TW201835307A - Method for producing aluminate phosphor, aluminate phosphor and illuminating device - Google Patents

Abstract

The present invention provides a method for producing an aluminate phosphor having a high luminous intensity, an aluminate phosphor, and a light-emitting device. The present invention relates to a method for producing an aluminate phosphor comprising the steps of: a compound comprising at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound containing Mn, and a compound containing Eu At least one compound, a compound containing Al, and optionally a compound containing Mg are mixed to obtain a first mixture, and the first mixture obtained is subjected to a first heat treatment to obtain an average particle measured by the FSSS method. a first calcined product having a diameter D1 of 6 μm or more; and a compound containing at least one metal element selected from the group consisting of Ba, Sr, and Ca, a compound containing Mn, and at least one compound containing a compound of Eu, including a compound of Al, a first calcined product having a content of 10% by mass or more and 90% by mass or less based on the total amount, and optionally a compound containing Mg, to obtain a second mixture, and a second mixture obtained A second heat treatment is performed to obtain a second calcined product.

Description

Method for producing aluminate phosphor, aluminate phosphor and illuminating device

The present invention relates to a method for producing an aluminate phosphor, an aluminate phosphor, and a light-emitting device.

The industry is developing various types of light-emitting devices that combine a light-emitting diode (LED) and a phosphor to emit white, warm white, orange light, and the like. The illuminating devices obtain the desired illuminating color by the principle of color mixing. As a light-emitting device, a light-emitting element that emits blue light as an excitation light source, a phosphor that emits green light by being excited by light from a light source, and a phosphor that emits red light are combined to emit white light. . These light-emitting devices are intended to be used in a wide range of fields such as general illumination, vehicle illumination, displays, and backlights for liquid crystals. As a phosphor that emits green light used in a light-emitting device, for example, Patent Document 1 discloses a manganese-activated aluminate phosphor having a composition represented by (Ba, Sr) MgAl ₁₀ O ₁₇ : Mn ²⁺ . [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-155907

[Problem to be Solved by the Invention] However, the manganese activated aluminate phosphor disclosed in Patent Document 1 is excited by vacuum ultraviolet rays having a wavelength of about 10 nm to 190 nm, specifically, 146 nm. When the luminescence intensity is higher than the range of 380 nm or more and 485 nm or less (hereinafter, sometimes referred to as "near ultraviolet to blue region"), the luminescence intensity is combined. Not enough. Therefore, an object of an aspect of the present invention is to provide a method for producing an aluminate phosphor having high luminescence intensity by excitation of light in a near ultraviolet to blue region, an aluminate phosphor and Light emitting device. [Technical means for solving the problem] The technical means for solving the above problems include the following aspects. A first aspect of the invention is a method for producing an aluminate phosphor, comprising the steps of: a compound comprising at least one metal element selected from the group consisting of Ba, Sr and Ca, a compound comprising Mn And the first mixture is obtained by mixing at least one compound containing a compound of Eu, a compound containing Al, and optionally a compound containing Mg, and subjecting the obtained first mixture to a first heat treatment, thereby obtaining a FSSS method ( a first calcined product having a mean particle diameter D1 of 6 μm or more as measured by Fisher's particle size measurement method: Fisher Sub-Sieve Sizer (hereinafter also referred to as "FSSS method"); and a material selected from the group consisting of Ba, Sr, and Ca a compound of at least one metal element of the composition group, at least one compound containing Mn, and at least one compound containing Eu, a compound containing Al, and the content of 10% by mass or more and 90% by mass or less based on the total amount a calcined product, and optionally a compound containing Mg, is mixed to obtain a second mixture, and the obtained second mixture is subjected to a second heat treatment to obtain a second calcined product. . A second aspect of the present invention is an aluminate phosphor characterized by an average particle diameter D2 measured by the FSSS method of 13 μm or more and/or by a laser diffraction scattering particle size distribution. The volume average particle diameter Dm2 measured by the method is 20 μm or more and has a composition represented by the following formula (I). X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I) (In the formula (I), X ¹ is at least one selected from the group consisting of Ba, Sr and Ca The elements, p, q, r, s, and t satisfy 0.5≦p≦1.0, 0≦q≦1.0, 0≦r≦0.7, 8.5≦s≦13.0, 0≦t≦0.5, 0.5≦p+t≦1.2, 0.1≦r+t≦0.7, 0.2≦q+r≦1.0) The third aspect of the present invention is an aluminate phosphor characterized in that the average equivalent circle diameter Dc is 13 μm or more and has the following formula ( I) The composition represented. X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I) (In the formula (I), X ¹ is at least one selected from the group consisting of Ba, Sr and Ca The elements, p, q, r, s, and t satisfy 0.5≦p≦1.0, 0≦q≦1.0, 0≦r≦0.7, 8.5≦s≦13.0, 0≦t≦0.5, 0.5≦p+t≦1.2, The fourth aspect of the present invention is a light-emitting device comprising the above-described aluminate phosphor and having an emission peak in a range of 380 nm or more and 485 nm or less. The excitation source of the wavelength. [Effects of the Invention] According to an aspect of the present invention, it is possible to provide a method for producing an aluminate phosphor having high luminescence intensity by excitation of light in a near ultraviolet to blue region, and aluminate fluorescing Body and illuminating device.

