WO2010016419A1 - 硫化亜鉛系蛍光体の製造方法 - Google Patents
硫化亜鉛系蛍光体の製造方法 Download PDFInfo
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- WO2010016419A1 WO2010016419A1 PCT/JP2009/063548 JP2009063548W WO2010016419A1 WO 2010016419 A1 WO2010016419 A1 WO 2010016419A1 JP 2009063548 W JP2009063548 W JP 2009063548W WO 2010016419 A1 WO2010016419 A1 WO 2010016419A1
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
- C09K11/621—Chalcogenides
- C09K11/625—Chalcogenides with alkaline earth metals
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/87—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing platina group metals
- C09K11/873—Chalcogenides
- C09K11/876—Chalcogenides with zinc or cadmium
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- H—ELECTRICITY
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- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B33/00—Electroluminescent light sources
- H05B33/12—Light sources with substantially two-dimensional radiating surfaces
- H05B33/14—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the electroluminescent material, or by the simultaneous addition of the electroluminescent material in or onto the light source
Definitions
- the present invention relates to a method for producing a zinc sulfide phosphor.
- Inorganic materials mainly composed of compound semiconductors having fluorescent emission characteristics have been used as light-emitting materials and phosphorescent materials. Recently, light-emitting materials having electroluminescence (EL) characteristics that emit light by electric energy are light sources. It is expected to be a new light emitting element material for display devices and is attracting attention. However, most of the currently available inorganic EL materials have insufficient light conversion efficiency of electric energy and have problems in terms of heat generation, power consumption, EL luminance, etc. Development research is being carried out.
- Patent Document 1 As a method for producing a phosphor using zinc sulfide as a base material, a method of thermally doping a luminescent center in zinc sulfide is known (for example, see Patent Document 1).
- a metal salt containing a metal element that becomes the emission center coexists with a zinc salt, and zinc sulfide is generated under hydrothermal conditions (for example, , Patent Document 2), and a manufacturing method such as a method of reacting a solution in which a metal salt containing a metal element serving as an emission center and a zinc salt is dissolved while adding an aqueous sulfiding agent solution (for example, see Patent Document 3) is known. It has been.
- Patent Documents 2 and 3 disclose that the obtained phosphor precursor is heated and fired and phosphorized by fixing and crystallizing the emission center.
- the mixing method of the metal salt supplying the metal dopant and zinc sulfide, and nonuniformity during mixing there is a problem that the metal dopant is clearly unevenly distributed between the particles, and the emission color is not uniform within and between the particles.
- the method of generating zinc sulfide under hydrothermal conditions has a problem that the reaction equipment used is significantly corroded by the generated hydrogen sulfide, which is a major obstacle to scale-up for industrialization.
- each metal salt is reacted with a sulfiding agent together with a metal salt supplying a metal dopant. Since the reaction rates of these are different, there is a problem that the distribution of the metal dopant in the particles is not uniform. In order to avoid this problem, a solution to reduce the apparent reaction rate difference by allowing the reaction to proceed under heating is conceivable, but in this case, the same problem as the above-described method of thermally doping a metal occurs. Since it becomes a result, it is not preferable.
- an object of the present invention is to provide a method for producing a zinc sulfide-based phosphor capable of industrially advantageously producing a practical and high-luminance phosphor.
- the present inventors paid attention to the fact that the processing conditions in each manufacturing process from the preparation of zinc sulfide-based phosphors to firing significantly affect the brightness of the obtained phosphors, and examined each process in detail. As a result, the inventors have found that the above object can be achieved and have completed the present invention. That is, according to the present invention, the following can be provided.
- a method for producing a zinc sulfide-based phosphor by firing a zinc sulfide-based phosphor precursor A first firing step of firing a mixture containing a zinc sulfide-based phosphor precursor, sulfur and a chlorine-containing flux; and Including a second firing step of further firing the fired product obtained from the first firing step,
- the mixture is heated and heated in an atmosphere into which oxygen is introduced from room temperature to a temperature at which the crystal system of the phosphor precursor transitions, and then exceeds the transition temperature. Then, the atmosphere is changed to a nitrogen atmosphere and heating is continued. When the temperature reaches a temperature in the range of 1000 ° C. or higher and 1200 ° C.
- the temperature is kept constant, and then the mixture is rapidly cooled and washed.
- the fired product obtained in the first firing step is heated in a nitrogen atmosphere to raise the temperature from room temperature to 650 ° C. to 1000 ° C., and then reaches the temperature.
- maintaining the temperature while introducing oxygen, and then quenching and washing the fired product to obtain a zinc sulfide-based phosphor The manufacturing method characterized by this.
- [2] The method for producing a zinc sulfide phosphor according to [1], wherein in the first firing step, the temperature switched to the nitrogen atmosphere is a temperature of 850 ° C. or lower.
- [3] The method for producing a zinc sulfide phosphor according to [1] or [2], wherein after the cleaning in the first firing step, the crystals of the fired product are distorted and the second firing step is performed.
- [4] The method for producing a zinc sulfide-based phosphor according to [3], wherein the cleaning and the imparting of strain are simultaneously performed.
- [5] The zinc sulfide according to any one of [1] to [4], wherein a compound containing copper, zinc and sulfur is added to the fired product obtained in the first firing step and a second firing step is performed. For producing a phosphor based on carbon.
- the phosphor precursor includes one or more kinds including a zinc compound, a sulfurizing agent, and at least one metal element selected from the group consisting of copper, silver, gold, manganese, iridium, and rare earth elements.
- a zinc compound obtained by adding an aqueous solution containing the metal compound to an organic solvent and then heating to perform azeotropic dehydration. Manufacturing method of zinc sulfide based phosphor.
- the phosphor precursor includes a zinc compound, and one or more kinds of metal compounds including at least one kind of metal element selected from the group consisting of copper, silver, gold, manganese, iridium, and rare earth elements;
- the phosphor precursor includes one or more metal compounds including zinc sulfide and at least one metal element selected from the group consisting of copper, silver, gold, manganese, iridium, and rare earth elements.
- the sulfide according to any one of [1] to [9], wherein the introduction of oxygen is performed by flowing a gas flow containing oxygen into an atmosphere around the phosphor precursor.
- a method for producing a zinc-based phosphor. [11]
- a highly practical phosphor with high EL brightness can be industrially advantageously produced by the method for producing a zinc sulfide phosphor of the present invention.
- a phosphor is produced by firing a zinc sulfide-based phosphor precursor.
- the phosphor precursor is not particularly limited as long as zinc sulfide is a matrix of the phosphor.
- the phosphor precursor is a substance at a stage before becoming a phosphor, which does not show fluorescence by excitation by light absorption, or shows fluorescence for the time being but is not sufficient from a practical viewpoint.
- the phosphor precursor may be simply referred to as a precursor.
- the precursor is manufactured through at least a process including a first baking process and a second baking process.
- the first firing step is a step of increasing the crystallinity of the zinc sulfide-based phosphor precursor to form a hexagonal crystal.
- appropriate amounts of sulfur and chlorine-containing flux are added to the precursor.
- Chlorine-containing fluxes include alkali metal chlorides such as lithium chloride, sodium chloride, potassium chloride, and cesium chloride, alkaline earth metal chlorides such as calcium chloride, magnesium chloride, barium chloride, and strontium chloride, ammonium chloride, and zinc chloride. And so on. In consideration of the persistence and the melting temperature of the flux, it is preferable to mix a plurality of chlorides. Preferably, a mixture of potassium chloride, sodium chloride and magnesium chloride is used.
- the amount of the chlorine-containing flux used is not particularly limited, but it is usually 0 to 80% by weight as the concentration in zinc sulfide, considering the influence of uniform dispersion of the flux and the like. It is used in the range of 5 to 60% by weight, more preferably 1 to 40% by weight.
- the method of adding the chlorine-containing flux is not particularly limited, and the chlorine-containing flux can be mixed with zinc sulfide and used, or the chlorine-containing flux is dissolved in water and then mixed with zinc sulfide. It is also possible to use a mixture prepared by further drying. In consideration of the chemical stability of the flux used, solid mixing and aqueous solution mixing can be used in combination.
- the amount of sulfur added is not particularly limited, but may be any amount that can suppress oxidation of zinc sulfide due to reaction with the reaction vessel, water adhering to zinc sulfide, and oxygen during firing. Therefore, in general, it is added in an amount of 0.01 to 2 times by weight, more preferably 0.02 to 1 times by weight of zinc sulfide.
