WO2010008020A1 - Vapor deposition material for the production of strontium /calcium composite oxide films - Google Patents

Vapor deposition material for the production of strontium /calcium composite oxide films Download PDF

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Publication number
WO2010008020A1
WO2010008020A1 PCT/JP2009/062809 JP2009062809W WO2010008020A1 WO 2010008020 A1 WO2010008020 A1 WO 2010008020A1 JP 2009062809 W JP2009062809 W JP 2009062809W WO 2010008020 A1 WO2010008020 A1 WO 2010008020A1
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Prior art keywords
strontium
calcium
vapor deposition
deposition material
range
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PCT/JP2009/062809
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French (fr)
Japanese (ja)
Inventor
彰 増田
薫 高崎
真人 財田
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宇部マテリアルズ株式会社
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Application filed by 宇部マテリアルズ株式会社 filed Critical 宇部マテリアルズ株式会社
Priority to CN2009801360529A priority Critical patent/CN102159502A/en
Priority to JP2010520881A priority patent/JP5543348B2/en
Publication of WO2010008020A1 publication Critical patent/WO2010008020A1/en

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/082—Oxides of alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/02—Oxides or hydroxides
    • C01F11/04—Oxides or hydroxides by thermal decomposition
    • C01F11/06—Oxides or hydroxides by thermal decomposition of carbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/34—Methods for preparing oxides or hydroxides in general by oxidation or hydrolysis of sprayed or atomised solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/28—Vacuum evaporation by wave energy or particle radiation
    • C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
    • H01J9/02—Manufacture of electrodes or electrode systems
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter

