimetric analysis (TG) -differential thermal analysis (DTA) of NH 4 Zr 2 P 3 O 12 (the pyrolysis product is HZr 2 P 3 O 12). (2) is related to Experimental Example 3 and shows the result of TG-DTA of (H 3 O) Zr 2 P 3 O 12 (the thermal decomposition product is HZr 2 P 3 O 12 ).
　以下に実験例を示して本発明を具体的に説明する。 The present invention will be specifically described below by showing experimental examples.
　実験例１（第１態様の蛍光体材料）
　実験例１で用いる結晶質リン酸ジルコニウム（試料１）として、直接結晶析出法より調製されたＮＨ４Ｚｒ２Ｐ３Ｏ１２を大気中５７５℃で５時間熱処理することにより得たＨＺｒ２Ｐ３Ｏ１２を用意した。 Experimental Example 1 (phosphor material of the first aspect)
HZr 2 P 3 obtained by heat-treating NH 4 Zr 2 P 3 O 12 prepared by the direct crystal precipitation method at 575 ° C. for 5 hours in the atmosphere as crystalline zirconium phosphate (sample 1) used in Experimental Example 1 the O 12 was prepared.
　試料１をアルミナボートに入れ、３質量％Ｈ２（Ｎ２バランス）ガス気流中３５０～９００℃（表１に示す１２種類の温度）で各２時間還元熱処理を行った。 Sample 1 was placed in an alumina boat and subjected to a reduction heat treatment for 2 hours at 350 to 900 ° C. (12 kinds of temperatures shown in Table 1) in a 3 mass% H 2 (N 2 balance) gas stream.
　表１に、各還元熱処理物における、励起光２５４ｎｍでの３９５ｎｍの相対蛍光強度値及び化学組成を示す。なお、相対蛍光強度値は、浜松ホトニクス株式会社製、絶対ＰＬ電子収率測定装置（Quantaurus-QY、C11347-01）を用いて測定した。 Table 1 shows the relative fluorescence intensity value and chemical composition at 395 nm with excitation light of 254 nm in each reduction heat treatment product. The relative fluorescence intensity value was measured using an absolute PL electron yield measuring device (Quantaurus-QY, C11347-01) manufactured by Hamamatsu Photonics Co., Ltd.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　４００～８５０℃における各還元熱処理物では、励起光２５４ｎｍで３９５ｎｍに蛍光が観測された。相対蛍光強度値は７００℃での還元熱処理物が最も高かった。 In each reduction heat treatment at 400 to 850 ° C., fluorescence was observed at 395 nm with excitation light of 254 nm. The relative fluorescence intensity value was highest for the heat-treated reduction at 700 ° C.
　他方、３５０℃（比較例）における還元熱処理物では、殆ど蛍光が観測されなくなり、９００℃（比較例）における還元熱処理物の場合も４００～８５０℃における還元熱処理物と比べて蛍光強度が低くなった。 On the other hand, almost no fluorescence was observed in the reduced heat-treated product at 350 ° C. (Comparative Example), and the fluorescence intensity was lower in the case of the reduced heat-treated product at 900 ° C. (Comparative Example) than the reduced heat-treated product at 400 to 850 ° C. It was.
　表１に示す通り、３５０℃における還元熱処理物は還元熱処理前のＨ１．００Ｚｒ２Ｐ３Ｏ１２．０００組成を維持していた。これに対して、４００～８５０℃における還元熱処理物の化学組成は、水素及び酸素がリン酸ジルコニウムから抜けた化学組成となった。水素及び酸素がリン酸ジルコニウムから抜ける量は、還元熱処理温度の上昇に従って多くなった。 As shown in Table 1, the reduction heat-treated product at 350 ° C. maintained the H 1.00 Zr 2 P 3 O 12.000 composition before the reduction heat treatment. In contrast, the chemical composition of the heat-treated reduction product at 400 to 850 ° C. was a chemical composition in which hydrogen and oxygen escaped from zirconium phosphate. The amount of hydrogen and oxygen released from the zirconium phosphate increased as the reduction heat treatment temperature increased.