- the precursor to which sulfur and a chlorine-containing flux are added is heated from room temperature to a temperature at which the crystal system of the precursor starts to transition in an atmosphere in which oxygen is introduced.
- the term “normal temperature” is a temperature when neither heating nor cooling is performed, and generally corresponds to an average atmospheric temperature (or ambient temperature). Accordingly, the room temperature may vary depending on the technical field and region, but, for example, it is a temperature in the range of about 5 ° C. to about 35 ° C. (however, it is not particularly limited to this temperature range).
- the heat treatment of the precursor can be performed using a firing furnace commonly used in the art for firing inorganic materials.
- the amount of moisture adsorbed on the furnace material can be reduced to an appropriate level by maintaining the furnace temperature at about 30 ° C. in advance before introducing the precursor. For this reason, it is preferable that the in-furnace temperature at the start of firing of the precursor is about 30 ° C. or higher. If oxygen is introduced into the firing furnace in a temperature range higher than the temperature at which the zinc sulfide crystal system transitions, it will be oxidized to the inside of the crystal particles, resulting in a decrease in the performance as the final phosphor. In the case of zinc sulfide, the beginning of the crystal system transition can be confirmed at 800 ° C. or higher, and the crystal system transition can be confirmed more clearly at 850 ° C. or higher.
- the introduction of oxygen is preferably performed by continuously flowing a gas flow containing oxygen into the inside of the firing furnace (particularly the atmosphere around the phosphor precursor).
- the concentration of oxygen to be introduced is not particularly limited, but is preferably 1 to 30% by volume in the introduced gas.
- an air flow for example, air in the atmosphere
- the transition of the crystal system of the phosphor precursor can be confirmed from the diffraction peak intensity on the (1, 0, 0) plane by analyzing the diffraction pattern by powder X-ray diffraction. The crystal system starts to transition from around 800 ° C. and completely transitions from cubic to hexagonal at 1020 ° C.
- the temperature is raised in a nitrogen atmosphere after the temperature at which the crystal system starts to transition.
- Switching to the nitrogen atmosphere is preferably carried out by switching the introduced oxygen-containing gas flow to a nitrogen flow. And after reaching
- the holding time is preferably about 1 to about 5 hours.
- Rapid cooling refers to cooling so that the rate of temperature decrease is larger than that of naturally cooling.
- the cooling rate for rapid cooling is not particularly limited, it is preferable to cool as quickly as possible, considering the cooling rate in the range of 10 ° C to 500 ° C per minute and the heat shock resistance of the container per minute.
- the rapid cooling is preferably performed at a cooling rate in the range of 12 ° C to 300 ° C.
- the cooled fired product is washed with an acidic aqueous solution.
- an acidic aqueous solution an organic acid aqueous solution such as formic acid or acetic acid, or a mineral acid aqueous solution such as hydrochloric acid, sulfuric acid or phosphoric acid can be used.
- acetic acid and hydrochloric acid are preferable to use.
- the fired product obtained in the first firing step is then subjected to the second firing step.
- the fired product is usually heated in a nitrogen atmosphere until it reaches a temperature of 650 ° C. or higher and 1000 ° C. or lower in 2 to 5 hours.
- oxygen is introduced immediately after reaching the predetermined temperature, and the temperature is maintained for a predetermined time.
- oxygen is preferably introduced continuously into the firing furnace (particularly the atmosphere around the phosphor precursor) as a gas stream containing oxygen, and the time for introducing oxygen is not limited, Usually, it may be in the range of 30 minutes to 2 hours.
- the concentration of oxygen to be introduced is not particularly limited, but is preferably 1 to 30% by volume in the introduced gas. In consideration of economy, air may be used for oxygen introduction. preferable. After that, it is preferable to switch the atmosphere into which the oxygen has been introduced to the nitrogen atmosphere again and hold the temperature for a certain period of time.
- the fired product is rapidly cooled.
- the cooling rate for rapid cooling is not particularly limited, it is preferable to cool as quickly as possible, considering the cooling rate in the range of 10 ° C to 500 ° C per minute and the heat shock resistance of the container per minute.
- the rapid cooling is preferably performed at a cooling rate in the range of 12 ° C to 300 ° C.
- the cooled fired product is washed with an acidic aqueous solution.
- an organic acid aqueous solution or a mineral acid aqueous solution can be used as in the case of the first baking step.
- acetic acid and hydrochloric acid it is preferable to use acetic acid and hydrochloric acid. After washing with an acidic aqueous solution, washing is performed with ion exchange water until the washing solution becomes neutral.
- the fired product obtained in the first firing step is subjected to the second firing step after the crystal is distorted after washing.
- the method for giving strain to the crystal is not particularly limited.
- the crystal may be strained by applying an impact to the fired product in a bulk state from the outside by a method such as shock wave or pressing.
- a method such as shock wave or pressing.
- the time for giving the impact is not particularly limited, but is usually in the range of 10 minutes to 3 hours, more preferably in the range of 15 minutes to 2 hours. It is preferable to perform the cleaning and the imparting of strain simultaneously.
- the fired product obtained in the first firing step is preferably subjected to the second firing step by adding a compound containing copper, zinc and sulfur.
- a compound containing copper, zinc and sulfur is contained in the calcined product so as to contain 0.1 to 5% by weight of a copper salt, 1 to 45% by weight of a zinc compound, and 0.1 to 6% by weight of sulfur. Added.
- Examples of the copper salt used in the present invention include copper (I) chloride, copper (II) chloride, copper sulfate, and copper acetate. These may be used alone or as a mixture of a plurality of types. From the viewpoints of economy and operability, copper sulfate and copper acetate are preferably used.
- Examples of the zinc compound used in the present invention include zinc oxide, zinc sulfide, zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, zinc acetate and formate. These may be used alone or as a mixture of a plurality of types. From the viewpoint of economy and operability, use of zinc sulfate and zinc oxide is preferable.
- sulfur-containing compound used in the present invention examples include sulfur, thioacetamide, thiourea and the like. These may be used alone or as a mixture of a plurality of types. From the viewpoint of economy and operability, use of sulfur is preferred.
- the second baking step may be performed twice or more times. In the case of carrying out a plurality of times, it is preferable that the final temperature is lower than the previous temperature. By firing at such a low temperature, the crystallinity may be stabilized and the characteristics as a zinc sulfide-based phosphor may be improved.
- the obtained zinc sulfide-based phosphor particles are subjected to a cleaning treatment in order to remove the extra zinc compound and the blackened metal compound that were not doped.
- Neutral water or acidic water is used for washing.
- the acid component contained in the acidic water is not particularly limited, and examples thereof include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid, and organic acids such as acetic acid, propionic acid, and butyric acid. Also, aqueous solutions of the respective acids can be used. These can be used alone, or a plurality of types can be mixed and used.
- zinc sulfide-based phosphors may be decomposed when contacted with high concentration acidic substances, when using acidic water, it is usually necessary to use an aqueous solution containing 0.1 to 20% by weight of an acid component. It is preferable to use an aqueous solution containing 1 to 10% by weight of an acid component. In consideration of decomposition of the zinc sulfide-based phosphor and ion persistence on the surface, it is preferable to use acetic acid.
- excess copper, silver, gold, manganese, iridium and rare earth elements can be removed by a cyanide solution.
- cyanide to be used sodium cyanide and potassium cyanide are generally used from the viewpoint of easy availability, and an aqueous solution containing cyanide is usually added at a concentration of 0.1 to 1% by weight as zinc sulfide. It is used in an amount of 10 to 100 parts by weight per 1 part by weight of the phosphor.
- After washing it is preferable from the viewpoint of safety to wash with ion-exchanged water until cyanide ions are no longer detected in order to prevent cyanide residue.
- the phosphor can be further dried by a method such as vacuum or hot air to obtain a phosphor as a final product.
- the phosphor precursor used in the present invention is not particularly limited as long as zinc sulfide is a base compound, but it is preferable that the metal dopant is distributed as homogeneously as possible in the zinc sulfide base.
- an aqueous solution containing a metal compound containing at least one metal element selected from the group consisting of copper, silver, gold, manganese, iridium, and rare earth elements in an organic solvent It is preferable to use a zinc sulfide-based phosphor precursor obtained by preparing a mixed solution, heating the reaction mixed solution, and removing water while azeotropically distilling water and an organic solvent.