Definitions

  • the present invention relates to a vapor deposition material that can be advantageously used when producing a strontium / calcium composite oxide film, particularly by an electron beam vapor deposition method, and a method for producing the vapor deposition material.
  • the present invention also relates to a method for producing a strontium / calcium composite oxide film using an electron beam evaporation method.
  • An AC type plasma display panel (hereinafter referred to as AC type PDP) is generally composed of a front plate serving as an image display surface and a back plate disposed so as to face each other across a discharge space filled with a discharge gas.
  • the front plate includes a front glass substrate, a pair of discharge electrodes formed on the front glass substrate, a dielectric layer covering the discharge electrodes, and a dielectric layer protective film formed on the surface of the dielectric layer.
  • the back plate is a back glass substrate, an address electrode formed on the back glass substrate, a partition that covers the back glass substrate and the address electrode and partitions the discharge space, and red and green disposed on the surface of the partition And a phosphor layer formed of a blue phosphor.
  • the following steps (1) to (4) are repeated to increase the number of charged particles in the discharge space.
  • Light is generated.
  • the generated vacuum ultraviolet light excites red, green, and blue phosphors to generate visible light, and an image is formed by a combination of the visible light.
  • An electric field is generated between the discharge electrodes, and charged particles such as ions and electrons existing in the discharge gas are accelerated and collide with the dielectric layer protective film.
  • Secondary electrons are emitted from the dielectric layer protective film by collision of charged particles.
  • the emitted secondary electrons collide with discharge gas atoms that are not ionized to generate discharge gas ions.
  • the generated discharge gas ions collide with the dielectric layer protective film through the process (1).
  • the dielectric layer protective film not only protects the dielectric layer from impact caused by collision of charged particles, but also functions as a secondary electron emission film.
  • the dielectric layer protective film has high impact resistance against charged particles (that is, high sputtering resistance) and a high secondary electron emission coefficient (that is, the effect of reducing the discharge start voltage and the discharge sustain voltage). High).
  • the magnesium oxide film for the dielectric layer protective film is formed by a physical vapor deposition method (PVD method) such as an electron beam evaporation method.
  • PVD method physical vapor deposition method
  • the strontium / calcium composite oxide film has a higher secondary electron emission coefficient than the magnesium oxide film.
  • Non-Patent Document 1 discloses that an AC type PDP using a strontium / calcium composite oxide film as a dielectric layer protective film has a lower discharge voltage than an AC type PDP using a magnesium oxide film as a dielectric layer protective film. It has been reported.
  • Vapor deposition material used to manufacture AC type PDP dielectric layer protective film by physical vapor deposition such as electron beam vapor deposition is difficult to adsorb water vapor or carbon dioxide gas in air and has low reactivity Is preferred. This is because the vapor deposition material altered by the adsorption of water vapor or carbon dioxide gas or reaction with them takes time to release the adsorbed gas in the vacuum chamber of the vapor deposition apparatus and evacuate the vacuum chamber. This is because it is difficult to maintain a constant degree of vacuum in the vacuum chamber.
  • oxides and composite oxides of alkaline earth metals such as magnesium, calcium, strontium, and barium are known to have high adsorptivity to or reactivity with water vapor and carbon dioxide gas.
  • Patent Document 1 discloses a vapor deposition material for an AC type PDP protective film, which is a sintered body having a relative density of 90% or more and made of an alkaline earth metal oxide or composite oxide and having an average particle diameter of 100 ⁇ m or more. It is described that the moisture resistance of the vapor deposition material is improved by subjecting the vapor deposition material to a surface treatment with an organic silicate.
  • Patent Document 2 describes a highly moisture-resistant vapor-deposited material formed of an alkaline earth metal oxide or composite oxide polycrystal, sintered body or single crystal whose surface is covered with a fluoride layer. There is a description of a strontium-calcium composite oxide polycrystal having a surface covered with a fluoride layer.
  • Patent Document 3 discloses a moisture-resistant material formed of a polycrystal, sintered body or single crystal of an alkaline earth metal oxide or composite oxide whose surface is covered with a sulfate layer and / or a sulfide layer.
  • a high vapor deposition material in which there is a description of a strontium / calcium composite oxide polycrystal whose surface is covered with a sulfate layer (sulfide layer).
  • the vapor deposition material described in Patent Document 1 has a large average particle diameter of 100 ⁇ m or more and the specific surface area of the crystal particles is small, so that each crystal particle has low adsorption of water vapor or carbon dioxide gas, Moreover, the reactivity with those gases is also low. However, as the size of the crystal particles increases, the gaps (pores) between the crystal particles usually increase. On the other hand, according to the study by the present inventor, when the average pore size is increased in the polycrystalline body of strontium / calcium composite oxide crystal particles, the mass increase due to contact with water vapor or carbon dioxide gas (that is, water vapor or carbon dioxide gas It has been found that the mass increase due to adsorption or reaction with them increases.
  • the method of coating the surface of the vapor deposition material described in Patent Documents 1 to 3 with a coating material is an effective method in terms of reducing the adsorption of water vapor or carbon dioxide gas or the reactivity with them.
  • a physical vapor deposition method such as an electron beam vapor deposition method using a vapor deposition material coated with a coating material, together with the film material in a vacuum chamber of the vapor deposition apparatus.
  • the coating material is also vaporized, the degree of vacuum in the vacuum chamber becomes unstable, and the uniformity and crystallinity of the resulting film may be reduced.
  • a physical vapor deposition method such as an electron beam vapor deposition method, which is composed of fine crystal particles whose average crystal particle diameter is smaller than 100 ⁇ m.
  • vapor deposition of a polycrystal of strontium / calcium complex oxide crystal particles that does not involve vaporization of impurities other than strontium / calcium complex oxide and has low adsorptivity to water vapor or carbon dioxide gas or low reactivity with them To provide materials.
  • the present inventor includes calcium carbonate particles and strontium carbonate particles in a ratio in which the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2.
  • An average crystal is obtained by a method in which a granule obtained by spray-drying a particle mixture dispersion in which a particle mixture in the range of 0.05 to 2.0 ⁇ m is dispersed in a liquid medium is formed into a pellet and then fired.
  • Sintered small and fine pores with an average pore diameter of 0.01 to 0.50 ⁇ m formed from a polycrystal of fine strontium / calcium complex oxide crystal particles with a particle diameter of 1.0 to 90 ⁇ m It has been found that body pellets can be obtained.
  • the particle mixture dispersion calcium and strontium are included at a molar ratio of 0.2: 0.8 to 0.8: 0.2, and the average particle diameter is 0.05 to Even if a strontium / calcium carbonate double salt particle dispersion liquid in which strontium / calcium carbonate double salt particles in the range of 2.0 ⁇ m are dispersed in a liquid medium is used, polycrystals of fine strontium / calcium composite oxide crystal particles are similarly obtained. It was found that a dense sintered body pellet formed from the body and having a small average pore diameter can be obtained. The sintered body pellet has a mass increase rate of 0.5% by mass or less when left at a temperature of 25 ° C.
  • the film is formed by electron beam evaporation using the sintered pellet, the degree of vacuum in the vacuum chamber of the evaporation system is highly stable, and the film is formed under stable conditions.
  • the present invention was completed by confirming that the obtained strontium / calcium composite oxide film showed high crystallinity.
  • the general formula is represented by Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8), and the average crystal particle diameter is in the range of 1.0 to 90 ⁇ m.
  • the preferable aspect of the vapor deposition material of this invention is as follows. (1) The relative density is 90% or more. (2) For producing a strontium / calcium composite oxide film by an electron beam vapor deposition method, the surface is not provided with a coating made of a material that is vaporized by electron beam irradiation. (3) The mass increase rate is 0.5% by mass or less when left at a temperature of 25 ° C. for 168 hours in an atmosphere with a relative humidity of 47%.
  • the general formula is represented by Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8), and the average crystal grain size is in the range of 1.0 to 90 ⁇ m. 168 in an atmosphere of a relative humidity of 47% at a temperature of 25 ° C. without being provided with a film made of a polycrystal of a strontium / calcium complex oxide crystal particle and made of a material that is vaporized by irradiation with an electron beam on the surface.
  • a vapor deposition material for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method having a mass increase rate of 0.5% by mass or less when left standing for a time.
  • the vapor deposition material of the present invention preferably has a relative density of 90% or more.
  • the vapor deposition material of the present invention is irradiated with an electron beam under reduced pressure to vaporize the strontium / calcium composite oxide, and deposit the vaporized strontium / calcium composite oxide on the substrate.
  • the present invention also includes calcium carbonate particles and strontium carbonate particles in a ratio in which the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2.
  • a method for producing a vapor deposition material of the present invention which includes a step of forming a pellet into a pellet and a step of firing the obtained pellet-shaped molded product.
  • the present invention further includes an average particle size in the range of 0.05 to 2.0 ⁇ m, containing calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2.
  • a step of preparing a strontium / calcium carbonate double salt particle dispersion in which the strontium / calcium carbonate double salt particles are dispersed in a liquid medium a step of spray-drying the dispersion to obtain carbonate double salt particle granules
  • There is also a method for producing a vapor deposition material of the present invention including a step of forming a granular body into a pellet and a step of firing the obtained pellet-shaped product.
  • the vapor deposition material of the present invention itself has low adsorptivity of water vapor and carbon dioxide gas or reactivity with them, it is not particularly necessary to cover the surface with a coating material. Therefore, by using the vapor deposition material of the present invention, a highly crystalline strontium / calcium composite oxide film can be produced under stable conditions using a physical vapor deposition method such as an electron beam vapor deposition method. It is known that strontium / calcium composite oxide films with high crystallinity generally have high sputtering resistance, and strontium / calcium composite oxide films have a higher secondary electron emission coefficient than magnesium oxide films. . Therefore, the strontium / calcium composite oxide film produced using the vapor deposition material of the present invention is useful as a dielectric layer protective film of the AC type PDP.
  • a polycrystalline body that can be advantageously used to form a strontium / calcium composite oxide film by physical vapor deposition is obtained by utilizing the method for producing a vapor deposition material of the present invention. Can be manufactured.
  • the vapor deposition material of the present invention comprises a polycrystalline body of strontium / calcium composite oxide crystal particles represented by a general formula Sr 1-x Ca x O.
  • x is a value in the range of 0.2 to 0.8, preferably a value in the range of 0.3 to 0.7.
  • the vapor deposition material of the present invention has an average pore diameter in the range of 0.01 to 0.50 ⁇ m, preferably in the range of 0.01 to 0.30 ⁇ m, particularly preferably in the range of 0.01 to 0.20 ⁇ m.
  • the average pore diameter is a value measured by a mercury intrusion method.
  • the average crystal particle diameter of the strontium / calcium complex oxide crystal particles constituting the vapor deposition material of the present invention is in the range of 1.0 to 90 ⁇ m, preferably in the range of 5.0 to 80 ⁇ m.
  • the shape of the vapor deposition material of the present invention is not particularly limited, but is preferably a disc shape.
  • the disk-shaped vapor deposition material preferably has a diameter in the range of 2.0 to 10 mm, and preferably has a thickness in the range of 1.0 to 5.0 mm. The thinner the thickness, the higher the deposition rate while maintaining the quality of the strontium / calcium composite oxide film (homogeneity of film density, uniformity of crystal orientation, etc.) obtained by the electron beam evaporation method.
  • the aspect ratio (thickness / diameter) of the disk-shaped vapor deposition material is preferably 1.0 or less.
  • the vapor deposition material of the present invention preferably has a relative density of 90% or more, particularly preferably 95% or more.
  • the relative density is a value representing the ratio between the bulk density and the true density as a percentage.
  • the true density of the vapor deposition material is as follows from the true density of calcium oxide, the true density of strontium oxide, and the molar ratio of calcium to strontium in the vapor deposition material when the total molar amount is 1. Calculated using the formula.
  • True density (g / cm 3) 3.350g / cm 3 ( true density of strontium oxide) ⁇ the molar ratio of calcium in the polycrystalline body + 5.009g / cm 3 (true density of calcium oxide) ⁇ polycrystalline body Molar ratio of strontium
  • the vapor deposition material of the present invention has a mass increase rate of 0.5% by mass or less, particularly in a range of 0.01 to 0.5% by mass when left at a temperature of 25 ° C. in an atmosphere of 47% relative humidity for 168 hours.
  • the adsorption property of water vapor and carbon dioxide gas or the reactivity with them is low. For this reason, it is not particularly necessary to coat the surface of the vapor deposition material of the present invention with a coating material.
  • the vapor deposition material of the present invention can be advantageously used to form a strontium / calcium composite oxide film by physical vapor deposition.
  • physical vapor deposition methods that can use the vapor deposition material of the present invention include electron beam vapor deposition, ion plating, and sputtering.
  • the vapor deposition material of the present invention can be advantageously used for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method. That is, the vapor deposition material of the present invention is placed in a vapor deposition chamber of an electron beam vapor deposition apparatus, and the vapor deposition material is irradiated with an electron beam under reduced pressure to vaporize the strontium / calcium composite oxide, thereby vaporizing the vaporized strontium / calcium composite oxide.
  • the pressure in the vapor deposition chamber at the time of film production is preferably 6.00 ⁇ 10 ⁇ 2 Pa or less in total pressure.
  • oxygen gas is present in the vapor deposition chamber in an oxygen partial pressure range of 0.10 to 5.99 ⁇ 10 ⁇ 2 Pa, particularly 0.50 to 4.00 ⁇ 10 ⁇ 2 Pa. Is preferred.
  • the vapor deposition material of the present invention contains, for example, calcium carbonate particles and strontium carbonate particles in a ratio such that the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2.
  • the average particle diameter means a value measured by a laser diffraction method when the value is 0.1 ⁇ m or more, and a value measured by a dynamic light scattering method when the value is less than 0.1 ⁇ m. means.
  • the particle mixture dispersion is obtained by adding calcium carbonate particles and strontium carbonate particles into a liquid medium, and using a pulverizer such as a ball mill or a media mill (stirring mill) to obtain calcium carbonate particles and strontium carbonate particles. And pulverizing with mixing.
  • the raw material calcium carbonate particles preferably have an average particle size in the range of 0.05 to 100 ⁇ m, and more preferably in the range of 0.08 to 100 ⁇ m.
  • the calcium carbonate particles preferably have a BET specific surface area in the range of 0.1 to 50 m 2 / g.
  • the calcium carbonate particles preferably have a cubic primary particle shape, and more preferably have a cubic shape with an aspect ratio in the range of 1 to 2.
  • the purity of the calcium carbonate particles is preferably 99% by mass or more.
  • the raw material strontium carbonate particles preferably have an average particle size in the range of 0.05 to 100 ⁇ m, and more preferably in the range of 0.08 to 100 ⁇ m.
  • the strontium carbonate particles preferably have a BET specific surface area in the range of 0.1 to 70 m 2 / g.
  • the primary particles are preferably needle-like or cubic.
  • the purity of the strontium carbonate particles is preferably 99% by mass or more.
  • the time required for pulverizing the average particle size of the particle mixture of calcium carbonate particles and strontium carbonate particles in the mixture dispersion to 2.0 ⁇ m or less is larger when the BET specific surface area is larger. Since it becomes short, it is preferable.
  • liquid medium water, monohydric alcohol and a mixture thereof can be used.
  • monohydric alcohols include ethanol, propanol and butanol.
  • the liquid medium is preferably water.
  • Polycarboxylic acid salt may be added to the particle mixture dispersion.
  • the polycarboxylate acts as a dispersant.
  • the polycarboxylate is preferably an ammonium salt or an alkyl ammonium salt.
  • the addition amount of the polycarboxylate is preferably in the range of 0.5 to 20 parts by mass, particularly preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the solid content in the particle mixture dispersion.
  • the polycarboxylate may be added to the particle mixture dispersion, or may be preliminarily attached to the surface of either or both of the raw material calcium carbonate particles and strontium carbonate particles.
  • a binder having compatibility with the liquid medium it is preferable to add a binder having compatibility with the liquid medium to the particle mixture dispersion.
  • the binder having compatibility with water include polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, and an acrylic copolymer.
  • the addition amount of the binder is preferably in the range of 0.10 to 10 parts by mass with respect to 100 parts by mass of the solid content in the particle mixture dispersion.
  • the binder may be added before mixing and grinding the calcium carbonate particles and strontium carbonate particles, or after mixing and grinding and before spray drying of the particle mixture dispersion.
  • the spray drying of the particle mixture dispersion can be performed using a normal spray dryer.
  • the spray drying temperature is preferably in the range of 150 to 280 ° C.
  • the dried mixed granule obtained by spray drying the particle mixture dispersion is formed into pellets, and the obtained pellets are fired to oxidize calcium carbonate and strontium carbonate while producing strontium
  • the vapor deposition material of the present invention can be obtained by sintering the calcium composite oxide.
  • a normal press molding method can be used for molding the pellet-shaped molded product.
  • the molding pressure is generally in the range of 0.3 to 3 ton / cm 2 .
  • the pellet-shaped molded product is preferably fired at a temperature of 1400 to 1800 ° C.
  • the firing time varies depending on requirements such as the size (particularly thickness) of the molded product and the firing temperature, and cannot be uniformly determined, but is generally 1 to 7 hours.
  • the vapor deposition material of the present invention can also be produced using strontium / calcium carbonate double salt particles as a raw material. That is, the vapor deposition material of the present invention contains calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2 and has an average particle size of 0.05 to 2.
  • a step of preparing a strontium / calcium carbonate double salt particle dispersion in which strontium / calcium carbonate double salt particles in a range of 0.0 ⁇ m are dispersed in a liquid medium, and spray-drying the dispersion to form a carbonate double salt particle granule It can also be produced by a method including a step of obtaining, a step of forming the granular body into a pellet, and a step of firing the obtained pellet-shaped product.
  • the strontium-calcium carbonate double salt particles used as a raw material contain a strontium-calcium aqueous solution containing calcium ions and strontium ions in an amount ranging from 0.2: 0.8 to 0.8: 0.2 in molar ratio Further, it can be synthesized by adding an aqueous ammonia solution to adjust the pH to the range of 7 to 14 and then supplying carbon dioxide gas. It can also be synthesized by supplying carbon dioxide gas to an aqueous solution containing calcium hydroxide and strontium hydroxide in a molar ratio of 0.2: 0.8 to 0.8: 0.2. can do.
  • the temperature of the aqueous solution when synthesizing the strontium / calcium carbonate double salt particles is preferably in the range of 5 to 80 ° C.
  • the strontium / calcium carbonate double salt produced by carbonation of calcium ions and strontium ions is preferably taken out from the aqueous solution, washed and dried, and then used as a material for the vapor deposition material.
  • the strontium / calcium carbonate double salt particle dispersion can be prepared by pulverizing the strontium / calcium carbonate double salt particles synthesized as described above in a liquid medium using a pulverizer such as a ball mill or a media mill. it can.
  • the liquid medium is preferably water.
  • a binder having compatibility with the liquid medium is preferably added to the carbonate double salt particle dispersion before spray drying.
  • the addition amount of the binder is preferably in the range of 0.10 to 10 parts by mass with respect to 100 parts by mass of the strontium / calcium carbonate double salt particles in the dispersion.
  • the step of spraying and drying carbonate double salt particle dispersion to obtain carbonate double salt particle granules the step of forming the granules into pellets, and the step of firing the obtained pellets, This can be the same as when calcium particles and strontium carbonate particles are used.
  • Example 1 (1) Preparation of Particle Mixture Dispersion Calcium carbonate particles (purity: 99.5% by mass, BET specific surface area: 44 m 2 / g, average particle size: 6.9 ⁇ m, primary particle shape: cubic) 101 g, strontium carbonate particles ( Purity: 99.5% by mass, BET specific surface area: 20 m 2 / g, average particle size: 1.2 ⁇ m, primary particle shape: needle shape) 149 g and 583 mL of water were mixed, and calcium carbonate particles and strontium carbonate particles were mixed. A mixed solution was obtained (the molar ratio of calcium to strontium was 0.5: 0.5).
  • This mixed solution was put into a ball mill filled with nylon balls with a core (diameter: 10 mm), and calcium carbonate particles and strontium carbonate particles were mixed and ground for 25 hours to prepare a particle mixture dispersion.
  • the average particle diameter and the BET specific surface area of the particle mixture in the particle mixture dispersion were measured by the following method. The results and the molar ratio of calcium and strontium in the particle mixture dispersion are shown in Table 1.
  • Measurement was performed using a laser diffraction particle size distribution analyzer (Microtrack 9320HRA, manufactured by Nikkiso Co., Ltd.). A sample for measuring the average particle size was prepared by diluting the particle mixture dispersion with 50 g of water with respect to 0.5 g of the solid content in the dispersion, followed by ultrasonic dispersion for 3 minutes.
  • BET specific surface area A part of the particle mixture dispersion is dried at a temperature of 120 ° C., and the BET specific surface area of the obtained dry powder is measured by a BET one-point method using a specific surface area measuring device (Monosorb, Yuasa Ionics Co., Ltd.). did.
  • the sintered pellet was cut in the diameter direction, and the cut surface was mirror polished. Then, the average crystal particle diameter of the strontium / calcium composite oxide crystal particles on the cut surface was measured using a field emission scanning electron microscope. The average crystal particle size was determined by observing 200 crystal particles at an enlargement magnification of 1500 times, measuring the longest diameter (Ferret diameter) of each crystal particle, and averaging this.
  • Average pore diameter 4 ⁇ cumulative pore volume / cumulative specific surface area
  • Mass increase rate The sintered pellets whose mass was measured in advance were allowed to stand for 168 hours in a constant temperature and humidity chamber prepared at a temperature of 25 ° C. and a relative humidity of 47%. The mass increase rate after standing was measured, and the mass increase rate was calculated.
  • the X-ray diffraction pattern of the strontium / calcium composite oxide film was measured using an X-ray diffractometer under the conditions of a tube voltage of 40 kV, a tube current of 200 mA, a scanning angle of 20 to 80 degrees, and a scanning speed of 0.02 degrees / second. The intensity of the diffraction line peak corresponding to the (111) plane was measured.
  • Example 2 In Example 1 (1), a mixed solution of calcium carbonate particles and strontium carbonate particles was charged into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 mm.
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding for 15 minutes, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 3 In Example 1 (1), a mixed solution of calcium carbonate particles and strontium carbonate particles was charged into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 mm.
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding for 60 minutes, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 4 In Example 1 (1), calcium carbonate particles having a purity of 99.5% by mass, a BET specific surface area of 0.22 m 2 / g, an average particle size of 13.8 ⁇ m, and a primary particle shape of cubic calcium carbonate particles. Used, a mixed solution of calcium carbonate particles and strontium carbonate particles is put into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 ⁇ m, and mixed and ground for 45 minutes. Sintered pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared, and the sintered pellets were evaluated.
  • MINIZETA manufactured by Ashizawa Finetech Co., Ltd.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 5 In Example 1 (1), the amount of calcium carbonate particles was 20.02 g, the amount of strontium carbonate particles was 118.10 g (the molar ratio of calcium to strontium was 0.2: 0.8), and the amount of water
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 322 mL, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 6 In Example 1 (1), the amount of calcium carbonate particles was 80.06 g, the amount of strontium carbonate particles was 29.52 g (the molar ratio of calcium to strontium was 0.8: 0.2), and the amount of water
  • a sintered body pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 256 mL, and the sintered body pellet was evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 7 (1) Preparation of strontium / calcium carbonate double salt particle dispersion calcium carbonate particles (purity: purity: 99.5% by mass, BET specific surface area: 44 m 2 / g, average particle size: 6.9 ⁇ m, primary particle shape: cubic ) 101 g and strontium carbonate particles (purity: 99.5% by mass, BET specific surface area: 20 m 2 / g, average particle size: 1.2 ⁇ m, primary particle shape: needle shape) are mixed with 149 g of water and 583 mL of water.
  • strontium-calcium carbonate double salt particles 247 g of the obtained strontium-calcium carbonate double salt particles and 576 mL of water are mixed and put into a ball mill filled with a nylon ball with a core (diameter 10 mm), and the strontium-calcium carbonate double salt particles are mixed for 25 hours. By pulverizing, a strontium / calcium carbonate double salt particle dispersion was prepared.
  • Example 8 In Example 7 (1), the amount of calcium carbonate particles was 80.06 g, the amount of strontium carbonate particles was 29.52 g (the molar ratio of calcium to strontium was 0.8: 0.2), and the amount of water was 256 mL. As described above, sintered pellets were manufactured in the same manner as in Example 7 except that the calcium / strontium aqueous solution was manufactured, and the sintered pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the carbonate double salt particle dispersion, the average particle diameter and BET specific surface area of the carbonate double salt particles, and Table 2 shows the average crystal particle diameter, average pore diameter of the sintered pellet, The relative density and the mass increase rate are shown in Table 3, and the measurement results of the average vapor deposition current value and the peak intensity of the (111) plane are shown.
  • Example 1 calcium carbonate particles having a purity of 99.5% by mass, a BET specific surface area of 0.22 m 2 / g, an average particle size of 13.8 ⁇ m, and a primary particle shape of cubic calcium carbonate particles.
  • a sintered body pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared using a mixed pulverization time of the mixed liquid of calcium carbonate particles and strontium carbonate particles for 24 hours.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 1 the sintered pellet was prepared in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding the mixed solution of calcium carbonate particles and strontium carbonate particles for 5 hours. Manufacture and evaluation of sintered compact pellets were performed. Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 3 In Example 1 (1), the amount of calcium carbonate particles was 10.01 g, the amount of strontium carbonate particles was 142.87 g (the molar ratio of calcium to strontium was 0.1: 0.9), and the amount of water A sintered pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 333 mL, and the sintered pellet was evaluated. Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • Example 1 the amount of calcium carbonate particles was 90.07 g, the amount of strontium carbonate particles was 14.76 g (the molar ratio of calcium to strontium was 0.9: 0.1), and the amount of water
  • the sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 245 mL, and the sintered body pellets were evaluated.
  • Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets.
  • Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
  • the peak intensity of the (111) plane is a relative value where the peak intensity of the (111) plane of the strontium / calcium composite oxide film obtained in Comparative Example 1 is 1.

