WO2016163330A1 - Matériau céramique diélectrique, son procédé de fabrication et matériau composite diélectrique - Google Patents

Matériau céramique diélectrique, son procédé de fabrication et matériau composite diélectrique Download PDF

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WO2016163330A1
WO2016163330A1 PCT/JP2016/060991 JP2016060991W WO2016163330A1 WO 2016163330 A1 WO2016163330 A1 WO 2016163330A1 JP 2016060991 W JP2016060991 W JP 2016060991W WO 2016163330 A1 WO2016163330 A1 WO 2016163330A1
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ceramic material
dielectric ceramic
surface area
specific surface
compound
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PCT/JP2016/060991
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Japanese (ja)
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田邉　信司
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日本化学工業株式会社
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Priority claimed from JP2016038713A external-priority patent/JP6047252B2/ja
Application filed by 日本化学工業株式会社 filed Critical 日本化学工業株式会社
Priority to CN201680019796.2A priority Critical patent/CN107531575B/zh
Priority to KR1020177027777A priority patent/KR102498656B1/ko
Publication of WO2016163330A1 publication Critical patent/WO2016163330A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/47—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on strontium titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics

Definitions

  • the present invention relates to a dielectric ceramic material useful as an inorganic filler for a composite dielectric, a manufacturing method thereof, and a composite dielectric material using the dielectric ceramic material.
  • This multilayer printed wiring board can cope with further downsizing, thinning, and high density of electronic equipment by providing a layer made of a high dielectric constant material on the inner layer or surface layer to improve the mounting density.
  • a ceramic sintered body obtained by firing a ceramic powder and then firing it has been used, so the dimensions and shape are restricted by the molding method. Further, since the sintered body is high in hardness and brittle, it is difficult to freely process it, and it is extremely difficult to obtain an arbitrary shape or a complicated shape.
  • Patent Document 1 there is no problem in handling properties, but the amount that can be filled in the resin is at most about 30% by volume, and the dielectric constant of the obtained composite dielectric is low.
  • Patent Document 2 proposes a spherical dielectric powder in which the sphericity of the particles is 0.82 to 1 and the ratio of the 10% diameter to the 90% diameter of the powder is 30 or less. Further, Patent Document 4 proposes a dielectric ceramic powder that is irregularly shaped particles by a pulverization method and has a specific surface area of 9 m 2 / cm 3 or less and a lattice strain of 0.2 or less.
  • Patent Documents 2 to 4 improve the dispersion and filling of a high dielectric constant inorganic filler in a resin, there is a need for a high dielectric constant inorganic filler excellent in filling and dispersibility. Yes.
  • an object of the present invention is to provide a dielectric ceramic material that is an inorganic filler having a high dielectric constant and excellent filling and dispersibility in a resin.
  • perovskite-type composite oxide particles having a specific shape and particle size distribution are excellent in dispersibility and filling properties in resins, and It came to complete.
  • the present invention (1) comprises perovskite (ABO 3 ) type complex oxide particles,
  • the particle diameter at which the cumulative value in the volume frequency particle size distribution measurement by the laser diffraction scattering method is 10% is D10
  • the particle diameter at 50% is D50
  • the particle diameter at 90% is D90
  • ((D90-D10 ) / D50) is 1.2 or less
  • the average particle diameter D50 is 3 to 15 ⁇ m
  • Relationship between the BET specific surface area determined theoretical specific surface area calculated from the average particle diameter D50 and (m 2 / g) by the BET method (m 2 / g) is, 0.5 ⁇ ((BET specific surface area - theoretical specific Surface area) / theoretical specific surface area) ⁇ 9.0
  • a dielectric ceramic material is provided.
  • the present invention (2) includes the dielectric ceramic material of (1) and perovskite (ABO 3 ) type composite oxide particles having an average particle diameter D50 of less than 3 ⁇ m in volume frequency particle size distribution measurement by a laser diffraction scattering method.
  • a dielectric ceramic material obtained by mixing the dielectric ceramic material is provided.
  • the present invention (3) is a liquid obtained by mixing oxalic acid and at least one compound (A element compound) selected from the group consisting of a Ba compound, Ca compound, Mg compound and Sr compound ( A solution containing at least one chloride selected from the group consisting of chloride of Ti and chloride of Zr (solution B) is added to the solution A to carry out the reaction, and from Ba, Ca, Mg and Sr A first step of obtaining an oxalate having at least one element selected from the group consisting of and at least one element selected from the group consisting of Ti and Zr; Firing the oxalate at a firing temperature of 1050 to 1400 ° C.