- Zinc compounds for preparing the phosphor precursor include mineral acid salts such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, organic acid salts such as formic acid, acetic acid, butyric acid and oxalic acid, and complex salts such as acetylacetonate. Can be mentioned. In view of the stability and persistence of the compound after removing water from the solvent contained in the reaction mixture by azeotropic dehydration, the use of an organic acid salt is preferred. These zinc compounds may be used alone or as a mixture of a plurality of types.
- the metal compound containing at least one metal element selected from the group consisting of copper, silver, gold, manganese, iridium and rare earth elements is not particularly limited, and minerals such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.
- a salt with an organic acid such as an acid salt, formic acid, acetic acid, butyric acid, or oxalic acid, or a complex salt with a ligand such as acetylacetonate can be used.
- an organic acid salt is preferred.
- a compound containing an element such as aluminum, gallium, or indium that acts as a donor for copper, silver, manganese, iridium, and a rare earth element as an acceptor is present in an aqueous solution, and such a donor is used.
- Elements may be incorporated into sulfides.
- the sulfurizing agent used in the present invention is not particularly limited, and alkali metal sulfides such as hydrogen sulfide, sodium sulfide and potassium sulfide, thioamides such as thioacetamide and thioformamide, and thiourea may be used. it can.
- alkali metal sulfides such as hydrogen sulfide, sodium sulfide and potassium sulfide
- thioamides such as thioacetamide and thioformamide
- thiourea it is preferable to use.
- hydrogen sulfide, thioacetamide, or thiourea it is preferable to use hydrogen sulfide, thioacetamide, or thiourea. Of these, thioacetamide and / or hydrogen sulfide are preferable.
- the water used for dissolving the zinc compound, the sulfiding agent, etc. usually has an ash content of 100 ppm or less, more preferably an ash content so as not to prevent the formation of the zinc sulfide phosphor due to the influence of impurities.
- the concentration of the zinc compound at the time of preparing the aqueous solution is not a problem in relation to the homogeneity of the distribution of the metal dopant as long as the zinc compound is completely dissolved.
- the concentration of the zinc compound is adjusted to a range of 0.01 to 2 mol / L, more preferably 0.1 to 1.5 mol / L.
- a compound containing copper, silver, gold, manganese, iridium and a rare earth element used in the present invention and a compound containing copper, silver, gold, manganese, iridium and an element acting as a donor for the rare earth element as an acceptor.
- the use ratio is in the range of 0.1 to 150,000 ppm, more preferably in the range of 1 ppm to 50000 ppm, based on the weight of the obtained phosphor precursor, based on the weight of the metal element to be doped. In consideration of the properties, the range of 2 to 10,000 ppm is even more preferable.
- Compounds containing these elements are also used in the presence of an aqueous solution in which a zinc compound is dissolved.
- the amount of the sulfurizing agent to be used may be an amount corresponding to 0.5 to 5 times the number of moles of zinc element contained in the zinc compound, but the zinc compound remains unreacted. Then, in addition to undesired effects on the reaction, the phosphor product may also have effects such as a decrease in color purity and limited use. Therefore, the sulfiding agent is usually used in an amount corresponding to 1.1 to 4 times, more preferably 1.1 to 2 times the number of moles of zinc element. A sulfiding agent is also used by dissolving in a zinc compound aqueous solution.
- the concentration of the sulfiding agent in the aqueous solution is not a problem in relation to the homogeneity of the distribution of the metal dopant as long as the sulfiding agent can be dissolved in the aqueous solution.
- concentration of the sulfiding agent is too high, unreacted sulfiding agent is deposited and remains in the target product, which is not preferable.
- concentration is too dilute, unreacted zinc compound is precipitated, Since it remains in the target product, it is not preferable. Therefore, it is adjusted to be in the range of 0.01 to 2 mol / L, more preferably 0.1 to 1.5 mol / L.
- hydrogen sulfide When hydrogen sulfide is used as the sulfurizing agent, it can be dissolved in water and added simultaneously with the zinc compound, or can be continuously supplied as a gas into the reaction solution.
- Examples of the supply method include a method of supplying hydrogen sulfide gas to the liquid phase part of the reactor and a method of supplying hydrogen sulfide gas to the gas phase part.
- the organic solvent used in the present invention is not particularly limited as long as it can remove water by azeotropic dehydration. That is, saturated hydrocarbons such as hexane, cyclohexane, heptane, octane, cyclooctane, nonane, decane, dodecane, cyclododecane, undecane, aromatic hydrocarbons such as toluene, xylene, mesitylene, carbon tetrachloride, 1,2-dichloroethane Halogenated hydrocarbons such as 1,1,2,2-tetrachloroethylene, halogenated aromatic hydrocarbons such as chlorobenzene and dichlorobenzene, dibutyl ether, diisobutyl ether, diamyl ether, diisoamyl ether, dihexyl ether, dicyclohexyl ether, Dioctyl ether, dicyclooctyl ether, ani
- use of saturated hydrocarbon or aromatic hydrocarbon is preferable.
- decane, dodecane, and xylene are preferred from the viewpoint of the azeotropic temperature with water and the azeotropic ratio with water.
- the heating temperature of the reaction mixture can be set to a temperature within the range of 30 ° C to 300 ° C. Temperature that does not require the use of a special experimental equipment, reactor, etc., that is, a temperature in the range of 40 to 230 ° C. is preferable, and a temperature in the range of 60 to 200 ° C. is considered in consideration of the decomposition rate of thioacetamide. More preferred is a temperature in the range of 80 ° C to 180 ° C.
- the reaction mixture can be prepared and heated in any atmosphere, but in the presence of oxygen, the suppression of product oxidation and the like cannot be completely controlled. Therefore, it is preferable to carry out in the presence of an inert gas such as nitrogen or argon, in the presence of hydrogen sulfide gas as a sulfiding agent, or in the presence of a mixed gas thereof.
- an inert gas such as nitrogen or argon
- an aqueous solution of a raw material compound is added to an organic solvent on the one hand to prepare a reaction mixture, and on the other hand, utilizing azeotropy of water and an organic substance. Remove water from the reaction mixture.
- the zinc metal sulfide precipitated in the reaction mixture is separated from the liquid phase medium and, if necessary, washed with water or the like and dried under heating and reduced pressure.
- the temperature at which the phosphor precursor is dried is not particularly limited, and can be usually carried out at 10 ° C. to 200 ° C. However, if a slight amount of water is present, the zinc precursor base material of the phosphor precursor Since it may cause oxidation, the drying treatment should be performed at 150 ° C. or lower, preferably 50 ° C. to 120 ° C.
- the phosphor precursor includes a zinc compound and a metal compound containing at least one metal element selected from the group consisting of copper, silver, gold, manganese, iridium and rare earth elements.
- a zinc sulfide-based phosphor precursor obtained by adding a sulfurizing agent to an aqueous solution and reacting in an aqueous phase can be used.
- the zinc compound, the metal compound containing at least one metal element selected from the group consisting of copper, silver, gold, manganese, iridium and rare earth elements, and the sulfiding agent are the same as those described above.
- the phosphor precursor obtained by the liquid phase reaction is separated from water and then, if necessary, subjected to a washing treatment such as washing with water and dried by heating or under reduced pressure.
- a mixture prepared by mixing zinc sulfide and a metal compound containing at least one metal element selected from copper, silver, gold, manganese, iridium and rare earth elements. Can be used as a phosphor precursor.
- the zinc sulfide used in the present invention is not particularly limited, and may belong to any crystal system of cubic and hexagonal.
- the particle size is not particularly limited, and the primary particle size may be in the range of 10 nm to 20 ⁇ m. Further, in the case of an aggregate of primary particles, it may be in the range of 1 ⁇ m to 20 ⁇ m.
- the purity of zinc sulfide used here is not particularly limited, but preferably does not include foreign metals such as iron, nickel, and chromium, and usually has a purity of 99% or more. .
- a metal compound containing an element such as aluminum, gallium, or indium that acts as a donor for copper, silver, manganese, iridium, and rare earth elements as an acceptor can be used.
- These metal compounds are not particularly limited, and include mineral salts such as hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, organic acid salts such as formic acid, acetic acid, butyric acid and oxalic acid, and complex salts such as acetylacetonate. Can be used.
- mineral acid salts and organic acid salts is preferred. These may be used alone or as a mixture of a plurality of types.
- the mixing method for preparing the mixture of the metal compound and zinc sulfide is not particularly limited, and various metal compounds to be mixed with zinc sulfide can be physically mixed.