Abstract

A vapor deposition material for the production of strontium/calcium composite oxide films, which consists of a polycrystalline material composed of strontium/calcium composite oxide grains having a general formula of Sr1-xCaxO (wherein x is 0.2 to 0.8) and an average grain diameter of 1.0 to 90µm and which has a mean pore diameter of 0.01 to 50µm.  The vapor deposition material in itself is lowly adsorptive for water vapor or carbon dioxide gas or lowly reactive therewith, so that the vapor deposition material need not be surface-coated specially with a coating material.

Description

ストロンチウム・カルシウム複合酸化物膜製造用の蒸着材Deposition material for strontium-calcium composite oxide film production
　本発明は、ストロンチウム・カルシウム複合酸化物膜を、特には電子ビーム蒸着法により製造する際に有利に用いることができる蒸着材及びその製造方法に関する。本発明はまた、電子ビーム蒸着法を用いたストロンチウム・カルシウム複合酸化物膜の製造方法に関する。 The present invention relates to a vapor deposition material that can be advantageously used when producing a strontium / calcium composite oxide film, particularly by an electron beam vapor deposition method, and a method for producing the vapor deposition material. The present invention also relates to a method for producing a strontium / calcium composite oxide film using an electron beam evaporation method.
　交流型プラズマディスプレイパネル（以下、ＡＣ型ＰＤＰという）は、一般に、画像表示面となる前面板と、放電ガスが充填された放電空間を挟んで対向配置された背面板とからなる。前面板は、前面ガラス基板、前面ガラス基板の上に形成された一対の放電電極、放電電極を被覆する誘電体層、そして誘電体層の表面に形成された誘電体層保護膜からなる。背面板は、背面ガラス基板、背面ガラス基板の上に形成されたアドレス電極、背面ガラス基板とアドレス電極とを被覆し、かつ放電空間を区画する隔壁、そして隔壁の表面に配置された赤、緑、青の蛍光体で形成された蛍光体層からなる。 An AC type plasma display panel (hereinafter referred to as AC type PDP) is generally composed of a front plate serving as an image display surface and a back plate disposed so as to face each other across a discharge space filled with a discharge gas. The front plate includes a front glass substrate, a pair of discharge electrodes formed on the front glass substrate, a dielectric layer covering the discharge electrodes, and a dielectric layer protective film formed on the surface of the dielectric layer. The back plate is a back glass substrate, an address electrode formed on the back glass substrate, a partition that covers the back glass substrate and the address electrode and partitions the discharge space, and red and green disposed on the surface of the partition And a phosphor layer formed of a blue phosphor.
　ＡＣ型ＰＤＰでは、前面板の放電電極に電圧を印加すると、次の（１）～（４）の過程を繰り返すことによって放電空間内の荷電粒子数が増加して、荷電粒子の放電により真空紫外光が発生する。そして、発生した真空紫外光により、赤、緑、青の蛍光体が励起されて可視光が発生し、この可視光の組み合わせによって画像を形成する。
（１）放電電極間に電界が発生して放電ガス中に存在するイオンや電子などの荷電粒子が加速され、誘電体層保護膜に衝突する。
（２）荷電粒子の衝突により、誘電体層保護膜から二次電子が放出される。
（３）放出された二次電子がイオン化していない放電ガス原子に衝突し、放電ガスイオンを生成する。
（４）生成した放電ガスイオンが上記（１）の過程により誘電体層保護膜に衝突する。 In the AC type PDP, when a voltage is applied to the discharge electrode on the front plate, the following steps (1) to (4) are repeated to increase the number of charged particles in the discharge space. Light is generated. The generated vacuum ultraviolet light excites red, green, and blue phosphors to generate visible light, and an image is formed by a combination of the visible light.
(1) An electric field is generated between the discharge electrodes, and charged particles such as ions and electrons existing in the discharge gas are accelerated and collide with the dielectric layer protective film.
(2) Secondary electrons are emitted from the dielectric layer protective film by collision of charged particles.
(3) The emitted secondary electrons collide with discharge gas atoms that are not ionized to generate discharge gas ions.
(4) The generated discharge gas ions collide with the dielectric layer protective film through the process (1).
　上記（１）～（４）の過程において、誘電体層保護膜は誘電体層を荷電粒子の衝突による衝撃から保護するだけでなく、二次電子放出膜としても機能する。一般に誘電体層保護膜の二次電子放出係数が高い方が、ＡＣ型ＰＤＰの放電開始電圧や放電維持電圧が低減する傾向がある。このため、誘電体層保護膜は、荷電粒子に対する耐衝撃性が高く（即ち、耐スパッタ性が高く）、かつ二次電子放出係数が高い（即ち、放電開始電圧や放電維持電圧の低減効果が高い）ことが要求される。 In the above processes (1) to (4), the dielectric layer protective film not only protects the dielectric layer from impact caused by collision of charged particles, but also functions as a secondary electron emission film. In general, the higher the secondary electron emission coefficient of the dielectric layer protective film, the lower the discharge start voltage and the discharge sustain voltage of the AC type PDP. For this reason, the dielectric layer protective film has high impact resistance against charged particles (that is, high sputtering resistance) and a high secondary electron emission coefficient (that is, the effect of reducing the discharge start voltage and the discharge sustain voltage). High).
　誘電体層保護膜としては、現在では酸化マグネシウム膜が広く用いられている。誘電体層保護膜用の酸化マグネシウム膜は、電子ビーム蒸着法などの物理気相成長法（ＰＶＤ法）によって形成されている。 As the dielectric layer protective film, a magnesium oxide film is currently widely used. The magnesium oxide film for the dielectric layer protective film is formed by a physical vapor deposition method (PVD method) such as an electron beam evaporation method.
　一方、ストロンチウム・カルシウム複合酸化物膜は、酸化マグネシウム膜よりも二次電子放出係数が高いことが知られている。 On the other hand, it is known that the strontium / calcium composite oxide film has a higher secondary electron emission coefficient than the magnesium oxide film.
　非特許文献１には、誘電体層保護膜にストロンチウム・カルシウム複合酸化物膜を用いたＡＣ型ＰＤＰは、誘電体層保護膜に酸化マグネシウム膜を用いたＡＣ型ＰＤＰよりも放電電圧が低減することが報告されている。 Non-Patent Document 1 discloses that an AC type PDP using a strontium / calcium composite oxide film as a dielectric layer protective film has a lower discharge voltage than an AC type PDP using a magnesium oxide film as a dielectric layer protective film. It has been reported.
　電子ビーム蒸着法などの物理気相成長法によりＡＣ型ＰＤＰの誘電体層保護膜を製造するのに用いる蒸着材は、空気中の水蒸気や二酸化炭素ガスを吸着し難く、かつ反応性が低い方が好ましい。これは水蒸気や二酸化炭素ガスの吸着もしくはそれらとの反応によって変質した蒸着材は、蒸着装置の真空チャンバー内にて吸着ガスを放出して、真空チャンバー内を真空にするのに時間が掛かり、また真空チャンバー内の真空度を一定に維持するのが難しくなるためである。一方、マグネシウム、カルシウム、ストロンチウム及びバリウムなどのアルカリ土類金属の酸化物や複合酸化物は、水蒸気や二酸化炭素ガスの吸着性もしくはそれらとの反応性が高いことが知られている。 Vapor deposition material used to manufacture AC type PDP dielectric layer protective film by physical vapor deposition such as electron beam vapor deposition is difficult to adsorb water vapor or carbon dioxide gas in air and has low reactivity Is preferred. This is because the vapor deposition material altered by the adsorption of water vapor or carbon dioxide gas or reaction with them takes time to release the adsorbed gas in the vacuum chamber of the vapor deposition apparatus and evacuate the vacuum chamber. This is because it is difficult to maintain a constant degree of vacuum in the vacuum chamber. On the other hand, oxides and composite oxides of alkaline earth metals such as magnesium, calcium, strontium, and barium are known to have high adsorptivity to or reactivity with water vapor and carbon dioxide gas.
　特許文献１には、アルカリ土類金属の酸化物や複合酸化物からなる相対密度が９０％以上の焼結体であって、平均粒子径が１００μｍ以上であるＡＣ型ＰＤＰ保護膜用の蒸着材の記載があり、該蒸着材を有機シリケートで表面処理することにより、蒸着材の耐湿性が向上することが記載されている。 Patent Document 1 discloses a vapor deposition material for an AC type PDP protective film, which is a sintered body having a relative density of 90% or more and made of an alkaline earth metal oxide or composite oxide and having an average particle diameter of 100 μm or more. It is described that the moisture resistance of the vapor deposition material is improved by subjecting the vapor deposition material to a surface treatment with an organic silicate.
　特許文献２には、表面がフッ化物層で覆われたアルカリ土類金属酸化物や複合酸化物の多結晶体、焼結体又は単結晶体により形成された耐湿性の高い蒸着材の記載があり、その中に表面がフッ化物層で覆われたストロンチウム・カルシウム複合酸化物多結晶体の記載がある。 Patent Document 2 describes a highly moisture-resistant vapor-deposited material formed of an alkaline earth metal oxide or composite oxide polycrystal, sintered body or single crystal whose surface is covered with a fluoride layer. There is a description of a strontium-calcium composite oxide polycrystal having a surface covered with a fluoride layer.
　特許文献３には、表面が硫酸化物層及び／又は硫化物層で覆われたアルカリ土類金属酸化物や複合酸化物の多結晶体、焼結体または単結晶体により形成された耐湿性の高い蒸着材の記載があり、その中に表面が硫酸化物層（硫化物層）で覆われたストロンチウム・カルシウム複合酸化物多結晶体の記載がある。 Patent Document 3 discloses a moisture-resistant material formed of a polycrystal, sintered body or single crystal of an alkaline earth metal oxide or composite oxide whose surface is covered with a sulfate layer and / or a sulfide layer. There is a description of a high vapor deposition material, in which there is a description of a strontium / calcium composite oxide polycrystal whose surface is covered with a sulfate layer (sulfide layer).
特開２００８－９１０７４号公報JP 2008-91074 A 特開２００２－２９４４３２号公報JP 2002-294432 A 特開２００４－２８１２７６号公報JP 2004-281276 A
　特許文献１に記載されている蒸着材は、結晶粒子の平均粒子径が１００μｍ以上と大きく、結晶粒子の比表面積が小さくなるため、各々の結晶粒子は水蒸気や二酸化炭素ガスの吸着性が低く、またそれらの気体との反応性も低い。しかし、結晶粒子のサイズが大きくなると、結晶粒子と結晶粒子との間の隙間（細孔）が通常は大きくなる。一方、本発明者の検討によると、ストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体では平均細孔径が大きくなると、水蒸気や二酸化炭素ガスとの接触による質量増加（すなわち、水蒸気や二酸化炭素ガスの吸着もしくはそれらとの反応による質量増加）が多くなることが判明した。 The vapor deposition material described in Patent Document 1 has a large average particle diameter of 100 μm or more and the specific surface area of the crystal particles is small, so that each crystal particle has low adsorption of water vapor or carbon dioxide gas, Moreover, the reactivity with those gases is also low. However, as the size of the crystal particles increases, the gaps (pores) between the crystal particles usually increase. On the other hand, according to the study by the present inventor, when the average pore size is increased in the polycrystalline body of strontium / calcium composite oxide crystal particles, the mass increase due to contact with water vapor or carbon dioxide gas (that is, water vapor or carbon dioxide gas It has been found that the mass increase due to adsorption or reaction with them increases.
　特許文献１～３に記載されている蒸着材の表面を被覆材で被覆する方法は、水蒸気や二酸化炭素ガスの吸着性もしくはそれらとの反応性を低くする点では有効な方法である。しかしながら、本発明者の検討によると、被覆材で被覆された蒸着材を用いて電子ビーム蒸着法などの物理気相成長法により膜を製造する際に、蒸着装置の真空チャンバー内で膜材料と共に被覆材も気化して、真空チャンバー内の真空度が不安定になり、得られる膜の均一性や結晶性が低下する可能性がある。 The method of coating the surface of the vapor deposition material described in Patent Documents 1 to 3 with a coating material is an effective method in terms of reducing the adsorption of water vapor or carbon dioxide gas or the reactivity with them. However, according to the study of the present inventor, when a film is produced by a physical vapor deposition method such as an electron beam vapor deposition method using a vapor deposition material coated with a coating material, together with the film material in a vacuum chamber of the vapor deposition apparatus. The coating material is also vaporized, the degree of vacuum in the vacuum chamber becomes unstable, and the uniformity and crystallinity of the resulting film may be reduced.
　本発明の目的は、結晶粒子の平均結晶粒子径が１００μｍよりも小さい微細な結晶粒子からなり、電子ビーム蒸着法などの物理気相成長法により、ストロンチウム・カルシウム複合酸化物蒸着材を気化させる際に、ストロンチウム・カルシウム複合酸化物以外の不純物の気化を伴うことがない、水蒸気や二酸化炭素ガスの吸着性もしくはそれらとの反応性が低いストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体からなる蒸着材を提供することにある。 It is an object of the present invention to vaporize a strontium / calcium composite oxide vapor-deposited material by a physical vapor deposition method such as an electron beam vapor deposition method, which is composed of fine crystal particles whose average crystal particle diameter is smaller than 100 μm. In addition, vapor deposition of a polycrystal of strontium / calcium complex oxide crystal particles that does not involve vaporization of impurities other than strontium / calcium complex oxide and has low adsorptivity to water vapor or carbon dioxide gas or low reactivity with them To provide materials.
　本発明者は、炭酸カルシウム粒子と炭酸ストロンチウム粒子とを、カルシウムとストロンチウムのモル比が０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にある粒子混合物が液体媒体中に分散されている粒子混合物分散液を噴霧乾燥して得た粒状体をペレット状に成形した後、焼成する方法によって、平均結晶粒子径が１．０～９０μｍの範囲と微細なストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体から形成された、平均細孔直径が０．０１～０．５０μｍの範囲と小さく緻密な焼結体ペレットを得ることができることを見出した。また、粒子混合物分散液の代わりに、カルシウムとストロンチウムとをモル比で０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にあるストロンチウム・カルシウム炭酸複塩粒子が液体媒体に分散されてなるストロンチウム・カルシウム炭酸複塩粒子分散液を用いても同様に微細なストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体から形成された、平均細孔直径が小さい緻密な焼結体ペレットを得ることができることを見出した。そして、その焼結体ペレットは、温度２５℃で、相対湿度４７％の雰囲気下において１６８時間静置したときの質量増加率が０．５質量％以下で、水蒸気や二酸化炭素ガスとの接触による質量増加が少なく、またその焼結体ペレットを用いて電子ビーム蒸着法により膜の形成を行なうと、蒸着装置の真空チャンバー内の真空度が高度に安定し、安定な条件で膜を形成することができ、さらに得られるストロンチウム・カルシウム複合酸化物膜は高い結晶性を示すことを確認して本発明を完成させた。 The present inventor includes calcium carbonate particles and strontium carbonate particles in a ratio in which the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2. An average crystal is obtained by a method in which a granule obtained by spray-drying a particle mixture dispersion in which a particle mixture in the range of 0.05 to 2.0 μm is dispersed in a liquid medium is formed into a pellet and then fired. Sintered small and fine pores with an average pore diameter of 0.01 to 0.50 μm formed from a polycrystal of fine strontium / calcium complex oxide crystal particles with a particle diameter of 1.0 to 90 μm It has been found that body pellets can be obtained. Further, instead of the particle mixture dispersion, calcium and strontium are included at a molar ratio of 0.2: 0.8 to 0.8: 0.2, and the average particle diameter is 0.05 to Even if a strontium / calcium carbonate double salt particle dispersion liquid in which strontium / calcium carbonate double salt particles in the range of 2.0 μm are dispersed in a liquid medium is used, polycrystals of fine strontium / calcium composite oxide crystal particles are similarly obtained. It was found that a dense sintered body pellet formed from the body and having a small average pore diameter can be obtained. The sintered body pellet has a mass increase rate of 0.5% by mass or less when left at a temperature of 25 ° C. in an atmosphere having a relative humidity of 47% for 168 hours, and is brought into contact with water vapor or carbon dioxide gas. When the film is formed by electron beam evaporation using the sintered pellet, the degree of vacuum in the vacuum chamber of the evaporation system is highly stable, and the film is formed under stable conditions. The present invention was completed by confirming that the obtained strontium / calcium composite oxide film showed high crystallinity.
