WO2023062927A1 - 赤色蛍光体及びその製造方法 - Google Patents
赤色蛍光体及びその製造方法 Download PDFInfo
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- WO2023062927A1 WO2023062927A1 PCT/JP2022/030651 JP2022030651W WO2023062927A1 WO 2023062927 A1 WO2023062927 A1 WO 2023062927A1 JP 2022030651 W JP2022030651 W JP 2022030651W WO 2023062927 A1 WO2023062927 A1 WO 2023062927A1
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- WO
- WIPO (PCT)
- Prior art keywords
- red phosphor
- general formula
- perovskite compound
- activated double
- ammonium
- Prior art date
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- 239000000126 substance Substances 0.000 title abstract description 6
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 12
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/61—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing fluorine, chlorine, bromine, iodine or unspecified halogen elements
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
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- 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
- C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Definitions
- the present invention relates to a red phosphor that emits red light when excited by excitation light such as ultraviolet light and blue light, and a method for producing the same. More specifically, in a red phosphor containing a Mn (manganese)-activated double fluoride and a perovskite compound, by allowing the perovskite compound to exist on the surface or inside the Mn-activated double fluoride, optical properties and high-temperature/high-humidity The present invention relates to a red phosphor excellent in environmental durability and a method for producing the same.
- White LEDs Light Emitting Diodes
- White LEDs in commercially available lighting fixtures are constructed by combining blue LEDs that emit near-ultraviolet light to blue light and yellow phosphors that are excited by those lights.
- the white LED can emit pseudo-white light by mixing the light emitted by the blue LED and the light emitted by the yellow phosphor.
- the pseudo-white light emitted by the white LED has little or no light-emitting component in the red light region, the pseudo-white light has a better color rendering property than natural light (or sunlight, black body radiation).
- a red phosphor that emits red light when excited by ultraviolet light emitted by a near-ultraviolet LED or blue light emitted by a blue LED.
- a phosphor composition composed of Mn-activated double fluoride (K 2 SiF 6 :Mn 4+ (KSF:Mn)) which emits red light with a transition metal Mn 4+ ion as a luminescence center has recently been used.
- KSF:Mn Mn-activated double fluoride
- KSF:Mn Mn-activated double fluoride
- KSF:Mn is formed by the K 2 SiF 6 crystal serving as the framework of the phosphor, and Mn 4+ ions form a solid solution at the Si 4+ positions of the hexacoordinated-octahedral sites formed by SiF 6 2- ions. It forms a MnF 6 2- octahedral site and acts as a luminescent center.
- this red phosphor made of KSF:Mn has a practical problem that the particle surface darkens when it comes into contact with water, steam, etc. in a high-temperature, high-humidity environment.
- manganese dioxide is generated by reacting tetravalent manganese ions and water that constitute the red phosphor, and this manganese dioxide absorbs excitation light and emits fluorescence. is suppressed, resulting in deterioration of optical characteristics and deterioration of optical characteristics with aging (decrease in durability).
- the present invention has been made in view of the above problems, and its object is to provide a red phosphor that has excellent optical properties and durability in a high-temperature, high-humidity environment, and a method for producing the same.
- the red phosphor according to the present invention is a Mn-activated double fluoride represented by the following general formula (1) and a perovskite compound represented by the following general formula (2). characterized by comprising
- L2MF6 Mn4 + (1) (wherein L represents at least one alkali metal element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and M represents silicon, germanium, tin, titanium, zirconium and hafnium) represents at least one selected tetravalent element.)
- ABX 3 (2) (Wherein A is from the group consisting of lithium, sodium, potassium, rubidium, cesium, silver, indium, gold, thallium, ammonium, primary ammonium, secondary ammonium, tertiary ammonium and quaternary ammonium The primary ammonium, the secondary ammonium, the tertiary ammonium and the quaternary ammonium are an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms.
- B is magnesium, calcium, barium, zinc, zirconium, strontium, manganese, iron, cobalt, nickel, copper, titanium, vanadium, chromium, mercury, cadmium, tin , lead, strontium, europium, yttrium, beryllium, indium, aluminum, ruthenium, osmium and antimony, wherein X is selected from the group consisting of fluorine, chlorine, bromine, iodine and sulfur represents at least one selected element.
- the perovskite compound represented by the general formula (2) adheres to at least part of the surface of the Mn-activated double fluoride represented by the general formula (1), and/or It may exist inside.
- the Mn-activated double fluoride represented by the general formula (1) adheres to at least part of the surface of the perovskite compound represented by the general formula (2), and/ Or it may exist inside.
- the perovskite compound represented by the general formula (2) preferably has an average particle size D50 of 0.002 ⁇ m to 20 ⁇ m as measured by a laser diffraction scattering method.
- the content ratio of the Mn-activated double fluoride represented by the general formula (1) and the perovskite compound represented by the general formula (2) is 10:90 on a mass basis. It is preferably in the range of ⁇ 99.999:0.001.
- the method for producing a red phosphor of the present invention comprises a Mn-activated double fluoride represented by the following general formula (1) and a perovskite represented by the following general formula (2): and the compound in the presence of a solvent.
- L2MF6 Mn4 + (1) (wherein L represents at least one alkali metal element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and M represents silicon, germanium, tin, titanium, zirconium and hafnium) represents at least one selected tetravalent element.)
- ABX 3 (2) (Wherein A is from the group consisting of lithium, sodium, potassium, rubidium, cesium, silver, indium, gold, thallium, ammonium, primary ammonium, secondary ammonium, tertiary ammonium and quaternary ammonium The primary ammonium, the secondary ammonium, the tertiary ammonium and the quaternary ammonium are an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms.
