WO2011120196A1 - 电介质陶瓷组合物、电介质陶瓷组合物的制备方法及电子元件 - Google Patents

电介质陶瓷组合物、电介质陶瓷组合物的制备方法及电子元件 Download PDF

Info

Publication number
WO2011120196A1
WO2011120196A1 PCT/CN2010/000415 CN2010000415W WO2011120196A1 WO 2011120196 A1 WO2011120196 A1 WO 2011120196A1 CN 2010000415 W CN2010000415 W CN 2010000415W WO 2011120196 A1 WO2011120196 A1 WO 2011120196A1
Authority
WO
WIPO (PCT)
Prior art keywords
dielectric
ceramic composition
weight
main component
parts
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2010/000415
Other languages
English (en)
French (fr)
Inventor
葛桂宾
林晖
张帆
庄剑勇
广濑正和
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TDK Corp
Original Assignee
TDK Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by TDK Corp filed Critical TDK Corp
Priority to JP2013501585A priority Critical patent/JP2013523574A/ja
Priority to PCT/CN2010/000415 priority patent/WO2011120196A1/zh
Priority to KR1020127016461A priority patent/KR101352607B1/ko
Priority to CN2010800537238A priority patent/CN102781874A/zh
Priority to TW100100171A priority patent/TWI412504B/zh
Publication of WO2011120196A1 publication Critical patent/WO2011120196A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth 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
    • C04B35/468—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
    • C04B35/468—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
    • C04B35/4682—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 based on BaTiO3 perovskite phase
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/6262—Milling of calcined, sintered clinker or ceramics
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62685—Treating the starting powders individually or as mixtures characterised by the order of addition of constituents or additives
    • 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
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/62695—Granulation or pelletising
    • 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
    • C04B35/64—Burning or sintering processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/003—Thick film resistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/1006—Thick film varistors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/115—Titanium dioxide- or titanate type
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3272—Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/327—Iron group oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3279—Nickel oxides, nickalates, or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3281—Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or Cu2O
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3284—Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
    • C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6567—Treatment time
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
    • H01C7/105—Varistor cores
    • H01C7/108—Metal oxide
    • H01C7/112—ZnO type