　なお、化学組成中の水素と酸素の定量は、（HORIBA製、EMGA-930）を用いて、「不活性ガス融解－非分散型赤外線吸収法」により行った。 The determination of hydrogen and oxygen in the chemical composition was carried out by “inert gas melting-non-dispersion type infrared absorption method” using (EMGA-930, manufactured by HORIBA).
　次いで、Ｘ線光電子分光装置を用いて各還元熱処理物中のＺｒ及びＰの価数の変化の有無を確認した。具体的には、還元熱処理前の試料１及び各還元熱処理物について、結合エネルギー分析範囲０～１４００ｅＶで広域光電子スペクトルを測定し、定性分析を行った。その後、定性分析で検出された元素Ｚｒ、Ｐ、Ｏの狭域光電子スペクトル測定を行い、光電子ピーク結合エネルギー位置からＺｒとＰの化学状態を推定した。 Next, the presence or absence of changes in the valence of Zr and P in each reduction heat-treated product was confirmed using an X-ray photoelectron spectrometer. Specifically, a wide-range photoelectron spectrum was measured in the binding energy analysis range of 0 to 1400 eV for the sample 1 before reduction heat treatment and each reduction heat treatment product, and qualitative analysis was performed. Thereafter, narrow-area photoelectron spectra of the elements Zr, P, and O detected by qualitative analysis were measured, and the chemical states of Zr and P were estimated from the photoelectron peak binding energy positions.
　還元熱処理前の試料１及び各還元熱処理物中において得られた結果には、差が認められなかった。よって、還元熱処理前の試料１及び各還元熱処理物共に、含有されるＺｒは４価であり、Ｐは５価であることが分かった。 No difference was found in the results obtained in Sample 1 before each reduction heat treatment and each reduction heat treatment product. Therefore, it was found that both the sample 1 before the reduction heat treatment and each reduction heat treatment product contained Zr was tetravalent and P was pentavalent.
　参考のため、還元熱処理前の試料１及び大気中３５０～９００℃（表１に示す１２種類の温度と同じ）で各２時間熱処理を行った各熱処理物の蛍光特性を調べたところ、いずれも蛍光は観察されなかった。 For reference, the fluorescence characteristics of Sample 1 before reduction heat treatment and each heat-treated product subjected to heat treatment for 2 hours at 350 to 900 ° C. (the same as 12 kinds of temperatures shown in Table 1) in the atmosphere were examined. Fluorescence was not observed.
　次いで、大気雰囲気中３５０～９００℃（表１に示す１２種類の温度と同じ）で各２時間熱処理を行った各熱処理物、並びに、３質量％Ｈ２（Ｎ２バランス）ガス気流中３５０～９００℃（表１に示す１２種類の温度）で各２時間還元熱処理を行った各還元熱処理物について、粉末Ｘ線回折測定結果から計算したセル体積値をまとめた（表２）。 Then, the heat-treated product was subjected to the heat treatment for 2 hours at 350 to 900 ° C. in an air atmosphere (same as 12 different temperature shown in Table 1), and, 3 wt% H 2 (N 2 Balance) gas stream 350 to The cell volume values calculated from the powder X-ray diffraction measurement results for each reduction heat-treated product subjected to reduction heat treatment for 2 hours at 900 ° C. (12 kinds of temperatures shown in Table 1) are summarized (Table 2).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　大気中熱処理及び３質量％Ｈ２ガス還元熱処理のいずれにおいても、８００℃以下で熱処理した場合には、ＨＺｒ２Ｐ３Ｏ１２に観測されるＸ線回折パターンが観測された。