- a metal compound containing at least one metal element selected from copper, silver, gold, manganese, iridium and rare earth elements, and, if necessary, the metal element as an acceptor A compound (one or more) containing at least one element selected from aluminum, gallium, indium and the like acting as a donor is once dissolved in water, and zinc sulfide is added, and then water is removed. By doing so, a mixture can also be prepared.
- Quantum efficiency is the ratio between the number of photons emitted by excitation by incident light and the number of photons of incident light absorbed by the material, and the larger this value, the higher the doping effect. Quantum efficiency can be measured with a spectrofluorometer.
- Measuring device FP-6500 manufactured by JASCO Corporation Excitation wavelength: 350 nm Excitation bandwidth: 5 nm
- Reference Example 1 (Production Example 1 of phosphor precursor) manufactured by JASCO Corporation: Zinc acetate dihydrate 65.9 g, copper nitrate trihydrate 0.056 g (equivalent to 700 ppm copper), gallium nitrate octahydrate 0.008 g (equivalent to 50 ppm gallium), thioacetamide 45.0 g, acetic acid 5 g was dissolved in 500 g of ion exchange water.
- a 2 L three-necked flask was equipped with a Dean-Stark apparatus, a reflux tube, a thermometer, and a stirrer, 800 ml of o-xylene was taken, and the inside of the system was purged with nitrogen.
- the temperature in the oil bath was adjusted to 150 ° C.
- raising the temperature of o-xylene in the reactor to 130 ° C. and adding a solution containing zinc acetate at 100 ml per hour
- the distilled water is added to the Dean-Stark device.
- the reaction proceeded while removing with. All aqueous solutions were fed in about 6 hours, and water in the system was removed for another 30 minutes.
- the precipitated sulfide was precipitated, the organic solvent was removed, and the target product was collected and dried at 100 ° C. for 12 hours in a vacuum dryer.
- the recovered amount was 28.9 g, which was 98% of the theoretical amount.
- Reference Example 2 Phosphor Precursor Production Example 2
- a 3 L three-necked flask is equipped with a stirrer, thermometer, reflux tube and solid feeder, 297.6 g of zinc nitrate hexahydrate, 0.186 g of copper nitrate trihydrate (equivalent to 500 ppm copper), iridium hexachloride 0.022 g of diammonium (equivalent to 100 ppm of iridium) was taken, and 1000 g of ion-exchanged water was added and dissolved. 60% nitric acid was added thereto, and the pH in the system was adjusted to 2. After replacing the system with nitrogen, the system was heated to 90 ° C.
- Reference Example 3 Phosphor Precursor Production Example 3 : Take 100 g of zinc sulfide (RAK-N manufactured by Sakai Chemical Industry Co., Ltd.) and 0.20 g of copper acetate trihydrate (equivalent to 500 ppm copper) in a 100 ml container of a THINKEY mixer (ARE-250) and dissolve for 30 minutes. Crush and mix.
- RAK-N zinc sulfide
- ARE-250 THINKEY mixer
- Comparative Example 1 To 27 g of the product obtained in Reference Example 1, 1.00 g of potassium chloride, 1.17 g of sodium chloride and 6.87 g of magnesium chloride hexahydrate were added and mixed with a ball mill. Thereto, 1.45 g of sulfur was added and the mixture was placed in a crucible. Thereafter, the crucible was transferred to a firing furnace and heated at a rate of 400 ° C. per hour in a nitrogen atmosphere. The temperature was raised to 1100 ° C. and held there for 3 hours. After holding for 3 hours, it was cooled to room temperature.
- the obtained fired product was added to 200 g of a 15% acetic acid solution to disperse the fired product.
- the acetic acid solution was removed by decantation and washed with 500 g of ion exchange water until the washing solution became neutral. After removing ion-exchanged water, vacuum drying was performed at 100 ° C. for 12 hours to obtain 24 g of a fired product from the first firing step.
- the crucible was transferred to a firing furnace and heated at a rate of 400 ° C. per hour in a nitrogen atmosphere. After completion of the temperature increase, the mixture was held for 3 hours and then cooled to room temperature.
- the cooled fired product was dispersed in 200 g of 5% aqueous hydrochloric acid and washed.
- the acidic aqueous solution was removed and washed with 500 g of ion-exchanged water until the washing solution became neutral.
- washing with 200 g of 1% aqueous sodium cyanide solution was performed to remove excess sulfide.
- vacuum drying was performed for 12 hours at 100 degreeC, and 22g of baked products from the 2nd baking process were obtained.
- the photoexcited fluorescence spectrum was measured for the obtained fired product (phosphor).
- the fluorescence spectrum of the phosphor is shown in FIG.
- the quantum yield of the phosphor is shown in Table 1.
- Fluorine binder (DuPont 7155) 1.0 g was added as a binder to 1.5 g of the obtained phosphor, mixed and degassed to prepare a light emitting layer paste.
- a 20 mm square screen plate 200 mesh, 25 ⁇ m
- a barium titanate paste (DuPont 7153) with a screen plate (150 mesh, 25 ⁇ m)
- the plate was made again and dried at 100 ° C. for 10 minutes to form a 20 ⁇ m dielectric layer.
- silver paste (461SS manufactured by Atchison Co., Ltd.) is made as an electrode using a screen plate (150 mesh, 25 ⁇ m), dried at 100 ° C. for 10 minutes to form an electrode, and a printing EL device is formed did.
- luminance was measured at 200V and 1 kHz, and evaluation as EL material was performed. The results are shown in Table 2.
- Comparative Example 2 The same as Comparative Example 1 except that 1.00 g of potassium chloride, 1.17 g of sodium chloride and 6.87 g of magnesium chloride hexahydrate were added to 27 g of the product obtained in Reference Example 2 and mixed with a ball mill. According to the procedure, the quantum efficiency and the fluorescence spectrum of the phosphor were measured, and further, a printing type EL element was prepared and the EL material was evaluated. The results are shown in Table 1, FIG.
- Comparative Example 3 The same as Comparative Example 1 except that 1.00 g of potassium chloride, 1.17 g of sodium chloride and 6.87 g of magnesium chloride hexahydrate were added to 27 g of the product obtained in Reference Example 3 and mixed with a ball mill. According to the procedure, the quantum efficiency and the fluorescence spectrum of the phosphor were measured, and further, a printing type EL element was prepared and the EL material was evaluated. The results are shown in Table 1, FIG.
- Example 1 To 27 g of the product obtained in Reference Example 1, 1.00 g of potassium chloride, 1.17 g of sodium chloride and 6.87 g of magnesium chloride hexahydrate were added and mixed with a ball mill. Thereto, 1.45 g of sulfur was added and the mixture was placed in a crucible. Thereafter, the crucible was transferred to a firing furnace and heated at a rate of 400 ° C. per hour in an atmosphere in which an air flow was introduced. When the furnace temperature reached 800 ° C., the gas to be introduced was switched from air to nitrogen, the temperature was raised to 1100 ° C., and the temperature was maintained for 3 hours. After holding for 3 hours, it was cooled at 500 ° C. per hour and cooled to room temperature.
- the obtained fired product was added to 200 g of a 15% acetic acid solution to disperse the fired product.
- the acetic acid solution was removed by decantation and washed with 500 g of ion-exchanged water until the washing became neutral to obtain a fired product. After removing the ion exchange water, vacuum drying was performed at 100 ° C. for 12 hours to obtain 24 g of a fired product from the first firing step.
- the crucible was transferred to a firing furnace and heated at a rate of 400 ° C. per hour in a nitrogen atmosphere. After completion of the temperature increase, when the inside of the firing furnace reached 850 ° C., the introduction of nitrogen was switched to air, and air was introduced for 1 hour. Thereafter, the introduced gas was switched to nitrogen and held for another 2 hours, and then cooled at 500 ° C. per hour and cooled to room temperature.
- the cooled fired product was dispersed in 200 g of 5% aqueous hydrochloric acid and washed.
- the acidic aqueous solution was removed and washed with 500 g of ion-exchanged water until the washing solution became neutral.
- washing with 200 g of 1% aqueous sodium cyanide solution was performed to remove excess sulfide.
- vacuum drying was performed for 12 hours at 100 degreeC, and 22g of baked products from the 2nd baking process were obtained.
- the photoexcited fluorescence spectrum was measured for the obtained fired product (phosphor).
- the fluorescence spectrum of the phosphor is shown in FIG.
- the quantum yield of the phosphor is shown in Table 1.