Definitions

  • Dielectric ceramic composition preparation method of dielectric ceramic composition and electronic component
  • the present invention relates to a dielectric ceramic composition, a method of preparing a dielectric ceramic composition, and an electronic component. Background technique
  • Ceramic capacitors which are an example of electronic components, are used in various electronic instruments, and in recent years, there has been an increasing demand for high performance.
  • a ceramic capacitor identified by a safety standard is likely to be subjected to a peak voltage due to a snubber circuit for a switching power supply. Therefore, in order to protect the circuit, it is most important not to cause the ceramic capacitor to be broken down, i.e., to improve the dielectric breakdown electric field (ACVB) of the dielectric ceramic composition.
  • ACVB dielectric breakdown electric field
  • a dielectric ceramic composition having a relatively high AC breakdown electric field is disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. 2003-104774. However, even if it is high, it is only about 5kV/mm. Summary of the invention
  • the present invention has been made in view of such circumstances, and an object thereof is to provide a dielectric shield ceramic composition having a high AC breakdown electric field, a high dielectric constant, and a low dielectric loss, and a method for preparing a dielectric shield ceramic composition. Further, it is an object of the invention to provide an electronic component having a dielectric layer composed of such a dielectric ceramic composition.
  • the present inventors have conducted intensive studies in order to achieve the above object, and as a result, have found that the above object can be attained by setting the composition of the dielectric ceramic composition to a specific component and setting the ratio thereof to a predetermined range, thereby completing the present invention.
  • y in the above composition formula is 0 y 0.08, and the total of x and y in the above composition formula is 0.975 ⁇ x + y ⁇ 1.010,
  • the content of the zinc oxide is from 2 parts by weight to 12 parts by weight based on 100 parts by weight of the above main component.
  • an AC breakdown electric field and a dielectric having a high dielectric constant and a low dielectric loss can be provided.
  • the head of the present invention ⁇ ⁇ ⁇ ⁇ ; p; ⁇ ,
  • y in the above composition formula is 0 y ⁇ 0.08, and the total of X and y in the above composition formula is 0.975 ⁇ x + y ⁇ 1.010,
  • the content of the zinc oxide is from 1.6 parts by weight to 12 parts by weight, based on 100 parts by weight of the above main component.
  • the preparation method has the following steps:
  • the electronic component according to the embodiment of the present invention is not particularly limited, and examples thereof include a single-plate type ceramic capacitor and a laminated ceramic capacitor.
  • Fig. 1(A) is a front view of a ceramic capacitor according to an embodiment of the present invention
  • Fig. 1(B) is a side cross-sectional view showing a ceramic capacitor according to an embodiment of the present invention.
  • Fig. 2 is a view showing the influence of the timing of adding zinc oxide and the content of zinc oxide on the alternating breakdown electric field in the preparation method of the dielectric shield ceramic composition according to the embodiment of the present invention. detailed description
  • a ceramic capacitor 2 As shown in FIG. 1 (A:) and FIG. 1 (B), a ceramic capacitor 2 according to an embodiment of the present invention is formed with a dielectric layer 10, a pair of terminal electrodes 12, 14 formed on a surface opposite thereto, and The lead terminals 6, 8 respectively connected to the terminal electrodes 12, 14 are covered by the protective resin 4.
  • the shape of the ceramic capacitor 2 can be appropriately determined depending on the purpose and application, but it is preferable that the dielectric layer 10 is formed into a disk-shaped disk-shaped capacitor. Further, the size thereof may be appropriately determined depending on the purpose and use, but usually the diameter is about 5 to 20 mm, preferably about 5 to 15 mm.
  • the dielectric layer 10 is composed of the dielectric ceramic composition according to the embodiment of the present invention.
  • the dielectric ceramic composition according to the embodiment of the present invention has a main component represented by a composition formula of (Ba x Ca y )Ti 0 3 and zinc oxide, and y in the above composition formula is 0 y 0.08, and in the above composition formula The total of X and y is 0.975 x + y 1.010.
  • X in the above composition formula represents the ratio of Ba, and X is 0.915 X 1.005, preferably 0.930 ⁇ x 1.000.
  • the dielectric constant tends to increase.
  • y in the above composition formula represents the ratio of Ca, which is 0 y 0.08, preferably 0 y 0.07.
  • Ca is an arbitrary component, and the AC breakdown electric field can be improved even when Ca is not contained.
  • the total of the ratio of X to y in the above composition formula i.e., the ratio of Ba to Ca, is preferably 0.975 ⁇ x + y ⁇ 1.010, and more preferably 0.980 x + y ⁇ 1.005.
  • the amount of x and y is in this range, there is a tendency that the sinterability, the alternating breakdown electric field, and the dielectric constant are improved.
  • the content of zinc oxide is from 1.6 parts by weight to 12 parts by weight, preferably from 2 parts by weight to 12 parts by weight, more preferably 2.3, based on 100 parts by weight of the main component.
  • the parts by weight are 10 parts by weight, and more preferably 4 parts by weight to 10 parts by weight.
  • the content of zirconia, iron oxide or nickel oxide is preferably less than 1.0 part by weight, more preferably from 0 part by weight to 0.5 part by weight, per 100 parts by weight of the main component. More preferably, it is 0 weight part. If the content of zirconia, iron oxide or nickel oxide exceeds this range, the alternating breakdown electric field tends to decrease. Further, if the content of the nickel oxide exceeds this range, not only the alternating breakdown electric field but also the dielectric loss tends to increase.
  • the thickness of the dielectric layer 10 is not particularly limited, and may be appropriately determined depending on the use, etc., but is preferably 0.3 to 2 mm. By making the thickness of the dielectric layer 10 within this range, it can be suitably used for medium and high pressure applications.
  • terminal electrodes 12, 14 are made of a conductive material.
  • Examples of the conductive material used for the terminal electrodes 12 and 14 include Cu, a Cu alloy, Ag, an Ag alloy, and an In-Ga alloy.
  • a dielectric ceramic composition powder in which the dielectric layer 10 shown in Fig. 1 is formed after firing is prepared.
  • Raw materials of the main components and raw materials of the respective components are prepared.
  • the raw material of the main component include various oxides of Ba, Ca, and Ti, and/or a raw material for forming an oxide by firing, or a composite oxide thereof.
  • BaC0 3 , CaC0 3 , Ti0 2 or the like can be used.
  • various compounds which form an oxide or a titanium compound after firing such as a hydroxide can also be used. At this time, it is also possible to appropriately change the content to match the number of elements of the metal element.
  • the raw material of the main component can be produced by a solid phase method or a liquid phase method such as hydrothermal synthesis or oxalate method, but it is preferably prepared by a solid phase method from the viewpoint of production cost.