  • a element compound selected from the group consisting of a Ba compound, Ca compound, Mg compound and Sr compound
  • a fired body The fired body is crushed, the particle diameter at which the cumulative value in the volume frequency particle size distribution measurement by laser diffraction scattering method is 10% is D10, the particle diameter at 50% is D50, and the particle diameter at 90% is D90.
  • the value of ((D90 ⁇ D10) / D50) is 1.2 or less, the average particle diameter D50 is 3 to 15 ⁇ m, and the theoretical specific surface area (m 2 / g calculated from the average particle diameter D50) )
  • the BET specific surface area (m 2 / g) measured by the BET method is 0.5 ⁇ ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 9.0. 3 ) a third step of obtaining a dielectric ceramic material comprising type complex oxide particles;
  • a method for producing a dielectric ceramic material characterized by comprising:
  • the present invention (4) provides a composite dielectric material comprising the dielectric ceramic material of (1) and a polymer material.
  • the present invention (5) provides a composite dielectric material comprising the mixed dielectric ceramic material of (2) and a polymer material.
  • a dielectric ceramic material which is an inorganic filler having a high dielectric constant and excellent filling and dispersibility in a resin.
  • Example 2 is a SEM photograph of barium titanate particles obtained in Example 2.
  • 3 is a particle size distribution of barium titanate particles obtained in Example 2.
  • 4 is a SEM photograph of strontium titanate particles obtained in Example 4.
  • 4 is a particle size distribution of strontium titanate particles obtained in Example 4.
  • the dielectric ceramic material of the present invention comprises perovskite (ABO 3 ) type complex oxide particles,
  • the particle diameter at which the cumulative value in the volume frequency particle size distribution by the laser diffraction scattering method is 10% is D10
  • the particle diameter at 50% is D50
  • the particle diameter at 90% is D90 ((D90-D10) / D50) is 1.2 or less
  • the average particle diameter D50 is 3 to 15 ⁇ m
  • Relationship between the BET specific surface area determined theoretical specific surface area calculated from the average particle diameter D50 and (m 2 / g) by the BET method (m 2 / g) is, 0.5 ⁇ ((BET specific surface area - theoretical specific Surface area) / theoretical specific surface area) ⁇ 9.0
  • a dielectric ceramic material characterized by the following.
  • the dielectric ceramic material of the present invention is composed of perovskite type complex oxide particles, that is, particles of perovskite type complex oxide (ABO 3 type complex oxide).
  • the A element (A site element) constituting the perovskite complex oxide may be one kind or two or more, and the B element (B site element constituting the perovskite complex oxide) ) May be one type or two or more types.
  • Examples of the perovskite complex oxide according to the dielectric ceramic material of the present invention include BaTiO 3 , CaTiO 3 , SrTiO 3 , Ba x Ca 1-x TiO 3 (where x is 0 ⁇ x ⁇ 1), Ba x Sr.
  • the perovskite type composite oxide particles that are the dielectric ceramic material of the present invention are not particularly limited as long as they are ABO 3 type composite oxides, but the A site element is selected from the group consisting of Ba, Ca, Mg, and Sr.
  • ABO 3 type composite oxide particles that are at least one and at least one selected from the group consisting of Ti and Zr as the B site element are preferred.
  • the particle diameter at which the volume cumulative value is 10% is D10
  • the particle diameter at which the volume cumulative value is 50% is D50 (average particle diameter).
  • the value of ((D90 ⁇ D10) / D50) is 1.2 or less, preferably 1.0 or less, particularly preferably 0.30 to 0. .95.
  • the value of ((D90-D10) / D50) is in the above range, the individual particles have similar sizes, and the dispersion stability and filling stability in the resin are increased, so that the composite obtained The dielectric properties of the dielectric are excellent.
  • the average particle diameter D50 of the ceramic material of the present invention is 3 to 15 ⁇ m, preferably 4 to 12 ⁇ m.
  • the average particle diameter is in the above range, for example, it is possible to cope with an element having a thickness of about 100 ⁇ m or less, the dispersibility and the filling property to the resin are improved, and the dielectric property of the obtained composite dielectric is excellent. It will be a thing. If the average particle size is less than the above range, handling in production becomes difficult, and if it exceeds the above range, a large restriction is imposed on the element size that can be handled.