８５０℃で熱処理した場合には、ＨＺｒ２Ｐ３Ｏ１２に観測されるＸ線回折パターンの他に、ＺｒＰ２Ｏ７（二リン酸ジルコニム）に観測されるＸ線回折ピークが観測された。９００℃で熱処理した場合には、ＺｒＰ２Ｏ７に観測されるＸ線回折ピーク強度がＨＺｒ２Ｐ３Ｏ１２に観測されるＸ線回折ピークより非常に強くなり、リン酸ジルコニウムのセル体積を求めることができなかった。前記表１で、９００℃における還元熱処理物の化学組成を記載していないのは、ＨＺｒ２Ｐ３Ｏ１２組成がＺｒＰ２Ｏ７に変化してしまったためである。 In both the atmospheric heat treatment and the 3 mass% H 2 gas reduction heat treatment, when heat treatment was performed at 800 ° C. or lower, an X-ray diffraction pattern observed in HZr 2 P 3 O 12 was observed. When heat-treated at 850 ° C., an X-ray diffraction peak observed in ZrP 2 O 7 (zirconium diphosphate) was observed in addition to the X-ray diffraction pattern observed in HZr 2 P 3 O 12 . When heat-treated at 900 ° C., the X-ray diffraction peak intensity observed in ZrP 2 O 7 becomes much stronger than the X-ray diffraction peak observed in HZr 2 P 3 O 12, and the cell volume of zirconium phosphate is reduced. I could not ask. The reason why the chemical composition of the reduced heat-treated product at 900 ° C. is not described in Table 1 is that the HZr 2 P 3 O 12 composition has been changed to ZrP 2 O 7 .
　同じ熱処理温度では、大気熱処理物のセル体積と比べて還元熱処理物のセル体積の方が小さくなった。このことは、表１に示す化学組成の結果から分かるように、還元熱処理によって水素及び酸素がリン酸ジルコニウムから抜けた現象を支持している。 At the same heat treatment temperature, the cell volume of the reduced heat treatment was smaller than the cell volume of the atmospheric heat treatment. This supports the phenomenon that hydrogen and oxygen escaped from zirconium phosphate by the reduction heat treatment, as can be seen from the chemical composition results shown in Table 1.
　最も高い相対蛍光強度値を示した７００℃における還元熱処理物の蛍光スペクトル及び励起スペクトルを図２に示す。また、この還元熱処理物の内部量子収率は４１％、吸収率は４３％、外部量子収率は１８％であった。更に、この還元熱処理物の蛍光寿命を浜松ホトニクス株式会社製の小型蛍光寿命測定装置（Quantaurus-Tau、C11267-01）で測定したところ、６．４ｎｓであった。 FIG. 2 shows the fluorescence spectrum and excitation spectrum of the reduced heat-treated product at 700 ° C. that showed the highest relative fluorescence intensity value. Moreover, the internal quantum yield of this heat-reduced product was 41%, the absorption rate was 43%, and the external quantum yield was 18%. Further, the fluorescence lifetime of this reduced heat-treated product was measured with a small fluorescence lifetime measuring device (Quantaurus-Tau, C11267-01) manufactured by Hamamatsu Photonics Co., Ltd., and found to be 6.4 ns.
　実験例２（第１態様の蛍光体材料）
　実験例２で用いる結晶質リン酸ジルコニウム（試料２）として、直接結晶析出法より調製されたＮＨ４Ｚｒ２Ｐ３Ｏ１２を用意した。 Experimental Example 2 (phosphor material of the first aspect)
As crystalline zirconium phosphate (sample 2) used in Experimental Example 2, NH 4 Zr 2 P 3 O 12 prepared by a direct crystal precipitation method was prepared.