  • the raw materials of the respective subcomponents are not particularly limited, and various compounds such as carbonates, nitrates, and hydrogens may be formed from the oxides or composite oxides of the above-mentioned respective subcomponents or by firing to form these oxides or composite oxides.
  • An oxide, an organometallic compound or the like is appropriately selected and used.
  • the raw material of the main component or the raw material of the main component is blended with the raw material of the subcomponent, and wet-mixed using a ball mill or the like using a zirconia ball or the like. When the subcomponent is blended at this time, each subcomponent may be blended, or only a part of the subcomponent may be blended, and the remaining subcomponent may be added after calcination to form the composition of the dielectric ceramic composition.
  • the obtained mixture is granulated and molded, and the obtained molded product is calcined in an air atmosphere, whereby a calcined powder can be obtained.
  • the calcination conditions for example, the calcination temperature may preferably be 1100 to 1300 ° C, more preferably 1150 to 1250 ° C, and the calcination time may preferably be 0.5 to 4 hours.
  • the raw material of the main component and the raw material of the auxiliary component may be separately calcined and then mixed to form a dielectric ceramic composition powder.
  • the obtained calcined powder was coarsely pulverized.
  • the subcomponent is added to form the composition of the dielectric ceramic composition together with the raw material of the subcomponent added before calcination.
  • the calcined powder or the calcined powder and the raw material of the subcomponent are wet-pulverized by a ball mill or the like, and further mixed and dried to obtain a dielectric ceramic composition powder.
  • a ball mill or the like wet-pulverized by a ball mill or the like, and further mixed and dried to obtain a dielectric ceramic composition powder.
  • the obtained dielectric ceramic composition powder is preferably 1200 to 1400 ° C, more preferably 1250 to 1350 ° C, and preferably the firing atmosphere is air.
  • the terminal electrodes are printed on the main surface of the sintered body of the obtained dielectric ceramic composition, and are baked as necessary to form terminal electrodes 12 and 14. Then, the terminal electrodes 12 and 14 are joined to the lead terminals 6 and 8 by soldering or the like, and finally the element body is covered with the protective resin 4, whereby the single-plate type ceramic capacitor shown in Fig. 1 (A) and Fig. 1 (B) is obtained. .
  • the ceramic capacitor of the present invention thus produced is mounted on a printed circuit board or the like by lead terminals 6, 8 and used for various electronic instruments and the like.
  • the electronic component according to the present invention is a single-plate type ceramic capacitor in which the dielectric layer is a single layer.
  • the electronic component according to the present invention is not limited to a single-plate type; A laminated ceramic capacitor manufactured by a method or a sheet method. , 'Example
  • BaC0 3 , CaC0 3 and Ti0 2 were separately prepared. Then, the prepared raw materials were weighed to form the compositions shown in the samples 1 to 31 and 3a of Table 1, and wet-mixed by using a pure water as a solvent and a ball mill using an oxidized sphere.
  • the obtained green body was fired in the air at 1,250 to 1,350 ° C for 2 hours to obtain a disk-shaped sintered body. Further, an Ag electrode was applied to both surfaces of the main surface of the obtained sintered body, and further subjected to a heat treatment at 650 ° C for 20 minutes in the air to obtain a sample of the disk-shaped ceramic capacitor shown in Fig. 1 . .
  • the dielectric layer 10 of the obtained capacitor sample had a thickness of about 1 mm and the burn-in electrode had a diameter of 12 mm. Further, for each of the obtained capacitor samples, the alternating breakdown electric field, dielectric constant, and dielectric loss were evaluated by the following methods. The evaluation results are shown in Table 1.
  • AC breakdown voltage was measured as follows: For the capacitor sample, an alternating electric field was applied slowly at both ends of the capacitor at 100 V/s, and the electric field value at the time of leakage current of 100 mA was measured, and this was taken as an alternating current breakdown electric field.
  • the AC breakdown electric field is high, and in the present embodiment, 6.0 kV/mm or more is good.
  • the dielectric constant ⁇ was calculated as follows: For a capacitor sample, a digital LCR meter (4274A, manufactured by Agilent Technologies, Inc.) at a reference temperature of 20 ° C at a frequency of 1 kHz and an input signal level (measured voltage) of 1.0 rmrms The electrostatic capacity was measured, and the dielectric constant ⁇ (no unit) was calculated from the electrostatic capacity.
  • the dielectric constant is high, and in the present embodiment, 2000 or more is good.
  • the dielectric loss tanS is measured for a capacitor sample at a reference temperature of 2 (TC, using a digital LCR meter (4274A, manufactured by Agilent Technologies) at a frequency of 1 kHz and an input signal level (measured voltage) of 1.0 rmrms.
  • the dielectric loss is preferably small, and 3% or less in the present embodiment is good.
  • the calcined powder of the main component raw material is coarsely pulverized by a crusher and sieved, and then weighed to form a composition shown in the samples 41a to 43a of Table 2.
  • the amount of ZnO was added to the calcined powder, and the firing temperature of the molded body was 1250 ° C. Otherwise, each capacitor sample was obtained in the same manner as the samples 1 to 9, and the alternating breakdown electric field, dielectric constant, and dielectric constant were applied. The electrical loss was evaluated. Namely, in the samples 41a to 43a, ZnO was added after the calcination of the main component raw material in the same manner as the samples 1 to 9. The AC breakdown electric field is measured on four samples and averaged. The composition and evaluation results of each sample are shown in Table 2. Table 2
  • the calcined powder of the main component raw material is roughly pulverized by a crusher and sieved to form a composition of the samples shown in Table 3, ls ⁇ 6s, lsa. Add ZnO, Bi 2 0 3 , Zr0 2 , Fe 2 0 3 or NiO, and obtain the capacitor samples in the same manner as samples 1 to 9, respectively, for the AC breakdown electric field, dielectric constant and dielectric loss. Conduct an evaluation. The composition and evaluation results of each sample are shown in Table 3.
  • each of the capacitor samples was obtained in the same manner as the samples 41 to 43 except that ZnO, Nb 2 O 5 or CuO weighed in the amount of the composition shown in the samples 6sa and 6sb of Table 3 was calcined together with the main component raw materials. , respectively, the AC breakdown electric field, dielectric constant and dielectric loss were evaluated. The composition and evaluation results of each sample are shown in Table 3. Sample 7s ⁇ 13s
  • the content of zinc oxide is from 1.6 parts by weight to 12. parts by weight (samples 3 to 8, 3a, 4a, 42, 43, 42a) , 43a)
  • the alternating breakdown electric field is increased, and when the content of zinc oxide is 2 parts by weight to 12 parts by weight, the alternating current is applied. The electric field is further increased.
  • the electrical constant is lowered.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electromagnetism (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Inorganic Insulating Materials (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)