- B is magnesium, calcium, barium, zinc, zirconium, strontium, manganese, iron, cobalt, nickel, copper, titanium, vanadium, chromium, mercury, cadmium, tin , lead, strontium, europium, yttrium, beryllium, indium, aluminum, ruthenium, osmium and antimony, wherein X is selected from the group consisting of fluorine, chlorine, bromine, iodine and sulfur represents at least one selected element.
- the perovskite compound represented by the general formula (2) preferably has an average particle diameter D50 of 0.002 ⁇ m to 20 ⁇ m as measured by a laser diffraction scattering method.
- Mn activation in the red phosphor obtained by contacting the Mn-activated double fluoride represented by the general formula (1) with the perovskite compound represented by the general formula (2) The content ratio of the double fluoride and the perovskite compound is preferably in the range of 10:90 to 99.999:0.001 on a mass basis.
- the solvent is preferably water, an organic solvent, a mixed solvent thereof, or an acidic solvent thereof.
- the mixing ratio of the solvent, the Mn-activated double fluoride represented by the general formula (1), and the perovskite compound represented by the general formula (2) is 2 on a mass basis. :1 to 100:1.
- the acidic solvent is an acidic solvent containing hydrogen fluoride
- the concentration of the hydrogen fluoride in the acidic solvent containing hydrogen fluoride is 1 with respect to the total mass of the acidic solvent. It is preferably in the range of mass % to 70 mass %.
- the present invention has the following effects by means of the above-described means. That is, according to the red phosphor of the present invention, the presence of the Mn-activated double fluoride and the perovskite compound reduces or prevents the reaction of Mn 4+ and water to produce colored manganese dioxide. . As a result, it is possible to prevent the absorption of excitation light and fluorescence by manganese dioxide, as well as the deterioration of fluorescence emission due to the absorption of excitation light. It is possible to provide a red phosphor with reduced carbon content and excellent durability.
- a red phosphor composed of an Mn-activated double fluoride and a perovskite compound is produced by bringing a treatment liquid containing a perovskite compound into contact with the Mn-activated double fluoride.
- 1 is a graph showing an X-ray diffraction pattern of KMgF 3 according to Example 1 of the present invention
- 1 is a SEM photograph of KMgF 3 according to Example 1 of the present invention
- 1 is a graph showing an X-ray diffraction pattern of a red phosphor according to Example 1 of the present invention
- 1 is a SEM photograph of a red phosphor according to Example 1 of the present invention
- red phosphor A red phosphor according to this embodiment will be described below.
- the red phosphor according to the present embodiment includes a Mn-activated double fluoride represented by the following general formula (1) (hereinafter sometimes referred to as "Mn-activated double fluoride”) and the following general formula ( 2) (hereinafter sometimes referred to as "perovskite compound").
- L2MF6 Mn4 + (1) (wherein L represents at least one alkali metal element selected from the group consisting of lithium, sodium, potassium, rubidium and cesium, and M represents silicon, germanium, tin, titanium, zirconium and hafnium) represents at least one selected tetravalent element.)
- ABX 3 (2) (Wherein A is from the group consisting of lithium, sodium, potassium, rubidium, cesium, silver, indium, gold, thallium, ammonium, primary ammonium, secondary ammonium, tertiary ammonium and quaternary ammonium The primary ammonium, the secondary ammonium, the tertiary ammonium and the quaternary ammonium are an alkyl group having 1 to 10 carbon atoms or an alkyl group having 1 to 10 carbon atoms.
- B is magnesium, calcium, barium, zinc, zirconium, strontium, manganese, iron, cobalt, nickel, copper, titanium, vanadium, chromium, mercury, cadmium, tin , lead, strontium, europium, yttrium, beryllium, indium, aluminum, ruthenium, osmium and antimony, wherein X is selected from the group consisting of fluorine, chlorine, bromine, iodine and sulfur represents at least one selected element.
- the red phosphor of the present embodiment may be a single red phosphor or a mixture of two or more red phosphors.
- L 2 MF 6 :Mn 4+ representing the Mn-activated double fluoride
- L 2 MF 6 represents the composition of the host crystal of the red phosphor.
- Mn 4+ represents an activating ion serving as a luminescence center.
- activation means addition of Mn 4+ as an activator to L 2 MF 6 as a host crystal in order to express fluorescence.
- Activated forms include forms in which Mn 4+ is partially substituted with any atom that makes up L 2 MF 6 .
- Mn 4+ preferably replaces M in the host crystal.
- Mn-activated double fluoride represented by the general formula L 2 MF 6 :Mn 4+ include Li 2 SiF 6 :Mn 4+ , Na 2 SiF 6 :Mn 4+ and K 2 SiF 6 :Mn 4+ , Rb2SiF6 : Mn4 + , Cs2SiF6 : Mn4 + , Li2GeF6 : Mn4 + , Na2GeF6 :Mn4 + , K2GeF6 : Mn4 + , Rb2GeF6:Mn4 + , Cs2GeF6 : Mn4 + , Li2SnF6 :Mn4 + , Na2SnF6 : Mn4 + , K2SnF6 : Mn4 + , Rb2SnF6 : Mn4 + , Cs2SnF6: Mn4+ , Li2 TiF6 : Mn4 + , Na2
- K 2 SiF 6 :Mn 4+ , K 2 TiF 6 :Mn 4+ , K 2 GeF 6 :Mn 4+ , Na 2 SiF 6 :Mn 4+ , Na 2 TiF 6 :Mn 4+ and Na 2 GeF 6 :Mn 4+ are preferred, and K 2 SiF 6 :Mn 4+ and K 2 TiF 6 :Mn 4+ are more preferred.
- the Mn-activated double fluoride can be selected according to the optical properties required for various uses. Therefore, it is not particularly limited to the Mn-activated double fluorides exemplified.
- the term "optical properties" as used herein means the absorptance, internal quantum efficiency, etc. of a red phosphor or the like.