　試料２をアルミナボートに入れ、３質量％Ｈ２（Ｎ２バランス）ガス気流中４００～９００℃（表１に示す１２種類の温度と同じ）で各２時間還元熱処理を行った。また、大気雰囲気中４００～９００℃（表１に示す１２種類の温度と同じ）で各２時間熱処理を行った。 Sample 2 was placed in an alumina boat and subjected to reduction heat treatment for 2 hours at 400 to 900 ° C. (same as twelve temperatures shown in Table 1) in a 3% by mass H 2 (N 2 balance) gas stream. Further, heat treatment was performed for 2 hours at 400 to 900 ° C. (same as twelve kinds of temperatures shown in Table 1) in an air atmosphere.
　試料２を出発物質とした場合も、試料１を出発物質とした実験例１と全く同じ結果（相対蛍光強度値、化学組成及びセル体積の評価）が得られた。 When Sample 2 was used as the starting material, the same results (evaluation of relative fluorescence intensity value, chemical composition and cell volume) as in Experimental Example 1 using Sample 1 as the starting material were obtained.
　実験例１と全く同じ結果が得られた理由としては、図３（１）に示す２０ｍｌ・ｍｉｎ－１の空気気流中で昇温速度１０・ｍｉｎ－１にて測定した試料２の熱重量分析（ＴＧ）－示差熱分析（ＤＴＡ）の結果から明らかな通り、試料２：ＮＨ４Ｚｒ２Ｐ３Ｏ１２は３５０℃以上で２時間熱処理することによって、一旦、ＨＺｒ２Ｐ３Ｏ１２に変化し、更にＨ１－ＸＺｒ２Ｐ３Ｏ１２－（Ｘ／２）に変化しているためであると考えられる。 The reason why exactly the same result as in Experimental Example 1 was obtained is that thermogravimetric analysis of Sample 2 measured at a heating rate of 10 · min −1 in an air stream of 20 ml · min −1 shown in FIG. (TG) —As is clear from the results of differential thermal analysis (DTA), Sample 2: NH 4 Zr 2 P 3 O 12 is temporarily changed to HZr 2 P 3 O 12 by heat treatment at 350 ° C. or higher for 2 hours. Further, this is considered to be due to the change to H 1-X Zr 2 P 3 O 12- (X / 2) .
　実験例３（第１態様の蛍光体材料）
　実験例３で用いる結晶質リン酸ジルコニウム（試料３）として、（Ｈ３Ｏ）Ｚｒ２Ｐ３Ｏ１２を用意した。具体的には、直接結晶析出法より調製されたＮＨ４Ｚｒ２Ｐ３Ｏ１２を大気中５７５℃で５時間熱処理して得たＨＺｒ２Ｐ３Ｏ１２を純水中に３日間浸することにより（Ｈ３Ｏ）Ｚｒ２Ｐ３Ｏ１２を得た。 Experimental Example 3 (phosphor material of the first aspect)
(H 3 O) Zr 2 P 3 O 12 was prepared as crystalline zirconium phosphate (sample 3) used in Experimental Example 3. Specifically, be immersed 3 days HZr 2 P 3 O 12 where the NH 4 Zr 2 P 3 O 12 prepared from direct crystallization method was obtained by heat treatment for 5 hours at 575 ° C. in air into pure water (H 3 O) Zr 2 P 3 O 12 was obtained.
　試料３をアルミナボートに入れ、３質量％Ｈ２（Ｎ２バランス）ガス気流中４００～９００℃（表１に示す１２種類の温度と同じ）で各２時間還元熱処理を行った。また、大気雰囲気中４００～９００℃（表１に示す１２種類の温度と同じ）で各２時間熱処理を行った。 Sample 3 was placed in an alumina boat and subjected to a reduction heat treatment for 2 hours at 400 to 900 ° C. (same as twelve temperatures shown in Table 1) in a 3% by mass H 2 (N 2 balance) gas stream. Further, heat treatment was performed for 2 hours at 400 to 900 ° C. (same as twelve kinds of temperatures shown in Table 1) in an air atmosphere.