Hereinafter, a method for producing an aluminate phosphor, an aluminate phosphor, and a light-emitting device according to an embodiment of the present invention will be described. However, the embodiment shown below is an example for embodying the technical idea of the present invention, and the present invention is not limited to the following method for producing an aluminate phosphor, an aluminate phosphor, and the like. Light emitting device. Furthermore, the relationship between the color name and the chromaticity coordinate, the relationship between the wavelength range of light and the color name of the monochromatic light are in accordance with JIS Z8110. Method for Producing Aluminate Phosphor The method for producing an aluminate phosphor according to the first embodiment of the present invention includes the step of containing at least one metal element selected from the group consisting of Ba, Sr, and Ca. The first mixture is obtained by mixing a compound, a compound containing Mn, and at least one compound containing a compound of Eu, a compound containing Al, and, if necessary, a compound containing Mg, to obtain a first mixture, and performing a first heat treatment on the obtained first mixture. Obtaining a first calcined product having a Fisher sub-sieve sizer's number D1 of 6 μm or more as measured by the FSSS method; and containing at least one metal selected from the group consisting of Ba, Sr, and Ca a compound of the element, a compound containing Mn, at least one compound containing a compound of Eu, a compound containing Al, and the above first calcined product in an amount of 10% by mass or more and 90% by mass or less based on the total amount, and optionally The compound containing Mg is mixed to obtain a second mixture, and the obtained second mixture is subjected to a second heat treatment to obtain a second calcined product. According to this embodiment, crystal growth can be promoted, and a second calcined product having a large average particle diameter can be obtained. The second calcined product has a large average particle diameter and can be used as an aluminate phosphor having a high luminous intensity. The first heat treatment first mixture contains a compound containing at least one metal element selected from the group consisting of Ba, Sr, and Ca, a compound containing Mn, and at least one compound containing a compound of Eu, a compound containing Al, and optionally A compound containing Mg. Regarding the first mixture, it is preferred to include a flux in the first mixture, and perform a first heat treatment together with the flux to obtain a first calcined product having an average particle diameter D1 of 6 μm or more as measured by the FSSS method. . The first mixture preferably contains a compound comprising Mn. The FSSS method is a method of obtaining a particle diameter by measuring a specific surface area by using a flow resistance of air. The first mixture may be subjected to pulverization and mixing after weighing the compound containing each element in such a manner as to achieve a desired compounding ratio, for example, using a ball mill, a vibrating mill, a hammer mill, a mortar, and a mortar. Further, the first mixture may be mixed by, for example, a mixer such as a belt mixer, a Henschel mixer, or a V-type agitator, or may be pulverized and mixed using both a dry pulverizer and a mixer. Further, the mixing may be dry mixing, or a solvent or the like may be added for wet mixing. The mixing is preferably dry mixing. The reason is that, in the case of the wet type, the dry type can shorten the step time and bring about an increase in productivity. The first mixture may be added to a carbon material such as graphite, a boron nitride (BN), an alumina, a tungsten (W), a molybdenum (Mo) material, a boat, a can, or the like for heat treatment. The first heat treatment temperature is preferably 1000 ° C or more and 1800 ° C or less, more preferably 1100 ° C or more and 1750 ° C or less, further preferably 1200 ° C or more and 1700 ° C or less, and more preferably 1300 ° C or more and 1650 ° C or less. More preferably, it is 1400 ° C or more and 1600 ° C or less. For the heat treatment, for example, an electric furnace, a gas furnace, or the like can be used. The gas atmosphere of the first heat treatment can be carried out under an atmosphere of an inert gas containing argon gas, nitrogen gas, a reducing gas atmosphere containing hydrogen, or an oxidizing gas containing oxygen such as the atmosphere. The gas atmosphere of the first heat treatment is preferably a reducing gas atmosphere, and more specifically, a reducing gas atmosphere containing hydrogen gas and nitrogen gas. In a gas atmosphere having a high reducing power of a reducing gas atmosphere containing hydrogen and nitrogen, the reactivity of the first mixture becomes good, and the heat treatment can be performed under atmospheric pressure. In the reducing gas atmosphere, the hydrogen gas is preferably 0.5% by volume or more, more preferably 1% by volume or more, and still more preferably 3% by volume or more. The first heat treatment time differs depending on the temperature increase rate, the heat treatment gas atmosphere, and the like, and after the first heat treatment temperature in the range of 1000 ° C or more and 1800 ° C or less, it is preferably 1 hour or longer, more preferably 2 hours or longer, and further preferably It is 3 hours or more, and preferably 20 hours or less, more preferably 18 hours or less, further preferably 15 hours or less. The first calcined product may be subjected to a dispersion treatment by a dispersion treatment step described below after the first heat treatment and before the second heat treatment. For the dispersion treatment step of the first calcined material, for example, the first calcined product may be subjected to classification treatment such as wet dispersion, wet sieve, dehydration, drying, dry sieve, etc., and the average particle diameter D1 measured by the FSSS method is obtained. The first calcined product of 6 μm or more. As the solvent used for the wet dispersion, for example, deionized water can be used. The time for performing the wet dispersion varies depending on the solid dispersion medium or solvent to be used, and is preferably 30 minutes or longer, more preferably 60 minutes or longer, further preferably 90 minutes or longer, further preferably 120 minutes or longer, and more preferably It is 420 minutes or less. Preferably, the first calcined material is wet-dispersed in a range of 30 minutes or more and 420 minutes or less, whereby when the obtained aluminate phosphor is used in a light-emitting device, the light-emitting device can be formed. The dispersibility in the resin of the fluorescent member is good. The average particle diameter D1 of the first calcined product measured by the FSSS method is 6 μm or more, preferably 6.5 μm or more, more preferably 7 μm or more, and still more preferably 7.5 μm or more. Preferably, the first calcined product has a larger average particle diameter D1 as measured by the FSSS method, and the average particle diameter D1 of the first calcined product is usually less than 13 μm. When the first calcined product has an average particle diameter D1 of 6 μm or more as measured by the FSSS method, the first calcined product becomes a seed crystal in the second heat treatment, which promotes crystal growth and can be measured by the FSSS method. A second calcined product having an average particle diameter of 13 μm or more was obtained. The second heat treatment second mixture contains a compound containing at least one metal element selected from the group consisting of Ba, Sr, and Ca, a compound containing Mn, and at least one compound containing a compound of Eu, a compound containing Al, and the first The content of the entire amount of the mixture is 10% by mass or more and 90% by mass or less of the first calcined product and, if necessary, a compound containing Mg. The second mixture is subjected to a second heat treatment of the obtained second mixture to obtain a second calcined product. The second mixture preferably contains a compound comprising Mn. The content of the first calcined product contained in the second mixture is preferably 15% by mass or more and 85% by mass or less, more preferably 20% by mass or more and 80% by mass or less based on the total amount of the second mixture. Further, it is preferably 25% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 80% by mass or less. In the second mixture, the first calcined product having an average particle diameter D1 of 6 μm or more is contained in the second mixture in a range of 10% by mass or more and 90% by mass or less based on the total amount of the second mixture. A calcined product is seeded to promote crystal growth, and a second second calcined product having an average particle diameter of 13 μm or more as measured by the FSSS method can be obtained, and the second calcined product can be used as the aluminate flake. Use in light body. If the content of the first calcined product is less than 10% by mass based on the total amount of the second mixture, the content of the first calcined product which becomes the seed crystal is too small, and the crystal growth does not be promoted in the second heat treatment, and it is difficult to obtain the particle diameter. Large second calcined product. When the content of the first calcined product exceeds 90% by mass based on the total amount of the second mixture, the amount of the compound to be used as the raw material contained in the second mixture is relatively small, and crystal growth is not promoted, and a large particle diameter cannot be obtained. The second calcined product. In the case of mixing the second mixture, a mixing method, a mixer, and the like exemplified in the case of obtaining the first mixture may be used. Further, the second mixture may be heat-treated by adding a boat, a can, or the like of the same material as the first mixture. The second mixture preferably contains a flux, and the second calcined material can be obtained by performing a second heat treatment together with the flux contained in the second mixture. The second heat treatment temperature may be applied to a temperature in the same range as the above first heat treatment temperature. The second heat treatment temperature may be the same temperature as the first heat treatment temperature described above, or may be a different temperature. At the time of heat treatment, for example, an electric furnace, a gas furnace, or the like can be used. The gas atmosphere of the second heat treatment may be applied to the same gas atmosphere as the first heat treatment gas atmosphere described above. The second heat treatment gas atmosphere may be the same gas atmosphere as the first heat treatment gas atmosphere, or may be a different gas atmosphere. The second heat treatment time may be applied for the same period as the first heat treatment time described above. The second heat treatment time may be the same time as the first heat treatment time described above, or may be a different time. Post-treatment The first calcined product or the second calcined product obtained by the first heat treatment or the second heat treatment is preferably subjected to post-treatment to obtain an aluminate phosphor. As the post-treatment, for example, at least one of wet dispersion, wet sieving, dehydration, drying, and dry sieving is preferably carried out. When the calcined product is subjected to wet dispersion and wet sieving as a post-treatment, specifically, the obtained calcined product is dispersed in a solvent, and the dispersed second calcined product is placed on a sieve and sieved through a sieve. The various vibrations cause the solvent to flow, and the calcined material is passed through a sieve to perform wet sieving. After passing through the wet sieve, precipitation classification can be performed to remove the fine particles. The fine particles removed by the precipitation classification from the calcined material differ depending on the particle diameter of the target or the like. In the case where the obtained calcined material is subjected to post-treatment to remove fine particles after the second heat treatment, it is preferably 15% by mass or more and 20% by mass or less or less of the total amount of the calcined product obtained after the second heat treatment. . The precipitation fraction can be repeated a plurality of times. After the precipitation is classified, the phosphor can be obtained by dehydration, drying, and dry sieving. By