　従って、本発明は、一般式がＳｒ1-xＣａxＯ（但し、ｘは、０．２～０．８の範囲の値）で表され、平均結晶粒子径が１．０～９０μｍの範囲にあるストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体から形成された、平均細孔直径が０．０１～０．５０μｍの範囲にあるストロンチウム・カルシウム複合酸化物膜製造用の蒸着材にある。 Therefore, in the present invention, the general formula is represented by Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8), and the average crystal particle diameter is in the range of 1.0 to 90 μm. The deposition material for producing a strontium / calcium composite oxide film having an average pore diameter in the range of 0.01 to 0.50 μm formed from a polycrystal of strontium / calcium composite oxide crystal particles in FIG.
　本発明の蒸着材の好ましい態様は、次の通りである。
（１）相対密度が９０％以上である。
（２）電子ビーム蒸着法によるストロンチウム・カルシウム複合酸化物膜製造用であって、表面に電子ビームの照射によって気化する材料からなる被膜を備えていない。
（３）温度２５℃で、相対湿度４７％の雰囲気下において１６８時間静置したときの質量増加率が０．５質量％以下である。 The preferable aspect of the vapor deposition material of this invention is as follows.
(1) The relative density is 90% or more.
(2) For producing a strontium / calcium composite oxide film by an electron beam vapor deposition method, the surface is not provided with a coating made of a material that is vaporized by electron beam irradiation.
(3) The mass increase rate is 0.5% by mass or less when left at a temperature of 25 ° C. for 168 hours in an atmosphere with a relative humidity of 47%.
　本発明はまた、一般式がＳｒ1-xＣａxＯ（但し、ｘは、０．２～０．８の範囲の値）で表され、平均結晶粒子径が１．０～９０μｍの範囲にあるストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体から形成された、表面に電子ビームの照射によって気化する材料からなる被膜を備えることなく、温度２５℃で、相対湿度４７％の雰囲気下において１６８時間静置したときの質量増加率が０．５質量％以下である電子ビーム蒸着法によるストロンチウム・カルシウム複合酸化物膜製造用の蒸着材にもある。この本発明の蒸着材は、相対密度が９０％以上であることが好ましい。 In the present invention, the general formula is represented by Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8), and the average crystal grain size is in the range of 1.0 to 90 μm. 168 in an atmosphere of a relative humidity of 47% at a temperature of 25 ° C. without being provided with a film made of a polycrystal of a strontium / calcium complex oxide crystal particle and made of a material that is vaporized by irradiation with an electron beam on the surface. There is also a vapor deposition material for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method having a mass increase rate of 0.5% by mass or less when left standing for a time. The vapor deposition material of the present invention preferably has a relative density of 90% or more.
　本発明はまた、上記本発明の蒸着材に、減圧下にて電子ビームを照射して、ストロンチウム・カルシウム複合酸化物を気化させ、気化したストロンチウム・カルシウム複合酸化物を基板の上に堆積させることからなる基板の上にストロンチウム・カルシウム複合酸化物膜を製造する方法にもある。 In the present invention, the vapor deposition material of the present invention is irradiated with an electron beam under reduced pressure to vaporize the strontium / calcium composite oxide, and deposit the vaporized strontium / calcium composite oxide on the substrate. There is also a method for producing a strontium / calcium composite oxide film on a substrate made of
　本発明はまた、炭酸カルシウム粒子と炭酸ストロンチウム粒子とを、カルシウムとストロンチウムのモル比が０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にある粒子混合物が液体媒体中に分散されている粒子混合物分散液を用意する工程、該分散液を噴霧乾燥して粒子混合物粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む上記本発明の蒸着材の製造方法にもある。 The present invention also includes calcium carbonate particles and strontium carbonate particles in a ratio in which the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2. A step of preparing a particle mixture dispersion in which a particle mixture in the range of 0.05 to 2.0 μm is dispersed in a liquid medium, a step of spray-drying the dispersion to obtain a particle mixture granule, the granule There is also a method for producing a vapor deposition material of the present invention, which includes a step of forming a pellet into a pellet and a step of firing the obtained pellet-shaped molded product.
　本発明はさらに、カルシウムとストロンチウムとをモル比で０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にあるストロンチウム・カルシウム炭酸複塩粒子が液体媒体に分散されてなるストロンチウム・カルシウム炭酸複塩粒子分散液を用意する工程、該分散液を噴霧乾燥して炭酸複塩粒子粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む上記本発明の蒸着材の製造方法にもある。 The present invention further includes an average particle size in the range of 0.05 to 2.0 μm, containing calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2. A step of preparing a strontium / calcium carbonate double salt particle dispersion in which the strontium / calcium carbonate double salt particles are dispersed in a liquid medium, a step of spray-drying the dispersion to obtain carbonate double salt particle granules, There is also a method for producing a vapor deposition material of the present invention including a step of forming a granular body into a pellet and a step of firing the obtained pellet-shaped product.
　本発明の蒸着材は、それ自体が水蒸気や二酸化炭素ガスの吸着性もしくはそれらとの反応性が低いため、特に表面を被覆材で被覆する必要がない。このため本発明の蒸着材を用いることよって、結晶性の高いストロンチウム・カルシウム複合酸化物膜を、電子ビーム蒸着法などの物理気相成長法を利用して安定した条件で製造することができる。結晶性の高いストロンチウム・カルシウム複合酸化物膜は、一般に耐スパッタ性が高く、またストロンチウム・カルシウム複合酸化物膜は、酸化マグネシウム膜と比べて、二次電子放出係数が高いことは知られている。従って、本発明の蒸着材を用いて製造したストロンチウム・カルシウム複合酸化物膜は、ＡＣ型ＰＤＰの誘電体層保護膜として有用である。 Since the vapor deposition material of the present invention itself has low adsorptivity of water vapor and carbon dioxide gas or reactivity with them, it is not particularly necessary to cover the surface with a coating material. Therefore, by using the vapor deposition material of the present invention, a highly crystalline strontium / calcium composite oxide film can be produced under stable conditions using a physical vapor deposition method such as an electron beam vapor deposition method. It is known that strontium / calcium composite oxide films with high crystallinity generally have high sputtering resistance, and strontium / calcium composite oxide films have a higher secondary electron emission coefficient than magnesium oxide films. . Therefore, the strontium / calcium composite oxide film produced using the vapor deposition material of the present invention is useful as a dielectric layer protective film of the AC type PDP.
　また、本発明の蒸着材の製造方法を利用することによって、物理気相成長法により、ストロンチウム・カルシウム複合酸化物膜を形成するのに有利に用いることができる多結晶体を、工業的に有利に製造することができる。 In addition, a polycrystalline body that can be advantageously used to form a strontium / calcium composite oxide film by physical vapor deposition is obtained by utilizing the method for producing a vapor deposition material of the present invention. Can be manufactured.
　本発明の蒸着材は、一般式がＳｒ1-xＣａxＯで表されるストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体からなる。但し、ｘは、０．２～０．８の範囲の値、好ましくは０．３～０．７の範囲の値である。 The vapor deposition material of the present invention comprises a polycrystalline body of strontium / calcium composite oxide crystal particles represented by a general formula Sr 1-x Ca x O. However, x is a value in the range of 0.2 to 0.8, preferably a value in the range of 0.3 to 0.7.
　本発明の蒸着材は、平均細孔直径が０．０１～０．５０μｍの範囲、好ましくは０．０１～０．３０μｍの範囲、特に好ましくは０．０１～０．２０μｍの範囲にある。なお、本明細書において、平均細孔直径は水銀圧入法により測定した値である。 The vapor deposition material of the present invention has an average pore diameter in the range of 0.01 to 0.50 μm, preferably in the range of 0.01 to 0.30 μm, particularly preferably in the range of 0.01 to 0.20 μm. In the present specification, the average pore diameter is a value measured by a mercury intrusion method.
　本発明の蒸着材を構成するストロンチウム・カルシウム複合酸化物結晶粒子の平均結晶粒子径は１．０～９０μｍの範囲、好ましくは５．０～８０μｍの範囲にある。 The average crystal particle diameter of the strontium / calcium complex oxide crystal particles constituting the vapor deposition material of the present invention is in the range of 1.0 to 90 μm, preferably in the range of 5.0 to 80 μm.
　本発明の蒸着材の形状は特に限定されるものではないが、円板状であることが好ましい。円板状蒸着材は、直径が２．０～１０ｍｍの範囲であることが好ましく、厚みが１．０～５．０ｍｍの範囲であることが好ましい。厚みが薄い方が電子ビーム蒸着法により得られるストロンチウム・カルシウム複合酸化物膜の品質（膜密度の均質性、結晶配向性の均一性等）を保ちつつ蒸着速度が向上する。円板状蒸着材のアスペクト比（厚み／直径）は、１．０以下であることが好ましい。 The shape of the vapor deposition material of the present invention is not particularly limited, but is preferably a disc shape. The disk-shaped vapor deposition material preferably has a diameter in the range of 2.0 to 10 mm, and preferably has a thickness in the range of 1.0 to 5.0 mm. The thinner the thickness, the higher the deposition rate while maintaining the quality of the strontium / calcium composite oxide film (homogeneity of film density, uniformity of crystal orientation, etc.) obtained by the electron beam evaporation method. The aspect ratio (thickness / diameter) of the disk-shaped vapor deposition material is preferably 1.0 or less.
　本発明の蒸着材は、相対密度が９０％以上であることが好ましく、９５％以上であることが特に好ましい。相対密度は、嵩密度と真密度との比を百分率で表した値である。なお、本明細書において、蒸着材の真密度は、酸化カルシウムの真密度と酸化ストロンチウムの真密度と、合計モル量を１としたときの蒸着材中のカルシウムとストロンチウムのモル比とから下記の式を用いて算出した。
　真密度（ｇ／ｃｍ3）＝３．３５０ｇ／ｃｍ3（酸化カルシウムの真密度）×多結晶体中のカルシウムのモル比＋５．００９ｇ／ｃｍ3（酸化ストロンチウムの真密度）×多結晶体中のストロンチウムのモル比 The vapor deposition material of the present invention preferably has a relative density of 90% or more, particularly preferably 95% or more. The relative density is a value representing the ratio between the bulk density and the true density as a percentage. In the present specification, the true density of the vapor deposition material is as follows from the true density of calcium oxide, the true density of strontium oxide, and the molar ratio of calcium to strontium in the vapor deposition material when the total molar amount is 1. Calculated using the formula.
True density (g / cm 3) = 3.350g / cm 3 ( true density of strontium oxide) × the molar ratio of calcium in the polycrystalline body + 5.009g / cm 3 (true density of calcium oxide) × polycrystalline body Molar ratio of strontium
　本発明の蒸着材は、温度２５℃で、相対湿度４７％の雰囲気下において１６８時間静置したときの質量増加率が０．５質量％以下、特に０．０１～０．５質量％の範囲にあり、水蒸気や二酸化炭素ガスの吸着性もしくはそれらとの反応性が低い。このため、本発明の蒸着材は被覆材で表面を被覆する必要は特にない。 The vapor deposition material of the present invention has a mass increase rate of 0.5% by mass or less, particularly in a range of 0.01 to 0.5% by mass when left at a temperature of 25 ° C. in an atmosphere of 47% relative humidity for 168 hours. The adsorption property of water vapor and carbon dioxide gas or the reactivity with them is low. For this reason, it is not particularly necessary to coat the surface of the vapor deposition material of the present invention with a coating material.
　本発明の蒸着材は、物理気相成長法により、ストロンチウム・カルシウム複合酸化物膜を形成するのに有利に用いることができる。本発明の蒸着材を用いることができる物理気相成長法の例としては、電子ビーム蒸着法、イオンプレーティング法、スパッタ法を挙げることができる。 The vapor deposition material of the present invention can be advantageously used to form a strontium / calcium composite oxide film by physical vapor deposition. Examples of physical vapor deposition methods that can use the vapor deposition material of the present invention include electron beam vapor deposition, ion plating, and sputtering.
　本発明の蒸着材は、特に電子ビーム蒸着法によりストロンチウム・カルシウム複合酸化物膜を製造するのに有利に用いることができる。即ち、本発明の蒸着材を電子ビーム蒸着装置の蒸着チャンバーに配置し、減圧下にて蒸着材に電子ビームを照射して、ストロンチウム・カルシウム複合酸化物を気化させ、気化したストロンチウム・カルシウム複合酸化物を基板の上に堆積させる方法により、基板の上にストロンチウム・カルシウム複合酸化物膜を有利に製造することができる。膜製造時の蒸着チャンバー内の圧力は、全圧で６．００×１０-2Ｐａ以下であることが好ましい。また、蒸着チャンバー内には酸素ガスが酸素分圧で０．１０～５．９９×１０-2Ｐａの範囲、特に０．５０～４．００×１０-2Ｐａの範囲で存在していることが好ましい。 The vapor deposition material of the present invention can be advantageously used for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method. That is, the vapor deposition material of the present invention is placed in a vapor deposition chamber of an electron beam vapor deposition apparatus, and the vapor deposition material is irradiated with an electron beam under reduced pressure to vaporize the strontium / calcium composite oxide, thereby vaporizing the vaporized strontium / calcium composite oxide. By the method of depositing an object on a substrate, a strontium-calcium composite oxide film can be advantageously produced on the substrate. The pressure in the vapor deposition chamber at the time of film production is preferably 6.00 × 10 −2 Pa or less in total pressure. In addition, oxygen gas is present in the vapor deposition chamber in an oxygen partial pressure range of 0.10 to 5.99 × 10 −2 Pa, particularly 0.50 to 4.00 × 10 −2 Pa. Is preferred.
　本発明の蒸着材は、例えば、炭酸カルシウム粒子と炭酸ストロンチウム粒子とを、カルシウムとストロンチウムのモル比が０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にある粒子混合物が液体媒体中に分散されている粒子混合物分散液を用意する工程、該分散液を噴霧乾燥して粒子混合物粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む方法によって製造することができる。なお、本明細書において、平均粒子径は、その値が０．１μｍ以上の場合はレーザー回折法により測定した値を意味し、０．１μｍ未満の場合は動的光散乱法により測定した値を意味する。 The vapor deposition material of the present invention contains, for example, calcium carbonate particles and strontium carbonate particles in a ratio such that the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2. A step of preparing a particle mixture dispersion in which a particle mixture having an average particle size in the range of 0.05 to 2.0 μm is dispersed in a liquid medium, and a step of spray-drying the dispersion to obtain a particle mixture granule , And can be produced by a method including a step of forming the granular material into a pellet and a step of firing the obtained pellet-shaped product. In this specification, the average particle diameter means a value measured by a laser diffraction method when the value is 0.1 μm or more, and a value measured by a dynamic light scattering method when the value is less than 0.1 μm. means.
　粒子混合物分散液は、炭酸カルシウム粒子と炭酸ストロンチウム粒子とを液体媒体に投入して得た混合液を、ボールミルもしくはメディアミル（撹拌ミル）などの粉砕装置を用いて、炭酸カルシウム粒子と炭酸ストロンチウム粒子とを混合しながら粉砕することによって調製することができる。 The particle mixture dispersion is obtained by adding calcium carbonate particles and strontium carbonate particles into a liquid medium, and using a pulverizer such as a ball mill or a media mill (stirring mill) to obtain calcium carbonate particles and strontium carbonate particles. And pulverizing with mixing.
　原料の炭酸カルシウム粒子は、平均粒子径が０．０５～１００μｍの範囲にあることが好ましく、０．０８～１００μｍの範囲にあることがより好ましい。炭酸カルシウム粒子はＢＥＴ比表面積が０．１～５０ｍ2／ｇの範囲にあることが好ましい。炭酸カルシウム粒子は、一次粒子が立方体状であることが好ましく、アスペクト比が１～２の範囲にある立方体状であることがより好ましい。炭酸カルシウム粒子の純度は９９質量％以上であることが好ましい。 The raw material calcium carbonate particles preferably have an average particle size in the range of 0.05 to 100 μm, and more preferably in the range of 0.08 to 100 μm. The calcium carbonate particles preferably have a BET specific surface area in the range of 0.1 to 50 m 2 / g. The calcium carbonate particles preferably have a cubic primary particle shape, and more preferably have a cubic shape with an aspect ratio in the range of 1 to 2. The purity of the calcium carbonate particles is preferably 99% by mass or more.