- the Mn-activated double fluoride is solid and preferably particulate.
- its average particle size should be such that it does not cause too much scattering rather than absorption and conversion of the excitation light, and is mixed with a resin for mounting in the LED device. It is not particularly limited as long as it does not cause any inconvenience.
- the molar ratio of Mn is preferably in the range of 0.005 to 0.15 with respect to the total number of moles of M and Mn in the red phosphor (or Mn-activated double fluoride), and 0.01 to A range of 0.12 is more preferred, and a range of 0.02 to 0.1 is particularly preferred.
- the molar ratio By setting the molar ratio to 0.005 or more, the good emission intensity of the red phosphor can be maintained.
- the molar ratio to 0.15 or less it is possible to suppress excessive deterioration in the durability of the red phosphor in a high-temperature, high-humidity environment.
- the term "durability" means the degree to which the initial optical properties of the red phosphor are maintained when the red phosphor is stored for a certain period of time in a high-temperature, high-humidity environment. .
- the meaning of the optical properties is as described above.
- perovskite compounds represented by the general formula ABX 3 include LiBaF 3 , LiMgF 3 , LiMnF 3 , LiFeF 3 , LiCoF 3 , LiNiF 3 , LiCuF 3 , NaCaF 3 , NaMgF 3 , NaZnF 3 , NaZrF3 , NaMnF3 , NaFeF3 , NaCoF3 , NaNiF3, NaCuF3, NaTiF3 , NaSnF3 , NaBeF3, KCaF3 , KBaF3 , KMgF3 , KZnF3, KZrF3 , KMnF3 , KFeF3 , KCoF3 , KNiF3 , KCuF3 , KTiF3 , KHgF3 , KCdF3 , KSnF3 , KPbF3, KSrF3 , RbCaF3 ,
- NaCaF 3 , KCaF 3 , NaFeF 3 , KFeF 3 , NaNiF 3 , KNiF 3 , NaZnF 3 , NaZrF 3 , KZnF 3 and KZrF 3 are preferred from the standpoint of availability and ease of synthesis.
- NaMgF 3 and KMgF 3 are preferred, and NaMgF 3 and KMgF 3 are more preferred.
- a in the general formula (2) is a primary ammonium, secondary ammonium, tertiary ammonium or quaternary ammonium
- A has 1 to 10 carbon atoms, preferably 1 to 6, more preferably 1 to 5 alkyl groups.
- A has an alkyl group with heteroatoms in the range of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms.
- heteroatom means atoms such as oxygen, nitrogen, and sulfur.
- the range is meant to include all integer carbon numbers included in the range. Therefore, for example, an alkyl group having 1 to 3 carbon atoms means all alkyl groups having 1, 2 and 3 carbon atoms.
- B in the perovskite compound is any one of magnesium, calcium, zinc, iron, nickel and titanium. combination is preferred. Furthermore, when M in the Mn-activated double fluoride is silicon, B in the perovskite compound is more preferably magnesium.
- the perovskite compound can be selected according to the durability required for various uses. Therefore, it is not particularly limited to the exemplified perovskite compounds.
- the content ratio of the Mn-activated double fluoride and the perovskite compound is preferably in the range of 10:90 to 99.999:0.001 on the mass basis, and in the range of 10:90 to 99.99:0.01 15:85 to 99.97:0.03 is particularly preferred.
- the content ratio of the Mn-activated double fluoride to the perovskite compound is preferably in the range of 10:90 to 99.999:0.001 on the mass basis, and in the range of 10:90 to 99.99:0.01 15:85 to 99.97:0.03 is particularly preferred.
- the (initial) absorption rate of the red phosphor is preferably in the range of 30% to 100%, more preferably in the range of 40% to 100%, and even more preferably in the range of 50% to 100%.
- the absorptivity is preferably in the range of 30% to 100%, more preferably in the range of 40% to 100%, and even more preferably in the range of 50% to 100%.
- the numerical range of the absorptance described above applies not only to the initial absorptance of the red phosphor, but also to the absorptance after the red phosphor has been stored for a certain period of time in a high-temperature, high-humidity environment.
- the definition of absorption rate is as described above.
- the (initial) internal quantum efficiency of the red phosphor is preferably in the range of 60% to 100%, more preferably in the range of 75% to 100%, and even more preferably in the range of 80% to 100%.
- the numerical range of the internal quantum efficiency described above applies not only to the initial internal quantum efficiency of the red phosphor, but also to the internal quantum efficiency after the red phosphor has been stored for a certain period of time in a high-temperature, high-humidity environment.
- the definition of internal quantum efficiency is as described above.
- the Mn-activated double fluoride and perovskite compound can exist in various forms.
- the perovskite compound can be present on at least part of the surface of the Mn-activated double fluoride. It is believed that Mn-activated double fluoride reacts with water to form tetravalent manganese ions, thereby producing colored manganese dioxide and causing the Mn-activated double fluoride to darken. It is presumed that the occurrence of this darkening is accelerated under high temperature and high humidity conditions, leading to deterioration of the optical properties of the red phosphor and deterioration of its durability.
- the perovskite compound by allowing the perovskite compound to exist on at least part of the surface of the Mn-activated double fluoride, it is possible to reduce or prevent the tetravalent manganese ion from contacting and reacting with water.
- the perovskite compound exists as a coating layer covering the entire surface of the Mn-activated double fluoride, it suppresses the intrusion of moisture and water vapor into the red phosphor, thereby improving durability in high-temperature and high-humidity environments. It is possible to improve the properties and optical properties.
- the perovskite compound exists as a coating layer on the entire surface of the Mn-activated double fluoride.
- having a perovskite compound covering the entire surface of the Mn-activated double fluoride may not be industrially suitable from the viewpoint of production cost and ease of production. According to the results of intensive studies by the present inventors, even when a perovskite compound is present on a part of the surface of the Mn-activated double fluoride, the durability is improved and the optical properties are improved in a high-temperature and high-humidity environment.