  • the dielectric average theoretical specific surface area calculated from the particle diameter D50 (m 2 / g) and BET specific surface area measured by the BET method of the ceramic material of the present invention (m 2 / g) is, 0.5 ⁇ ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 9.0, preferably 0.6 ⁇ ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 8.0.
  • the shape of the dielectric ceramic material of the present invention is a shape with a bumpy surface. Particles with a rugged surface consume more resin, so when the same amount of resin is used, particles with a rugged surface will have less particles than smooth particles with a little bump on the surface. It is possible to reduce the amount of the resin that is not attached to the surface. Therefore, the distance between the particles in the resin can be reduced, and the filling property can be increased. For this reason, it becomes possible to reflect the characteristic of a dielectric ceramic material more strongly with respect to electrical characteristics, such as a dielectric constant expressed as a resin composite.
  • the shape of the dielectric ceramic material of the present invention is a rugged surface, the dispersibility and filling properties of the resin are increased, which makes it efficient for improving the electrical properties and modifying the resin composite. Can contribute well.
  • the degree of surface roughness increases, the shape moves away from the true sphere. Therefore, the larger the value of ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area), the greater the degree of irregularity on the particle surface. growing. Therefore, the value of ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) of the dielectric ceramic material of the present invention indicates the degree of unevenness of the particle surface, and 0.5 ⁇ ((BET specific surface area ⁇ theoretical specific surface area). ) / Theoretical specific surface area) ⁇ 9.0, preferably 0.6 ⁇ ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 8.0. It means that it is specified in the range.
  • the BET specific surface area of the dielectric ceramic material of the present invention is preferably 0.1 to 1.1 m 2 / g, particularly preferably 0.12 to 0.98 m 2 / g.
  • the BET specific surface area is in the above range, the dispersibility and the filling property to the resin are enhanced.
  • the chlorine content of the dielectric ceramic material of the present invention is 50 mass ppm or less, preferably 40 mass ppm or less, and the lower limit is preferably close to 0 mass ppm.
  • the chlorine content is a value obtained by measuring and quantifying the chlorine ions eluted by boiling the dielectric ceramic material with pure water, using an ion chromatograph.
  • the method for producing a dielectric ceramic material of the present invention is obtained by mixing oxalic acid and at least one compound (A element compound) selected from the group consisting of a Ba compound, a Ca compound, an Mg compound, and an Sr compound.
  • a liquid (liquid B) containing at least one chloride selected from the group consisting of Ti chloride and Zr chloride is added to the liquid (liquid A) to be reacted, and Ba, Ca, Mg
  • a fired body The fired body is crushed, the particle diameter at which the cumulative value in the volume frequency particle size distribution measurement by laser diffraction scattering method is 10% is D10, the particle diameter at 50% is D50, and the particle diameter at 90% is D90.
  • the value of ((D90 ⁇ D10) / D50) is 1.2 or less, the average particle diameter D50 is 3 to 15 ⁇ m, and the theoretical specific surface area (m 2 / g calculated from the average particle diameter D50) )
  • the BET specific surface area (m 2 / g) measured by the BET method is 0.5 ⁇ ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 9.0. 3 ) a third step of obtaining a dielectric ceramic material comprising type complex oxide particles; It is a manufacturing method of the dielectric ceramic material characterized by having.
  • the first step according to the method for producing a dielectric ceramic material of the present invention comprises oxalic acid and at least one compound (A element compound) selected from the group consisting of a Ba compound, a Ca compound, a Mg compound, and an Sr compound.
  • a element compound selected from the group consisting of a Ba compound, a Ca compound, a Mg compound, and an Sr compound.
  • a liquid (B liquid) containing a chloride is added to the liquid (A liquid) obtained by mixing to perform a reaction to obtain a complex oxalate of A element and B element.
  • the liquid A according to the first step is oxalic acid (H 2 C 2 O 4 ) and at least one compound selected from the group consisting of a Ba compound, a Ca compound, a Mg compound, and an Sr compound (element A). Compound) and a slurry-like liquid obtained by mixing.
  • a Ba compound, Ca atom, Mg atom and Sr atom are generically called A atom
  • Ti atom and Zr atom are generically called B atom.
  • Ba element, Ca element, Mg element, and Sr element are collectively referred to as A element
  • Ti element and Zr element are collectively referred to as B element.