　原料の炭酸ストロンチウム粒子は、平均粒子径が０．０５～１００μｍの範囲にあることが好ましく、０．０８～１００μｍの範囲にあることがより好ましい。炭酸ストロンチウム粒子はＢＥＴ比表面積が０．１～７０ｍ2／ｇの範囲にあることが好ましい。炭酸ストロンチウム粒子は、一次粒子が針状もしくは立方体状であることが好ましい。炭酸ストロンチウム粒子の純度は９９質量％以上であることが好ましい。 The raw material strontium carbonate particles preferably have an average particle size in the range of 0.05 to 100 μm, and more preferably in the range of 0.08 to 100 μm. The strontium carbonate particles preferably have a BET specific surface area in the range of 0.1 to 70 m 2 / g. In the strontium carbonate particles, the primary particles are preferably needle-like or cubic. The purity of the strontium carbonate particles is preferably 99% by mass or more.
　炭酸カルシウム粒子及び炭酸ストロンチウム粒子は、ＢＥＴ比表面積が大きい方が、混合物分散液中の炭酸カルシウム粒子と炭酸ストロンチウム粒子との粒子混合物の平均粒子径を２．０μｍ以下に粉砕するのに要する時間が短くなるので好ましい。 As for the calcium carbonate particles and strontium carbonate particles, the time required for pulverizing the average particle size of the particle mixture of calcium carbonate particles and strontium carbonate particles in the mixture dispersion to 2.0 μm or less is larger when the BET specific surface area is larger. Since it becomes short, it is preferable.
　液体媒体には、水、一価アルコール及びこれらの混合物を用いることができる。一価アルコールの例としては、エタノール、プロパノール及びブタノールを挙げることができる。液体媒体は、水であることが好ましい。 As the liquid medium, water, monohydric alcohol and a mixture thereof can be used. Examples of monohydric alcohols include ethanol, propanol and butanol. The liquid medium is preferably water.
　粒子混合物分散液には、ポリカルボン酸塩を添加してもよい。ポリカルボン酸塩は分散剤として作用する。ポリカルボン酸塩は、アンモニウム塩及びアルキルアンモニウム塩であることが好ましい。ポリカルボン酸塩の添加量は、粒子混合物分散液中の固形分１００質量部に対して０．５～２０質量部の範囲、特に１～１０質量部の範囲にあることが好ましい。ポリカルボン酸塩は粒子混合物分散液に添加してもよいし、原料の炭酸カルシウム粒子及び炭酸ストロンチウム粒子の両方もしくは一方の表面に予め付着させておいてもよい。 Polycarboxylic acid salt may be added to the particle mixture dispersion. The polycarboxylate acts as a dispersant. The polycarboxylate is preferably an ammonium salt or an alkyl ammonium salt. The addition amount of the polycarboxylate is preferably in the range of 0.5 to 20 parts by mass, particularly preferably in the range of 1 to 10 parts by mass with respect to 100 parts by mass of the solid content in the particle mixture dispersion. The polycarboxylate may be added to the particle mixture dispersion, or may be preliminarily attached to the surface of either or both of the raw material calcium carbonate particles and strontium carbonate particles.
　粒子混合物分散液には、さらに液体媒体と相溶性を有するバインダーを添加することが好ましい。水と相溶性を有するバインダーの例としては、ポリエチレングリコール、ポリビニルアルコール、ポリビニルブチラール及びアクリル系共重合物を挙げることができる。バインダーの添加量は、粒子混合物分散液中の固形分１００質量部に対して０．１０～１０質量部の範囲にあることが好ましい。バインダーは炭酸カルシウム粒子と炭酸ストロンチウム粒子との混合粉砕を行なう前に添加してもよいし、混合粉砕を行なった後、粒子混合物分散液の噴霧乾燥前に添加してもよい。 It is preferable to add a binder having compatibility with the liquid medium to the particle mixture dispersion. Examples of the binder having compatibility with water include polyethylene glycol, polyvinyl alcohol, polyvinyl butyral, and an acrylic copolymer. The addition amount of the binder is preferably in the range of 0.10 to 10 parts by mass with respect to 100 parts by mass of the solid content in the particle mixture dispersion. The binder may be added before mixing and grinding the calcium carbonate particles and strontium carbonate particles, or after mixing and grinding and before spray drying of the particle mixture dispersion.
　粒子混合物分散液の噴霧乾燥は、通常のスプレードライヤーを用いて行なうことができる。噴霧乾燥温度は、１５０～２８０℃の範囲にあることが好ましい。 The spray drying of the particle mixture dispersion can be performed using a normal spray dryer. The spray drying temperature is preferably in the range of 150 to 280 ° C.
　粒子混合物分散液の噴霧乾燥により得られた乾燥混合粒状体をペレット状に成形し、そして得られたペレット状成形物を焼成して、炭酸カルシウムと炭酸ストロンチウムとを酸化させながら、生成するストロンチウム・カルシウム複合酸化物を焼結させることにより、本発明の蒸着材を得ることができる。 The dried mixed granule obtained by spray drying the particle mixture dispersion is formed into pellets, and the obtained pellets are fired to oxidize calcium carbonate and strontium carbonate while producing strontium The vapor deposition material of the present invention can be obtained by sintering the calcium composite oxide.
　ペレット状成形物の成形には、通常のプレス成形法を用いることができる。成形圧力は、一般に０．３～３トン／ｃｍ2の範囲にある。 A normal press molding method can be used for molding the pellet-shaped molded product. The molding pressure is generally in the range of 0.3 to 3 ton / cm 2 .
　ペレット状成形物の焼成は、１４００～１８００℃の温度にて行なうことが好ましい。焼成時間は成形物のサイズ（特に厚さ）や焼成温度などの要件により変わるので、一律に定めることはできないが、一般に１～７時間である。 The pellet-shaped molded product is preferably fired at a temperature of 1400 to 1800 ° C. The firing time varies depending on requirements such as the size (particularly thickness) of the molded product and the firing temperature, and cannot be uniformly determined, but is generally 1 to 7 hours.
　本発明の蒸着材はまた、原料にストロンチウム・カルシウム炭酸複塩粒子を用いて製造することができる。即ち、本発明の蒸着材は、カルシウムとストロンチウムとをモル比で０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にあるストロンチウム・カルシウム炭酸複塩粒子が液体媒体に分散されてなるストロンチウム・カルシウム炭酸複塩粒子分散液を用意する工程、該分散液を噴霧乾燥して炭酸複塩粒子粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む方法によっても製造することができる。 The vapor deposition material of the present invention can also be produced using strontium / calcium carbonate double salt particles as a raw material. That is, the vapor deposition material of the present invention contains calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2 and has an average particle size of 0.05 to 2. A step of preparing a strontium / calcium carbonate double salt particle dispersion in which strontium / calcium carbonate double salt particles in a range of 0.0 μm are dispersed in a liquid medium, and spray-drying the dispersion to form a carbonate double salt particle granule It can also be produced by a method including a step of obtaining, a step of forming the granular body into a pellet, and a step of firing the obtained pellet-shaped product.
　原料として用いるストロンチウム・カルシウム炭酸複塩粒子は、カルシウムイオンとストロンチウムイオンとを、モル比で０．２：０．８～０．８：０．２の範囲となる量にて含むストロンチウム・カルシウム水溶液に、アンモニア水溶液を加えてｐＨを７～１４の範囲に調整した後、二酸化炭素ガスを供給することにより合成することができる。また、水酸化カルシウムと水酸化ストロンチウムとを、モル比で０．２：０．８～０．８：０．２の範囲となる量にて含む水溶液に二酸化炭素ガスを供給することによっても合成することができる。ストロンチウム・カルシウム炭酸複塩粒子を合成する際の水溶液の液温は５～８０℃の範囲にあることが好ましい。カルシウムイオンとストロンチウムイオンとの炭酸化により生成したストロンチウム・カルシウム炭酸複塩は、一旦水溶液から取り出して、水洗、乾燥した後、蒸着材の材料として用いることが好ましい。 The strontium-calcium carbonate double salt particles used as a raw material contain a strontium-calcium aqueous solution containing calcium ions and strontium ions in an amount ranging from 0.2: 0.8 to 0.8: 0.2 in molar ratio Further, it can be synthesized by adding an aqueous ammonia solution to adjust the pH to the range of 7 to 14 and then supplying carbon dioxide gas. It can also be synthesized by supplying carbon dioxide gas to an aqueous solution containing calcium hydroxide and strontium hydroxide in a molar ratio of 0.2: 0.8 to 0.8: 0.2. can do. The temperature of the aqueous solution when synthesizing the strontium / calcium carbonate double salt particles is preferably in the range of 5 to 80 ° C. The strontium / calcium carbonate double salt produced by carbonation of calcium ions and strontium ions is preferably taken out from the aqueous solution, washed and dried, and then used as a material for the vapor deposition material.
　ストロンチウム・カルシウム炭酸複塩粒子分散液は、上記のようにして合成したストロンチウム・カルシウム炭酸複塩粒子を液体媒体中にてボールミルもしくはメディアミルなどの粉砕装置を用いて粉砕することによって調製することができる。液体媒体は水であることが好ましい。炭酸複塩粒子分散液には、噴霧乾燥を行なう前に、液体媒体と相溶性を有するバインダーを添加することが好ましい。バインダーの添加量は、分散液中のストロンチウム・カルシウム炭酸複塩粒子１００質量部に対して０．１０～１０質量部の範囲にあることが好ましい。 The strontium / calcium carbonate double salt particle dispersion can be prepared by pulverizing the strontium / calcium carbonate double salt particles synthesized as described above in a liquid medium using a pulverizer such as a ball mill or a media mill. it can. The liquid medium is preferably water. A binder having compatibility with the liquid medium is preferably added to the carbonate double salt particle dispersion before spray drying. The addition amount of the binder is preferably in the range of 0.10 to 10 parts by mass with respect to 100 parts by mass of the strontium / calcium carbonate double salt particles in the dispersion.
　炭酸複塩粒子分散液を噴霧乾燥して炭酸複塩粒子粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程については、原料に炭酸カルシウム粒子と炭酸ストロンチウム粒子とを用いた場合と同様とすることができる。 Regarding the step of spraying and drying carbonate double salt particle dispersion to obtain carbonate double salt particle granules, the step of forming the granules into pellets, and the step of firing the obtained pellets, This can be the same as when calcium particles and strontium carbonate particles are used.
［実施例１］
（１）粒子混合物分散液の調製
　炭酸カルシウム粒子（純度：９９．５質量％、ＢＥＴ比表面積：４４ｍ2／ｇ、平均粒子径：６．９μｍ、一次粒子形状：立方体）１０１ｇ、炭酸ストロンチウム粒子（純度：９９．５質量％、ＢＥＴ比表面積：２０ｍ2／ｇ、平均粒子径：１．２μｍ、一次粒子形状：針状）１４９ｇ、そして水５８３ｍＬを混合して、炭酸カルシウム粒子と炭酸ストロンチウム粒子の混合液を得た（カルシウムとストロンチウムとのモル比は０．５：０．５）。この混合液を、鉄心入りナイロンボール（直径：１０ｍｍ）が充填されているボールミルに投入し、炭酸カルシウム粒子と炭酸ストロンチウム粒子とを２５時間混合粉砕して、粒子混合物分散液を調製した。粒子混合物分散液中の粒子混合物の平均粒子径とＢＥＴ比表面積とを下記の方法により測定した。その結果および粒子混合物分散液中のカルシウムとストロンチウムのモル比を表１に示す。 [Example 1]
(1) Preparation of Particle Mixture Dispersion Calcium carbonate particles (purity: 99.5% by mass, BET specific surface area: 44 m 2 / g, average particle size: 6.9 μm, primary particle shape: cubic) 101 g, strontium carbonate particles ( Purity: 99.5% by mass, BET specific surface area: 20 m 2 / g, average particle size: 1.2 μm, primary particle shape: needle shape) 149 g and 583 mL of water were mixed, and calcium carbonate particles and strontium carbonate particles were mixed. A mixed solution was obtained (the molar ratio of calcium to strontium was 0.5: 0.5). This mixed solution was put into a ball mill filled with nylon balls with a core (diameter: 10 mm), and calcium carbonate particles and strontium carbonate particles were mixed and ground for 25 hours to prepare a particle mixture dispersion. The average particle diameter and the BET specific surface area of the particle mixture in the particle mixture dispersion were measured by the following method. The results and the molar ratio of calcium and strontium in the particle mixture dispersion are shown in Table 1.
［平均粒子径］
　レーザー回折法粒度分布測定装置（マイクロトラック９３２０ＨＲＡ、日機装（株）製）を用いて測定した。平均粒子径測定用の試料は、粒子混合物分散液を、分散液中の固形分０．５ｇに対して５０ｇの水で希釈した後、超音波分散処理を３分間行なって調製した。 [Average particle size]
Measurement was performed using a laser diffraction particle size distribution analyzer (Microtrack 9320HRA, manufactured by Nikkiso Co., Ltd.). A sample for measuring the average particle size was prepared by diluting the particle mixture dispersion with 50 g of water with respect to 0.5 g of the solid content in the dispersion, followed by ultrasonic dispersion for 3 minutes.
［ＢＥＴ比表面積］
　粒子混合物分散液の一部を１２０℃の温度で乾燥し、得られた乾燥粉末のＢＥＴ比表面積を、比表面積測定装置（Ｍｏｎｏｓｏｒｂ、ユアサアイオニクス（株）製）を用いてＢＥＴ１点法により測定した。 [BET specific surface area]
A part of the particle mixture dispersion is dried at a temperature of 120 ° C., and the BET specific surface area of the obtained dry powder is measured by a BET one-point method using a specific surface area measuring device (Monosorb, Yuasa Ionics Co., Ltd.). did.
（２）焼結体ペレットの製造
　上記（１）で調製した粒子混合物分散液に、ポリビニルアルコールを固形分１００質量部に対して２．５質量部となる量にて、ポリエチレングリコールを固形分１００質量部に対して０．４質量部となる量にて添加し撹拌した。次いで、粒子混合物分散液を、スプレードライヤーを用いて噴霧乾燥（乾燥温度：２００℃）して、粒子混合物粒状体を得た。得られた粒子混合物粒状体を、成形圧０．６トン／ｃｍ2にて、ペレット状（直径：８ｍｍ、厚さ３．０ｍｍ、成形体密度：１．８５ｇ／ｃｍ3）に形成した。次いで、得られたペレット状成形物を１６５０℃の温度で５時間焼成した。得られた焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を下記の方法により測定した。その結果を表２に示す。 (2) Production of sintered pellets In the particle mixture dispersion prepared in (1) above, polyethylene glycol is added in an amount of 2.5 parts by mass with respect to 100 parts by mass of the solid content of polyethylene glycol. It added and stirred in the quantity used as 0.4 mass part with respect to a mass part. Next, the particle mixture dispersion was spray-dried using a spray dryer (drying temperature: 200 ° C.) to obtain particle mixture granules. The obtained particle mixture granulate was formed into pellets (diameter: 8 mm, thickness 3.0 mm, compact density: 1.85 g / cm 3 ) at a molding pressure of 0.6 ton / cm 2 . Next, the obtained pellet-shaped molded product was fired at a temperature of 1650 ° C. for 5 hours. The average crystal particle diameter, average pore diameter, relative density, and mass increase rate of the obtained sintered pellet were measured by the following methods. The results are shown in Table 2.
［平均結晶粒子径］
　焼結体ペレットを直径方向に切断し、その切断面を鏡面研磨処理した。そして、その切断面表層部のストロンチウム・カルシウム複合酸化物結晶粒子について、フィールドエミッション走査型電子顕微鏡を用いて、平均結晶粒子径の測定を行なった。平均結晶粒子径は、２００個の結晶粒子を１５００倍の拡大倍率で観察して、各結晶粒子の最長径（フェレ径）を測定し、これを平均して求めた。 [Average crystal particle size]
The sintered pellet was cut in the diameter direction, and the cut surface was mirror polished. Then, the average crystal particle diameter of the strontium / calcium composite oxide crystal particles on the cut surface was measured using a field emission scanning electron microscope. The average crystal particle size was determined by observing 200 crystal particles at an enlargement magnification of 1500 times, measuring the longest diameter (Ferret diameter) of each crystal particle, and averaging this.
［平均細孔直径］
　水銀ポロシメーター（Ｑｕｎｔａｃｈｒｏｍｅ製、ＰｏｒｅＭａｓｔｅｒ６０－ＧＴ）を用いて、細孔直径が０．００３６～４００μｍの範囲にある細孔の累積細孔容積と累積比表面積とを測定し、下記の式により平均細孔直径を算出した。
　平均細孔直径＝４×累積細孔容積／累積比表面積 [Average pore diameter]
Using a mercury porosimeter (manufactured by Quantachrome, Poremaster 60-GT), the cumulative pore volume and the cumulative specific surface area of pores having a pore diameter in the range of 0.0036 to 400 μm were measured. The diameter was calculated.
Average pore diameter = 4 × cumulative pore volume / cumulative specific surface area
［相対密度］
　ケロシンを媒液に用いたアルキメデス法により嵩密度を測定し、真密度を３．３５０ｇ／ｃｍ3（酸化カルシウムの真密度）×多結晶体中のカルシウムのモル比＋５．００９ｇ／ｃｍ3（酸化ストロンチウムの真密度）×多結晶体中のストロンチウムのモル比として、算出した。 [Relative density]
The bulk density was measured by the Archimedes method using kerosene as the medium, and the true density was 3.350 g / cm 3 (true density of calcium oxide) × the molar ratio of calcium in the polycrystal + 5.009 g / cm 3 (oxidation) The true density of strontium was calculated as the molar ratio of strontium in the polycrystal.
［質量増加率］
　予め質量を測定した焼結体ペレットを、温度２５℃、相対湿度４７％に調製した恒温恒湿器内に１６８時間静置した。静置後の質量増加量を測定して、質量増加率を算出した。 [Mass increase rate]
The sintered pellets whose mass was measured in advance were allowed to stand for 168 hours in a constant temperature and humidity chamber prepared at a temperature of 25 ° C. and a relative humidity of 47%. The mass increase rate after standing was measured, and the mass increase rate was calculated.
（３）焼結体ペレットの評価