- the adsorption layer of water molecules on the surface of the Mn-activated double fluoride can be regarded as a reaction liquid / treatment liquid, and a part of the surface of the Mn-activated double fluoride It is thought that the perovskite compound present in the surface acts as its reservoir, and it is thought that the durability in high-temperature and high-humidity environments is improved without covering the entire surface of the Mn-activated double fluoride. .
- the perovskite compound may exist inside the Mn-activated double fluoride.
- the perovskite compound present inside induces scattering of the excitation light, increases the chance of contact with Mn 4+ ions, and contributes to improvement of optical properties, particularly absorptivity.
- the Mn-activated double fluoride may be present on at least part of the surface of the perovskite compound.
- the amount of Mn-activated double fluoride containing Mn 4+ which is the emitting ion of the red phosphor can be reduced. It can contribute to cost reduction of phosphor materials used in light-emitting devices such as LEDs, lighting fixtures, and image display devices.
- the Mn-activated double fluoride may exist inside the perovskite compound. This prevents the tetravalent manganese ions from coming into contact with water, steam, or the like, and further prevents the production of manganese dioxide. As a result, the durability of the red phosphor under high-temperature and high-humidity environments can be further improved.
- the red phosphor of the present embodiment is solid, and preferably particulate.
- its average particle size should be such that the ratio of scattering to excitation light rather than absorption and conversion does not become too large, and when it is mixed with a resin for mounting on an LED device, etc. is not particularly limited as long as it does not cause any inconvenience.
- the red phosphor of the present embodiment is suitable, for example, as a red phosphor for a white LED using blue light as a light source.
- the red phosphor of this embodiment can be suitably used for light-emitting devices such as lighting fixtures and image display devices.
- One aspect of the method for producing a red phosphor according to the present embodiment includes, for example, a method including at least a step of contacting an Mn-activated double fluoride and a perovskite compound in the presence of a solvent. According to this method, a red phosphor having a perovskite compound present on at least a portion of the surface of the Mn-activated double fluoride, or a red phosphor having a Mn-activated double fluoride present on at least a portion of the surface of the perovskite compound Phosphors can be produced.
- solvents include water, organic solvents, mixed solvents thereof, and acidic solvents thereof.
- solvents include water, organic solvents, mixed solvents thereof, and acidic solvents thereof.
- those that completely dissolve the Mn-activated double fluoride may significantly reduce the yield of the red phosphor. Therefore, from the viewpoint of improving productivity, it is preferable to select a solvent in which the Mn-activated double fluoride does not completely dissolve.
- organic solvents include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, acetone, methyl acetate, ethyl acetate, tetrahydrofuran, 1,2-dimethoxyethane and the like.
- methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol and acetone are preferred, and ethyl alcohol, isopropyl alcohol and acetone are particularly preferred, from the viewpoint of availability and convenience of working environment.
- acidic solvents that is, solvents containing proton-bearing acids
- acidic solvents include, for example, hydrogen fluoride, nitric acid, sulfuric acid, hydrochloric acid, and hydrosilicofluoric acid.
- Hydrogen fluoride, nitric acid, and hydrosilicofluoric acid are preferable, and hydrogen fluoride is particularly preferable, from the viewpoint of the manufacturing process and the properties of the red phosphor.
- the amount of the perovskite compound added is appropriately set so that the content ratio of the Mn-activated double fluoride and the perovskite compound in the red phosphor obtained by the production method of the present embodiment is within the following range. is preferred. That is, the content ratio of the Mn-activated double fluoride and the perovskite compound is preferably in the range of 10:90 to 99.999:0.001 on a mass basis, and 10:90 to 99.99:0.01. A range is more preferred, and a range of 15:85 to 99.97:0.03 is particularly preferred.
- the optical properties of the red phosphor can be maintained satisfactorily.
- the optical properties and durability of the red phosphor under high-temperature and high-humidity environments can be further improved. .
- the mixing ratio of the solvent and the Mn-activated double fluoride and perovskite compound can be appropriately adjusted within a range that does not affect the subsequent stirring and filtration (the details of stirring and filtration will be described later).
- the mixing ratio of the two is preferably in the range of 2:1 to 100:1, more preferably in the range of 3:1 to 50:1, and more preferably in the range of 3:1 to 10 by mass. : 1 is particularly preferred.
- the mixing ratio is 2:1 or more, the dispersibility of the Mn-activated double fluoride and the perovskite compound in the solvent is improved, and the Mn-activated double fluoride and the perovskite compound exist non-uniformly. can be prevented.
- the concentration of hydrogen fluoride is 1 with respect to the total mass of the acidic solvent.
- the range is preferably from 5% by mass to 70% by mass, more preferably from 5% by mass to 60% by mass, and particularly preferably from 10% by mass to 50% by mass.
- the method of bringing the Mn-activated double fluoride and the perovskite compound into contact in the presence of a solvent is not particularly limited, and examples thereof include immersion (throwing in, addition) methods and spraying methods.
- immersion (throwing in, addition) methods and spraying methods for example, the Mn-activated double fluoride and the perovskite compound are charged (immersed) in the solvent in any order or simultaneously.
- a suspension in which the Mn-activated double fluoride and the perovskite compound are dispersed in the solvent is obtained.
- the number of additions is not particularly limited, and the Mn-activated double fluoride and the perovskite compound may be added into the solvent at once or may be added multiple times.
- a solvent containing a perovskite compound is sprayed onto the Mn-activated double fluoride.
- the spray amount of the solvent containing the perovskite compound is not particularly limited and can be set as appropriate.
- After spraying the solvent containing the perovskite compound onto the Mn-activated double fluoride it is preferable to distill off the solvent remaining on the surface of the Mn-activated double fluoride.