dispersing the calcined product after the heat treatment in a solvent, impurities such as a calcination residue of the flux or unreacted components of the raw material can be removed. In the case of wet dispersion, a solid dispersion medium such as alumina balls or zirconia balls can be used. As the solvent used for the wet dispersion, for example, deionized water can be used. The time for performing the wet dispersion varies depending on the solid dispersion medium or solvent to be used, and is preferably 10 minutes or longer, more preferably 20 minutes or longer, further preferably 30 minutes or longer, and preferably 240 minutes or shorter. The second calcined product is preferably subjected to wet dispersion in a range of from 10 minutes to 240 minutes, whereby the dispersibility of the obtained aluminate phosphor can be improved. As a post-treatment, when the calcined product is dried and sieved dry, specifically, the calcined product is dried at a temperature of about 80 ° C to 150 ° C. The dried calcined material can be passed through a dry sieve to remove particles having a large particle size that does not pass through the sieve. The drying time is preferably 1 hour or more and 20 hours or less, more preferably 2 hours or more and 18 hours or less. In the post-treatment, the mesh of the sieve used in the case of performing wet or dry sieve is not particularly limited, and a mesh sieve corresponding to the particle diameter of the first calcined product or the second calcined product may be used. The first calcined product and/or the second calcined material The first calcined product and/or the second calcined product preferably have a composition represented by the following formula (I). X¹ _p Eu_t Mg_q Mn_r Al_s O_{p + t + q + r + 1.5s} (I) (in formula (I), X¹ Is at least one element selected from the group consisting of Ba, Sr, and Ca, and p, q, r, s, and t satisfy 0.5≦p≦1.0, 0≦q≦1.0, 0≦r≦0.7, 8.5≦ ≦13.0, 0≦t≦0.5, 0.5≦p+t≦1.2, 0.1≦r+t≦0.7, 0.2≦q+r≦1.0) by the step of obtaining the first calcined product and/or the step of obtaining the second calcined product The obtained first calcined product and/or second calcined product can be used as an aluminate phosphor. Preferably, the flux comprises at least one of the first mixture and the second mixture comprising a flux, and the flux comprises a group selected from the group consisting of K, Na, Ba, Sr, Ca, Mg, Al, and Mn. a compound of at least one metal element. Preferably, the flux is a compound containing at least one metal element selected from the group consisting of Ba, Sr, and Ca, the compound containing Mn, and the above-mentioned first mixture and/or the second mixture. A compound containing Mg and a compound different from the above-mentioned compound containing Al. More preferably, the first mixture and the second mixture described above contain a flux at the same time. In the case where both the first mixture and the second mixture contain a flux, the flux contained in the first mixture may be the same as or different from the flux included in the second mixture. In the case where the first mixture contains a flux, the flux promotes the growth of the crystal by promoting the reaction of the raw materials in the first mixture with each other in the first heat treatment to make the solid phase reaction proceed more uniformly. The growth of the original crystals in the first mixture can be promoted by the presence of the flux, so that the first calcined product having a relatively large particle size can be obtained. The temperature of the first heat treatment is a temperature substantially the same as or higher than the temperature at which the compound used as the flux forms a liquid phase. It is considered that the formation of the liquid phase by the flux promotes the reaction of the raw materials in the first mixture with each other, so that the solid phase reaction proceeds more uniformly, thereby promoting crystal growth. It is considered that when the second mixture contains a flux, the flux promotes the reaction of the first calcined material which becomes the seed crystal in the second mixture with the other raw materials in the second heat treatment, so that the solid phase reaction proceeds more uniformly. Thereby, the seed crystal is used to further promote crystal growth. The flux is preferably a halide containing at least one metal element selected from the group consisting of K, Na, Ba, Sr, Ca, Mg, Al, and Mn, and examples thereof include, for example, selected from K, Na, Ba, and Sr. a fluoride, a chloride or the like of at least one of the metal elements of the group consisting of Ca, Mg, Al, and Mn. The flux is more preferably a fluoride containing the above metal element. Specific examples of the flux include KF, NaF, and BaF.₂ , SrF₂ CaF₂ , MgF₂ AlF₃ MnF₂ . The metal element contained in the flux may also be included in the composition of the first calcined material or the second calcined product. Preferably, the flux is set to 10 by the number of moles of Al contained in the first mixture containing no flux and/or the second mixture containing no flux, and the number of moles of the metal element contained in the flux becomes It is contained in the first mixture or the second mixture in a range of 0.03 or more and 0.60 or less, more preferably 0.04 or more and 0.55 or less, further preferably 0.05 or more and 0.50 or less, and still more preferably 0.06 or more and 0.40 or less. By being in the above range, the reaction of the raw materials in the first mixture or the reaction of the first calcined material in the second mixture with the raw material may be promoted in the first heat treatment or the second heat treatment, so that the solid phase reaction proceeds more uniformly, Thereby, the first calcined product or the second calcined product having a larger particle diameter can be obtained. In the case where the metal element contained in the flux constitutes a part of the composition of the first calcined material or the second calcined product obtained, the first mixture containing no flux or the second mixture containing no flux is included A flux is added to the first mixture or the second mixture in such a manner that the number of moles of Al is set to 10 and the number of moles of the metal element contained in the flux is within the above range. The flux preferably comprises two fluxes, a first flux and a second flux. In the case where two fluxes are included as the flux, it is preferred that the first flux is a compound containing at least one metal element selected from the group consisting of Ba, Sr, Ca, Mg, Al, and Mn, and second. The flux is a compound containing at least one metal element selected from the group consisting of K and Na. In the case of including the first flux and the second flux, at least one of the first mixture and the second mixture may comprise two fluxes, and both the first mixture and the second mixture may be included Two fluxes. As the first flux, by using a compound containing a metal element constituting the parent crystal of the first calcined product or the second calcined product, it is possible to suppress the incorporation of impurities into the crystal structure, and the constituents constituting the first calcined product or the second calcined product. The composition ratio (Morby ratio) is adjusted to the desired molar ratio. Further, by using a compound containing at least one metal element selected from K and Na as the second flux, the crystal can be easily grown in the c-axis direction and/or the in-plane direction in the hexagonal crystal structure. An aluminate phosphor having a high luminous intensity is obtained. Further, by including the first flux and the second flux having a melting point different from that of the first flux, crystal growth at a higher heat treatment temperature can be promoted, and the particle diameter can be increased. In the case of including the first flux and the second flux, it is preferably a molar amount of Al contained in the first mixture containing no flux and/or the second mixture containing no flux. The number of moles of the metal element contained in the first flux is 0.006 or more and 0.55 or less, more preferably 0.01 or more and 0.50 or less, further preferably 0.02 or more and 0.45 or less, and further preferably 0.03 or more and 0.40 or less. If it is in the above range, the reaction between the raw materials in the first mixture or the reaction of the first calcined material in the second mixture with the raw material may be promoted in the first heat treatment or the second heat treatment, so that the solid phase reaction proceeds more uniformly. Further, the crystal structure of the mother crystal is stabilized to obtain a first calcined product or a second calcined product having a larger particle diameter. In the case where the metal element contained in the first flux constitutes a part of the composition of the obtained first calcined product or the second calcined product, the first mixture containing no flux or the second mixture containing no flux is used The flux is added to the first mixture or the second mixture in such a manner that the number of moles of Al included is 10 and the number of moles of the metal element contained in the flux is in the range of 0.006 or more and 0.55 or less. When the metal element contained in the first flux is Mg or Al, and the metal element contained in the second flux is K or Na, the molar ratio (the number of moles of the metal element included in the first flux: second The molar amount of the metal element contained in the flux is preferably in the range of 20:1 to 1:5, more preferably in the range of 15:1 to 1:3, and still more preferably 10:1 to 1:2. range. If the molar ratio of the metal element contained in the first flux to the metal element contained in the second flux is in the range of 20:1 to 1:5, the reaction of the raw materials in the first mixture may be promoted or the second The reaction of the first calcined product in the mixture with the raw material causes the solid phase reaction to proceed more uniformly, and the crystal structure of the parent crystal is stabilized, thereby obtaining a first calcined product or a second calcined product having a larger particle diameter. There is a case where if the content of the second flux is too large, the alkali metal of Na or K which enters the crystal structure becomes large, and conversely, the luminescence intensity becomes low. The first mixture or the second mixture of the compound contained in the first mixture or the second mixture contains a compound containing at least one metal element (alkaline earth metal element) selected from the group consisting of Ba, Sr, and Ca, and a compound containing Mn and At least one compound containing a compound of Eu, and a compound containing Al. The first mixture or the second mixture may further optionally contain a compound containing Mg. Further, the first mixture and the second mixture preferably contain a compound containing Mn. The compound containing an alkaline earth metal element is a compound containing at least one alkaline earth metal element selected from the group consisting of Ba, Sr, and Ca, and includes at least one alkaline earth metal element selected from the group consisting of Ba, Sr, and Ca. Oxides, hydroxides, carbonates, nitrates, sulfates, carboxylates, halides, nitrides, and the like. These compounds can be in the form of hydrates. Specifically, BaO, Ba(OH)₂ ・8H₂ O, BaCO₃ , Ba(NO₃ )₂ BaSO₄ , Ba(HCOO)₂ , Ba(OCOCH₃ )₂ BaCl₂ ・6H₂ O, Ba₃ N₂ , SrO, Sr(OH)₂ ・8H₂ O, SrCO₃ , Sr (NO₃ )₂ ・4H₂ O, SrSO₄ , Sr (HCOO)₂ ・2H₂ O, Sr (OCOCH₃ )₂ ・0.5H₂ O, SrCl₂ ・6H₂ O, Sr₃ N₂ , CaO, Ca(OH)₂ CaCO₃ Ca(NO₃ )₂ CaSO₄ CaCl₂ Ca₃ N₂ Wait. These compounds may be used alone or in combination of two or more. Among these, carbonates and oxides are preferred in terms of ease of handling. More preferably, it is a carbonate containing at least one alkaline earth metal element selected from the group consisting of Ba, Sr, and Ca, because the stability in air is good, it is easily decomposed by heating, and the composition of the target is not easily retained. Other than the element, it is easy to suppress the decrease in the luminous intensity due to the residual impurity element. Compound Containing Mn As the compound containing Mn, an oxide containing Mn, a hydroxide, a carbonate, a nitrate, a sulfate, a carboxylate, a halide, a nitride, or the like can be given. The manganese-containing compound may be in the form of a hydrate. Specifically, exemplified by: MnO₂ Mn₂ O₂ Mn₃ O₄ , MnO, Mn(OH)₂ MnCO₃ Mn(NO₃ )₂ Mn(OCOCH₃ )₂ ・2H₂ O, Mn (OCOCH₃ )₃ ・2H₂ O, MnCl₂ ・4H₂ O and so on. The compound containing Mn may be used alone or in combination of two or more. Among these, carbonates and oxides are preferred in terms of ease of handling. More preferably carbonate containing Mn (MnCO)₃ The reason for this is that the stability in air is good, and it is easily decomposed by heating, and it is difficult to leave an element other than the target composition, and it is easy to suppress a decrease in luminous intensity due to residual impurity elements. Compound containing Eu As the compound containing Eu, an oxide, a hydroxide, a carbonate, a nitrate, a sulfate, a halide, a nitride, or the like containing Eu may be mentioned. The compounds containing Eu may be in the form of a hydrate. Specifically, it can be cited as: EuO, Eu₂ O₃ , Eu(OH)₃ , Eu₂ (CO₃ )₃ , Eu (NO₃ )₃ , Eu₂ (SO₄ )₃ EuCl₂ , EuF₃ Wait. The compound containing Eu may be used alone or in combination of two or more. Among these, carbonates and oxides are preferred in terms of ease of handling. More preferably, it contains Eu oxide (Eu₂ O₃ The reason for this is that the stability in air is good, and it is easily decomposed by heating, and it is difficult to leave an element other than the target composition, and it is easy to suppress a decrease in luminous intensity due to residual impurity elements. Compound Containing Al As the compound containing Al, an oxide containing Al, a hydroxide, a nitride, an oxynitride, a fluoride, a chloride, or the like can be given. These compounds can be hydrates. As the compound containing Al, an aluminum metal element or an aluminum alloy may be used, and a metal element or alloy may be used instead of at least a part of the compound. As a compound containing Al, specifically, Al is mentioned.