　上記（２）で製造した焼結体ペレットを蒸着材として、電子ビーム蒸着装置（ＥＸ－５５０－Ｄ１０型、ＵＬＶＡＣ社製）を用いて、蒸着電圧８ｋＶ、蒸着速度２ｎｍ／秒、蒸着チャンバー内の全圧４×１０-2Ｐａ、蒸着チャンバー内の酸素分圧３．９６×１０-2Ｐａ、基板温度２００℃の条件にて電子ビーム蒸着法により、石英基板の上に厚さ１０００ｎｍのストロンチウム・カルシウム複合酸化物膜を形成した。膜形成の際に要した蒸着平均電流値と、得られたストロンチウム・カルシウム複合酸化物膜の（１１１）面のピーク強度を下記の方法により測定した。その結果を表３に示す。 (3) Evaluation of sintered body pellets Using the sintered body pellets produced in (2) above as an evaporation material, using an electron beam evaporation apparatus (EX-550-D10 type, manufactured by ULVAC), an evaporation voltage of 8 kV and evaporation A quartz substrate is formed by electron beam evaporation under the conditions of a speed of 2 nm / second, a total pressure of 4 × 10 −2 Pa in the deposition chamber, an oxygen partial pressure of 3.96 × 10 −2 Pa in the deposition chamber, and a substrate temperature of 200 ° C. A strontium / calcium composite oxide film having a thickness of 1000 nm was formed thereon. The average vapor deposition current required for film formation and the peak intensity of the (111) plane of the obtained strontium / calcium composite oxide film were measured by the following method. The results are shown in Table 3.
［蒸着平均電流値］
　蒸着開始直後及び形成された膜の厚みが２００ｎｍ、４００ｎｍ、６００ｎｍ、８００ｎｍ、１０００ｎｍとなったときの電子ビーム蒸着装置に表示された蒸着電流値を読み取り、その平均値を蒸着平均電流値として算出した。 [Vapor deposition average current value]
Immediately after the start of deposition and when the thickness of the formed film was 200 nm, 400 nm, 600 nm, 800 nm, and 1000 nm, the deposition current value displayed on the electron beam deposition apparatus was read, and the average value was calculated as the deposition average current value. .
［（１１１）面のピーク強度］
　ストロンチウム・カルシウム複合酸化物膜のＸ線回折パターンを、Ｘ線回折装置を用い、管電圧４０ｋＶ、管電流２００ｍＡ、走査角度２０～８０度、走査速度０．０２度／秒の条件で測定し、（１１１）面に相当する回折線ピークの強度を測定した。 [(111) plane peak intensity]
The X-ray diffraction pattern of the strontium / calcium composite oxide film was measured using an X-ray diffractometer under the conditions of a tube voltage of 40 kV, a tube current of 200 mA, a scanning angle of 20 to 80 degrees, and a scanning speed of 0.02 degrees / second. The intensity of the diffraction line peak corresponding to the (111) plane was measured.
［実施例２］
　実施例１の（１）において、炭酸カルシウム粒子と炭酸ストロンチウム粒子の混合液を直径が０．３ｍｍの酸化ジルコニウムビーズが充填されているメディアミル（アシザワファインテック（株）製、ＭＩＮＩＺＥＴＡ）に投入し、１５分間混合粉砕して粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Example 2]
In Example 1 (1), a mixed solution of calcium carbonate particles and strontium carbonate particles was charged into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 mm. The sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding for 15 minutes, and the sintered body pellets were evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［実施例３］
　実施例１の（１）において、炭酸カルシウム粒子と炭酸ストロンチウム粒子の混合液を直径が０．３ｍｍの酸化ジルコニウムビーズが充填されているメディアミル（アシザワファインテック（株）製、ＭＩＮＩＺＥＴＡ）に投入し、６０分間混合粉砕して粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Example 3]
In Example 1 (1), a mixed solution of calcium carbonate particles and strontium carbonate particles was charged into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 mm. The sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding for 60 minutes, and the sintered body pellets were evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［実施例４］
　実施例１の（１）において、炭酸カルシウム粒子に、純度９９．５質量％、ＢＥＴ比表面積０．２２ｍ2／ｇ、平均粒子径が１３．８μｍ、そして一次粒子形状が立方体の炭酸カルシウム粒子を用い、炭酸カルシウム粒子と炭酸ストロンチウム粒子の混合液を直径が０．３μｍの酸化ジルコニウムビーズが充填されているメディアミル（アシザワファインテック（株）製、ＭＩＮＩＺＥＴＡ）に投入し、４５分間混合粉砕して粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Example 4]
In Example 1 (1), calcium carbonate particles having a purity of 99.5% by mass, a BET specific surface area of 0.22 m 2 / g, an average particle size of 13.8 μm, and a primary particle shape of cubic calcium carbonate particles. Used, a mixed solution of calcium carbonate particles and strontium carbonate particles is put into a media mill (MINIZETA, manufactured by Ashizawa Finetech Co., Ltd.) filled with zirconium oxide beads having a diameter of 0.3 μm, and mixed and ground for 45 minutes. Sintered pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared, and the sintered pellets were evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［実施例５］
　実施例１の（１）において、炭酸カルシウム粒子の量を２０．０２ｇ、炭酸ストロンチウム粒子の量を１１８．１０ｇ（カルシウムとストロンチウムとのモル比は０．２：０．８）、そして水の量を３２２ｍＬとして粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Example 5]
In Example 1 (1), the amount of calcium carbonate particles was 20.02 g, the amount of strontium carbonate particles was 118.10 g (the molar ratio of calcium to strontium was 0.2: 0.8), and the amount of water The sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 322 mL, and the sintered body pellets were evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［実施例６］
　実施例１の（１）において、炭酸カルシウム粒子の量を８０．０６ｇ、炭酸ストロンチウム粒子の量を２９．５２ｇ（カルシウムとストロンチウムとのモル比は０．８：０．２）、そして水の量を２５６ｍＬとして粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Example 6]
In Example 1 (1), the amount of calcium carbonate particles was 80.06 g, the amount of strontium carbonate particles was 29.52 g (the molar ratio of calcium to strontium was 0.8: 0.2), and the amount of water A sintered body pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 256 mL, and the sintered body pellet was evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［実施例７］
（１）ストロンチウム・カルシウム炭酸複塩粒子分散液の調製
　炭酸カルシウム粒子（純度：純度：９９．５質量％、ＢＥＴ比表面積：４４ｍ2／ｇ、平均粒子径：６．９μｍ、一次粒子形状：立方体）１０１ｇと炭酸ストロンチウム粒子（純度：９９．５質量％、ＢＥＴ比表面積：２０ｍ2／ｇ、平均粒子径：１．２μｍ、一次粒子形状：針状）１４９ｇと水５８３ｍＬとを混合し、硝酸を加えて炭酸カルシウム粒子と炭酸ストロンチウム粒子とを溶解させた後、アンモニア水を加えてｐＨが１２のカルシウム・ストロンチウム水溶液を得た（カルシウムとストロンチウムとのモル比は０．５：０．５）。このカルシウム・ストロンチウム水溶液を撹拌しながら、該水溶液に二酸化炭素ガスを供給して、ストロンチウム・カルシウム炭酸複塩粒子を析出させた。析出したストロンチウム・カルシウム炭酸複塩粒子を、ろ過により回収し、水洗した後乾燥した。得られたストロンチウム・カルシウム炭酸複塩粒子２４７ｇと水５７６ｍＬとを混合して、鉄芯入りナイロンボール（直径１０ｍｍ）が充填されているボールミルに投入し、ストロンチウム・カルシウム炭酸複塩粒子を２５時間混合粉砕して、ストロンチウム・カルシウム炭酸複塩粒子分散液を調製した。 [Example 7]
(1) Preparation of strontium / calcium carbonate double salt particle dispersion calcium carbonate particles (purity: purity: 99.5% by mass, BET specific surface area: 44 m 2 / g, average particle size: 6.9 μm, primary particle shape: cubic ) 101 g and strontium carbonate particles (purity: 99.5% by mass, BET specific surface area: 20 m 2 / g, average particle size: 1.2 μm, primary particle shape: needle shape) are mixed with 149 g of water and 583 mL of water. In addition, calcium carbonate particles and strontium carbonate particles were dissolved, and then aqueous ammonia was added to obtain a calcium / strontium aqueous solution having a pH of 12 (the molar ratio of calcium to strontium was 0.5: 0.5). While stirring this calcium / strontium aqueous solution, carbon dioxide gas was supplied to the aqueous solution to precipitate strontium / calcium carbonate double salt particles. The precipitated strontium / calcium carbonate double salt particles were collected by filtration, washed with water and dried. 247 g of the obtained strontium-calcium carbonate double salt particles and 576 mL of water are mixed and put into a ball mill filled with a nylon ball with a core (diameter 10 mm), and the strontium-calcium carbonate double salt particles are mixed for 25 hours. By pulverizing, a strontium / calcium carbonate double salt particle dispersion was prepared.
（２）焼結体ペレットの製造と焼結体ペレットの評価
　上記（１）で調製したストロンチウム・カルシウム炭酸複塩粒子分散液を用いたこと以外は、実施例１と同様にして、焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に炭酸複塩粒子分散液中のカルシウムとストロンチウムのモル比、炭酸複塩粒子の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 (2) Manufacture of sintered pellets and evaluation of sintered pellets A sintered body was obtained in the same manner as in Example 1 except that the strontium / calcium carbonate double salt particle dispersion prepared in (1) above was used. Pellets were manufactured and sintered pellets were evaluated.
Table 1 shows the molar ratio of calcium and strontium in the carbonate double salt particle dispersion, the average particle diameter and BET specific surface area of the carbonate double salt particles, and Table 2 shows the average crystal particle diameter, average pore diameter of the sintered pellet, The relative density and the mass increase rate are shown in Table 3, and the measurement results of the average vapor deposition current value and the peak intensity of the (111) plane are shown.
［実施例８］
　実施例７（１）において、炭酸カルシウム粒子の量を８０．０６ｇ、炭酸ストロンチウム粒子の量を２９．５２ｇ（カルシウムとストロンチウムとのモル比は０．８：０．２）、水の量を２５６ｍＬとして、カルシウム・ストロンチウム水溶液を製造したこと以外は、実施例７と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に炭酸複塩粒子分散液中のカルシウムとストロンチウムのモル比、炭酸複塩粒子の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Example 8]
In Example 7 (1), the amount of calcium carbonate particles was 80.06 g, the amount of strontium carbonate particles was 29.52 g (the molar ratio of calcium to strontium was 0.8: 0.2), and the amount of water was 256 mL. As described above, sintered pellets were manufactured in the same manner as in Example 7 except that the calcium / strontium aqueous solution was manufactured, and the sintered pellets were evaluated.
Table 1 shows the molar ratio of calcium and strontium in the carbonate double salt particle dispersion, the average particle diameter and BET specific surface area of the carbonate double salt particles, and Table 2 shows the average crystal particle diameter, average pore diameter of the sintered pellet, The relative density and the mass increase rate are shown in Table 3, and the measurement results of the average vapor deposition current value and the peak intensity of the (111) plane are shown.
［比較例１］
　実施例１の（１）において、炭酸カルシウム粒子に、純度９９．５質量％、ＢＥＴ比表面積０．２２ｍ2／ｇ、平均粒子径が１３．８μｍ、そして一次粒子形状が立方体の炭酸カルシウム粒子を用い、炭酸カルシウム粒子と炭酸ストロンチウム粒子の混合液の混合粉砕時間を２４時間として粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Comparative Example 1]
In Example 1 (1), calcium carbonate particles having a purity of 99.5% by mass, a BET specific surface area of 0.22 m 2 / g, an average particle size of 13.8 μm, and a primary particle shape of cubic calcium carbonate particles. A sintered body pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared using a mixed pulverization time of the mixed liquid of calcium carbonate particles and strontium carbonate particles for 24 hours. Was evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［比較例２］
　実施例１の（１）において、炭酸カルシウム粒子と炭酸ストロンチウム粒子の混合液の混合粉砕時間を５時間として粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Comparative Example 2]
In Example 1 (1), the sintered pellet was prepared in the same manner as in Example 1 except that the particle mixture dispersion was prepared by mixing and grinding the mixed solution of calcium carbonate particles and strontium carbonate particles for 5 hours. Manufacture and evaluation of sintered compact pellets were performed.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［比較例３］
　実施例１の（１）において、炭酸カルシウム粒子の量を１０．０１ｇ、炭酸ストロンチウム粒子の量を１４２．８７ｇ（カルシウムとストロンチウムとのモル比は０．１：０．９）、そして水の量を３３３ｍＬとして粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Comparative Example 3]
In Example 1 (1), the amount of calcium carbonate particles was 10.01 g, the amount of strontium carbonate particles was 142.87 g (the molar ratio of calcium to strontium was 0.1: 0.9), and the amount of water A sintered pellet was produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 333 mL, and the sintered pellet was evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
［比較例４］
　実施例１の（１）において、炭酸カルシウム粒子の量を９０．０７ｇ、炭酸ストロンチウム粒子の量を１４．７６ｇ（カルシウムとストロンチウムとのモル比は０．９：０．１）、そして水の量を２４５ｍＬとして粒子混合物分散液を調製したこと以外は、実施例１と同様にして焼結体ペレットを製造し、焼結体ペレットの評価を行なった。
　表１に粒子混合物分散液中のカルシウムとストロンチウムのモル比、粒子混合物の平均粒子径とＢＥＴ比表面積を、表２に焼結体ペレットの平均結晶粒子径、平均細孔直径、相対密度及び質量増加率を、表３に蒸着平均電流値と（１１１）面のピーク強度の測定結果をそれぞれ示す。 [Comparative Example 4]
In Example 1 (1), the amount of calcium carbonate particles was 90.07 g, the amount of strontium carbonate particles was 14.76 g (the molar ratio of calcium to strontium was 0.9: 0.1), and the amount of water The sintered body pellets were produced in the same manner as in Example 1 except that the particle mixture dispersion was prepared with 245 mL, and the sintered body pellets were evaluated.
Table 1 shows the molar ratio of calcium and strontium in the particle mixture dispersion, the average particle size and BET specific surface area of the particle mixture, and Table 2 shows the average crystal particle size, average pore diameter, relative density and mass of the sintered body pellets. Table 3 shows the increase rate, and Table 3 shows the measurement results of the average deposition current value and the peak intensity of the (111) plane.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の結果から、平均結晶粒子径と平均細孔直径が本発明の範囲にある焼結体ペレット（実施例１～８）は、平均細孔直径が本発明の範囲を超えて大きい焼結体ペレット（比較例１～４）と比較して質量増加率が顕著に低減しており、水蒸気や二酸化炭素ガスの吸着性もしくはそれとの反応性が低いことが分かる。 From the results of Table 2, sintered pellets (Examples 1 to 8) having an average crystal particle diameter and an average pore diameter within the range of the present invention were sintered with an average pore diameter exceeding the range of the present invention. Compared with the body pellets (Comparative Examples 1 to 4), the mass increase rate is remarkably reduced, and it can be seen that the adsorptivity or the reactivity with water vapor or carbon dioxide gas is low.
Figure JPOXMLDOC01-appb-T000003
 注）（１１１）面のピーク強度は、比較例１で得られたストロンチウム・カルシウム複合酸化物膜の（１１１）面のピーク強度を１とした相対値。
Figure JPOXMLDOC01-appb-T000003
 Note) The peak intensity of the (111) plane is a relative value where the peak intensity of the (111) plane of the strontium / calcium composite oxide film obtained in Comparative Example 1 is 1.
　表３の結果から、平均細孔直径が本発明の範囲にある焼結体ペレット（実施例１～８）は、平均細孔直径が本発明の範囲を超えて大きい焼結体ペレット（比較例１～４）と比べて、電子ビーム蒸着法によりストロンチウム・カルシウム複合酸化物膜を形成する際に要する蒸着平均電流値が低いことが分かる。また、平均細孔直径が本発明の範囲にある焼結体ペレットから形成されたストロンチウム・カルシウム複合酸化物膜は、平均細孔直径が本発明の範囲を超えて大きい焼結体ペレットから形成されたストロンチウム・カルシウム複合酸化物膜と比べて結晶性が高いことが分かる。 From the results shown in Table 3, sintered pellets (Examples 1 to 8) having an average pore diameter in the range of the present invention were found to be larger than the range of the present invention (Examples 1 to 8). Compared with 1 to 4), it can be seen that the deposition average current value required for forming the strontium / calcium composite oxide film by the electron beam deposition method is lower. Further, the strontium / calcium composite oxide film formed from the sintered pellet having an average pore diameter within the range of the present invention is formed from the sintered pellet having an average pore diameter larger than the range of the present invention. It can be seen that the crystallinity is higher than that of the strontium / calcium composite oxide film.