- the method of distillation is not particularly limited, and for example, a drying step, which will be described later, can be performed. From the viewpoint of industrial production of a red phosphor, a method of adding (immersing) the Mn-activated double fluoride and the perovskite compound in a solvent is preferable.
- the step of contacting the Mn-activated double fluoride and the perovskite compound is performed by the immersion method, after the contacting step, a stirring step of stirring the obtained suspension, a solid-liquid separation step of the suspension, and a solid-liquid separation. It is preferable to sequentially perform a step of washing the solids thus washed and a step of drying the washed solids.
- the stirring method in the stirring step is not particularly limited, and a known stirring device or the like can be used.
- the stirring time of the suspension is not particularly limited, and can be appropriately adjusted based on the efficiency of the production equipment.
- the stirring speed is also not particularly limited, and can be appropriately set as required.
- the solid-liquid separation step is a step of separating dispersed solid particles from the suspension after the stirring step.
- the method of solid-liquid separation is not particularly limited, and for example, a method of filtering the suspension, a method of allowing the suspension to stand still or centrifuging to precipitate dispersed solid particles, and then a method of decanting. etc.
- the standing time of the suspension, the number of rotations of centrifugation, and the time are not particularly limited, and may be sufficient so long as the solid particles can be sufficiently precipitated.
- the washing step is performed to wash the cake obtained by solid-liquid separation.
- water, an organic solvent, a mixed solvent thereof, or an acidic solvent thereof can be used as a cleaning agent.
- the washing time and the number of times of washing are not particularly limited, and can be appropriately set as necessary.
- the organic solvent used in the washing step is not particularly limited, and examples include methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol, acetone, methyl acetate, ethyl acetate, tetrahydrofuran, 1,2-dimethoxyethane, and the like. From the viewpoint of availability and convenience of working environment, methyl alcohol, ethyl alcohol, isopropyl alcohol, isobutyl alcohol and acetone are preferable, and ethyl alcohol, isopropyl alcohol and acetone are particularly preferable.
- the acidic solvent used in the washing step means a solution containing an acid having protons.
- Acids having protons are not particularly limited, and examples thereof include hydrogen fluoride, nitric acid, sulfuric acid, hydrochloric acid, and hydrosilicofluoric acid.
- the content of the proton-bearing acid is preferably in the range of 0.1% by mass to 70% by mass, more preferably in the range of 1% by mass to 55% by mass, and 5% by mass to 50% by mass, relative to the total mass of the acidic solvent. Within the mass % range is particularly preferred.
- the drying process is performed on the cake after the washing process.
- the drying method is not particularly limited, and examples thereof include heat drying and hot air drying.
- the drying temperature is preferably in the range of 60°C to 200°C, more preferably in the range of 70°C to 150°C, and particularly preferably in the range of 80°C to 110°C.
- the drying temperature is set to 200° C. or lower, it is possible to prevent the obtained red phosphor from deteriorating due to heat.
- the drying time is preferably in the range of 0.5 hours to 20 hours, more preferably in the range of 2 hours to 15 hours. By setting the drying time to 0.5 hours or longer, it is possible to prevent impurities from remaining, and to suppress deterioration of the optical properties of the red phosphor due to the remaining impurities. On the other hand, by setting the drying time to 20 hours or less, it is possible to prevent a decrease in production efficiency of the red phosphor.
- a red phosphor having a perovskite compound present on at least a portion of the surface of the Mn-activated double fluoride, or a red phosphor having a Mn-activated double fluoride present on at least a portion of the surface of the perovskite compound can be obtained. can be manufactured.
- Another aspect of the method for producing a red phosphor according to the present embodiment is, for example, a method of adding a perovskite compound during the production process of Mn-activated double fluoride. With this method, it is possible to produce a red phosphor in which a perovskite compound is present inside an Mn-activated double fluoride, or a red phosphor in which an Mn-activated double fluoride is present inside a perovskite compound. .
- a perovskite compound is dissolved or dispersed in a hydrogen fluoride solution in which an Mn-activated double fluoride is dissolved. Then, a solid substance containing no elemental Mn is added to the hydrogen fluoride solution containing the Mn-activated double fluoride and the perovskite compound. As a result, the solubility of the Mn-activated double fluoride decreases with the dissolution of the solid substance, resulting in precipitation of the Mn-activated double fluoride.
- a red phosphor in which the perovskite compound exists inside the Mn-activated double fluoride can be produced.
- a raw material containing element L, element M and element Mn is dissolved or dispersed in a hydrogen fluoride solution.
- a solution in which the perovskite compound is dissolved is added to the hydrogen fluoride solution containing the raw material.
- a red phosphor in which the Mn-activated double fluoride exists inside the perovskite compound can be produced.
- the ratio of the Mn-activated double fluoride to the perovskite compound is not particularly limited, and can be appropriately set according to the amount of raw materials used, the application of the red phosphor, and the performance required according to the application.
- the method for producing the Mn-activated double fluoride which is the raw material for the red phosphor, is not particularly limited, and known methods can be employed.
- a method of dissolving a compound containing constituent elements of an Mn-activated double fluoride in a hydrofluoric acid solution, mixing them, and subjecting them to reaction crystallization HD Nguyen, C.C. Lin, RS. Liu, Angew.
- a method see Japanese Patent Application Publication No.
- Mn-activated double fluoride H. D. Nguyen, C.; C. Lin, R. S. Liu, Angew. Chem. Based on the method described in Vol. 54, No. 37, page 10866 (2015), Mn-activated double fluoride was synthesized by the following method.
- FIG. 1 is a graph showing the X-ray diffraction pattern of KMgF 3 of Example 1.
- SEM scanning electron microscope
- FIG. 4 is a SEM photograph of the red phosphor.