  • the concentration of oxalic acid in the liquid A is preferably 0.5 to 6.5 mol / L, more preferably 0.7 to 6.0 mol / L in terms of oxalic acid (H 2 C 2 O 4 ). Particularly preferred is 1.0 to 4.5 mol / L.
  • the total concentration in terms of atoms of element A in the liquid A is preferably 0.4 to 4.0 mol / L, particularly Preferably, it is 0.7 to 3.5 mol / L.
  • the ratio of oxalic acid to the total number of moles of element A in the liquid A in terms of atoms is preferably 1.5 to 2.5, Particularly preferred is 1.8 to 2.2.
  • the method for preparing the liquid A is not particularly limited.
  • the method of preparing by contacting oxalic acid and the A element compound in an aqueous solvent is preferable in that the reactivity with the B liquid described later is increased.
  • the A element compound is a compound having an A element, and examples of the A element compound include chloride, hydroxide, sulfide, sulfate, nitrate, carbonate, and the like.
  • the element A compound is preferably a chloride, a hydroxide or a carbonate because it is economical and excellent in that an impure component does not remain and has high reactivity.
  • the B liquid according to the first step is a liquid containing at least one or two kinds of chlorides selected from the group consisting of Ti chlorides and Zr chlorides.
  • the total concentration in terms of atoms of the B element in the liquid B is preferably 0.1 to 2.0 mol / L, and particularly preferably 0.3 to 1. 7 mol / L.
  • the method for preparing the liquid B is not particularly limited, and examples thereof include a method in which an element B chloride is added to an aqueous solvent and dissolved.
  • the liquid B is added to the liquid A to react, and at least one element selected from the group consisting of Ba, Ca, Mg, and Sr (element A), and a group consisting of Ti and Zr.
  • An oxalate salt (complex oxalate salt of element A and element B) having at least one element selected from (B element) is obtained.
  • Ratio of total number of moles of element A in terms of atoms in liquid A to the total number of moles of element B in terms of atoms in liquid B (total number of moles of element A in terms of atoms in liquid A / element B in liquid B
  • the total number of moles in terms of atoms) is appropriately selected depending on the composition of the perovskite complex oxide to be produced, preferably 0.95 to 1.30, more preferably 0.98 to 1.25, and particularly preferably 1. 02 to 1.20.
  • the ratio of the total number of moles of the element A in the liquid A to the total number of moles of the element B in the liquid B is in the above range, so that the composite oxalate having a composition near the stoichiometry is obtained. It is possible to synthesize with good reproducibility.
  • the addition time is preferably 5 to 240 minutes, particularly preferably 10 to 210 minutes, with respect to the total number of moles of the B element in terms of atoms in the B liquid described above.
  • the ratio of the total number of moles of element A in the liquid A in terms of atoms is 0.95 to Liquid B is added to liquid A so that the amount is 1.30, more preferably 0.98 to 1.25, and particularly preferably 1.02 to 1.20.
  • the addition time is within this range, it becomes easy to control the nucleation of the composite oxalate, and particles having a fine and sharp particle size distribution can be obtained.
  • the B solution When performing the reaction by adding the B solution to the A solution, the B solution is added to the A solution while stirring the A solution.
  • the reaction temperature when the A liquid and the B liquid are reacted is preferably 60 ° C. or less, particularly preferably 25 to 58 ° C. Since the reaction temperature is in the above range, elution of the produced complex oxalate component into the solvent can be suppressed, and the change in the molar ratio of the fine complex oxalate can be suppressed with a high reaction yield. , Those having an A atom / B atom molar ratio closer to 1 are easily obtained.
  • B liquid is added to A liquid under stirring.
  • the stirring speed at this time is appropriately selected depending on the size of the reaction vessel, the diameter of the stirring blade, the amount of the reaction solution, and the like.
  • the aging time is preferably 0.1 hour or more, particularly preferably 0.1 to 2 hours.
  • the oxalate produced in the reaction solution (complex oxalate of element A and element B) is solid-liquid separated by filtration, centrifugation, etc., washed with water, Subsequently, if necessary, drying and pulverization are performed to obtain an oxalate (complex oxalate of element A and element B).
  • the oxalate obtained by performing the first step is a complex oxalate of element A and element B.
  • Ratio of the total number of moles of element A converted to atoms to the total number of moles of element B converted to atoms in the composite oxalate obtained by performing the first step total number of moles converted to atoms of element A / converted to atoms of element B
  • the total number of moles is appropriately selected depending on the composition of the perovskite complex oxide to be produced, and is preferably 0.995 to 1.005, more preferably 0.998 to 1.002, and particularly preferably 0.999 to 1. .001.