Claims (11)

  1. 　一般式がＳｒ1-xＣａxＯ（但し、ｘは、０．２～０．８の範囲の値）で表され、平均結晶粒子径が１．０～９０μｍの範囲にあるストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体から形成された、平均細孔直径が０．０１～０．５０μｍの範囲にあるストロンチウム・カルシウム複合酸化物膜製造用の蒸着材。 A strontium-calcium composite having a general formula of Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8) and an average crystal particle size in the range of 1.0 to 90 μm A vapor deposition material for producing a strontium / calcium composite oxide film formed from a polycrystal of oxide crystal particles and having an average pore diameter in the range of 0.01 to 0.50 μm.
  2. 　相対密度が９０％以上である請求項１に記載の蒸着材。 The vapor deposition material according to claim 1, wherein the relative density is 90% or more.
  3. 　電子ビーム蒸着法によるストロンチウム・カルシウム複合酸化物膜製造用であって、表面に電子ビームの照射によって気化する材料からなる被膜を備えていない請求項１に記載の蒸着材。 2. The vapor deposition material according to claim 1, which is used for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method, and does not have a coating made of a material which is vaporized by electron beam irradiation on the surface.
  4. 　温度２５℃で、相対湿度４７％の雰囲気下において１６８時間静置したときの質量増加率が０．５質量％以下である請求項１に記載の蒸着材。 The vapor deposition material according to claim 1, wherein the rate of mass increase when it is allowed to stand for 168 hours in an atmosphere having a temperature of 25 ° C and a relative humidity of 47% is 0.5 mass% or less.
  5. 　請求項１に記載の蒸着材に、減圧下にて電子ビームを照射して、ストロンチウム・カルシウム複合酸化物を気化させ、気化したストロンチウム・カルシウム複合酸化物を基板の上に堆積させることからなる基板の上にストロンチウム・カルシウム複合酸化物膜を製造する方法。 A substrate comprising: depositing the vaporized strontium / calcium composite oxide on the substrate by irradiating the vapor deposition material according to claim 1 with an electron beam under reduced pressure to vaporize the strontium / calcium composite oxide For producing a strontium-calcium composite oxide film on the substrate.
  6. 　炭酸カルシウム粒子と炭酸ストロンチウム粒子とを、カルシウムとストロンチウムのモル比が０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にある粒子混合物が液体媒体中に分散されている粒子混合物分散液を用意する工程、該分散液を噴霧乾燥して粒子混合物粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む請求項１に記載の蒸着材の製造方法。 An average particle size of 0.05 to 2 containing calcium carbonate particles and strontium carbonate particles in a ratio such that the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2. A step of preparing a particle mixture dispersion in which a particle mixture in a range of 0.0 μm is dispersed in a liquid medium, a step of spray-drying the dispersion to obtain a particle mixture granule, and molding the granule into a pellet The manufacturing method of the vapor deposition material of Claim 1 including the process of baking, and the process of baking the obtained pellet-shaped molding.
  7. 　カルシウムとストロンチウムとをモル比で０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にあるストロンチウム・カルシウム炭酸複塩粒子が液体媒体に分散されてなるストロンチウム・カルシウム炭酸複塩粒子分散液を用意する工程、該分散液を噴霧乾燥して炭酸複塩粒子粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む請求項１に記載の蒸着材の製造方法。 Strontium calcium containing calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2 and having an average particle size in the range of 0.05 to 2.0 μm A step of preparing a strontium / calcium carbonate double salt particle dispersion in which carbonate double salt particles are dispersed in a liquid medium, a step of spray-drying the dispersion to obtain carbonate double salt particle granules, and the granules in pellet form The manufacturing method of the vapor deposition material of Claim 1 including the process of shape | molding and the process of baking the obtained pellet-shaped molding.
  8. 　一般式がＳｒ1-xＣａxＯ（但し、ｘは、０．２～０．８の範囲の値）で表され、平均結晶粒子径が１．０～９０μｍの範囲にあるストロンチウム・カルシウム複合酸化物結晶粒子の多結晶体から形成された、表面に電子ビームの照射によって気化する材料からなる被膜を備えることなく、温度２５℃で、相対湿度４７％の雰囲気下において１６８時間静置したときの質量増加率が０．５質量％以下である電子ビーム蒸着法によるストロンチウム・カルシウム複合酸化物膜製造用の蒸着材。 A strontium-calcium composite having a general formula of Sr 1-x Ca x O (where x is a value in the range of 0.2 to 0.8) and an average crystal particle size in the range of 1.0 to 90 μm When it is left to stand for 168 hours in an atmosphere of a relative humidity of 47% at a temperature of 25 ° C. without being provided with a film made of a polycrystal of oxide crystal particles and made of a material that is vaporized by electron beam irradiation on the surface. A vapor deposition material for producing a strontium / calcium composite oxide film by an electron beam vapor deposition method in which the rate of mass increase of the carbon is 0.5 mass% or less.
  9. 　相対密度が９０％以上である請求項８に記載の蒸着材。 The vapor deposition material according to claim 8, wherein the relative density is 90% or more.
  10. 　炭酸カルシウム粒子と炭酸ストロンチウム粒子とを、カルシウムとストロンチウムのモル比が０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にある粒子混合物が液体媒体中に分散されている粒子混合物分散液を用意する工程、該分散液を噴霧乾燥して粒子混合物粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む請求項８に記載の蒸着材の製造方法。 An average particle size of 0.05 to 2 containing calcium carbonate particles and strontium carbonate particles in a ratio such that the molar ratio of calcium to strontium is in the range of 0.2: 0.8 to 0.8: 0.2. A step of preparing a particle mixture dispersion in which a particle mixture in a range of 0.0 μm is dispersed in a liquid medium, a step of spray-drying the dispersion to obtain a particle mixture granule, and molding the granule into a pellet The manufacturing method of the vapor deposition material of Claim 8 including the process of baking, and the process of baking the obtained pellet-shaped molding.
  11. 　カルシウムとストロンチウムとをモル比で０．２：０．８～０．８：０．２の範囲となる割合にて含む、平均粒子径が０．０５～２．０μｍの範囲にあるストロンチウム・カルシウム炭酸複塩粒子が液体媒体に分散されてなるストロンチウム・カルシウム炭酸複塩粒子分散液を用意する工程、該分散液を噴霧乾燥して炭酸複塩粒子粒状体を得る工程、該粒状体をペレット状に成形する工程、そして得られたペレット状成形物を焼成する工程を含む請求項８に記載の蒸着材の製造方法。 Strontium calcium containing calcium and strontium in a molar ratio of 0.2: 0.8 to 0.8: 0.2 and having an average particle size in the range of 0.05 to 2.0 μm A step of preparing a strontium / calcium carbonate double salt particle dispersion in which carbonate double salt particles are dispersed in a liquid medium, a step of spray-drying the dispersion to obtain carbonate double salt particle granules, and the granules in pellet form The manufacturing method of the vapor deposition material of Claim 8 including the process of shape | molding and the process of baking the obtained pellet-shaped molding.
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Cited By (1)