　試料３を出発物質とした場合も、試料１を出発物質とした実験例１と全く同じ結果（相対蛍光強度値、化学組成及びセル体積の評価）が得られた。 When Sample 3 was used as the starting material, the same results (evaluation of relative fluorescence intensity value, chemical composition and cell volume) as in Experimental Example 1 using Sample 1 as the starting material were obtained.
　試料３を出発物質とした場合も、試料１を出発物質とした実験例１と全く同じ結果（相対蛍光強度値、化学組成及びセル体積の評価）が得られた。 When Sample 3 was used as the starting material, the same results (evaluation of relative fluorescence intensity value, chemical composition and cell volume) as in Experimental Example 1 using Sample 1 as the starting material were obtained.
　実験例１と全く同じ結果が得られた理由としては、図３（２）に示す２０ｍｌ・ｍｉｎ－１の空気気流中で昇温速度１０・ｍｉｎ－１にて測定した試料３の熱重量分析（ＴＧ）－示差熱分析（ＤＴＡ）の結果から明らかな通り、試料３：（Ｈ３Ｏ）Ｚｒ２Ｐ３Ｏ１２は２００℃以上で２時間熱処理することによって、一旦、ＨＺｒ２Ｐ３Ｏ１２に変化し、更にＨ１－ＸＺｒ２Ｐ３Ｏ１２－（Ｘ／２）に変化しているためであると考えられる。 The reason why exactly the same result as in Experimental Example 1 was obtained is that the thermogravimetric analysis of Sample 3 measured at a heating rate of 10 · min −1 in an air stream of 20 ml · min −1 shown in FIG. As is clear from the results of (TG) -differential thermal analysis (DTA), Sample 3: (H 3 O) Zr 2 P 3 O 12 was once heat treated at 200 ° C. or higher for 2 hours, and then temporarily treated with HZr 2 P 3 O. This is considered to be due to the change to 12 and further to H 1-X Zr 2 P 3 O 12- (X / 2) .
　実験例４（第２態様の蛍光体材料）
　実験例４で用いる結晶質リン酸ジルコニウム（試料４）として、直接結晶析出法より調製されたＮＨ４Ｚｒ２Ｐ３Ｏ１２を大気中５７５℃で５時間熱処理することにより得たＨＺｒ２Ｐ３Ｏ１２を用意した。 Experimental Example 4 (phosphor material of the second aspect)
HZr 2 P 3 obtained by heat-treating NH 4 Zr 2 P 3 O 12 prepared by the direct crystal precipitation method at 575 ° C. for 5 hours in the atmosphere as crystalline zirconium phosphate (sample 4) used in Experimental Example 4 the O 12 was prepared.
　試料４に、ＨＺｒ２Ｐ３Ｏ１２及び各金属硝酸塩ＬｉＮＯ３、Ｓｒ（ＮＯ３）２の水溶液をそれぞれ加えて混練した。ＬｉＮＯ３を加える際は、ＨＺｒ２Ｐ３Ｏ１２とＬａ（ＮＯ３）３とのモル比が、ＬｉＮＯ３／ＨＺｒ２Ｐ３Ｏ１２＝０．９０未満となるように加えた。また、Ｓｒ（ＮＯ３）２を加える際は、ＨＺｒ２Ｐ３Ｏ１２とＳｒ（ＮＯ３）２とのモル比が、Ｓｒ（ＮＯ３）２／ＨＺｒ２Ｐ３Ｏ１２＝０．４５未満になるように加えた。 An aqueous solution of HZr 2 P 3 O 12 and each of the metal nitrates LiNO 3 and Sr (NO 3 ) 2 was added to the sample 4 and kneaded. When adding LiNO 3, the molar ratio of HZr 2 P 3 O 12 and La (NO 3) 3 was added to a LiNO 3 / HZr 2 P 3 O 12 = less than 0.90. When Sr (NO 3 ) 2 is added, the molar ratio of HZr 2 P 3 O 12 and Sr (NO 3 ) 2 is less than Sr (NO 3 ) 2 / HZr 2 P 3 O 12 = 0.45. It was added to become.