Description

电介质陶瓷组合物、 电介质陶瓷组合物的制备方法及电子元件 技术领域
本发明涉及电介质陶瓷组合物、电介质陶瓷组合物的制备方法以及电 子元件。 背景技术
作为电子元件的一个实例的陶瓷电容器被用于各种电子仪器， 近年 来， 对高性能化的要求越来越高。
例如，安全标准认定的陶瓷电容器由于用于开关电源的緩冲电路， 因 此有可能受到峰值电压。 因此， 为了保护电路， 不使陶瓷电容器被击穿， 即提高电介质陶瓷组合物的绝缘击穿电场 (ACVB)是最重要的。
曰本特开 2006-096576号公 4艮和日本特开 2003-104774号公报中公开 了交流击穿电场比较高的电介质陶瓷组合物。但是， 都是即使高也不过为 5kV/mm左右。 发明内容
本发明是鉴于这种现状而作出的， 其目的在于，提供交流击穿电场和 介电常数高、介电损耗低的电介盾陶瓷组合物以及电介盾陶瓷组合物的制 备方法。 此外， 本发明的目的在于， 提供具有由这种电介质陶瓷组合物构 成的电介质层的电子元件。
本发明人等为了达到上述目的而进行了深入研究， 结果发现，通过使 电介质陶瓷组合物的组成为特定的成分、使它们的比率为规定范围， 可以 达到上述目的， 从而完成本发明。 有用（BaxCay)Ti03的组成式表示的主要成分和氧化辞的电介质陶瓷组合 物， 其中，
上述组成式中的 y为 0 y 0.08,且上述组成式中的 x与 y的总计为 0.975 < x + y < 1.010,
相对于上述主要成分 100重量份，上述氧化锌的含量为 2重量份 ~ 12 重量份。
根据本发明， 可以提供交流击穿电场和介电常数高、介电损耗低的电 介质陶瓷组合物，
匕夕卜，本发明的头^万^; p;^ 的 、
有用（BaxCay)Ti03的组成式表示的主要成分和氧化锌的电介质陶瓷组合物 的制备方法， 其中，
上述组成式中的 y为 0 y < 0.08,且上述组成式中的 X与 y的总计为 0.975 < x + y < 1.010,
相对于上述主要成分 100重量份， 上述氧化锌的含量为 1.6重量份- 12重量份，
该制备方法具有下述步骤：
对上述主要成分的原料进行煅烧， 得到经过了煅烧的粉末的步骤， 向上述经过了煅烧的粉末中添加上述氧化辞的原料，得到电介质陶瓷 组合物粉末的步骤， 和
将上述电介质陶瓷组合物粉末成型并烧制的步骤。 或通过上述制 方法^到的电介质陶瓷组合物构成的电介质层。 '
对本发明的实施方式涉及的电子元件不特别限定，可以列举单板型陶 瓷电容器、 叠层陶瓷电容器。 附图说明
图 1(A)为本发明的一个实施方式所涉及的陶瓷电容器的主视图， 图 1(B)为本发明的一个实施方式所涉及的陶瓷电容器的側面截面图。
图 2 为表示本发明的一个实施方式所涉及的电介盾陶瓷组合物的制 备方法中添加氧化锌的时机、 与氧化锌的含量对交流击穿电场的影响的 图。 具体实施方式
以下基于附图所示的实施方式对本发明的实施方式进行说明。
陶瓷电容器 2
如图 1(A：)、 图 1(B)所示， 本发明的实施方式所涉及的陶瓷电容器 2 形成具有电介质层 10、在与其相对的表面上形成的一对端子电极 12、 14, 和分别与该端子电极 12、 14连接的引线端子 6、 8的结构， 它们被保护树 脂 4覆盖。 陶瓷电容器 2的形状可以根据目的、用途来适当决定，但是优选电介 质层 10形成圆板形状的圆板型电容器。 此外， 其尺寸可以根据目的、 用 途来适当决定， 但是通常直径为 5 ~ 20mm左右， 优选为 5 ~ 15mm左右。
(电介质层 10)
电介质层 10由本发明的实施方式所涉及的电介质陶瓷组合物构成。 本发明的实施方式所涉及的电介质陶瓷组合物具有用（BaxCay)Ti03的 组成式表示的主要成分和氧化锌， 上述组成式中的 y为 0 y 0.08， 且上 述组成式中的 X与 y的总计为 0.975 x + y 1.010。
上述组成式中的 X表示 Ba的比率， X为 0.915 X 1.005，优选为 0.930 < x 1.000。 通过以该范围含有 Ba, 有介电常数提高的倾向。
上述组成式中的 y表示 Ca的比率，为 0 y 0.08，优选为 0 y 0.07。 通过在该范围含有 Ca， 有烧结性和交流击穿电场提高的倾向。 应予说明， 本实施方式中， Ca为任意的成分，不含有 Ca时也可以提高交流击穿电场。
上述组成式中的 X与 y的总计、 即 Ba与 Ca的比率的总计， 优选为 0.975 < x + y < 1.010, 更优选为 0.980 x + y < 1.005。 通过使 x与 y 量在该范围， 有烧结性、 交流击穿电场和介电常数提高的倾向。
本发明的实施方式所涉及的电介质陶瓷组合物中，相对于上述主要成 分 100重量份，氧化锌的含量为 1.6重量份 ~ 12重量份，优选为 2重量份 ~ 12重量份， 更优选为 2.3重量份 ~ 10重量份， 进一步优选为 4重量份 ~ 10 重量份。 通过以在该范围含有氧化锌， 有交流击穿电场和介电常数提 高、 介电损耗降低的倾向。
本发明的实施方式所涉及的电介质陶瓷组合物中，相对于上述主要成 分 100重量份， 氧化锆、 氧化铁或氧化镍的含量优选小于 1.0重量份， 更 优选为 0重量份 ~ 0.5重量份， 进一步优选为 0重量份。 若氧化锆、 氧化 铁或氧化镍的含量超过该范围， 则有交流击穿电场降低的倾向。 此外， 若 氧化镍的含量超过该范围， 则不仅交流击穿电场降低，还有介电损耗升高 的倾向。
以下以氧化辞作为 "副成分" 。
对电介质层 10的厚度不特别限定， 根据用途等适当决定即可， 但是 优选为 0.3 ~ 2mm。通过使电介质层 10的厚度在该范围，可以适用于中高 压用途。
(端子电极 12、 14) 端子电极 12、 14由导电材料构成。 作为用于端子电极 12、 14的导电 材料， 例如， 可以举出 Cu、 Cu合金、 Ag、 Ag合金、 In-Ga合金等。
陶瓷电容器的制备方法
以下对陶瓷电容器的制造方法进行说明。
首先， 制备烧制后形成图 1所示的电介质层 10的电介质陶瓷组合物 粉末。
准备主要成分的原料和各副成分的原料。作为主要成分的原料，可以 举出 Ba、 Ca、 Ti的各氧化物和 /或通过烧制形成氧化物的原料， 或它们的 复合氧化物等， 例如可以使用 BaC03、 CaC03、 Ti02等。 此外， 例如还可 以使用氢氧化物等烧制后形成氧化物或钛化合物的各种化合物。此时， 还 可以适当改变含量以符合金属元素的元素数。
此外， 主要成分的原料可以通过固相法制备，还可以通过水热合成法 或草酸盐法等液相法来制备， 但是从制备成本方面考虑， 优选通过固相法 制备。