- Example 2 In this example, the isopropyl alcohol used in Example 1 was changed to pure water. A red phosphor according to Example 2 was produced in the same manner as in Example 1 except for the above.
- Example 3 In this example, the isopropyl alcohol used in Example 1 was changed to hydrofluoric acid having a concentration of 1% by mass. A red phosphor according to Example 3 was produced in the same manner as in Example 1 except for the above.
- Example 4 In this example, the isopropyl alcohol used in Example 1 was changed to hydrofluoric acid having a concentration of 43% by mass. Also, the amount of potassium magnesium fluoride added was changed from 2 g to 0.12 g. A red phosphor according to Example 4 was produced in the same manner as in Example 1 except for these.
- Example 5 In this example, the isopropyl alcohol used in Example 1 was changed to hydrofluoric acid having a concentration of 43% by mass. Also, the amount of potassium magnesium fluoride added was changed from 2 g to 0.02 g. A red phosphor according to Example 5 was produced in the same manner as in Example 1 except for these.
- Example 6 In this example, the perovskite compound was changed from potassium magnesium fluoride to sodium magnesium fluoride (NaMgF 3 ). A red phosphor according to Example 6 was produced in the same manner as in Example 4 except for these.
- Comparative example 1 In this comparative example, the aforementioned K 2 SiF 6 :Mn 4+ was used as the red phosphor.
- the absorption rate and internal quantum efficiency were measured using a quantum efficiency measurement system (trade name: QE-2000, manufactured by Otsuka Electronics Co., Ltd.). That is, the samples of the red phosphors of Examples 1 to 6 and Comparative Example 1 were each packed into a cell for powder measurement and measured. As a result, the absorption rates of the red phosphors according to Examples 1 to 6 were 62%, 68%, 67%, 72%, 73%, and 72% in order, and the internal quantum efficiency was 90%. On the other hand, the red phosphor according to Comparative Example 1 had an absorptance of 72% and an internal quantum efficiency of 90%.
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Abstract
Description
(式中、前記Lはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群より選ばれる少なくとも1種のアルカリ金属元素を表し、前記Mはケイ素、ゲルマニウム、錫、チタン、ジルコニウム及びハフニウムからなる群より選ばれる少なくとも1種の4価の元素を表す。)
ABX3 (2)
(式中、前記Aはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、銀、インジウム、金、タリウム、アンモニウム、第1級アンモニウム、第2級アンモニウム、第3級アンモニウム及び第4級アンモニウムからなる群より選ばれる少なくとも1種を表す。前記第1級アンモニウム、前記第2級アンモニウム、前記第3級アンモニウム及び前記第4級アンモニウムは、炭素数1~10のアルキル基、又は炭素数が1~10の範囲であって、ヘテロ原子を有するアルキル基を有する。前記Bはマグネシウム、カルシウム、バリウム、亜鉛、ジルコニウム、ストロンチウム、マンガン、鉄、コバルト、ニッケル、銅、チタン、バナジウム、クロム、水銀、カドニウム、錫、鉛、ストロンチウム、ユーロピウム、イットリウム、ベリリウム、インジウム、アルミニウム、ルテニウム、オスミウム及びアンチモンからなる群より選ばれる少なくとも1種の元素を表す。前記Xはフッ素、塩素、臭素、ヨウ素及び硫黄からなる群より選ばれる少なくとも1種の元素を表す。)
(式中、前記Lはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群より選ばれる少なくとも1種のアルカリ金属元素を表し、前記Mはケイ素、ゲルマニウム、錫、チタン、ジルコニウム及びハフニウムからなる群より選ばれる少なくとも1種の4価の元素を表す。)