- a printing type EL device was constructed in the same procedure as in Comparative Example 1 using 1.5 g of the obtained phosphor. About the obtained element, EL brightness
- luminance was measured at 200V and 1 kHz, and evaluation as EL material was performed. The results are shown in Table 2.
- Example 2 Using 27 g of the product obtained in Reference Example 2, the same procedure as in Example 1 was repeated to obtain 25 g of a fired product from the first firing step. Subsequently, 21 g of a fired product from the second firing step was obtained according to the same procedure as in Example 1. The photoexcited fluorescence spectrum of the fired product (phosphor) thus obtained was measured. The fluorescence spectrum of the phosphor is shown in FIG. The quantum yield of the phosphor is shown in Table 1.
- a printing type EL element was constructed using 1.5 g of the obtained phosphor according to the same procedure as in Example 1. About the obtained element, EL brightness
- Example 3 Using 25 g of the product obtained in Reference Example 3, the same procedure as in Example 1 was repeated to obtain 23 g of a fired product from the first firing step. Subsequently, 21 g of a fired product from the second firing step was obtained according to the same procedure as in Example 1. The photoexcited fluorescence spectrum was measured for the obtained fired product (phosphor). The fluorescence spectrum of the phosphor is shown in FIG. The quantum yield of the phosphor is shown in Table 1. In addition, a printing type EL element was constructed using 1.5 g of the obtained phosphor according to the same procedure as in Example 1. About the obtained element, EL brightness
- Comparative Example 4 To 27 g of the product obtained in Reference Example 1, 1.00 g of potassium chloride, 1.17 g of sodium chloride and 6.87 g of magnesium chloride hexahydrate were added and mixed with a ball mill. Thereto, 1.45 g of sulfur was added and the mixture was placed in a crucible. Thereafter, the crucible was transferred to a firing furnace and heated at a rate of 400 ° C. per hour in an atmosphere in which an air flow was introduced. When the furnace temperature reached 300 ° C., the gas to be introduced was switched from air to nitrogen without changing the crystal system of zinc sulfide, which is the base material compound, and the temperature was raised to 1100 ° C., and the temperature was increased for 3 hours. Retained.
- Comparative Example 8 Although the 1st baking process was implemented according to the procedure similar to Example 1, the procedure similar to Example 1 was followed except not having implemented the 2nd baking process at all after that. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Example 4 The first firing step was performed according to the same procedure as in Example 1, and 100 g of the fired product obtained after washing was dispersed in ion-exchanged water, and output 60 with an ultrasonic vibrator (manufactured by BRANSON, Digital Sonifier). % was applied for 30 minutes. After removing the ion exchange water, vacuum drying was performed at 100 ° C. for 12 hours to obtain 24 g of a fired product from the first firing step. Subsequently, the second baking step was performed according to the same procedure as in Example 1, and after baking, a fired product (phosphor) was obtained. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Example 5 The first firing step was performed according to the same procedure as in Example 1, and 100 g of the fired product obtained after washing was dispersed in ion-exchanged water, and output 60 with an ultrasonic vibrator (manufactured by BRANSON, Digital Sonifier). % was applied for 30 minutes. After removing the ion exchange water, vacuum drying was performed at 100 ° C. for 12 hours to obtain 24 g of a fired product from the first firing step.
- an ultrasonic vibrator manufactured by BRANSON, Digital Sonifier
- Example 6 The first firing step was performed according to the same procedure as in Example 2, 50 g of methanol was added to 25 g of the fired product obtained after washing, 10 g of ceramic balls having a diameter of 1 mm ⁇ were added, and a ball mill (manufactured by FRITSCH, (Puleriseette), an impact was applied for 30 minutes at 100 revolutions per minute. After removing the methanol, vacuum drying was performed at 100 ° C. for 12 hours to obtain 25 g of a fired product from the first firing step. Subsequently, according to the same procedure as in Example 2, the second baking step was performed, and after washing, a fired product (phosphor) was obtained. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Example 7 The first firing step was performed according to the same procedure as in Example 2, 50 g of methanol was added to 25 g of the fired product obtained after washing, 10 g of ceramic balls having a diameter of 1 mm ⁇ were added, and a ball mill (manufactured by FRITSCH, (Puleriseette), an impact was applied for 30 minutes at 100 revolutions per minute. After removing the methanol, vacuum drying was performed at 100 ° C. for 12 hours to obtain 25 g of a fired product from the first firing step.
- Example 8 The first firing step was performed according to the same procedure as in Example 3, 50 g of methanol was added to 25 g of the fired product obtained after washing, 10 g of ceramic balls having a diameter of 1 mm ⁇ were added, and a ball mill (manufactured by FRITSCH, (Puleriseette), an impact was applied for 30 minutes at 100 revolutions per minute. After removing the methanol, vacuum drying was performed at 100 ° C. for 12 hours to obtain 23.3 g of a fired product from the first firing step. Subsequently, a second baking step was performed according to the same procedure as in Example 3, and after baking, a fired product (phosphor) was obtained. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Example 9 The first firing step was performed according to the same procedure as in Example 3, 50 g of methanol was added to 25 g of the fired product obtained after washing, 10 g of ceramic balls having a diameter of 1 mm ⁇ were added, and a ball mill (manufactured by FRITSCH, (Puleriseette), an impact was applied for 30 minutes at 100 revolutions per minute. After removing the methanol, vacuum drying was performed at 100 ° C. for 12 hours to obtain 25 g of a fired product from the first firing step.
- Example 10 In the first firing step, the same procedure as in Example 5 was repeated except that the maximum temperature reached in the furnace was kept at 1150 ° C. for 1.5 hours, and the fired product (phosphor) from the second firing step was obtained. Obtained. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Example 11 Except for changing the maximum temperature in the furnace to 800 ° C. in the second firing step, the same procedure as in Example 5 was repeated to obtain a fired product (phosphor) from the second firing step. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Example 12 The first firing step was performed according to the same procedure as in Example 5, and 50 g of methanol was added to the fired product obtained after washing, 10 g of ceramic balls having a diameter of 1 mm ⁇ were added, and a ball mill (Pulerisette manufactured by FRITSCH) was added. The impact was applied for 30 minutes at 100 revolutions per minute. After removing methanol, vacuum drying was performed at 100 ° C. for 12 hours to obtain 25 g of a fired product from the first firing step. Subsequently, the second firing step was performed according to the same procedure as in Example 5, and after washing, a fired product (phosphor) from the second firing step was obtained. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Comparative Example 9 In the first firing step, the same procedure as in Example 5 was repeated except that the air flow was not introduced and the nitrogen flow was continuously introduced from the beginning of the first firing step, and the firing from the second firing step. A product (phosphor) was obtained. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Comparative Example 10 The same procedure as in Example 5 was repeated except that the air flow was not introduced and the nitrogen flow was continuously introduced in the second firing step to obtain a fired product (phosphor) from the second firing step. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Comparative Example 11 The same procedure as in Example 5 was repeated except that the first firing step was carried out while always introducing an air flow from the start to the end, and a fired product (phosphor) from the second firing step was obtained. It was. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Comparative Example 12 The same procedure as in Example 5 was repeated except that the second firing step was performed while always introducing an air flow from the start to the end, and a fired product (phosphor) from the second firing step was obtained. It was. The quantum efficiency and fluorescence spectrum of the obtained phosphor were measured, and further, a printing type EL element was prepared and evaluated for EL material. The results are shown in Table 1, FIG.
- Comparative Example 13 To 27 g of the product obtained in Reference Example 1, 1.00 g of potassium chloride, 1.17 g of sodium chloride and 6.87 g of magnesium chloride hexahydrate were added and mixed with a ball mill. Thereto, 1.45 g of sulfur was added and the mixture was placed in a crucible. Thereafter, the crucible was transferred to a firing furnace and heated at a rate of 400 ° C. per hour in an atmosphere in which an air flow was introduced. The temperature was raised to 1100 ° C. and held there for 3 hours. After holding for 3 hours, it was cooled at 500 ° C. per hour and cooled to room temperature.
- the obtained fired product was added to 200 g of a 15% acetic acid solution to disperse the fired product.
- the acetic acid solution was removed by decantation and washed with 500 g of ion-exchanged water until the washing became neutral to obtain a fired product. After removing the ion exchange water, vacuum drying was performed at 100 ° C. for 12 hours to obtain 10.2 g of a fired product from the first firing step.
- the crucible was transferred to a firing furnace, and the temperature was raised to 850 ° C. at a rate of 400 ° C. per hour in an atmosphere in which an air flow was introduced. After holding for 3 hours, it was cooled at 500 ° C. per hour and cooled to room temperature.