₂ O₃ , Al(OH)₃ , AlN, AlF₃ AlCl₃ Wait. The compound containing Al may be used alone or in combination of two or more. The compound containing Al is preferably an oxide (Al)₂ O₃ ). The reason for this is that the oxide does not contain other elements than the composition of the target of the aluminate phosphor, and it is easy to obtain a phosphor of the target composition. Further, when a compound having an element other than the target composition is used, there is a case where a residual impurity element exists in the obtained phosphor, and the residual impurity element becomes a killing component in terms of light emission, and has a light-emitting property. The intensity is clearly reduced. Compound Containing Mg As the compound containing Mg, an oxide containing Mg, a hydroxide, a carbonate, a nitrate, a sulfate, a carboxylate, a halide, a nitride, or the like can be given. The magnesium-containing compound may be in the form of a hydrate. Specifically, it can be mentioned that MgO and Mg(OH)₂ , 3MgCO₃ ・Mg(OH)₂ ・3H₂ O, MgCO₃ ・Mg(OH)₂ , Mg (NO₃ )₂ ・6H₂ O, MgSO₄ , Mg (HCOO)₂ ・2H₂ O, Mg (OCOCH₃ )₂ ・4H₂ O, MgCl₂ , Mg₃ N₂ Wait. The compound containing Mg may be used alone or in combination of two or more. Among these, carbonates and oxides are preferred in terms of ease of handling. More preferably, it contains Mg oxide (MgO) because it has good stability in air, is easily decomposed by heating, does not easily retain elements other than the target composition, and easily suppresses light emission due to residual impurity elements. Reduced strength. Aluminate Phosphor The average particle size D2 (Fisher sub-sieve sizer's number) measured by the FSSS (Fisher sub-sieve sizer) method is 13 for the aluminate phosphor of the second embodiment of the present invention. The volume average particle diameter Dm2 measured by a laser diffraction scattering particle size distribution measurement of μm or more and/or is 20 μm or more and has a composition represented by the following formula (I). The volume average particle diameter Dm2 is a 50% by volume particle diameter of the particle size distribution measured by a laser diffraction scattering particle size distribution measurement method. X¹ _p Eu_t Mg_q Mn_r Al_s O_{p + t + q + r + 1.5s} (I) (in formula (I), X¹ Is at least one element selected from the group consisting of Ba, Sr, and Ca, and p, q, r, s, and t satisfy 0.5≦p≦1.0, 0≦q≦1.0, 0≦r≦0.7, 8.5≦ ≦13.0, 0≦t≦0.5, 0.5≦p+t≦1.2, 0.1≦r+t≦0.7, 0.2≦q+r≦1.0) The aluminate phosphor having the composition represented by the formula (I) (hereinafter, also The average particle diameter D2 measured by the FSSS method, called "aluminate phosphor (I)"), is 13 μm or more, or the volume measured by laser diffraction scattering particle size distribution measurement. The average particle diameter Dm2 is 20 μm or more, and the particle diameter is large, and the luminescence intensity is high. The aluminate phosphor (I) is preferably produced by the above-described method for producing an aluminate phosphor. The average particle diameter D2 of the aluminate phosphor (I) measured by the FSSS method is preferably 14 μm or more, more preferably 15 μm or more. The average particle diameter D2 is, for example, 50 μm or less. The aluminate phosphor (I) has a higher average luminescence intensity than the average particle diameter D2. The volume average particle diameter (Dm2) of the aluminate phosphor (I) measured by laser diffraction scattering particle size distribution measurement is preferably 20.5 μm or more, more preferably 21 μm or more, and further preferably It is 22 μm or more. The volume average particle diameter Dm2 is 100 μm or less, for example, less than 80 μm. The larger the volume average particle diameter Dm2 of the aluminate phosphor (I) has a higher luminous intensity. The laser diffraction scattering type particle size distribution measuring method is a method of measuring the particle size by using the scattered light of the laser light irradiated to the particles without distinguishing the primary particles from the secondary particles. The aluminate phosphor (I) preferably has a degree of dispersion Dm2/D2 defined by a ratio of the volume average particle diameter Dm2 to the average particle diameter D2 of 1.0 or more and less than 1.6. The degree of dispersion Dm2/D2 indicates the particle size obtained by measuring the primary particles without distinguishing between the primary particles and the secondary particles. The larger the value of the dispersion Dm2/D2, the inclusion in the aluminate phosphor (I) The more the amount of secondary particles. The closer the dispersion Dm2/D2 is to the value of 1, the smaller the amount containing the secondary particles. Regarding the degree of dispersion Dm2/D2, when the aluminate phosphor (I) is used in a light-emitting device, it can be used as a dispersibility to indicate a fluorescent member described below or include a fluorescent member constituting the following. One of the indexes of the dispersibility of the composition for a fluorescent member of a resin. The higher the value of the dispersion degree Dm2/D2, the higher the apparent density of the powder of the aluminate phosphor (I) tends to be, and the case where the aluminate phosphor (I) is used for the light-emitting device At the time, there is a tendency that the packing density of the fluorescent member described below becomes higher. When the degree of dispersion Dm2/D2 of the aluminate phosphor (I) is less than 2.0, there is a tendency that the smaller the value of the dispersity Dm2/D2 is, the smaller the luminescence intensity is. If the degree of dispersion Dm2/D2 of the aluminate phosphor (I) is 1.0 or more and less than 1.6, on the contrary, the luminescence of the aluminate phosphor (I) having the dispersion Dm2/D2 in this range is used. The luminous flux of the device becomes high. This is because the dispersibility of the aluminate phosphor (I) having the degree of dispersion Dm2/D2 within the above range is good in the fluorescent member of the light-emitting device, and it is presumed that the efficiency of extracting light from the light-emitting device is improved. The degree of dispersion Dm2/D2 of the aluminate phosphor (I) is more preferably 1.0 or more and 1.5 or less. The aluminate phosphor (I) having a degree of dispersion Dm2/D2 of 1.0 or more and less than 1.6 can be, for example, by a dispersion treatment step for the first calcined product and/or a post treatment of the second calcined product. In the step, the time of the wet dispersion was adjusted to obtain an aluminate phosphor (I) having a degree of dispersion Dm2/D2 of 1.0 or more and less than 1.6. In order to obtain an aluminate phosphor (I) having a preferred degree of dispersion Dm2/D2, the time of the wet dispersion differs depending on the solvent or solid dispersion medium used for the wet dispersion. For example, when deionized water is used as a solvent and an alumina ball is used as a solid dispersion medium, in order to obtain an aluminate phosphor (I) having a degree of dispersion Dm2/D2 of 1.0 or more and less than 1.6, wet The time for dispersion is preferably 30 minutes or longer, more preferably 60 minutes or longer, further preferably 90 minutes or longer, and still more preferably 120 minutes or longer. Further, the time for wet dispersion is preferably 420 minutes or less in consideration of the efficiency of production. The aluminate phosphor (I) is preferably a 90% by volume particle diameter D90 accumulated from a small diameter side in a particle size distribution obtained by a laser diffraction scattering particle size distribution measurement with respect to a 10% volume particle diameter. D10 has a particle diameter ratio of D90/D10 of 3.0 or less. The particle diameter ratio D90/D10 of 90% by volume particle diameter D90 to 10% by volume particle diameter D10 also becomes one of the indexes indicating the degree of dispersion of the particle size distribution based on the volume basis. When the particle diameter ratio D90/D10 of the aluminate phosphor (I) is 3.0 or less, it means that the size of each aluminate phosphor (I) particle is small and the size is relatively uniform. When the particle diameter ratio D90/D10 is 3.0 or less, the size of each aluminate phosphor (I) particle is small and relatively uniform, and the aluminate phosphor (I) is in the fluorescent member. The dispersibility becomes good, and the luminous flux extracted from the self-illuminating device can be improved. The aluminate phosphor of the third embodiment of the present invention has an average equivalent circle diameter Dc of 13 μm or more and has a composition represented by the above formula (I). Since the aluminate phosphor (I) has an average equivalent circle diameter Dc of 13 μm or more, the aluminate phosphor has a large particle diameter and a high luminous intensity. The aluminate phosphor (I) is preferably produced by the above-described method for producing an aluminate phosphor. The average equivalent circle diameter Dc of the aluminate phosphor (I) is preferably 13.5 μm or more, and more preferably 14 μm or more. The average circular equivalent diameter Dc of the aluminate phosphor (I) may be 30 μm or less. In the present specification, the equivalent circle diameter means a value measured as follows. An SEM image of an aluminate phosphor obtained by using a scanning electron microscope (SEM) was subjected to image analysis using an image analysis software (for example, WinROOF 2013, manufactured by Mitani Co., Ltd.), except for pelletization. For the phosphor particles having a diameter of 1 μm or less, 20 or more aluminate phosphor particles having a shape other than each of the phosphor particles can be identified for binarization on the SEM image. The particle size of the range which can be confirmed on the SEM image means the longest diameter of the particle. Regarding the 20 or more samples subjected to the binarization treatment, the shape of the binarized particle was assumed to be a circle, and the diameter of a perfect circle equal to the area of the circle was taken as a circle-equivalent diameter. The average value Av and the standard deviation σ of the particle diameter distribution of the circle-equivalent diameter of the measured 20 or more samples are not satisfied (the average value Av-standard deviation σ) or more and (the average value Av + the standard deviation σ) The circle-equivalent diameter of the numerical value is excluded, and the arithmetic mean value of the circle-equivalent diameter of the remaining sample is taken as the average circle-equivalent diameter Dc. In formula (I), X¹ It is preferred to contain Ba. By the composition of the aluminate phosphor (I), the X in the formula (I)¹ Contains Ba to increase the luminous intensity. The variable p in the formula (I) is a