　次いで、蒸発乾固した後、７００℃で熱処理することでＨ＋と各金属イオンとのイオン置換を行い、更に純水中にて洗浄後、１００℃で乾燥し、それぞれＬｉｙＲ１－ｙＺｒ２Ｐ３Ｏ１２（ｙ：０．９０未満）、ＳｒｙＲ１－２ｙＺｒ２Ｐ３Ｏ１２（ｙ：０．４５未満）を得た。 Next, after evaporating to dryness, ion exchange between H + and each metal ion is performed by heat treatment at 700 ° C., washing in pure water, drying at 100 ° C., and Li y R 1-y Zr 2 P 3 O 12 (y: less than 0.90), Sr y R 1-2y Zr 2 P 3 O 12 (y: less than 0.45) were obtained.
　得られたＬｉｙＲ１－ｙＺｒ２Ｐ３Ｏ１２（ｙ：０．９０未満）、ＳｒｙＲ１－２ｙＺｒ２Ｐ３Ｏ１２（ｙ：０．４５未満）をそれぞれアルミナボートに入れ、３質量％Ｈ２（Ｎ２バランス）ガス気流中４００～９００℃（表１に示す１１種類の温度と同じ）で各２時間還元熱処理を行った。各還元熱処理物の励起光２５４ｎｍでの３９５ｎｍの相対蛍光強度値は、すべて０．１０以上であった。 The obtained Li y R 1-y Zr 2 P 3 O 12 (y: less than 0.90) and Sr y R 1-2y Zr 2 P 3 O 12 (y: less than 0.45) were put in an alumina boat, respectively. Reductive heat treatment was performed for 2 hours at 400 to 900 ° C. (same as 11 kinds of temperatures shown in Table 1) in a 3 mass% H 2 (N 2 balance) gas stream. The relative fluorescence intensity values at 395 nm with excitation light of 254 nm of all the heat-treated products were all 0.10 or more.
　参考のために、ＬｉｙＲ１－ｙＺｒ２Ｐ３Ｏ１２（ｙ：０．９０以上）、ＳｒｙＲ１－２ｙＺｒ２Ｐ３Ｏ１２（ｙ：０．４５以上）をそれぞれアルミナボートに入れ、３質量％Ｈ２（Ｎ２バランス）ガス気流中４００～９００℃（表１に示す１１種類の温度と同じ）で各２時間還元熱処理を行った。各還元熱処理物の励起光２５４ｎｍでの３９５ｎｍの相対蛍光強度値は、すべて０．０５以下であった。 For reference, Li y R 1-y Zr 2 P 3 O 12 (y: 0.90 or more) and Sr y R 1-2y Zr 2 P 3 O 12 (y: 0.45 or more) were each used as an alumina boat. Then, reduction heat treatment was performed for 2 hours at 400 to 900 ° C. (the same as 11 kinds of temperatures shown in Table 1) in a gas flow of 3 mass% H 2 (N 2 balance). The relative fluorescence intensity values at 395 nm with excitation light of 254 nm of each heat-treated product were all 0.05 or less.