- the cooled fired product was dispersed in 200 g of 5% aqueous hydrochloric acid and washed.
- the acidic aqueous solution was removed and washed with 500 g of ion-exchanged water until the washing solution became neutral.
- cleaning liquid showed neutrality with ion-exchange water vacuum drying was performed at 100 degreeC for 12 hours, and 4.1g of baked products from a 2nd baking process were obtained.
- the photoexcited fluorescence spectrum was measured for the obtained fired product (phosphor).
- the fluorescence spectrum of the phosphor is shown in FIG.
- the quantum yield of the phosphor is shown in Table 1.
- a printing type EL device was constructed in the same procedure as in Comparative Example 1 using 1.5 g of the obtained phosphor. About the obtained element, EL brightness
- luminance was measured at 200V and 1 kHz, and evaluation as EL material was performed. The results are shown in Table 2.
- the zinc sulfide-based phosphor obtained by the production method of the present invention is not only high in fluorescence quantum efficiency but also processed into an EL element. Later, high EL luminance is exhibited. Therefore, the present invention has great industrial utility in that a more practical phosphor material suitable for manufacturing a high-luminance EL element can be industrially advantageously provided.
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Abstract
Description
[1] 硫化亜鉛系蛍光体前駆体を焼成して硫化亜鉛系蛍光体を製造する方法であって、少なくとも、
硫化亜鉛系蛍光体前駆体、硫黄及び塩素含有融剤を含有する混合物を焼成する第一焼成工程、及び、
第一焼成工程から得られた焼成物を更に焼成する第二焼成工程
を含み、
前記第一焼成工程では、前記混合物を加熱し、常温から前記蛍光体前駆体の結晶系が転移する温度まで、酸素が導入されている雰囲気下で昇温させ、次に、該転移温度を越えたところから該雰囲気を窒素雰囲気に切り替えて更に加熱を継続し、1000℃以上1200℃以下の範囲内の温度に到達したところで該温度を一定に維持し、その後に、該混合物を急冷し、洗浄して焼成物を得ること、及び、
前記第二焼成工程では、前記第一焼成工程で得られた焼成物を窒素雰囲気下で加熱して、常温から650℃以上1000℃以下の温度まで昇温させ、次に、該温度に到達したところで酸素を導入しながら該温度を保持し、その後に、該焼成物を急冷し、洗浄して、硫化亜鉛系蛍光体を得ること、
を特徴とする製造方法。
[2] 前記第一焼成工程において、窒素雰囲気に切り替える温度が850℃以下の温度である[1]記載の硫化亜鉛系蛍光体の製造方法。
[3] 前記第一焼成工程における洗浄の後、焼成物の結晶に歪みを与えて第二の焼成工程を行う前記[1]又は[2]に記載の硫化亜鉛系蛍光体の製造方法。
[4] 前記洗浄と前記歪み付与を同時に行う前記[3]に記載の硫化亜鉛系蛍光体の製造方法。
[5] 前記第一焼成工程で得られた焼成物に銅、亜鉛及び硫黄を含む化合物を添加して第二の焼成工程を行う前記[1]~[4]のいずれかに記載の硫化亜鉛系蛍光体の製造方法。
[6] 前記蛍光体前駆体が、亜鉛化合物、硫化剤、並びに、銅、銀、金、マンガン、イリジウム及び希土類元素からなる群から選ばれる少なくとも1種類以上の金属元素を含む1種類又は複数種類の金属化合物を含む水溶液を有機溶媒中に添加した後、加熱して共沸脱水を行うことにより得られた硫化亜鉛系蛍光体前駆体である前記[1]~[5]のいずれかに記載の硫化亜鉛系蛍光体の製造方法。
[7] 前記蛍光体前駆体が、亜鉛化合物と、銅、銀、金、マンガン、イリジウム及び希土類元素からなる群から選ばれる少なくとも1種類以上の金属元素を含む1種類又は複数種類の金属化合物とを含む水溶液に硫化剤を添加して反応させることにより反応生成物として得られた硫化亜鉛系蛍光体前駆体である前記[1]~[5]のいずれかに記載の硫化亜鉛系蛍光体の製造方法。
[8] 前記硫化剤がチオアセトアミドおよび/または硫化水素である前記[6]又は[7]に記載の硫化亜鉛系蛍光体の製造方法。
[9] 前記蛍光体前駆体が、硫化亜鉛、並びに、銅、銀、金、マンガン、イリジウム及び希土類元素からなる群から選ばれる少なくとも1種類以上の金属元素を含む1種類又は複数種類の金属化合物を含む混合物である前記[1]~[5]のいずれかに記載の硫化亜鉛系蛍光体の製造方法。
[10]前記酸素の導入は、酸素を含む気体流を蛍光体前駆体の周囲の雰囲気に流入させることによって行うことを特徴とする、前記[1]~[9]のいずれかに記載の硫化亜鉛系蛍光体の製造方法。
[11]前記酸素を含む気体流が空気流であることを特徴とする、前記[10]に記載の硫化亜鉛系蛍光体の製造方法。
励起波長:350nm
励起バンド幅:5nm
ソフトウェア:Spectra Manager for Windows(登録商標)95/NT Ver1.00.00 2005 日本分光株式会社製
参考例1(蛍光体前駆体の製造例1):
酢酸亜鉛・2水和物65.9g、硝酸銅・3水和物0.056g(銅700ppm相当)、硝酸ガリウム・8水和物0.008g(ガリウム50ppm相当)、チオアセトアミド45.0g、酢酸5gをイオン交換水500gに溶解した。2L三つ口フラスコに、ディーン・スターク装置、還流管、温度計、攪拌器を装着し、o-キシレン800mlを取り、系内を窒素置換した。オイル浴内の温度を150℃に調整し、反応器内のo-キシレンを130℃に昇温したのち、酢酸亜鉛を含有する溶液を毎時100mlで加えながら、留出する水をディーン・スターク装置で除去しながら反応を進めた。約6時間で全ての水溶液をフィードし、更に30分間系内の水分を除去した。室温に冷却後、析出した硫化物を沈殿させ、有機溶剤を除去して、目的物を回収し、真空乾燥機にて、100℃で12時間乾燥した。回収量は28.9gであり、理論量の98%であった。
3L三口フラスコに、攪拌器、温度計、還流管および固体フィーダを装着し、硝酸亜鉛・6水和物297.6g、硝酸銅・3水和物0.186g(銅500ppm相当)、六塩化イリジウム二アンモニウム0.022g(イリジウム100ppm相当)を取り、イオン交換水1000gを加えて溶解した。そこに、60%硝酸を添加し、系内のpHを2に調整した。系内を窒素で置換した後、加熱して90℃まで昇温した。所定温度に到達したところで、チオアセトアミド113.0gを固体フィーダより投入し、反応を開始させた。反応をそのまま2時間継続した後、室温に冷却後、析出した硫化物を沈殿させ、デカンテーションにより上澄み液を除去し、更に、イオン交換水3Lを使用して、系内のpHが中性域を示すまで洗浄を行った。目的物を回収し、真空乾燥機にて、100℃で12時間乾燥した。回収量は94.16gであり、理論量の96.6%であった。
THINKEY社製混合器(ARE-250)の100ml容器に、硫化亜鉛(堺化学工業社製RAK-N)100gと酢酸銅・3水和物0.20g(銅500ppm相当)を取り、30分間解砕混合した。
参考例1で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム6水和物6.87gを加え、ボールミルで混合した。そこに、硫黄1.45gを添加し、混合物を坩堝に入れた。その後、該坩堝を焼成炉に移し、窒素雰囲気下で、毎時400℃の速度で昇温した。1100℃まで昇温、そのまま3時間保持した。3時間保持した後、室温まで冷却した。
参考例2で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム・6水和物6.87gを加え、ボールミルで混合する以外は、比較例1と同様の手順に従い、蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図2、表2に示す。
参考例3で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム・6水和物6.87gを加え、ボールミルで混合する以外は、比較例1と同様の手順に従い、蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図3、表2に示す。
参考例1で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム・6水和物6.87gを加え、ボールミルで混合した。そこに、硫黄1.45gを添加し、混合物を坩堝に入れた。その後、該坩堝を焼成炉に移し、空気流が導入されている雰囲気下、毎時400℃の速度で昇温した。炉内温度が800℃に到達したところで、導入する気体を空気から窒素に切り替え、1100℃まで昇温、そのまま3時間保持した。3時間保持した後、毎時500℃で冷却し、室温まで冷却した。