total molar ratio selected from at least one element selected from the group consisting of Ba, Sr and Ca. When the variable p does not satisfy 0.5 ≦p ≦ 1.0 in the formula (I), the crystal structure of the aluminate phosphor (I) may become unstable, and the luminescence intensity may be lowered. The variable p is preferably 0.60 or more, more preferably 0.80 or more. Further, the variable p can be 0.99 or less. When the variable q in the formula (I) is a molar ratio of Mg, when the variable q exceeds 1.0, the molar ratio of Mg becomes high, and the amount of Mn or Eu which becomes activating element relatively decreases, and the relative luminous intensity decreases. The tendency. Mg may not be contained in the aluminate phosphor (I). The variable q in the formula (I) preferably satisfies 0 < q ≦ 0.7, more preferably satisfies 0 < q ≦ 0.6. The lower limit of the variable q in the formula (I) is more preferably 0.05, still more preferably 0.1. In the composition of the aluminate phosphor (I), the variable q in the formula (I) is a number satisfying 0≦q≦1.0, and there is a tendency to be excited by light of the near ultraviolet to blue region. The luminescence spectrum has an emission peak wavelength in the range of 510 nm or more and 525 nm or less, and the reflectance is relatively low, and the luminescence intensity is high. The variable r in the formula (I) is the molar ratio of Mn. Mn is an activating element of the aluminate phosphor (I). Further, the aluminate phosphor (I) preferably contains at least one of Mn and Eu as an activating element, and more preferably contains Mn. The aluminate phosphor (I) may contain a rare earth element such as Eu or Ce in addition to Mn. In particular, the aluminate phosphor (I) contains Mn and Eu as an activating element, and it is expected that Eu absorbs light and excites electrons, and the excitation energy is transmitted from Eu to Mn, thereby contributing to luminescence of Mn. Therefore, the luminescence intensity of the aluminate phosphor (I) can be increased by excitation of light in the near ultraviolet to blue region. The variable r in the formula (I) is a molar ratio of Mn. When the variable r exceeds 0.7, the activation amount of Mn becomes excessive, and the aluminate phosphor (I) produces concentration extinction, and the luminescence intensity becomes low. tendency. In the formula (I), the variable r preferably satisfies the number of 0.2≦r≦0.7, more preferably 0.4≦r≦0.6. In the formula (I), the variable r is more preferably 0.45 or more, and more preferably 0.55 or less. The variable t in the formula (I) is the molar ratio of Eu. Eu is an activating element of the aluminate phosphor (I). When the variable t exceeds 0.5, the aluminate phosphor (I) tends to have a lower luminous intensity. In the formula (I), the variable t is preferably such that it satisfies 0.1≦t≦0.5, more preferably satisfies 0.2≦t≦0.4. The total value of the variable p and the variable t in the formula (I) (hereinafter, also referred to as "variable p + t") is the molar ratio of the alkaline earth metal element to the total of Eu, and if the variable p + t is less than 0.5 or exceeds 1.2, the aluminum The acid crystal phosphor (I) tends to be unstable in crystal structure, and has a low luminous intensity. The variable p+t is preferably 0.55 or more, more preferably 0.60 or more. Further, the variable p + t is preferably 1.10 or less, more preferably 1.05 or less. The total of the variable r and the variable t in the formula (I) (hereinafter, also referred to as "variable r + t") is the molar ratio of the active element, that is, the total of Mn and Eu. If the variable r + t exceeds 0.7, the aluminate fluorescence For example, when the body (I) is excited by light in the near ultraviolet to blue region, the reflectance becomes high, and the luminescence intensity tends to be low. In the formula (I), when the variable r+t is less than 0.1, the amount of activation is small, and when the aluminate phosphor (I) is excited by light in the near ultraviolet to blue region, the light absorption is higher. There are few cases where it is difficult to increase the luminous intensity. The sum of the variable q and the variable r in the formula (I) (hereinafter, also referred to as "variable q + r") is a number satisfying 0.2 ≦ q + r ≦ 1.0. If the variable q+r is less than 0.2 or exceeds 1, there is a case where sufficient relative luminescence intensity cannot be obtained. The variable q + r is preferably 0.3 or more, more preferably 0.4 or more, and more preferably 0.99 or less, more preferably 0.98 or less. The variable s in the formula (I) is the molar ratio of Al. When the variable s is less than 8.5 or exceeds 13, the crystal structure becomes unstable, and the aluminate phosphor (I) is subjected to near ultraviolet to blue. When the light in the color region is excited, there is a tendency that the luminous intensity is lowered. In the formula (I), the variable s preferably satisfies the number of 9.0 ≦s ≦ 13.0. In the formula (I), the variable s is more preferably 12.0 or less, further preferably 11.0 or less. The aluminate phosphor (I) having an average particle diameter D2 of 13 μm or more or a volume average particle diameter Dm2 of 20 μm or more is preferably produced by the production method of the first embodiment of the present invention. In the case where the aluminate phosphor (I) is used as the second flux in the production method of the first embodiment, a compound containing at least one metal element selected from the group consisting of K and Na is present, and the self-aluminate phosphor is present. (I) A case where a trace amount of at least one metal element selected from K and Na is detected. Even in this case, the composition of the aluminate phosphor (I) is such that it satisfies the formula (I). The aluminate phosphor (I) is activated by manganese (Mn) and emits green light by excitation of light in the near ultraviolet to blue region. Regarding the aluminate phosphor (I), specifically, the luminescence peak wavelength in the luminescence spectrum of light having a wavelength range of 380 nm or more and 485 nm or less is preferably 485 nm or more and 570 nm or less, more preferably It is in the range of 505 nm or more and 550 nm or less, and more preferably 515 nm or more and 523 nm or less. Light Emitting Device An example of a light emitting device using an aluminate phosphor (I) according to an embodiment of the present invention will be described with reference to the drawings. Fig. 1 is a schematic cross-sectional view showing a light-emitting device 100 according to a third embodiment of the present invention. The light-emitting device 100 includes a molded body 40, a light-emitting element 10, and a fluorescent member 50. The molded body 40 is formed by integrally molding the first lead 20 and the second lead 30 and the resin portion 42 containing a thermoplastic resin or a thermosetting resin. The molded body 40 is formed with a concave portion having a bottom surface and a side surface, and the light-emitting element 10 is placed on the bottom surface of the concave portion. The light-emitting element 10 has a pair of positive and negative electrodes, and the pair of positive and negative electrodes are electrically connected to the first lead 20 and the second lead 30 via wires 60, respectively. The light emitting element 10 is covered by the fluorescent member 50. The fluorescent member 50 includes, for example, a phosphor 70 and a resin that wavelength-convert light from the light-emitting element 10. Further, the phosphor 70 includes a first phosphor 71 and a second phosphor 72. The first lead 20 and the second lead 30 connected to the pair of positive and negative electrodes of the light-emitting element 10 face the outer side of the package constituting the light-emitting device 100, and one of the first lead 20 and the second lead 30 is partially exposed. The light-emitting device 100 can be made to emit light by receiving the supply of electric power from the outside via the first lead 20 and the second lead 30. The light-emitting element 10 is used as an excitation light source, and preferably has a light-emitting peak in a wavelength range of 380 nm or more and 485 nm or less. The range of the emission peak wavelength of the light-emitting element 10 is more preferably 390 nm or more and 480 nm or less, and further preferably 420 nm or more and 470 nm or less. The aluminate phosphor is efficiently excited by light from an excitation light source having an emission peak wavelength in a range of 380 nm or more and 485 nm or less, by aluminate fluorescence having a high luminous intensity. The body can constitute a light-emitting device 100 that emits mixed light from the light of the light-emitting element 10 and the fluorescent light from the phosphor 70. The half value width of the light emission spectrum of the light emitting element 10 can be, for example, 30 nm or less. The light-emitting element 10 is preferably, for example, a nitride-based semiconductor (In_X Al_Y Ga_1-XY Semiconductor light-emitting elements of N, 0≦X, 0≦Y, X+Y≦1). By using the semiconductor light-emitting element as a light source, it is possible to obtain a light-emitting device having high linearity with respect to the input output and stable mechanical shock with high efficiency. The light-emitting device 100 includes at least an aluminate phosphor (I) according to the second embodiment of the present invention and an excitation light source having an emission peak wavelength in a range of 380 nm or more and 485 nm or less. The first phosphor 71 mainly includes the aluminate phosphor (I) of the second embodiment of the present invention, and is contained, for example, in the fluorescent member 50 covering the light-emitting element 10. In the light-emitting device 100 in which the light-emitting element 10 is covered by the fluorescent member 50 including the first phosphor 71, a part of the light emitted from the light-emitting element 10 is partially absorbed by the aluminate phosphor and radiated in the form of green light. By using the light-emitting element 10 which emits light having an emission peak wavelength in the range of 380 nm or more and 485 nm or less, it is possible to provide a light-emitting device having high luminous efficiency. The content of the first phosphor 71 can be, for example, 10 parts by mass or more and 200 parts by mass or less, preferably 2 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the resin. The fluorescent member 50 preferably includes a second phosphor 72 having an emission peak wavelength different from that of the first phosphor 71. For example, the light-emitting device 100 can have a light-emitting element 10 that emits light having an emission peak wavelength in a range of 380 nm or more and 485 nm or less, and a first phosphor 71 and a second phosphor that are excited by the light. Body 72, to obtain a wider color reproduction range or higher color rendering. The second phosphor 72 may be any light that absorbs light from the light-emitting element 10 and converts the wavelength to a wavelength different from that of the first phosphor 71. For example, (Ca, Sr, Ba)₂ SiO₄ :Eu, (Ca, Sr, Ba)₈ MgSi₄ O₁₆ (F, Cl, Br)₂ :Eu, Si_6-z Al_z O_z N_8-z :Eu(0<z≦4.2), (Sr, Ba, Ca)Ga₂ S₄ :Eu, (Lu, Y, Gd, Lu)₃ (Ga, Al)₅ O₁₂ :Ce, (La, Y, Gd)₃ Si₆ N₁₁ :Ce, Ca₃ Sc₂ Si₃ O₁₂ :Ce, CaSc₄ O₄ :Ce, K₂ (Si, Ge, Ti)F₆ :Mn, (Ca, Sr, Ba)₂ Si₅ N₈ :Eu, CaAlSiN₃ :Eu, (Ca,Sr)AlSiN₃ :Eu, (Sr, Ca) LiAl₃ N₄ :Eu, (Ca, Sr)₂ Mg₂ Li₂ Si₂ N₆ :Eu, 3.5MgO・0.5MgF₂ ・GeO₂ :Mn, etc. In the case where the fluorescent member 50 further includes the second phosphor 72, the second phosphor 72 is preferably a red phosphor that emits red light, and preferably absorbs a wavelength range of 380 nm or more and 485 nm or less. The light emits light in the wavelength range of 610 nm or more and 780 nm or less. The light-emitting device includes a red phosphor, and can be more preferably applied to an illumination device, a liquid crystal display device, or the like. As a red phosphor, the composition formula is K.