对各副成分的原料不特别限定，可以从上述各副成分的氧化物或复合 氧化物、或通过烧制形成这些氧化物或复合氧化物的各种化合物， 例如碳 酸盐、 硝酸盐、 氢氧化物、 有机金属化合物等中适当选择来使用。 将主要成分的原料^或主 ^成分的原料与副成 的原料配合，使用利用氧 化锆球等的球磨机等进行湿式混合。在此时间点配合副成分时， 可以配合 各副成分， 也可以仅配合一部分副成分、在煅烧后添加其余的副成分以形 成上述电介质陶瓷组合物的组成。
将所得到的混合物进行造粒并成型，将得到的成型物在空气氛围中进 行煅烧， 由此可以得到煅烧粉末。 作为煅烧条件， 例如煅烧温度可以优选 为 1100 ~ 1300°C、 更优选为 1150 ~ 1250°C , 煅烧时间可以优选为 0.5 ~ 4 小时。 此外， 还可以将主要成分的原料和副成分的原料分别煅烧后， 混合 制成电介质陶瓷组合物粉末。
其次， 将得到的煅烧粉末粗粉碎。 其中， 添加副成分使其与在煅烧前 添加的副成分的原料一起形成上述电介质陶瓷组合物的组成，但是对于氧 化锌的原料，优选将其至少一部分在主要成分的原料煅烧后添加， 更优选 将其全部在主要成分的原料煅烧后添加。如此可以进一步提高电介盾陶瓷 组合物的交流击穿电场， 即使氧化辞的添加量少、也可以提高交流击穿电 场。
将煅烧粉末或煅烧粉末与副成分的原料通过球磨机等进行湿式粉碎， 进而进行混合、 干燥， 制成电介质陶瓷组合物粉末。 如上所述， 通过固相 法制备电介质陶瓷组合物粉末， 可以实现所需的特性， 同时可以谋求降低 制备成本。
然后，在所得到的电介质陶瓷组合物粉末中添加适量粘合剂，进行造 粒， 将得到的造粒物成型为具有规定大小的圆板状， 由此形成成型坯体。 并且， 将得到的成型坯体烧制， 由此得到电介质陶瓷组合物的烧结体。 而 且， 对烧制的条件不特别限定， 但是保持温度优选为 1200 ~ 1400°C、 更 优选为 1250 ~ 1350°C， 优选烧制氛围为空气中。
在所得到的电介质陶瓷组合物的烧结体的主表面上印刷端子电极，根 据需要进行烧接， 由此形成端子电极 12、 14。 然后， 通过焊接等将端子 电极 12、 14与引线端子 6、 8接合， 最后用保护树脂 4覆盖元件主体， 由 此得到图 1(A)、 图 1(B)所示的单板型陶瓷电容器。
如此制造的本发明的陶瓷电容器通过引线端子 6、 8安装在印刷基板 上等， 用于各种电子仪器等。
以上对本发明的实施方式进行了说明，但是本发明不限于这些实施方 式， 在不脱离本发明主旨的范围内当然可以以各种不同的方式来实施。
例如， 上述实施方式中，作为本发明涉及的电子部件列举了电介质层 为单层的单板型陶瓷电容器，但是本发明涉及的电子部件不限定为单板型 才 ;胡料通 ^通常的印刷法或薄片法而制造的叠层型陶瓷电容器。、 ' 实施例
以下，基于实施例对本发明进行更具体的说明，但是本发明不限于这 些实施例。
样品 1 - 31、 3a
作为主要成分的原料， 分别准备 BaC03、 CaC03和 Ti02。 并且， 分 别称量所准备的这些原料以形成表 1的样品 1 ~ 31、 3a所示的组成， 通过 使用纯水作为溶剂、 利用氧化倍球的球磨机进行湿式混合。
然后， 将得到的混合物干燥后， 加入 5重量％的水进行造粒、 成型。 并且, 将所得到的成型物在空气中、 1150°C的条件下进行 2小时煅烧。 将 煅烧后的粉末用碎石机进行粗粉碎并过筛后，以形成表 1所示的组成的量 称量并添加 ZnO， 进行湿式粉碎。对其进行干燥， 由此得到具有表 1所示 的各组成 (样品 1 ~ 31、 3a的各组成)的电介质陶瓷组合物粉末。
相对于所得到的电介质陶瓷组合物粉末 100重量份，添加聚乙烯醇水 溶液 10重量份， 接着进行造粒， 过筛后， 得到的造粒粉末在 396MPa的 压力下得到直径 16.5mm、 厚度约 1.2mm的圆板状的成型坯体。
将得到的成型坯体在空气中、 1250 ~ 1350°C的条件下烧制 2小时， 由 此得到圆板状的烧结体。 并且， 在得到的烧结体的主表面的两面上涂布 Ag电极， 进而在空气中、 650°C下进行 20分钟烧接处理， 由此得到图 1 所示的圆板状的陶瓷电容器的样品。 得到的电容器样品的电介质层 10的 厚度约为 1mm, 烧接电极的直径为 12mm。 并且， 对于得到的各电容器样 品，利用以下的方法分别对交流击穿电场、介电常数、介电损耗进行评价。 评价结果如表 1所示。
(交流击穿电压 (ACVB))
交流击穿电压 (ACVB)如下测定： 对于电容器样品， 在电容器的两端 以 100 V/s緩慢地施加交流电场，测定在流通 100mA的漏电流时的电场值， 将其作为交流击穿电场。 优选交流击穿电场高， 本实施例中， 6.0kV/mm 以上为良好。
(介电常数 (ε))
介电常数 ε如下算出： 对于电容器样品， 在基准温度 20°C下， 用数 字 LCR测量仪 ( Agilent Technologies公司制 4274A ) ， 在频率为 lkHz、 输入信号水平 (测定电压)为 l.OVrms的条件下测定静电容量， 由该静电容 量算出介电常数 ε (无单位)。 优选介电常数高， 本实施例中， 2000 以上为 良好。
(介电损耗 (tanS))
介电损耗 tanS是对于电容器样品， 在基准温度 2(TC下， 用数字 LCR 测量仪（Agilent Technologies社制 4274A ) ， 在频率为 lkHz、 输入信号 水平（测定电压）为 l.OVrms的条件下测定得到的。 优选介电损耗小， 本 实施例中 3%以下为良好。 主要成分（BaxCay)Ti03 ZnO 交流击穿电场 介电常数 样品 介电损耗
(ACVB) ( ε ) (tan 6 )
No X y x+y [重量份]
[kV/mm] Η [%]
1 0.930 0.06 0.990 0.0 SO 1703 1.6
* 2 0.930 0.06 0.990 1.5 5 2272 1.5
3 0.930 0.06 0.990 2.0 7.8 2213 1.5
3a 0.930 0.06 0.990 2.3 8.0 2267 1.5
4 0.930 0.06 0.990 2.5 8.1 2340 1.7
4a 0.930 0.06 0.990 4.0 8.3 2255 1.7
5 0.930 0.06 0.990 5.0 8.7 2206 1.7
6 0.930 0.06 0.990 7.0 6.2 21 18 1.7
7 0.930 0.06 0.990 10.0 6.1 2027 1.8
8 0.930 0.06 0.990 12.0 6.1 2007 1.9
* 9 0.930 0.06 0.990 1 5.0 M 1835 2.0
* 10 0.900 0.06 0.960 2.5 6.5 1811 0.9
1 1 0.915 0.06 0.975 2.5 8.0 2054 1.1
12 0.920 0.06 0.980 2.5 8.3 21 12 1.2