参考例2で得られた生成物27gを用いて、実施例1と同様の手順を繰り返し、第一の焼成工程からの焼成物25gを得た。引き続き、実施例1と同様の手順に従い、第二の焼成工程からの焼成物21gを得た。このようにして得られた焼成物(蛍光体)について光励起蛍光スペクトルを測定した。蛍光体の蛍光スペクトルを図5に示す。蛍光体の量子収率を表1に示す。また、得られた蛍光体1.5gを用いて、実施例1と同様の手順に従い、印刷型EL素子を構成した。得られた素子について、200V、1kHzでEL輝度を測定し、EL材料としての評価を行った。結果を表2に示す。
参考例3で得られた生成物25gを用いて、実施例1と同様の手順を繰り返し、第一の焼成工程からの焼成物23gを得た。引き続き、実施例1と同様の手順に従い、第二の焼成工程からの焼成物21gを得た。得られた焼成物(蛍光体)について光励起蛍光スペクトルを測定した。蛍光体の蛍光スペクトルを図6に示す。蛍光体の量子収率を表1に示す。また、得られた蛍光体1.5gを用いて実施例1と同様の手順に従い、印刷型EL素子を構成した。得られた素子について、200V、1kHzでEL輝度を測定し、EL材料評価を行なった。結果を表2に示す。
参考例1で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム・6水和物6.87gを加え、ボールミルで混合した。そこに、硫黄1.45gを添加し、混合物を坩堝に入れた。その後、該坩堝を焼成炉に移し、空気流が導入されている雰囲気下、毎時400℃の速度で昇温した。炉内温度が、300℃に到達したところで、母材化合物である硫化亜鉛の結晶系を転移させることなく、導入する気体を空気から窒素に切り替え、1100℃まで昇温し、その温度で3時間保持した。3時間保持した後、毎時500℃の速度で冷却し、室温まで冷却した。その後の操作は実施例1と同様の手順に従って実施した。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図7、表2に示す。
参考例1で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム6水和物6.87gを加え、ボールミルで混合した。更に、硫黄1.45gを添加し、混合物を坩堝に入れた。その後、該坩堝を焼成炉に移し、空気流が導入されている雰囲気下、毎時400℃の速度で昇温した。炉内温度が900℃に到達したところで、導入する気体を空気から窒素に切り替え、1100℃まで昇温し、その温度で3時間保持した。3時間保持した後、毎時500℃の速度で冷却し、室温まで冷却した。その後の操作は実施例1と同様の手順に従って実施した。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図8、表2に示す。
参考例1で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム6水和物6.87gを加え、ボールミルで混合した。そこに、硫黄1.45gを添加し、混合物を坩堝に入れた。その後、該坩堝を焼成炉に移し、空気流が導入されている雰囲気下、毎時400℃の速度で昇温した。炉内温度が800℃に到達したところで、導入する気体を空気から窒素に切り替え、1250℃まで昇温し、その温度で3時間保持した。3時間保持した後、毎時500℃の速度で冷却し、室温まで冷却した。その後の操作は実施例1と同様の手順に従って実施した。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図9、表2に示す。
参考例1で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム6水和物6.87gを加え、ボールミルで混合した。そこに、硫黄1.45gを添加し、混合物を坩堝に入れた。その後、該坩堝を焼成炉に移し、空気流が導入されている雰囲気下、毎時400℃の速度で昇温した。炉内温度が300℃に到達したところで、導入する気体を空気から窒素に切り替え、1100℃まで昇温し、その温度で3時間保持した。3時間保持した後、放冷により室温まで冷却した。冷却に8時間を要した。その後の操作は実施例1と同様の手順に従って実施した。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図10、表2に示す。
実施例1と同様の手順に従って第一の焼成工程を実施したが、その後に第二の焼成工程を全く実施しなかった以外は実施例1と同様の手順に従った。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図11、表2に示す。
実施例1と同様の手順に従って第一の焼成工程を実施し、洗浄後に得られた焼成物100gをイオン交換水に分散させ、超音波振動器(BRANSON社製、Degital Sonifier)にて、出力60%で30分超音波振動を加えた。イオン交換水を除去した後、真空乾燥を100℃で12時間行い、第一の焼成工程からの焼成物24gを得た。引き続き、実施例1と同様の手順に従って第二の焼成工程を実施し、洗浄後、焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図12、表2に示す。
実施例1と同様の手順に従って第一の焼成工程を実施し、洗浄後に得られた焼成物100gをイオン交換水に分散させ、超音波振動器(BRANSON社製、Degital Sonifier)にて、出力60%で30分超音波振動を加えた。イオン交換水を除去した後、真空乾燥を100℃で12時間行い、第一の焼成工程からの焼成物24gを得た。この焼成物に、酢酸銅0.24g、硫酸亜鉛3.6gおよび硫黄0.4gを添加し、混合した後、実施例1と同様の手順に従って第二の焼成工程を実施し、洗浄後、焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図13、表2に示す。
実施例2と同様の手順に従って第一の焼成工程を実施し、洗浄後に得られた焼成物25gに、50gのメタノールを添加し、直径1mmφのセラミックボール10gを加えて、ボールミル(FRITSCH社製、Puluerisette)にて、毎分100回転で30分衝撃を付与した。メタノールを除去した後、真空乾燥を100℃、12時間行い、第一の焼成工程からの焼成物25gを得た。引き続き、実施例2と同様の手順に従い、第二の焼成工程を実施し、洗浄後、焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図14、表2に示す。
実施例2と同様の手順に従って第一の焼成工程を実施し、洗浄後に得られた焼成物25gに、50gのメタノールを添加し、直径1mmφのセラミックボール10gを加えて、ボールミル(FRITSCH社製、Puluerisette)にて、毎分100回転で30分衝撃を加えた。メタノールを除去した後、真空乾燥を100℃、12時間行い、第一の焼成工程からの焼成物25gを得た。この焼成物に酢酸銅0.25g、硫酸亜鉛3.8gおよび硫黄0.4gを添加混合して、引き続き、実施例2と同様の手順に従って第二の焼成工程を実施し、洗浄後、焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図15、表2に示す。
実施例3と同様の手順に従って第一の焼成工程を実施し、洗浄後に得られた焼成物25gに、50gのメタノールを添加し、直径1mmφのセラミックボール10gを加えて、ボールミル(FRITSCH社製、Puluerisette)にて、毎分100回転で30分衝撃を加えた。メタノールを除去した後、真空乾燥を100℃、12時間行い、第一の焼成工程からの焼成物23.3gを得た。引き続き、実施例3と同様の手順に従って第二の焼成工程を実施し、洗浄後、焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図16、表2に示す。
実施例3と同様の手順に従って第一の焼成工程を実施し、洗浄後に得られた焼成物25gに、50gのメタノールを添加し、直径1mmφのセラミックボール10gを加えて、ボールミル(FRITSCH社製、Puluerisette)にて、毎分100回転で30分衝撃を付与した。メタノールを除去した後、真空乾燥を100℃、12時間行い、第一の焼成工程からの焼成物25gを得た。この焼成物に酢酸銅0.22g、硫酸亜鉛3.4gおよび硫黄0.4gを添加混合して、引き続き、実施例3と同様の手順に従って第二の焼成工程を実施し、洗浄後、焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図17、表2に示す。
第一の焼成工程において、炉内の最高到達温度を1150℃として1.5時間保持した以外は、実施例5と同様の手順を繰り返し、第2の焼成工程からの焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図18、表2に示す。
第二の焼成工程において炉内の最高到達温度を800℃に変更した以外は、実施例5と同様の手順を繰り返し、第2の焼成工程からの焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図19、表2に示す。
実施例5と同様の手順に従って第一の焼成工程を実施し、洗浄後に得られた焼成物に、50gのメタノールを添加、直径1mmφのセラミックボール10gを加えて、ボールミル(FRITSCH社製、Puluerisette)にて、毎分100回転で30分衝撃を付与した。メタノールを除去した後、真空乾燥を100℃で12時間行い、第一の焼成工程からの焼成物25gを得た。引き続き、実施例5と同様の手順に従って第二の焼成工程を実施し、洗浄後、第二の焼成工程からの焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図20、表2に示す。
第一の焼成工程において、空気流を導入せず、第1焼成工程の開始当初から窒素流を導入し続けた以外は、実施例5と同様の手順を繰り返し、第二の焼成工程からの焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を、表1、図21、表2に示す。
第二の焼成工程において空気流を導入せず、窒素流を導入し続けた以外は、実施例5と同様の手順を繰り返し、第二の焼成工程からの焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図22、表2に示す。