* Cited by examiner, † Cited by third party
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JP2011146194A (en) * 2010-01-13 2011-07-28 Ube Material Industries Ltd Vapor deposition material for manufacturing oxide film containing strontium and calcium

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CN103694998B (en) * 2014-01-08 2018-07-20 中国科学院福建物质结构研究所 A kind of oxysulfide red long afterglow luminous material and preparation method thereof
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002294432A (en) * 2001-01-25 2002-10-09 Mitsubishi Materials Corp Evaporation material for protective coating of fpd, and manufacturing method therefor
JP2008091074A (en) * 2006-09-29 2008-04-17 Tateho Chem Ind Co Ltd Vapor deposition material for plasma display panel protective film excellent in humidity-proofing

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* Cited by examiner, † Cited by third party
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JP3893793B2 (en) 1999-04-05 2007-03-14 三菱マテリアル株式会社 MgO vapor deposition material and method for producing the same
JP4147988B2 (en) 2003-03-17 2008-09-10 三菱マテリアル株式会社 Deposition material for protective film of FPD and method for producing the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002294432A (en) * 2001-01-25 2002-10-09 Mitsubishi Materials Corp Evaporation material for protective coating of fpd, and manufacturing method therefor
JP2008091074A (en) * 2006-09-29 2008-04-17 Tateho Chem Ind Co Ltd Vapor deposition material for plasma display panel protective film excellent in humidity-proofing

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011146194A (en) * 2010-01-13 2011-07-28 Ube Material Industries Ltd Vapor deposition material for manufacturing oxide film containing strontium and calcium

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