13 0.925 0.06 0.985 2.5 8.1 2202 1.4
14 0.935 0.06 0.995 2.5 7.9 2308 2.0
15 0.940 0.06 1.000 2.5 7.8 2287 2.1
16 0.950 0.06 1.010 2.5 6.9 2D13 0.8
* 17 0.960 0.06 1.020 2.5 在 1350 TC未完成烧结
18 0.990 0.00 0.990 2.5 6.3 3104 0.9
19 0.980 0.01 0.990 2.5 7.0 3009 1.2
20 0.970 0.02 0.990 2.5 7.3 2954 1.7
21 0.960 0.03 0.990 2.5 6.2 2778 1.7
22 0.940 0.05 0.990 2.5 6.5 261 1 1.7
23 0.920 0.07 0.990 2.5 6.9 2475 1.6
24 0.910 0.08 0.990 2.5 7.0 2012 1.4
* 25 0.890 0.10 0.990 2.5 6.8 1569 1.1
* 26 0.790 0.20 0.990 2.5 7.1 1122 0.7
27 0.980 0.00 0.980 2.5 6.5 2736 0.8
28 0.985 0.00 0.985 2.5 6.3 3184 1.0
29 0.995 0.00 0.995 2.5 7.5 2794 0.8
30 1.000 0.00 1.000 2.5 6.3 2030 0.4
31 1.005 0.00 1.005 2.5 6.1 2005 0.4
※ "*" 表示本申请发明的比较例。 样品 41 ~ 43
将以形成表 2的样品 41 ~ 43所示的组成的量称量的 ZnO与主要成 原料一起进行煅烧， 煅烧后不添加 ZnO而得到成型坯体， 使成型坯体的 烧制温度为 1250°C , 除此之外以与样品 1 ~ 9同样的方式得到各电容器样 品， 对交流击穿电场、 介电常数和介电损耗进行评价。 即， 在样品 41 ~ 43中在主要成分原料的煅烧之前添加 ZnO。 交流击穿电场是对 4个样品 进行测定， 求平均值。 各样品的组成和评价结果如表 2所示。 样品 41a ~ 43a
在电介盾陶瓷组合物粉末的制备中，将主要成分原料的煅烧后的粉末 用碎石机进行粗粉碎并过筛后， 将以形成表 2的样品 41a ~ 43a所示的组 成的量称量的 ZnO添加到煅烧粉末中， 成型坯体的烧制温度为 1250°C， 除此之外以与样品 1 ~ 9同样的方式得到各电容器样品，对交流击穿电场、 介电常数和介电损耗进行评价。 即， 在样品 41a ~ 43a中， 与样品 1 ~ 9同 样地，在主要成分原料的煅烧之后添加 ZnO。 交流击穿电场是对 4个样品 进行测定， 求平均值。 各样品的组成和评价结果如表 2所示。 表 2
Figure imgf000009_0001
样品 Is ~ 6s、 lsa
在电介盾陶瓷组合物粉末的制备中，将主要成分原料的煅烧后的粉末 用碎石机进行粗粉碎并过筛后， 以形成表 3的样品 ls ~ 6s、 lsa所示的组 成的量添加 ZnO、 Bi203、 Zr02、 Fe203或 NiO， 除此之外以与样品 1 ~ 9 同样的方式得到各电容器样品，分别对交流击穿电场、介电常数和介电损 耗进行评价。 各样品的组成和评价结果如表 3所示。
Figure imgf000010_0001
样品 6sa、 6sb
除了将以形成表 3的样品 6sa、 6sb所示的组成的量称量的 ZnO、 Nb205 或 CuO与主要成分原料一起煅烧之外， 以与样品 41 ~ 43同样的方式得到 各电容器样品， 分别对交流击穿电场、 介电常数和介电损耗进行评价。 各 样品的组成和评价结果如表 3所示。 样品 7s ~ 13s
除了不含有 ZnO,将以形成表 3的样品 7s ~ 13s所示的组成的量称量 的 Bi203、 Zr02、 Fe203或 NiO与主要成分原料一起煅烧之外， 以与样品 41 - 43 同样的方式得到各电容器样品， 分别对交流击穿电场、 介电常数 和介电损耗进行评价。 各样品的组成和评价结果如表 3所示。
由样品 1 ~ 9、 3a和 4a或 41 ~ 43、 41a ~ 43a可以确认， 氧化锌的含 量为 1.6重量份 ~ 12.重量份的情况 (样品 3 ~ 8、 3a、 4a、 42、 43、 42a、 43a) 与氧化锌含量不在上述范围的情况 (样品 1、 2、 9、 41、 41a)相比， 交流击 穿电场升高， 氧化锌的含量为 2重量份 ~ 12重量份时， 交流击穿电场更 进一步升高。 此外可以确认， 氧化锌的含量超过 12重量份时 (样品 9)， 介 电常数降低。
由样品 10 - 17可以确认， 组成式中的 X与 y的总计为 0.975 x + y < 1.010的情况 (样品 11 ~ 16)和 X与 y的总计小于 0.975的情况 (样品 10) 相比， 交流击穿电场升高。 此外可以确认， X与 y的总计超过 1.010时 (样 品 17), 在 135CTC下未完成烧结。 考虑到对生产性或炉的部件的影响， 不 优选使烧制温度高于 1350°C。
由样品 18 ~ 31可以确认， 组成式中的 y为 0 y 0.08的情况 (样品 18 - 24, 27 ~ 31)与 y超过 0.08的情况 (样品 25、 26)相比， 介电常数升高。
由样品 42、 43、 42a、 43a可以确认， 在主要成分的原料煅烧后添加 氧化锌的情况 (样品 42a、 43a)与将主要成分的原料和氧化锌一起煅烧的情 况 (样品 42、 43)相比， 交流击穿电场升高。
此外， 由样品 41 ~ 43、 41a ~ 43a可以确认， 在主要成分的原料煅烧 后添加氧化锌的情况与将主要成分的原料和氧化锌一起煅烧的情况相比， 交流击穿电场升高的效果在含有 1.6重量份以上的氧化锌时表现出来。
由样品 Is可以确认， 氧化铋含量超过 1重量份时， 交流击穿电场和 介电常数降低。
由样品 2s可以确认， 含有 2.0重量份的氧化锆时， 交流击穿电场降 低。
由样品 3s、 4s可以确认， 含有 0.2 ~ 2重量份的氧化铁时， 交流击穿 电场降 ^氐。
由样品 5s、 6s可以确认， 含有 0.2 ~ 2重量份的氧化镍时， 交流击穿 电场降低、 介电损耗升高。
由样品 6sa、 6sb可以确认， 氧化铌含量超过 2重量份、 氧化铜含量 为 0.1重量份以上时 (样品 6sa), 交流击穿电场降低。
由样品 7s ~ 13s可以确认， 即使主要成分的组成式中的 y为 0 y 0.08、 且 x + y 为 0.975 x + y 1.010, 不含有氧化锌而含有氧化倍、 氧 化铁或氧化镍时， 交流击穿电压和介电常数降低、 介电损耗升高。