  • the second step according to the method for producing a dielectric ceramic material of the present invention is a step of firing the oxalate (complex oxalate of element A and element B) obtained by performing the first step to obtain a fired body. It is.
  • the firing temperature at the time of firing in the second step is 1050 to 1400 ° C., preferably 1060 to 1380 ° C.
  • the value of ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) of the dielectric ceramic material obtained by performing the third step is set to 0.5 ⁇ ((BET ratio Surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 9.0, preferably 0.6 ⁇ ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 8.0, and chlorine
  • the content can be 50 mass ppm or less, preferably 40 mass ppm or less.
  • the firing temperature is less than the above range, the chlorine content will be high, and the value of ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) will exceed the upper limit, resulting in a rough shape. The crystallinity does not increase and the dielectric properties are affected.
  • the firing temperature exceeds the above range, the value of ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) is below the lower limit value, resulting in an uneven shape and large particle size variation. The dispersion into the resin becomes difficult, or the reaction proceeds so much that the particles themselves cannot be obtained.
  • the chlorine content is a value obtained by measuring the chlorine ions eluted by boiling the dielectric ceramic material with pure water, using an ion chromatograph.
  • the firing time at the time of firing in the second step is preferably 2 to 30 hours, particularly preferably 5 to 20 hours.
  • the firing atmosphere at the time of firing in the second step is an oxidizing atmosphere such as an oxygen gas atmosphere or an air atmosphere.
  • the fired body obtained by performing the second step is crushed to obtain perovskite (ABO 3 ) type composite oxide particles having predetermined physical properties, that is, This is a step of obtaining the dielectric ceramic material of the present invention.
  • the method for crushing the fired body is not particularly limited as long as it is a crushing method capable of obtaining perovskite (ABO 3 ) type composite oxide particles having predetermined physical properties.
  • the crushing apparatus used for crushing include a mortar, a hammer mill, a jet mill, a pulverizer, and an impeller mill.
  • the crushing conditions may be any conditions as long as the perovskite (ABO 3 ) type composite oxide particles can be crushed so as to have a predetermined particle shape and particle size distribution. If necessary, the crushed perovskite (ABO 3 ) type composite oxide particles may be sieved or classified.
  • the perovskite (ABO 3 ) type composite oxide particles (dielectric ceramic material) obtained by performing the third step have a particle diameter of D10, 50% with a cumulative value in volume frequency particle size distribution measurement by laser diffraction scattering method of 10%.
  • the value of ((D90 ⁇ D10) / D50) is 1.2 or less, preferably 1.0 or less, particularly preferably 0.30, where D50 is the particle size of D90 and the particle size of 90% is D90. ⁇ 0.95.
  • the average particle diameter D50 of the perovskite (ABO 3 ) type composite oxide particles (dielectric ceramic material) obtained by performing the third step is 3 to 15 ⁇ m, preferably 4 to 12 ⁇ m.
  • the specific specific surface area (m 2 / g) calculated from the average particle diameter D50 of the perovskite (ABO 3 ) type composite oxide particles (dielectric ceramic material) obtained by performing the third step is measured by the BET method.
  • the relationship with the BET specific surface area (m 2 / g) is 0.5 ⁇ ((BET specific surface area ⁇ theoretical specific surface area) / theoretical specific surface area) ⁇ 9.0, preferably 0.6 ⁇ ((BET specific surface area ⁇ Theoretical specific surface area) / theoretical specific surface area) ⁇ 8.0.
  • the BET specific surface area of the perovskite (ABO 3 ) type composite oxide particles (dielectric ceramic material) obtained by performing the third step is preferably 0.1 to 1.1 m 2 / g, particularly preferably 0.12. ⁇ 0.98 m 2 / g.
  • the chlorine content of the perovskite (ABO 3 ) type composite oxide particles (dielectric ceramic material) obtained by performing the third step is 50 mass ppm or less, preferably 40 mass ppm or less.
  • the complex oxalate of element A and element B obtained by performing the first step is fired, and in the temperature rising process, first, particles of complex oxalate of element A and element B
  • carbon dioxide generated by thermal decomposition of oxalic acid is released, and a perovskite complex oxide having a large number of pores is obtained.