ABX3 (2)
(式中、前記Aはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、銀、インジウム、金、タリウム、アンモニウム、第1級アンモニウム、第2級アンモニウム、第3級アンモニウム及び第4級アンモニウムからなる群より選ばれる少なくとも1種を表す。前記第1級アンモニウム、前記第2級アンモニウム、前記第3級アンモニウム及び前記第4級アンモニウムは、炭素数1~10のアルキル基、又は炭素数が1~10の範囲であって、ヘテロ原子を有するアルキル基を有する。前記Bはマグネシウム、カルシウム、バリウム、亜鉛、ジルコニウム、ストロンチウム、マンガン、鉄、コバルト、ニッケル、銅、チタン、バナジウム、クロム、水銀、カドニウム、錫、鉛、ストロンチウム、ユーロピウム、イットリウム、ベリリウム、インジウム、アルミニウム、ルテニウム、オスミウム及びアンチモンからなる群より選ばれる少なくとも1種の元素を表す。前記Xはフッ素、塩素、臭素、ヨウ素及び硫黄からなる群より選ばれる少なくとも1種の元素を表す。)
即ち、本発明の赤色蛍光体によれば、Mn賦活複フッ化物とペロブスカイト化合物とが存在することにより、Mn4+と水が反応して有色の二酸化マンガンが生成するのを低減し、又は防止する。その結果、二酸化マンガンによる励起光および蛍光の吸収や励起光の吸収に伴う蛍光発光の低下を防止できるので、光学特性が良好で、高温・高湿度環境下での経時変化による光学特性の低下を低減し、耐久性に優れた赤色蛍光体を提供することができる。
本実施の形態に係る赤色蛍光体について、以下に説明する。
本実施の形態に係る赤色蛍光体は、以下の一般式(1)で表されるMn賦活複フッ化物(以下、「Mn賦活複フッ化物」という場合がある。)と、以下の一般式(2)で表されるペロブスカイト化合物(以下、「ペロブスカイト化合物」という場合がある。)とを含む。
(式中、前記Lはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群より選ばれる少なくとも1種のアルカリ金属元素を表し、前記Mはケイ素、ゲルマニウム、錫、チタン、ジルコニウム及びハフニウムからなる群より選ばれる少なくとも1種の4価の元素を表す。)
ABX3 (2)
(式中、前記Aはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、銀、インジウム、金、タリウム、アンモニウム、第1級アンモニウム、第2級アンモニウム、第3級アンモニウム及び第4級アンモニウムからなる群より選ばれる少なくとも1種を表す。前記第1級アンモニウム、前記第2級アンモニウム、前記第3級アンモニウム及び前記第4級アンモニウムは、炭素数1~10のアルキル基、又は炭素数が1~10の範囲であって、ヘテロ原子を有するアルキル基を有する。前記Bはマグネシウム、カルシウム、バリウム、亜鉛、ジルコニウム、ストロンチウム、マンガン、鉄、コバルト、ニッケル、銅、チタン、バナジウム、クロム、水銀、カドニウム、錫、鉛、ストロンチウム、ユーロピウム、イットリウム、ベリリウム、インジウム、アルミニウム、ルテニウム、オスミウム及びアンチモンからなる群より選ばれる少なくとも1種の元素を表す。前記Xはフッ素、塩素、臭素、ヨウ素及び硫黄からなる群より選ばれる少なくとも1種の元素を表す。)
吸収率α(%)=(Ex1-Ex2)/Ex1×100 (1)
内部量子効率η(%)=Em/(Ex1-Ex2)×100 (2)
次に、本実施の形態に係る赤色蛍光体の製造方法について、以下に説明する。
本実施の形態に係る赤色蛍光体の製造方法の一態様としては、例えば、Mn賦活複フッ化物とペロブスカイト化合物とを、溶媒の存在下で接触させる工程を少なくとも含む方法が挙げられる。この方法であると、Mn賦活複フッ化物の表面の少なくとも一部にペロブスカイト化合物が存在する形態の赤色蛍光体、又はペロブスカイト化合物の表面の少なくとも一部にMn賦活複フッ化物が存在する形態の赤色蛍光体を製造することができる。
赤色蛍光体の原料であるMn賦活複フッ化物の製造方法については特に限定されず、公知の方法を採用することができる。例えば、Mn賦活複フッ化物の構成元素を含む化合物をフッ化水素酸溶液に溶解させてそれらを混合し、反応晶析させる方法(H.D.Nguyen, C.C.Lin, R.S.Liu、Angew. Chem. 54巻37号10866ページ(2015年)参照。)、Mn賦活複フッ化物の構成元素を含む化合物をフッ化水素酸溶液に全て溶解又は分散させ、さらに蒸発濃縮させて析出させる方法(特表2009-528429号公報参照。)、フッ化水素酸溶液にMn賦活複フッ化物の構成元素を含む化合物を順次溶解させ、これに固体のMn賦活複フッ化物のマンガン非含有構成元素の一つを添加し、K2SiF6:Mn4+の結晶を析出させ、濾過・乾燥させる方法(WO2015/093430号参照。)等が挙げられる。
H.D.Nguyen, C.C.Lin, R.S.Liu、Angew. Chem. 54巻37号10866ページ(2015年)に記載されている方法に準拠し、以下の方法でMn賦活複フッ化物を合成した。
RAJAMANI NAGARAJAN、Bull. Mater. Sci., Vol. 32, No.6, December 2009, pp. 583-587に記載されている方法に準拠し、以下の方法でフッ化マグネシウムカリウムを合成した。
本実施例に於いては、実施例1で使用したイソプロピルアルコールを純水に変更した。それ以外は実施例1と同様にして、実施例2に係る赤色蛍光体を作製した。
本実施例に於いては、実施例1で使用したイソプロピルアルコールを濃度1質量%のフッ化水素酸に変更した。それ以外は実施例1と同様にして、実施例3に係る赤色蛍光体を作製した。
本実施例に於いては、実施例1で使用したイソプロピルアルコールを濃度43質量%のフッ化水素酸に変更した。また、フッ化マグネシウムカリウムの添加量を2gから0.12gに変更した。それら以外は実施例1と同様にして、実施例4に係る赤色蛍光体を作製した。
本実施例に於いては、実施例1で使用したイソプロピルアルコールを濃度43質量%のフッ化水素酸に変更した。また、フッ化マグネシウムカリウムの添加量を2gから0.02gに変更した。それら以外は実施例1と同様にして、実施例5に係る赤色蛍光体を作製した。
本実施例に於いては、ペロブスカイト化合物として、フッ化マグネシウムカリウムからフッ化マグネシウナトリウム(NaMgF3)に変更した。それら以外は実施例4と同様にして、実施例6に係る赤色蛍光体を作製した。
本比較例では、前述のK2SiF6:Mn4+を赤色蛍光体として用いた。