Claims

权 利 要 求
1. 电介质陶瓷组合物，该电介质陶瓷组合物具有用（BaxCay)Ti03的组 成式表示的主要成分和氧化辞， 并且，
上述组成式中的 y为 0 y 0.08,且上述组成式中的 x与 y的总计为 0.975 < x + y < 1.010，
相对于所述主要成分 100重量份，所述氧化锌的含量为 2重量份 ~ 12 重量份。
2. 电子元件， 其具有由权利要求 1所述的电介质陶瓷组合物构成的 电介盾层。
3. 电介质陶瓷组合物的制备方法， 该电介质陶瓷组合物具有用 (BaxCay)Ti03的组成式表示的主要成分和氧化锌， 并且，
上述组成式中的 y为 0 < y < 0.08,且上述组成式中的 x与 y的总计为 0.975 < x + y < 1.010,
相对于所述主要成分 100重量份， 所述氧化锌的含量为 1.6重量份- 12重量份； 其中，
该制备方法具有下述步骤：
对所述主要成分的原料进行煅烧， 得到经过了煅烧的粉末的步骤 , 向所述经过了煅烧的粉末中添加所述氧化锌的原料，得到电介质陶瓷 组合物粉末的步骤， 和
将所述电介质陶瓷组合物粉末成型并烧制的步骤。
4. 电子元件， 其具有由通过权利要求 3所述的制备方法制备的电介 质陶瓷组合物构成的电介质层。
PCT/CN2010/000415 2010-03-31 2010-03-31 电介质陶瓷组合物、电介质陶瓷组合物的制备方法及电子元件 Ceased WO2011120196A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2013501585A JP2013523574A (ja) 2010-03-31 2010-03-31 誘電体磁器組成物、誘電体磁器組成物の製造方法および電子部品
PCT/CN2010/000415 WO2011120196A1 (zh) 2010-03-31 2010-03-31 电介质陶瓷组合物、电介质陶瓷组合物的制备方法及电子元件
KR1020127016461A KR101352607B1 (ko) 2010-03-31 2010-03-31 유전체 자기 조성물, 유전체 자기 조성물의 제조 방법 및 전자 부품
CN2010800537238A CN102781874A (zh) 2010-03-31 2010-03-31 电介质陶瓷组合物、电介质陶瓷组合物的制备方法及电子元件
TW100100171A TWI412504B (zh) 2010-03-31 2011-01-04 A dielectric ceramic composition, a method for preparing a dielectric ceramic composition, and an electronic component