₂ SiF₆ :Mn, 3.5MgO・0.5MgF₂ ・GeO₂ :Mn Mn activated phosphor, CaSiAlN₃ :Eu, (Ca,Sr)AlSiN₃ :Eu, SrLiAl₃ N₄ : Eu-activated nitride phosphor represented by Eu. Among these, the red phosphor is preferably a Mn-activated fluoride phosphor having a half-value width of the emission spectrum of 20 nm or less from the viewpoint of improving color purity and expanding the color reproduction range. The first phosphor 71 and the second phosphor 72 (hereinafter also referred to simply as "the phosphor 70") together with the sealing material constitute a fluorescent member 50 covering the light-emitting element. Examples of the sealing material constituting the fluorescent member 50 include a thermosetting resin such as a polyfluorene resin or an epoxy resin. EXAMPLES Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not limited to the Examples. Production Example 1 Adding Mohr Ratio to Ba_1.0 Mg_0.45 Mn_0.5 Al₁₀ O_16.95 The first mixture is produced in the manner indicated by the composition. Use BaCO₃ Al₂ O₃ , MgO, MnCO₃ As raw materials, the respective raw materials were mixed in such a manner as to have a molar ratio shown in Table 1, to obtain a first mixture. Adding MgF as the first flux to the first mixture₂ And add NaF as the second flux. The first flux is MgF₂ And the second flux, NaF, has a molar number of 10 with respect to Al contained in the first mixture containing no flux, a molar amount of Mg contained in the first flux, and a Na contained in the second flux. The molar number was added to the first mixture in such a manner as to show the molar number shown in Table 1. Filling the first mixture containing the first flux and the second flux in the alumina crucible and capping it on the H₂ 3 vol%, N₂ The first calcination product 1 was obtained by performing a first heat treatment at 1500 ° C for 5 hours in a reducing gas atmosphere of 97% by volume. Production Examples 2 to 21 Each of the raw materials was mixed so as to have a molar ratio shown in Table 1, to obtain each first mixture. Use Eu₂ O₃ As a compound containing Eu. Also, using a selected from MgF₂ Or AlF₃ At least one of them is used as the first flux, and at least one selected from the group consisting of NaF and KF is used as the second flux. The first calcined materials 2 to 21 were obtained in the same manner as in Example 1 except that each of the first mixtures was used. Measurement of the average particle diameter (D1) In the first calcined materials 1 to 21, a Fisher Sub-Sieve Sizer Model 95 (manufactured by Fisher Scientific Co., Ltd.) was used, and the temperature was measured at a temperature of 25 ° C and a humidity of 70% RH.³ The sample was divided and sealed in a dedicated tubular container, and then a fixed-pressure dry air was passed, and the specific surface area was read based on the differential pressure, and the average particle diameter D1 obtained by the FSSS method was calculated. The results are shown in Table 1. [Table 1] As shown in Table 1, the average particle diameter D1 of the first calcined products 1 to 19 of Production Examples 1 to 19 measured by the FSSS method was 6 μm or more. On the other hand, the average particle diameter D1 of the first calcined products 20, 21 of Production Examples 20 and 21 was less than 6 μm. Examples 1 to 7 were added to the Ba as shown in Table 2 by adding a molar ratio._1.0 Mg_0.45 Mn_0.5 Al₁₀ O_16.95 The composition of the composition is represented by the first calcined material 1, BaCO₃ , MgO, MnCO₃ And Al₂ O₃ Each amount of the first calcined product 1 and each raw material are mixed to obtain each second mixture. The content of the first calcined product of each of the examples shown in Table 2 is represented by mass% with respect to 100% by mass of the second mixture. Further, using MgF as the first flux₂ And the NaF as the second flux, the number of moles of Mg contained in the first flux relative to the number of moles of Al contained in the second mixture containing no flux, and the second flux included in the first flux The molar amount of Na was added to the second mixture in such a manner as to show the molar number shown in Table 2. Filling the aluminum oxide crucible with a second mixture comprising the first flux and the second flux, and capping the cover₂ 3 vol%, N₂ In a reducing gas atmosphere of 97% by volume, a second heat treatment was performed at 1500 ° C for 5 hours to obtain a calcined product. The calcined product was dispersed in deionized water in a polyethylene container for 30 minutes using an alumina ball as a solid dispersion medium, after which the coarse particles were removed by a wet sieve using a mesh of 48 μm, and removed by precipitation fractionation. The particles on the small particle side of the obtained calcined product were 15% by mass to 20% by mass, and subjected to dehydration and drying, followed by treatment to obtain the aluminate phosphors of Examples 1 to 7, that is, the respective second calcined products. Comparative Example 1 In Comparative Example 1, the second mixture was not prepared, and the first calcined product 1 was used as the aluminate phosphor without performing the second heat treatment. Comparative Example 2 In Comparative Example 2, the aluminate phosphor of Comparative Example 2 was obtained in the same manner as in Example 1 except that the second mixture was not prepared and the first calcined product 1 was subjected to the second heat treatment. Second calcined product. The molar ratio of the second calcined product of Comparative Example 2 shown in Table 2 was the same as the molar ratio of the first calcined product of Production Example 1 in Table 1. Comparative Example 3 In Comparative Example 3, the second mixture was not prepared, and the second calcination was not carried out, and the first calcined product 2 was used as the aluminate phosphor. Example 8 Example 8 uses the first calcined product 2, and further uses BaCO.₃ , MgO, MnCO₃ Al₂ O₃ To become Ba shown in Table 2._1.0 Mg_0.45 Mn_0.5 Al₁₀ O_16.95 The first calcined product 2 and each raw material are mixed in a manner of adding a molar ratio to obtain a second mixture. The content of the first calcined product of each of the examples shown in Table 2 is represented by mass% with respect to 100% by mass of the second mixture. An aluminate phosphor of Example 8, that is, a second calcined product, was obtained in the same manner as in Example 2 except that the second mixture was used. Comparative Example 4 Comparative Example 4 used the first calcined product 20, and further used BaCO.₃ , MgO, MnCO₃ Al₂ O₃ To become Ba shown in Table 2._1.0 Mg_0.45 Mn_0.5 Al₁₀ O_16.95 The first calcined product 20 is mixed with each raw material in a manner of adding a molar ratio to obtain a second mixture. An aluminate phosphor of Comparative Example 4, that is, a second calcined product, was obtained in the same manner as in Example 2 except that each of the second mixtures was used. Comparative Example 5 Comparative Example 5 used the first calcined product 21, and further used BaCO.₃ , MgO, MnCO₃ Al₂ O₃ To become Ba shown in Table 2._1.0 Mg_0.45 Mn_0.5 Al₁₀ O_16.95 The first calcined product 21 is mixed with each raw material in a manner of adding a molar ratio to obtain a second mixture. The content of the first calcined product of each of the examples shown in Table 2 is represented by mass% with respect to 100% by mass of the second mixture. Aluminate phosphor of Comparative Example 5, that is, a second calcined product, was obtained in the same manner as in Example 2 except that each of the second mixtures was used. Comparative Example 6 In Comparative Example 6, the second mixture was not prepared, and the second calcination was not carried out, and the first calcined product 3 was used as the aluminate phosphor. Example 9 Example 9 uses the first calcined product 3, and further uses BaCO.₃ , MgO, MnCO₃ Al₂ O₃ To become Ba shown in Table 2._1.0 Mg_0.45 Mn_0.5 Al₁₀ O_16.95 The first calcined product 3 and each raw material are mixed in a manner of adding a molar ratio to obtain a second mixture. The content of the first calcined product of each of the examples shown in Table 2 is represented by mass% with respect to 100% by mass of the second mixture. An aluminate phosphor of Example 9, that is, a second calcined product, was obtained in the same manner as in Example 2 except that the second mixture was used. Comparative Example 7 In Comparative Example 7, the second mixture was not prepared, and the second calcination was not carried out, and the first calcined product 4 was used as the aluminate phosphor. Examples 10, 11, and 12 Examples 10, 11, and 12 used the first calcined product 4, and further used BaCO.₃ MnCO₃ Al₂ O₃ To become Ba shown in Table 2._1.0 Mn_0.5 Al₁₀ O_16.5 The first calcined product 4 and each raw material are mixed in a manner of adding a molar ratio to obtain each second mixture. The content of the first calcined product of each of the examples shown in Table 2 is represented by mass% with respect to 100% by mass of the second mixture. Further using AlF as the first flux for the second mixture₃ And NaF as the second flux, relative to the first flux-free AlF₃ And the second flux of the second flux, that is, the second mixture of NaF, the number of moles of Al of 10, the number of moles of Al contained in the first flux, and the number of moles of Na contained in the second flux are as shown in Table 2. An aluminate phosphor of Examples 10, 11 and 12, that is, a second calcined product, was obtained in the same manner as in Example 1 except that the molar number was added. Comparative Example 8 Comparative Example 8 was obtained in the same manner as in Comparative Example 2 except that the second mixture was not prepared, and the first calcined product 4 was subjected to the second heat treatment, and the aluminate phosphor of Comparative Example 8 was obtained in the same manner as in Comparative Example 2. Calcined product. The addition molar ratio of the second calcined product of Comparative Example 8 shown in Table 2 was the same as that of the first calcined product of Production Example 4. Comparative Example 9 In Comparative Example 9, the second mixture was not prepared, and the second calcination was not carried out, and the first calcined product 5 was used as the aluminate phosphor. Example 13 Example 13 uses the first calcined product 5, and further uses BaCO.₃ , Eu₂ O₃ , MgO, MnCO₃ Al₂ O₃ To become Ba shown in Table 2._0.9 Eu_0.1 Mg_0.5 Mn_0.5 Al₁₀ O₁₇ The first calcined product 5 and each raw material are mixed in a manner of adding a molar ratio to obtain a second mixture. The content of the first calcined product of each of the examples shown in Table 2 is represented by mass% with respect to 100% by mass of the second mixture. An aluminate phosphor of Example 13, i.e., a second calcined product, was obtained in the same manner as in Example 2 except that the second mixture was used. Example 2A Example 2A An aluminate phosphor of Example 2A, that is, a second calcined product, was obtained in the same manner as in Example 2. Example 14 In Example 14, the first calcined product 1 obtained in Production Example 1 was dispersed in deionized water in a polyethylene container, and the alumina ball was dispersed as a solid dispersion medium for 240 minutes, after which, The dispersion treatment is carried out in the order of wet sieving, classification, dehydration, drying, and dry sieving. Using the first calcined product 1 after the dispersion treatment, a calcined product was obtained in the same manner as in Example 2, and post-treated in the same manner as in Example 2 to obtain an aluminate phosphor of Example 14 as a second calcination. Things. In Example 14, the molar ratio of the added molar ratio of the first calcined product 1, the molar ratio of the flux, and the second calcined product were the same as in the second embodiment. Measurement of Particle Size and Dispersion For the aluminate phosphors of Examples 1 to 13, 2A, and 14 and Comparative Examples 1 to 9, in the same manner as the first calcined product of each of the production examples, by the FSSS method The average particle diameter D2 was measured, and the volume average particle diameter Dm2 (50% by volume particle diameter) was measured by a laser diffraction scattering type particle size distribution measurement method. The degree of dispersion Dm2/D2 of each of the examples and the comparative examples was calculated from the equivalent values. The results are shown in Table 2 or Table 4. Further, with respect to the aluminate phosphors of Example 2A and Example 14, the particle size distribution obtained by the laser diffraction scattering particle size distribution measurement was 10% by volume of the particle diameter D10 accumulated from the small diameter side. And 90% by volume particle diameter D90 was measured, and the particle diameter ratio D90/D10 was computed. The results are shown in Table 4. Measurement of luminescence spectrum The luminescence properties of the aluminate phosphors of Examples 1 to 13, 2A, and 14 and Comparative Examples 1 to 9 were measured. Each of the phosphors was irradiated with