  • the perovskite complex oxide having a large number of pores is further fired at a high temperature of 1050 ° C. or more, preferably 1060 ° C. or more, so that a plurality of sintered bodies of primary particles are aggregated. Become secondary particles.
  • the average particle size D50 has a particle shape and particle size distribution of 3 to 15 ⁇ m, preferably 4 to 12 ⁇ m.
  • Perovskite complex oxide particles can be obtained.
  • the dielectric ceramic material of the present invention may be used alone as an inorganic filler filled into a resin, or a perovskite having an average particle diameter D50 of less than 3 ⁇ m in volume frequency particle size distribution measurement by a laser diffraction scattering method It may be used as a mixed dielectric ceramic material by mixing with a fine particle dielectric ceramic material made of (ABO 3 ) type complex oxide fine particles. That is, the mixed dielectric ceramic material of the present invention includes the dielectric ceramic material of the present invention and a perovskite (ABO 3 ) type composite oxide having an average particle diameter D50 of less than 3 ⁇ m in volume frequency particle size distribution measurement by a laser diffraction scattering method.
  • the ratio of the mixing amount of the dielectric ceramic material of the present invention to the mixing amount of the fine particle dielectric ceramic material is preferably a mass ratio of 3: 7 to 8: 2, particularly preferably. 4: 6 to 7: 3.
  • the composite dielectric can be obtained by dispersing the dielectric ceramic material of the present invention or the mixed dielectric ceramic material of the present invention in a resin. That is, the dielectric ceramic material of the present invention or the mixed dielectric ceramic material of the present invention is a ceramic material for a composite dielectric inorganic filler used by being dispersed in a resin.
  • the composite dielectric material according to the first aspect of the present invention is a composite dielectric material including the dielectric ceramic material of the present invention and a polymer material.
  • the composite dielectric material according to the second aspect of the present invention is a composite dielectric material comprising the mixed dielectric ceramic material of the present invention and a polymer material.
  • the resin used for the composite dielectric material of the first aspect of the present invention and the composite dielectric material of the second aspect of the present invention is not particularly limited as long as it is used as a resin for a composite dielectric.
  • Thermosetting resin thermoplastic resin or photosensitive resin.
  • thermosetting resins include epoxy resins, phenol resins, polyimide resins, melamine resins, cyanate resins, bismaleimides, addition polymers of bismaleimides and diamines, polyfunctional cyanate ester resins, and double resins.
  • Examples thereof include bond-added polyphenylene oxide resin, unsaturated polyester resin, polyvinyl benzyl ether resin, polybutadiene resin, and fumarate resin.
  • thermosetting resins may be used singly or in combination of two or more.
  • thermoplastic resin include (meth) acrylic resin, hydroxystyrene resin, novolac resin, polyester resin, polyimide resin, nylon resin, polyetherimide resin, and silicon resin.
  • thermoplastic resins may be used alone or in combination of two or more.
  • the photosensitive resin include those containing an acrylic copolymer (photosensitive oligomer) having an ethylenically unsaturated group, a photopolymerizable compound (photosensitive monomer) and a photopolymerization initiator, an epoxy resin and a photocation. The thing containing a polymerization initiator etc. are mentioned.
  • Photosensitive oligomers include those obtained by adding acrylic acid to an epoxy resin, those obtained by reacting them with an acid anhydride, and (meth) acrylic acid on a copolymer containing a (meth) acrylic monomer having a glycidyl group. Those obtained by reacting them with acid anhydride, those obtained by reacting glycidyl (meth) acrylate with a copolymer containing a (meth) acrylic monomer having a hydroxyl group, and those obtained by reacting acid anhydride with it.
  • Examples include those obtained by reacting a copolymer containing maleic anhydride with a (meth) acrylic monomer having a hydroxyl group or a (meth) acrylic monomer having a glycidyl group. These may be used alone or in combinations of two or more.
  • the dielectric ceramic material of the present invention has the above particle shape and particle size distribution
  • the mixed dielectric ceramic material of the present invention has the above particle shape and particle size distribution. Since it contains, the filling property to a resin and dispersibility become high. That is, the composite dielectric material of the first aspect of the present invention and the composite dielectric material of the second aspect of the present invention are the dielectric ceramic material of the present invention or the mixture of the present invention as an inorganic filler of the composite dielectric. By using the dielectric ceramic material, it is possible to obtain a composite dielectric having a high filling factor and high dispersibility of the dielectric ceramic material.