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2010/000415 WO2011120196A1 (zh) 2010-03-31 2010-03-31 电介质陶瓷组合物、电介质陶瓷组合物的制备方法及电子元件

Publications (1)

Publication Number Publication Date
WO2011120196A1 true WO2011120196A1 (zh) 2011-10-06

Family

ID=44711284

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2010/000415 Ceased WO2011120196A1 (zh) 2010-03-31 2010-03-31 电介质陶瓷组合物、电介质陶瓷组合物的制备方法及电子元件

Country Status (5)

Country Link
JP (1) JP2013523574A (zh)
KR (1) KR101352607B1 (zh)
CN (1) CN102781874A (zh)
TW (1) TWI412504B (zh)
WO (1) WO2011120196A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013173662A (ja) * 2012-01-27 2013-09-05 Tdk Corp 誘電体磁器組成物および電子部品

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016056058A (ja) 2014-09-09 2016-04-21 エプコス アクチエンゲゼルシャフトＥｐｃｏｓ Ａｇ 誘電体組成物、誘電体素子、電子部品および積層電子部品

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065349A (zh) * 1991-03-27 1992-10-14 天津大学 高压陶瓷电容器介质的制造方法
US5264402A (en) * 1992-05-01 1993-11-23 Murata Manufacturing Co., Ltd. Non-reducible dielectric ceramic composition
GB2340488A (en) * 1998-08-11 2000-02-23 Murata Manufacturing Co Dielectric ceramic composition and laminated capacitors
CN1837145A (zh) * 2006-04-25 2006-09-27 清华大学 低温烧结的温度稳定型多层陶瓷电容器介质材料

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5162400A (zh) * 1974-11-29 1976-05-29 Juzo Ogawa
JPS606535B2 (ja) * 1977-09-07 1985-02-19 富士チタン工業株式会社 磁器組成物
JPS5918161A (ja) * 1982-07-20 1984-01-30 三菱鉱業セメント株式会社 誘電体磁器組成物
JPS5994302A (ja) * 1982-11-19 1984-05-31 株式会社村田製作所 積層コンデンサ用誘電体磁器組成物
JP3780405B2 (ja) * 2000-08-11 2006-05-31 株式会社村田製作所 微粒チタン酸バリウム粉末、カルシウム変性微粒チタン酸バリウム粉末、ならびにその製造方法
EP1767507B1 (en) * 2004-07-08 2011-08-10 Murata Manufacturing Co., Ltd. Dielectric ceramic composition and laminated ceramic capacitor
JP5089870B2 (ja) 2004-08-27 2012-12-05 昭和電工株式会社 チタン酸バリウムカルシウムおよびその製造方法ならびにコンデンサ
JP5272754B2 (ja) * 2008-02-05 2013-08-28 Ｔｄｋ株式会社 誘電体磁器組成物および電子部品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065349A (zh) * 1991-03-27 1992-10-14 天津大学 高压陶瓷电容器介质的制造方法
US5264402A (en) * 1992-05-01 1993-11-23 Murata Manufacturing Co., Ltd. Non-reducible dielectric ceramic composition
GB2340488A (en) * 1998-08-11 2000-02-23 Murata Manufacturing Co Dielectric ceramic composition and laminated capacitors
CN1837145A (zh) * 2006-04-25 2006-09-27 清华大学 低温烧结的温度稳定型多层陶瓷电容器介质材料

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013173662A (ja) * 2012-01-27 2013-09-05 Tdk Corp 誘電体磁器組成物および電子部品

Also Published As

Publication number Publication date
JP2013523574A (ja) 2013-06-17
TW201132610A (en) 2011-10-01
TWI412504B (zh) 2013-10-21
KR20120096550A (ko) 2012-08-30
KR101352607B1 (ko) 2014-01-17
CN102781874A (zh) 2012-11-14

Similar Documents

Publication Publication Date Title
JP5332807B2 (ja) 誘電体磁器組成物
JP5272754B2 (ja) 誘電体磁器組成物および電子部品
JP5664228B2 (ja) 誘電体磁器組成物および電子部品
CN103449812B (zh) 电介质陶瓷组合物以及电子元件
TW201945315A (zh) 介電體磁器組成物及陶瓷電子零件
JP5418323B2 (ja) 誘電体磁器組成物および電子部品
TWI476170B (zh) Dielectric ceramic compositions and electronic components
CN103502178A (zh) 电介质陶瓷和单板电容器
TWI412504B (zh) A dielectric ceramic composition, a method for preparing a dielectric ceramic composition, and an electronic component
KR101429034B1 (ko) 유전체 자기 조성물 및 전자 부품
TWI443079B (zh) Dielectric ceramic compositions and electronic components
JP2006096574A (ja) 誘電体磁器組成物、積層型セラミックコンデンサ、および電子部品
JP6020068B2 (ja) 誘電体磁器組成物および電子部品
JP5354834B2 (ja) 誘電体磁器組成物及び磁器コンデンサとそれらの製造方法
JP2010235325A (ja) 誘電体磁器組成物
JP2009227483A (ja) 誘電体磁器組成物
JP2023117901A (ja) 誘電体磁器組成物および単板型コンデンサ
CN116598045A (zh) 电介质陶瓷组合物

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080053723.8

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2013501585

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10848658

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20127016461

Country of ref document: KR

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 10848658

Country of ref document: EP

Kind code of ref document: A1