light having an excitation wavelength of 450 nm using a quantum efficiency measuring device (manufactured by Otsuka Electronics Co., Ltd., QE-2000), and the emission spectrum at room temperature (25 ° C ± 5 ° C) was measured. In FIG. 2, the aluminate phosphors of Example 2 and Comparative Example 1 show the luminescence spectra of the relative luminescence intensity (%) with respect to the wavelength. Light-Emitting Peak Wavelength (nm) The aluminate phosphors of Examples 1 to 13 and Comparative Examples 1 to 9 were measured for the maximum wavelength of the emission spectrum as the emission peak wavelength (nm). The results are shown in Table 2. Relative luminescence intensity (%) For the aluminate phosphors of Examples 1 to 8, 2A, and 14 and Comparative Examples 1 to 5, the luminescence intensity at the luminescence peak wavelength of Comparative Example 1 was measured based on the measured luminescence spectrum. Set to 100% and calculate the relative luminescence intensity. The results are shown in Table 2 or Table 4. With respect to the aluminate phosphors of Example 9 and Comparative Example 6, the luminescence intensity at the luminescence peak wavelength of Comparative Example 6 was set to 100% based on the measured luminescence spectrum, and the relative luminescence intensity was calculated. The results are shown in Table 2. With respect to the aluminate phosphors of Examples 10 to 12 and Comparative Examples 7 and 8, the luminescence intensity at the luminescence peak wavelength of Comparative Example 7 was set to 100% based on the measured luminescence spectrum, and the relative luminescence intensity was calculated. The results are shown in Table 2. With respect to the aluminate phosphors of Example 13 and Comparative Example 9, the luminescence intensity at the luminescence peak wavelength of Comparative Example 9 was set to 100% based on the measured luminescence spectrum, and the relative luminescence intensity was calculated. The results are shown in Table 2. SEM photograph The SEM photograph of the aluminate phosphor of Example 2 and the aluminate phosphor of Comparative Example 1 was obtained using a scanning electron microscope (SEM). 3 is a SEM photograph of the aluminate phosphor of Example 2, and FIG. 4 is a SEM photograph of the aluminate phosphor of Comparative Example 1. SEM image of the aluminate phosphor of Example 2 and the aluminate phosphor of Comparative Example 1 were obtained by a scanning electron microscope (SEM) at a magnification of 1000 times. Image analysis using image analysis software (WinROOF2013, manufactured by Mitani Corporation), in addition to phosphor particles having a particle size of 1 μm or less, it is possible to confirm the shape of each phosphor particle on the SEM image. More than 20 phosphor particles are binarized. On the SEM image, the particle size of the phosphor particles is the longest diameter of the particles. For the 20 or more samples subjected to binarization, the shape of the binarized particle is assumed to be a circle, and the diameter of a perfect circle equal to the area of the circle is taken as the circle-equivalent diameter. The average value Av and the standard deviation σ of the particle diameter distributions of the circle-equivalent diameters of the measured 20 or more samples are not satisfied (average Av-standard deviation σ) or more and (average Av + standard deviation σ) or less The circle-equivalent diameter of the numerical value is excluded, and the arithmetic mean of the circle-equivalent diameters of the remaining samples (15 samples in Example 2 and 16 samples in Comparative Example 1) is taken as the average equivalent circle diameter Dc. The results are shown in Table 3. The average value of the circle-equivalent diameter of the aluminate phosphor of Example 2 was 13.8 μm, and the standard deviation σ was 3.95. Further, the average value Av of the circle-equivalent diameter of the aluminate phosphor of Comparative Example 1 was 12.2 μm, and the standard deviation was 4.00. In the light-emitting device, each of the aluminate phosphors of the second embodiment and the fourteenth embodiment is used as the first phosphor, and the second phosphor and the polyoxynoxy resin are mixed and dispersed, and defoaming is performed to obtain a fluorescent member. Use the composition. The composition for the fluorescent member is prepared by mixing the color light emitted by the light-emitting device manufactured by CIE1931, and the ratio is x 0.26 and y is 0.22 (x=0.26, y=0.22). Adjustment. The composition for a fluorescent member was filled and cured on a blue light-emitting LED (light-emitting element) having an emission peak wavelength of 450 nm, and a light-emitting device 100 as shown in FIG. 1 was produced, respectively. Relative luminous flux The luminous flux of each of the light-emitting devices using the aluminate phosphors of Examples 2A and 14 was measured using a total luminous flux measuring apparatus using an integrating sphere. The luminous flux of the light-emitting device using the aluminate phosphor of Example 2 was set to 100%, and the luminous flux of the light-emitting device using the aluminate phosphor of Example 14 was calculated as the luminous flux. The results are shown in Table 4. [Table 2] As shown in Table 2, the aluminate fluorescent systems of Examples 1 to 13 were subjected to the second mixture obtained by using a second mixture having a first calcined product having an average particle diameter D1 of 6 μm or more. The second heat treatment causes the first calcined material to become seed crystals to promote growth, and the average volume diameter D2 obtained by the FSSS method is 13 μm or more, and the volume average obtained by the laser diffraction scattering particle size distribution measurement method is obtained. The aluminate phosphor having a particle diameter Dm2 of 20 μm or more and having a large average particle diameter. The aluminate phosphors of Examples 1 to 13 had higher relative luminescence intensity than Comparative Examples 1, 6, 7, and 9. As shown in Examples 2 to 6, when a second mixture containing 30% by mass or more and 80% by mass or less of the first calcined product having an average particle diameter D1 of 6 μm or more is used, the relative luminous intensity becomes large and exceeds 110. %. On the other hand, in the aluminate phosphors of Comparative Examples 2 and 8, since the second mixture was not prepared and the second heat treatment was performed without using the flux, the crystal growth was insufficient, and the average was obtained by the FSSS method. The particle diameter D2 is less than 13 μm, and the volume average particle diameter Dm2 obtained by the laser diffraction scattering particle size distribution measurement is less than 20 μm. The aluminate phosphor of Comparative Example 2 had a lower relative luminescence intensity than the aluminate phosphors of Examples 1 to 7. The aluminate phosphor of Comparative Example 8 also had a lower relative luminescence intensity than the aluminate phosphors of Examples 10, 11, and 12. The aluminate fluorescent system of Example 8 uses a first calcined material 2 having a particle diameter smaller than that of the first calcined product 1 used in Comparative Example 1, by heat treatment of a second mixture comprising a first flux and a second flux. The crystal growth was carried out, and the average particle diameter D2 and the volume average particle diameter Dm2 of the second calcined product were simultaneously larger than that of Comparative Example 1, and the relative luminous intensity was also increased. On the other hand, the relative luminescence intensity of the aluminate phosphor of Comparative Example 3 was lower than that of Example 8 or Comparative Example 1. The reason is considered to be that the average particle diameter D1 of the first calcined product is smaller than the average particle diameter D1 of the first calcined product used as the aluminate phosphor of Comparative Example 1. With respect to the aluminate phosphors of Comparative Examples 4 and 5, the relative luminescence intensity was lower than that of the aluminate phosphor of Example 8, and the relative luminescence was higher than that of the aluminate phosphor of Comparative Example 1. The intensity is low. The reason is considered to be that even if a second mixture containing the first calcined product having an average particle diameter D1 of less than 6 μm obtained by the FSSS method is used, the second mixture is subjected to the second heat treatment, and the crystal growth is insufficient. . [table 3] As shown in Table 3, the average equivalent diameter Dc of the aluminate phosphor of Example 2 was large and 14.3 μm. On the other hand, the average equivalent circle diameter Dc of the aluminate phosphor of Comparative Example 1 was less than 13 μm. The aluminate phosphor of Example 2 had higher relative luminescence intensity than the aluminate phosphor of Comparative Example 1. [Table 4] As shown in Table 4, the dispersity Dm2/D2 of the aluminate phosphor of Example 14 was 1.3. On the other hand, the dispersion degree Dm2/D2 of the aluminate phosphor of Example 2A was more than 1.6. The aluminate phosphor of Example 14 had a lower relative luminescence intensity than the aluminate phosphor of Example 2A, and conversely, the relative luminous flux became high. According to the results, the dispersibility Dm2/D2 of the aluminate phosphor of Example 14 is 1.3, the dispersibility in the fluorescent member of the light-emitting device 100 is good, and the filling ratio in the fluorescent member becomes high. Since the thickness of the deposited layer of the phosphor can be made thin, it is presumed that the luminous flux extracted from the light-emitting device becomes large. Further, as shown in Table 4, the aluminate phosphor of Example 14 had a particle diameter ratio of D90/D10 of 2.5, and the degree of dispersion in the volume-based particle size distribution was good, and the difference in size of each phosphor particle was Less, relatively consistent size. Therefore, it is presumed that the dispersibility in the fluorescent member of the light-emitting device 100 is further improved, and the luminous flux extracted from the light-emitting device becomes large. As shown in FIG. 2, it was confirmed that the luminescence spectrum of the aluminate phosphor of Example 2 had no change in the luminescence peak wavelength and the relative luminescence intensity as compared with the luminescence spectrum of the aluminate phosphor of Comparative Example 1. . As shown in the SEM photograph of Fig. 3, the aluminate phosphor of Example 2 is a plate-like crystal body in which at least one side of the hexagonal crystal structure is hexagonal. As shown in the SEM photograph of Fig. 4, the aluminate phosphor of Comparative Example 1 is also a plate-like crystal body in which at least one side of the crystal structure of the hexagonal crystal system is hexagonal. The average particle diameter of the aluminate phosphor of Example 2 shown in Fig. 3 is larger than the average particle diameter of the aluminate phosphor of Comparative Example 1 shown in Fig. 4, but it can be confirmed that there is no difference in particle shape. Great difference. 5 is a conceptual diagram of binarization treatment of any 20 or more phosphor particles in an SEM photograph of the aluminate phosphor of Example 2, and FIG. 6 is an aluminate phosphor of Comparative Example 1. A conceptual diagram of binarization processing of any 20 or more phosphor particles in the SEM photograph. A conceptual diagram of binarization of 20 or more phosphor particles in an SEM photograph of the aluminate phosphor of Example 2 of FIG. 5, and an aluminate phosphor of Comparative Example 1 of FIG. In the conceptual diagram of binarization of 20 or more phosphor particles in the SEM photograph, it is seen that the aluminate phosphor of Example 2 of Fig. 5 has a large number of phosphor particles having a large particle diameter. The average equivalent circle diameter Dc of the aluminate phosphor of Example 2 was 14.1 μm, and the average equivalent circle diameter Dc of the aluminate phosphor of Comparative Example 1 was less than 13 μm. [Industrial Applicability] The aluminate phosphor obtained by the production method of one embodiment of the present invention has high luminous intensity, and the illuminating device using the aluminate phosphor can be used for general lighting and vehicles. It is used in a wide range of fields such as lighting, displays, backlights for liquid crystals, signal amplifiers, and lighting switches.