  • the dielectric ceramic material of the present invention or the mixed dielectric ceramic material of the present invention is used as an inorganic filler for a composite dielectric, thereby increasing electrostatic capacity, electromagnetic wave absorption, electric field relaxation, dielectric loss and temperature characteristics. Since an effect such as quality can be obtained, it is used for, for example, a substrate material, a built-in capacitor element, a film capacitor, an electromagnetic wave absorber, a semiconductor circuit sealing material, an insulating coating material such as a transmission cable, and the like. That is, the composite dielectric material according to the first aspect of the present invention and the composite dielectric material according to the second aspect of the present invention can increase capacitance, absorb electromagnetic waves, relax electric fields, modify dielectric loss, temperature characteristics, etc. Since the effect is obtained, for example, it is used as a substrate material, a built-in capacitor element, a film capacitor, an electromagnetic wave absorber, a semiconductor circuit sealing material, an insulating coating material such as a transmission cable, and the like.
  • Example 1 ⁇ Production of barium titanyl oxalate> A suspension obtained by adding 720 g of pure water to 130 g of barium chloride dihydrate and 130 g of oxalic acid dihydrate and stirring the mixture at a temperature of 55 ° C. for 0.5 hours was designated as solution A.
  • a solution B was prepared by adding 560 g of pure water to 256 g of a 15.3% by mass titanium tetrachloride aqueous solution in terms of TiO 2 and diluting it. Next, solution B was added to solution A over 30 minutes at a reaction temperature of 55 ° C. with stirring, and after the addition, aging was performed for 0.5 hours while continuing stirring.
  • Example 2 ⁇ Production of barium titanyl oxalate>
  • barium titanyl oxalate powder was obtained.
  • the firing temperature was 1200 ° C.
  • Table 1 shows the physical properties of the obtained barium titanate particles.
  • SEM photograph of the obtained barium titanate particles is shown in FIG. 1, and the particle size distribution is shown in FIG.
  • Example 3 ⁇ Production of barium titanyl oxalate> In the same manner as in Example 1, barium titanyl oxalate powder was obtained. ⁇ Manufacture of barium titanate> Barium titanate particles were obtained in the same manner as in Example 1 except that the firing temperature was 1250 ° C. Table 1 shows the physical properties of the obtained barium titanate particles.
  • Example 4 ⁇ Production of strontium titanyl oxalate> A suspension obtained by adding 550 g of pure water to 325 g of strontium hydroxide octahydrate and 300 g of oxalic acid dihydrate and stirring at a temperature of 55 ° C. for 0.5 hour was designated as solution A.
  • a solution B was prepared by adding 430 g of pure water to 590 g of a 15.3% by mass titanium tetrachloride aqueous solution in terms of TiO 2 and diluting it. Next, the liquid B was added to the liquid A over 180 minutes at a reaction temperature of 55 ° C. while stirring, and after the addition, aging was performed for 0.5 hours while continuing stirring.
  • Examples 5 to 7 and Comparative Example 3 Barium titanate particles obtained in Examples 1 to 3 and Comparative Example 2 and barium titanate fine particles as a filling aid (manufactured by Nippon Chemical Industry Co., Ltd., Parserum BT-4M, average particle diameter 0.7 ⁇ m, BET specific surface area) 2.0 m 2 / g) was mixed at a mass ratio shown in Table 2 with a commercially available mixer to obtain mixed dielectric ceramic materials of Examples 5 to 7 and Comparative Example 3. Next, the mixed dielectric ceramic materials of Examples 5 to 7 and Comparative Example 3 and the epoxy resin were kneaded at the blending ratio shown in Table 2 to prepare an epoxy resin composition.
  • a filling aid manufactured by Nippon Chemical Industry Co., Ltd., Parserum BT-4M, average particle diameter 0.7 ⁇ m, BET specific surface area 2.0 m 2 / g
  • the epoxy resin used here is a 99% by mass thermosetting epoxy resin (manufactured by Mitsubishi Chemical Corporation, trade name: JER (registered trademark) 828EL, molecular weight of about 370, specific gravity of 1.17, nominal at 25 ° C. Viscosity of 120 to 150 P) and 1% by weight of an imidazole curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2E4MZ).
  • Example 8 The strontium titanate particles obtained in Example 4 and strontium titanate fine particles (manufactured by Nippon Chemical Industry Co., Ltd., Parseram STG, average particle size 0.8 ⁇ m, BET specific surface area 2.1 m 2 / g) as a filling aid.