実施例1~6及び比較例1に係る赤色蛍光体について、以下に述べる方法で各評価を行った。
実施例1~6及び比較例1の各赤色蛍光体の光学特性を評価するため、それぞれの吸収率と内部量子効率を求めた。
耐久性試験は、以下の様にして行った。先ず、実施例1~6又は比較例1の赤色蛍光体0.3gをそれぞれPFAトレーに入れ、温度85℃、相対湿度85%に制御した恒温恒湿器の中にセットし、64時間及び232時間保管した。その後、前述の方法により吸収率及び内部量子効率をそれぞれ求めた。
(耐久性の指標)=(耐久試験後の内部量子効率)/(耐久試験前の内部量子効率)×100 (3)
尚、数式(3)中の「耐久試験後」とは、温度85℃、相対湿度85%の環境下で64時間保管した後の場合と、232時間保管した後の場合とを意味する。
表1に示される様に、ペロブスカイト化合物がMn賦活複フッ化物の表面に存在する実施例1~6の赤色蛍光体では、ペロブスカイト化合物を含まない比較例1の赤色蛍光体と比較して、高温・高湿度環境下での変化率が低く、耐久性が改善されていることが認められた。
Claims (11)
- 以下の一般式(1)で表されるMn賦活複フッ化物と、以下の一般式(2)で表されるペロブスカイト化合物とを含む赤色蛍光体。
L2MF6:Mn4+ (1)
(式中、前記Lはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群より選ばれる少なくとも1種のアルカリ金属元素を表し、前記Mはケイ素、ゲルマニウム、錫、チタン、ジルコニウム及びハフニウムからなる群より選ばれる少なくとも1種の4価の元素を表す。)
ABX3 (2)
(式中、前記Aはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、銀、インジウム、金、タリウム、アンモニウム、第1級アンモニウム、第2級アンモニウム、第3級アンモニウム及び第4級アンモニウムからなる群より選ばれる少なくとも1種を表す。前記第1級アンモニウム、前記第2級アンモニウム、前記第3級アンモニウム及び前記第4級アンモニウムは、炭素数1~10のアルキル基、又は炭素数が1~10の範囲であって、ヘテロ原子を有するアルキル基を有する。前記Bはマグネシウム、カルシウム、バリウム、亜鉛、ジルコニウム、ストロンチウム、マンガン、鉄、コバルト、ニッケル、銅、チタン、バナジウム、クロム、水銀、カドニウム、錫、鉛、ストロンチウム、ユーロピウム、イットリウム、ベリリウム、インジウム、アルミニウム、ルテニウム、オスミウム及びアンチモンからなる群より選ばれる少なくとも1種の元素を表す。前記Xはフッ素、塩素、臭素、ヨウ素及び硫黄からなる群より選ばれる少なくとも1種の元素を表す。) - 前記一般式(2)で表されるペロブスカイト化合物が、前記一般式(1)で表されるMn賦活複フッ化物の表面の少なくとも一部に付着し、及び/又は内部に存在する請求項1に記載の赤色蛍光体。
- 前記一般式(1)で表されるMn賦活複フッ化物が、前記一般式(2)で表されるペロブスカイト化合物の表面の少なくとも一部に付着し、及び/又は内部に存在する請求項1に記載の赤色蛍光体。
- 前記一般式(2)で表されるペロブスカイト化合物の平均粒径D50が、レーザー回折散乱法に於いて0.002μm~20μmである請求項1~3の何れか1項に記載の赤色蛍光体。
- 前記一般式(1)で表されるMn賦活複フッ化物と、前記一般式(2)で表されるペロブスカイト化合物との含有比が、質量基準で10:90~99.999:0.001の範囲である請求項1~4の何れか1項に記載の赤色蛍光体。
- 以下の一般式(1)で表されるMn賦活複フッ化物と、以下の一般式(2)で表されるペロブスカイト化合物とを、溶媒の存在下で接触させる工程を含む赤色蛍光体の製造方法。
L2MF6:Mn4+ (1)
(式中、前記Lはリチウム、ナトリウム、カリウム、ルビジウム及びセシウムからなる群より選ばれる少なくとも1種のアルカリ金属元素を表し、前記Mはケイ素、ゲルマニウム、錫、チタン、ジルコニウム及びハフニウムからなる群より選ばれる少なくとも1種の4価の元素を表す。)
ABX3 (2)
(式中、前記Aはリチウム、ナトリウム、カリウム、ルビジウム、セシウム、銀、インジウム、金、タリウム、アンモニウム、第1級アンモニウム、第2級アンモニウム、第3級アンモニウム及び第4級アンモニウムからなる群より選ばれる少なくとも1種を表す。前記第1級アンモニウム、前記第2級アンモニウム、前記第3級アンモニウム及び前記第4級アンモニウムは、炭素数1~10のアルキル基、又は炭素数が1~10の範囲であって、ヘテロ原子を有するアルキル基を有する。前記Bはマグネシウム、カルシウム、バリウム、亜鉛、ジルコニウム、ストロンチウム、マンガン、鉄、コバルト、ニッケル、銅、チタン、バナジウム、クロム、水銀、カドニウム、錫、鉛、ストロンチウム、ユーロピウム、イットリウム、ベリリウム、インジウム、アルミニウム、ルテニウム、オスミウム及びアンチモンからなる群より選ばれる少なくとも1種の元素を表す。前記Xはフッ素、塩素、臭素、ヨウ素及び硫黄からなる群より選ばれる少なくとも1種の元素を表す。) - 前記一般式(2)で表されるペロブスカイト化合物の平均粒径D50が、レーザー回折散乱法に於いて0.002μm~20μmである請求項6に記載の赤色蛍光体の製造方法。
- 前記一般式(1)で表されるMn賦活複フッ化物と前記一般式(2)で表されるペロブスカイト化合物との接触により得られる赤色蛍光体に於けるMn賦活複フッ化物とペロブスカイト化合物との含有比が、質量基準で10:90~99.999:0.001の範囲である請求項6又は7に記載の赤色蛍光体の製造方法。
- 前記溶媒が、水、有機溶媒、それらの混合溶媒、又はそれらの酸性溶媒である請求項6~8の何れか1項に記載の赤色蛍光体の製造方法。
- 前記溶媒と、前記一般式(1)で表されるMn賦活複フッ化物及び前記一般式(2)で表されるペロブスカイト化合物との混合比が、質量基準で2:1~100:1の範囲である請求項6~9の何れか1項に記載の赤色蛍光体の製造方法。
- 前記酸性溶媒がフッ化水素を含む酸性溶媒であり、
前記フッ化水素を含む酸性溶媒に於ける当該フッ化水素の濃度が、酸性溶媒の全質量に対し1質量%~70質量%の範囲である請求項9又は10に記載の赤色蛍光体の製造方法。
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JP2023058394A (ja) | 2023-04-25 |
KR20240073124A (ko) | 2024-05-24 |
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