10‧‧‧Lighting elements

20‧‧‧1st lead

30‧‧‧2nd lead

40‧‧‧Formed body

42‧‧‧Resin Department

50‧‧‧Fluorescent components

60‧‧‧ line

70‧‧‧Fluorite

71‧‧‧First phosphor

72‧‧‧Secondary phosphor

100‧‧‧Lighting device

Fig. 1 is a schematic cross-sectional view showing an example of a light-emitting device. Fig. 2 is a graph showing the relative luminescence intensity (%) of the aluminate phosphor of Example 2 and the aluminate phosphor of Comparative Example 1 with respect to the wavelength. Fig. 3 is a SEM (scanning electron microscope) photograph of the aluminate phosphor of Example 2. 4 is a SEM photograph of the aluminate phosphor of Comparative Example 1. Fig. 5 is a conceptual diagram showing a state in which 20 or more aluminate phosphor particles are binarized in the SEM photograph of the aluminate phosphor of Example 2. 6 is a conceptual diagram showing a state in which 20 or more aluminate phosphor particles are binarized in an SEM photograph of the aluminate phosphor of Comparative Example 1.

Claims (17)

A method for producing an aluminate phosphor, comprising the steps of: at least one of a compound containing at least one metal element selected from the group consisting of Ba, Sr, and Ca, a compound containing Mn, and a compound containing Eu The compound, the compound containing Al, and optionally the compound containing Mg are mixed to obtain a first mixture, and the first mixture obtained is subjected to a first heat treatment to obtain an average particle diameter D1 measured by the FSSS method. a first calcined product of 6 μm or more; and a compound containing at least one metal element selected from the group consisting of Ba, Sr, and Ca, a compound containing Mn, and at least one compound containing a compound of Eu, a compound containing Al The first calcined product having a content of 10% by mass or more and 90% by mass or less based on the total amount is mixed with a compound containing Mg as necessary to obtain a second mixture, and the second mixture obtained is subjected to a second Heat treatment to obtain a second calcined product. The method for producing an aluminate phosphor according to claim 1, wherein at least one of the first mixture and the second mixture further comprises a flux, and the flux is selected from the group consisting of K, Na, Ba, Sr, A compound of at least one metal element of the group consisting of Ca, Mg, Al, and Mn. A method of producing an aluminate phosphor according to claim 2, wherein the flux is a fluoride. The method for producing an aluminate phosphor according to claim 2 or 3, wherein the number of moles of Al contained in the first mixture containing no flux and/or the second mixture containing no flux is set to 10, and the number of moles of the metal element contained in the flux is in a range of 0.03 or more and 0.6 or less. The method for producing an aluminate phosphor according to any one of claims 2 to 4, wherein the flux comprises two fluxes of a first flux and a second flux, and the first flux is selected from the group consisting of Ba a compound of at least one metal element selected from the group consisting of Sr, Ca, Mg, Al, and Mn, and the second flux is a compound containing at least one metal element selected from the group consisting of K and Na. The method for producing an aluminate phosphor according to claim 5, wherein the number of moles of Al contained in the first mixture containing no flux and/or the second mixture containing no flux is set to 10, and the above The number of moles of the metal element contained in the first flux is in the range of 0.006 or more and 0.55 or less. The method for producing an aluminate phosphor according to claim 5, wherein when the metal element contained in the first flux is Mg or Al and the metal element contained in the second flux is K or Na, The molar ratio of the metal element contained in the first flux to the metal element contained in the second flux is in the range of 20:1 to 1:5. The method for producing an aluminate phosphor according to any one of claims 1 to 7, wherein the first calcined product and/or the second calcined product has a composition represented by the following formula (I): X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I) (In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, p, q, r, s, t satisfy 0.5≦p≦1.0, 0≦q≦1.0, 0≦r≦0.7, 8.5≦s≦13.0, 0≦t≦0.5, 0.5≦p+t≦1.2, 0.1≦r+t≦0.7 , 0.2≦q+r≦1.0). The method for producing an aluminate phosphor according to any one of claims 1 to 8, wherein in the step of obtaining the second calcined product, the content of the first calcined product in the second mixture is 25% by mass or more And 80% by mass or less. An aluminate phosphor characterized by an average particle diameter D2 measured by the FSSS method of 13 μm or more and/or a volume average particle measured by a laser diffraction scattering particle size distribution measurement method The diameter Dm2 is 20 μm or more and has a composition represented by the following formula (I): X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I) (Formula (I) Wherein X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s, t satisfy 0.5≦p≦1.0, 0≦q≦1.0, 0≦r≦0.7 8.5≦s≦13.0, 0≦t≦0.5, 0.5≦p+t≦1.2, 0.1≦r+t≦0.7, 0.2≦q+r≦1.0). The aluminate phosphor of claim 10, wherein the degree of dispersion Dm2/D2 defined by the ratio of the volume average particle diameter Dm2 to the average particle diameter D2 is 1.0 or more and less than 1.6. The aluminate phosphor of claim 11, wherein the dispersion Dm2/D2 is 1.0 or more and 1.5 or less. The aluminate phosphor according to any one of claims 10 to 12, wherein the particle size distribution obtained by the laser diffraction scattering particle size distribution measurement is 90% by volume of the particle diameter D90 accumulated from the small diameter side. The particle diameter ratio D90/D10 with respect to 10% by volume particle diameter D10 is 3.0 or less. An aluminate phosphor characterized by having an average equivalent circle diameter Dc of 13 μm or more and having a composition represented by the following formula (I): X ¹ _p Eu _t Mg _q Mn _r Al _s O _{p + t + q + r + 1.5s} (I) (In the formula (I), X ¹ is at least one element selected from the group consisting of Ba, Sr and Ca, and p, q, r, s, t satisfy 0.5≦ P≦1.0, 0≦q≦1.0, 0≦r≦0.7, 8.5≦s≦13.0, 0≦t≦0.5, 0.5≦p+t≦1.2, 0.1≦r+t≦0.7, 0.2≦q+r≦1.0). The aluminate phosphor of any one of claims 10 to 14, wherein in the above formula (I), X ¹ comprises Ba. The aluminate phosphor according to any one of claims 10 to 15, wherein in the above formula (I), q, r, s satisfy 0 < q ≦ 0.7, 0.2 ≦ r ≦ 0.7, 9.0 ≦ ≦ ≦ The number of 13.0. A light-emitting device comprising the aluminate phosphor according to any one of claims 10 to 16, and an excitation light source having an emission peak wavelength in a range of 380 nm or more and 485 nm or less.