  • the mixed dielectric ceramic material of Example 8 was obtained by mixing with a commercially available mixer at a mass ratio shown in Table 2. Next, the mixed dielectric ceramic material of Example 8 and the same epoxy resin as in Examples 5 to 7 were kneaded at the blending ratio shown in Table 2 to prepare an epoxy resin composition.
  • kneading can be performed without any problem, and a product obtained with a uniform epoxy resin composition is evaluated as ⁇ , and kneading can be performed, but foaming occurs due to thickening of the epoxy resin composition, and fluidity is remarkably deteriorated. What was evaluated as (triangle
  • the epoxy resin composition was cured at 140 ° C. for 5 hours to prepare a composite dielectric sample.
  • an impedance analyzer Solartron 1255B
  • an interface Solartron 1296

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Abstract

L'invention concerne un matériau céramique diélectrique qui est caractérisé en ce que : le matériau céramique diélectrique comprend des particules d'oxyde composite de pérovskite (ABO3) ; la valeur de ((D90-D10)/D50) vaut 1,2 ou moins, où D10 représente la grosseur de particule à laquelle une valeur cumulée dans une mesure de distribution granulométrique en fréquence volumique par un procédé de diffraction/diffusion au laser est de 10 %, D50 représente la grosseur de particule à laquelle la valeur cumulée dans celle-ci est de 50 % et D90 représente la grosseur de particule à laquelle la valeur cumulée dans celle-ci est de 90 % ; la grosseur moyenne D50 des particules est de 3 à 15 μm ; et la relation entre l'aire de surface spécifique théorique (m2/g), calculée par la grosseur moyenne D50 de particule, et l'aire de surface spécifique BET (m2/g), mesurée par le procédé BET, est de 0,5≤((aire de surface spécifique BET-aire de surface spécifique théorique)/aire de surface spécifique théorique)≤9,0.
PCT/JP2016/060991 2015-04-07 2016-04-04 Matériau céramique diélectrique, son procédé de fabrication et matériau composite diélectrique WO2016163330A1 (fr)

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KR1020177027777A KR102498656B1 (ko) 2015-04-07 2016-04-04 유전체 세라믹 재료, 그 제조 방법 및 복합 유전체 재료

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210065978A1 (en) * 2019-08-28 2021-03-04 Murata Manufacturing Co., Ltd. Multilayer electronic component and method for manufacturing multilayer electronic component
WO2024009615A1 (fr) * 2022-07-08 2024-01-11 チタン工業株式会社 Oxyde multiple de titane de magnésium qui est approprié en tant que charge inorganique dans un matériau d'étanchéité en résine pour semi-conducteurs, et sa méthode de production

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0388720A (ja) * 1989-08-30 1991-04-15 Tdk Corp シュウ酸チタニルバリウム粒子の製造方法
JP2005033070A (ja) * 2003-07-09 2005-02-03 Tdk Corp 積層セラミックコンデンサおよびその製造方法
JP2005213070A (ja) * 2004-01-28 2005-08-11 Tdk Corp ペロブスカイト構造を有する酸化物粉末の製造方法
WO2013115045A1 (fr) * 2012-01-30 2013-08-08 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 Composition de résine dotée de propriétés d'isolation diélectrique élevée

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0388720A (ja) * 1989-08-30 1991-04-15 Tdk Corp シュウ酸チタニルバリウム粒子の製造方法
JP2005033070A (ja) * 2003-07-09 2005-02-03 Tdk Corp 積層セラミックコンデンサおよびその製造方法
JP2005213070A (ja) * 2004-01-28 2005-08-11 Tdk Corp ペロブスカイト構造を有する酸化物粉末の製造方法
WO2013115045A1 (fr) * 2012-01-30 2013-08-08 モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 Composition de résine dotée de propriétés d'isolation diélectrique élevée

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210065978A1 (en) * 2019-08-28 2021-03-04 Murata Manufacturing Co., Ltd. Multilayer electronic component and method for manufacturing multilayer electronic component
US11581142B2 (en) * 2019-08-28 2023-02-14 Murata Manufacturing Co., Ltd. Multilayer electronic component and method for manufacturing multilayer electronic component
WO2024009615A1 (fr) * 2022-07-08 2024-01-11 チタン工業株式会社 Oxyde multiple de titane de magnésium qui est approprié en tant que charge inorganique dans un matériau d'étanchéité en résine pour semi-conducteurs, et sa méthode de production

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