第一の焼成工程を、開始時から終了時まで常時空気流を導入しながら実施した以外は、実施例5と同様の手順を繰り返し、第二の焼成工程からの焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図23、表2に示す。
第二の焼成工程を、開始時から終了時まで常時空気流を導入しながら実施した以外は、実施例5と同様の手順を繰り返し、第二の焼成工程からの焼成物(蛍光体)を得た。得られた蛍光体の量子効率、蛍光スペクトルを測定し、さらに印刷型EL素子を作成してEL材料評価を行った。結果を表1、図24、表2に示す。
参考例1で得られた生成物27gに、塩化カリウム1.00g、塩化ナトリウム1.17g、塩化マグネシウム・6水和物6.87gを加え、ボールミルで混合した。そこに、硫黄1.45gを添加し、混合物を坩堝に入れた。その後、該坩堝を焼成炉に移し、空気流が導入されている雰囲気下、毎時400℃の速度で昇温した。1100℃まで昇温、そのまま3時間保持した。3時間保持した後、毎時500℃で冷却し、室温まで冷却した。
Claims (11)
- 硫化亜鉛系蛍光体前駆体を焼成して硫化亜鉛系蛍光体を製造する方法であって、少なくとも、
硫化亜鉛系蛍光体前駆体、硫黄及び塩素含有融剤を含有する混合物を焼成する第一焼成工程、及び、
第一焼成工程から得られた焼成物を更に焼成する第二焼成工程
を含み、
前記第一焼成工程では、前記混合物を加熱し、常温から前記蛍光体前駆体の結晶系が転移する温度まで、酸素が導入されている雰囲気下で昇温させ、次に、該転移温度を越えたところから該雰囲気を窒素雰囲気に切り替えて更に加熱を継続し、1000℃以上1200℃以下の範囲内の温度に到達したところで該温度を一定に維持し、その後に、該混合物を急冷し、洗浄して焼成物を得ること、及び、
前記第二焼成工程では、前記第一焼成工程で得られた焼成物を窒素雰囲気下で加熱して、常温から650℃以上1000℃以下の温度まで昇温させ、次に、該温度に到達したところで酸素を導入しながら該温度を保持し、その後に、該焼成物を急冷し、洗浄して、硫化亜鉛系蛍光体を得ること、
を特徴とする製造方法。 - 前記第一焼成工程において、窒素雰囲気に切り替える温度が850℃以下の温度である請求項1に記載の硫化亜鉛系蛍光体の製造方法。
- 前記第一焼成工程における洗浄の後、焼成物の結晶に歪みを与えて第二の焼成工程を行う請求項1又は2に記載の硫化亜鉛系蛍光体の製造方法。
- 前記洗浄と前記歪み付与を同時に行う請求項3に記載の硫化亜鉛系蛍光体の製造方法。
- 前記第一焼成工程で得られた焼成物に銅、亜鉛及び硫黄を含む化合物を添加して第二の焼成工程を行う請求項1~4のいずれか1項に記載の硫化亜鉛系蛍光体の製造方法。
- 前記蛍光体前駆体が、亜鉛化合物、硫化剤、並びに、銅、銀、金、マンガン、イリジウム及び希土類元素からなる群から選ばれる少なくとも1種類以上の金属元素を含む1種類又は複数種類の金属化合物を含む水溶液を有機溶媒中に添加した後、加熱して共沸脱水を行うことにより得られた硫化亜鉛系蛍光体前駆体である請求項1~5のいずれか1項に記載の硫化亜鉛系蛍光体の製造方法。
- 前記蛍光体前駆体が、亜鉛化合物と、銅、銀、金、マンガン、イリジウム及び希土類元素からなる群から選ばれる少なくとも1種類以上の金属元素を含む1種類又は複数種類の金属化合物とを含む水溶液に硫化剤を添加して反応させることにより反応生成物として得られた硫化亜鉛系蛍光体前駆体である請求項1~5のいずれか1項に記載の硫化亜鉛系蛍光体の製造方法。
- 前記硫化剤がチオアセトアミドおよび/または硫化水素である請求項6又は7記載の硫化亜鉛系蛍光体の製造方法。
- 前記蛍光体前駆体が、硫化亜鉛、並びに、銅、銀、金、マンガン、イリジウム及び希土類元素からなる群から選ばれる少なくとも1種類以上の金属元素を含む1種類又は複数種類の金属化合物を含む混合物である請求項1~5のいずれか1項に記載の硫化亜鉛系蛍光体の製造方法。
- 前記酸素の導入は、酸素を含む気体流を蛍光体前駆体の周囲の雰囲気に流入させることによって行うことを特徴とする、請求項1~9のいずれか1項に記載の硫化亜鉛系蛍光体の製造方法。
- 前記酸素を含む気体流が空気流であることを特徴とする、請求項10に記載の硫化亜鉛系蛍光体の製造方法。
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CN2009801305485A CN102112576B (zh) | 2008-08-06 | 2009-07-30 | 硫化锌系荧光体的制造方法 |
US13/057,168 US8337722B2 (en) | 2008-08-06 | 2009-07-30 | Method for producing zinc sulfide based phosphor |
EP09804903A EP2319896B1 (en) | 2008-08-06 | 2009-07-30 | Method for manufacturing zinc sulfide based phosphor |
JP2010523836A JP5337158B2 (ja) | 2008-08-06 | 2009-07-30 | 硫化亜鉛系蛍光体の製造方法 |
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US (1) | US8337722B2 (ja) |
EP (1) | EP2319896B1 (ja) |
JP (1) | JP5337158B2 (ja) |
KR (1) | KR20110044743A (ja) |
CN (1) | CN102112576B (ja) |
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WO (1) | WO2010016419A1 (ja) |
Cited By (2)
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WO2010147180A1 (ja) * | 2009-06-18 | 2010-12-23 | 株式会社クラレ | 硫化亜鉛系青色蛍光体の製造方法 |
US20130105737A1 (en) * | 2010-05-14 | 2013-05-02 | Sakai Chemical Industry Co., Ltd. | Zinc sulfide blue phosphor and a method for producing the same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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EP2511236B1 (en) * | 2011-04-14 | 2015-07-01 | Rohm and Haas Company | Improved quality multi-spectral zinc sulfide |
CN102618917A (zh) * | 2012-03-22 | 2012-08-01 | 桂林理工大学 | 水热法结合脉冲电沉积制备宽禁带ZnS薄膜材料的方法 |
JP6384806B2 (ja) * | 2014-03-18 | 2018-09-05 | 国立研究開発法人日本原子力研究開発機構 | ZnS蛍光体及びその製造方法 |
CN103992793A (zh) * | 2014-05-04 | 2014-08-20 | 徐州工程学院 | 一种高色度绿色荧光粉的制造方法 |
JP2022531428A (ja) * | 2019-05-02 | 2022-07-06 | ソルグロ,インコーポレイテッド | 蛍光体を合成する方法及び組成物並びに光変換用重合体マトリクスへのその取込み |
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- 2009-07-30 JP JP2010523836A patent/JP5337158B2/ja not_active Expired - Fee Related
- 2009-07-30 US US13/057,168 patent/US8337722B2/en not_active Expired - Fee Related
- 2009-07-30 EP EP09804903A patent/EP2319896B1/en not_active Not-in-force
- 2009-07-30 CN CN2009801305485A patent/CN102112576B/zh not_active Expired - Fee Related
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US20130105737A1 (en) * | 2010-05-14 | 2013-05-02 | Sakai Chemical Industry Co., Ltd. | Zinc sulfide blue phosphor and a method for producing the same |
Also Published As
Publication number | Publication date |
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JP5337158B2 (ja) | 2013-11-06 |
TW201012900A (en) | 2010-04-01 |
US20110147663A1 (en) | 2011-06-23 |
US8337722B2 (en) | 2012-12-25 |
EP2319896B1 (en) | 2013-03-13 |
KR20110044743A (ko) | 2011-04-29 |
CN102112576A (zh) | 2011-06-29 |
EP2319896A1 (en) | 2011-05-11 |
EP2319896A4 (en) | 2011-09-07 |
TWI464237B (zh) | 2014-12-11 |
CN102112576B (zh) | 2013-07-31 |
JPWO2010016419A1 (ja) | 2012-01-19 |
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