　これらの結果を表３にまとめて示す。 These results are summarized in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　実験例５
　Ｍｇ（ＮＯ３）２を用いて実験例４と同様に還元熱処理物を調製し、相対蛍光強度を測定した結果を表４に示す。 Experimental Example 5
Table 4 shows the results of preparing a reduction heat treatment using Mg (NO 3 ) 2 in the same manner as in Experimental Example 4 and measuring the relative fluorescence intensity.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

Claims (6)

  1. 　Ｈ１－ｘＺｒ２Ｐ３Ｏ１２－（ｘ／２）　（１）
    〔式中、ｘは０．００５以上０．４未満である。〕
    で表されることを特徴とする蛍光体材料。     H 1-x Zr 2 P 3 O 12- (x / 2) (1)
    [Wherein x is 0.005 or more and less than 0.4. ]
    A phosphor material characterized by the following:
  2. 　（Ｍｎ＋ ｙＨ１－ｎｙ）１－ｘＺｒ２Ｐ３Ｏ１２－（ｘ／２）　（２）
    〔式中、Ｍは金属元素を示し、ｎは金属元素Ｍの平均価数を示す。また、ｘは０．００５以上０．４未満であり、ｙは０．０１以上０．９０／ｎ未満である。〕
    で表されることを特徴とする蛍光体材料。     (M n + y H 1-ny ) 1-x Zr 2 P 3 O 12- (x / 2) (2)
    [In the formula, M represents a metal element, and n represents an average valence of the metal element M. Moreover, x is 0.005 or more and less than 0.4, and y is 0.01 or more and less than 0.90 / n. ]
    A phosphor material characterized by the following:
  3. 　ＲＺｒ２Ｐ３Ｏ１２（但し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。）で表される出発原料Ａを還元性雰囲気中４００～８５０℃で熱処理することを特徴とする蛍光体材料の製造方法。 A phosphor material characterized by heat-treating a starting material A represented by RZr 2 P 3 O 12 (wherein R represents H, H 3 O or NH 4 ) in a reducing atmosphere at 400 to 850 ° C. Manufacturing method.
  4. 　請求項１に記載の蛍光体材料の製造方法である、請求項３に記載の製造方法。 The manufacturing method according to claim 3, which is a manufacturing method of the phosphor material according to claim 1.
  5. 　Ｍｎ＋ ｙＲ１－ｎｙＺｒ２Ｐ３Ｏ１２（但し、Ｍは金属元素を示し、ｎは金属元素Ｍの平均価数を示し、ＲはＨ、Ｈ３Ｏ又はＮＨ４を示す。また、ｙは金属元素Ｍのモル数であり、ｙは０．０１以上０．９０／ｎ未満である。）で表される出発原料Ｂを還元性雰囲気中４００～８５０℃で熱処理することを特徴とする蛍光体材料の製造方法。 M n + y R 1-ny Zr 2 P 3 O 12 (M represents a metal element, n represents an average valence of the metal element M, and R represents H, H 3 O, or NH 4. ) y is the number of moles of the metal element M, and y is 0.01 or more and less than 0.90 / n.), and the starting material B is heat-treated at 400 to 850 ° C. in a reducing atmosphere. A method for manufacturing a phosphor material.
  6. 　請求項２に記載の蛍光体材料の製造方法である、請求項５に記載の製造方法。 The manufacturing method according to claim 5, which is a manufacturing method of the phosphor material according to claim 2.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298583A (en) * 2004-04-08 2005-10-27 Shin Etsu Chem Co Ltd Oxide containing zirconium or hafnium
JP2005298584A (en) * 2004-04-08 2005-10-27 Shin Etsu Chem Co Ltd Rare earth element phosphoric acid salt composition and method for producing the same
JP2006206619A (en) * 2005-01-25 2006-08-10 Osaka Univ Phosphor
JP2006282907A (en) * 2005-04-01 2006-10-19 Shin Etsu Chem Co Ltd Phosphoric acid salt containing zirconium or hafnium and manganese

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005298583A (en) * 2004-04-08 2005-10-27 Shin Etsu Chem Co Ltd Oxide containing zirconium or hafnium
JP2005298584A (en) * 2004-04-08 2005-10-27 Shin Etsu Chem Co Ltd Rare earth element phosphoric acid salt composition and method for producing the same
JP2006206619A (en) * 2005-01-25 2006-08-10 Osaka Univ Phosphor
JP2006282907A (en) * 2005-04-01 2006-10-19 Shin Etsu Chem Co Ltd Phosphoric acid salt containing zirconium or hafnium and manganese

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