WO2021256253A1 - Ｎｉペーストおよび積層セラミックコンデンサ - Google Patents

Ｎｉペーストおよび積層セラミックコンデンサ Download PDF

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WO2021256253A1
WO2021256253A1 PCT/JP2021/020941 JP2021020941W WO2021256253A1 WO 2021256253 A1 WO2021256253 A1 WO 2021256253A1 JP 2021020941 W JP2021020941 W JP 2021020941W WO 2021256253 A1 WO2021256253 A1 WO 2021256253A1
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paste
mass
parts
ceramic
internal electrode
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French (fr)
Japanese (ja)
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寛志 岡村
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Shoei Chemical Inc
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Shoei Chemical Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24—Electrically-conducting paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
    • 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
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a Ni paste for forming an internal electrode for manufacturing a highly reliable monolithic ceramic capacitor, and a monolithic ceramic capacitor manufactured by using the Ni paste.
  • the dielectric layer constituting the monolithic ceramic capacitor is being thinned.
  • the electric field strength applied to each layer becomes relatively high. Therefore, it is required to improve the reliability when a voltage is applied.
  • the monolithic ceramic capacitor is generally manufactured as follows. First, a dielectric ceramic raw material powder is dispersed in a resin binder and formed into a sheet, which is then formed into a ceramic green sheet. The conductive paste of No. 1 is printed in a predetermined pattern and dried to remove the powder to form an internal electrode drying film. Next, a plurality of ceramic sheets having the obtained internal electrode dry film are stacked and pressure-bonded to form a laminate, cut into a predetermined shape, and then fired at a high temperature to obtain a ceramic element. After that, a conductive paste for an external electrode is applied to both end faces of the ceramic element and then fired to obtain a laminated ceramic capacitor. The external electrode may be fired at the same time as the ceramic element by applying the paste for the external electrode to the unfired laminate. As the internal electrode, one using Ni as a main component is known (for example, Patent Document 1).
  • Patent Document 2 discloses an invention in which the height of the electrical barrier at the interface between the dielectric layer and the electrode layer is changed by using an internal electrode in which Sn is dissolved in Ni, thereby achieving a high temperature load life. Is described.
  • an object of the present invention is to provide a Ni paste for an internal electrode capable of improving the high temperature load life without deteriorating the continuity of the electrode film.
  • Another object of the present invention is to provide a monolithic ceramic capacitor that exhibits excellent reliability even when the dielectric layer is further thinned and a voltage having a high electric field strength is applied.
  • the additive containing (E) Ti is added to the additive containing (E) Ti per 100.0 parts by mass of the conductive powder mainly containing (A) Ni, from 0.05 to 1.30 in terms of TiO 2.
  • the additive containing (F) Zr is 0.05 to 1.80 mass by mass in terms of ZrO 2 per 100.0 parts by mass of the conductive powder mainly composed of (A) Ni. It provides the Ni paste of (1), which is characterized by containing within the range of the portion.
  • the present invention (3) is a ceramic laminate in which a plurality of ceramic dielectric layers and a plurality of internal electrode layers containing Ni are alternately laminated.
  • An external electrode formed on the outer surface of the ceramic laminate and Equipped with Having a diffusion region of Ti element and / or Zi element at the interface between the adjacent internal electrode layer and the ceramic dielectric layer and its vicinity. It is intended to provide a monolithic ceramic capacitor characterized by.
  • the present invention (4) is a ceramic laminate in which a plurality of ceramic dielectric layers and a plurality of internal electrode layers containing Ni are alternately laminated.
  • An external electrode formed on the outer surface of the ceramic laminate and Equipped with The internal electrode layer is formed of a fired product obtained by firing the Ni paste of (1) or (2) at 900 to 1400 ° C. It is intended to provide a monolithic ceramic capacitor characterized by.
  • Ni paste for an internal electrode that can improve the high temperature load life without deteriorating the continuity of the electrode film. Further, according to the present invention, it is possible to provide a monolithic ceramic capacitor showing excellent reliability even when the dielectric layer is further thinned and a voltage having a high electric field strength is applied.
  • the Ni paste of the present invention is (A) Conductive powder mainly composed of Ni and (B) Binder resin and (C) Organic solvent and (D) Co-material powder and Contains, Further, the additive containing (E) Ti is added in the range of 0.05 to 3.50 parts by mass in terms of TiO 2 per 100.0 parts by mass of the conductive powder mainly containing (A) Ni and / or. (F) The additive containing Zr shall be contained in the range of 0.05 to 2.80 parts by mass in terms of ZrO 2 per 100.0 parts by mass of the conductive powder mainly containing (A) Ni. It is a Ni paste characterized by.
  • Ni paste of the present invention is suitably used for forming internal electrodes of multilayer ceramic capacitors, and can also be applied to other ceramic electronic components such as laminated ceramic actuators.
  • the Ni paste of the present invention contains at least (A) a conductive powder mainly containing Ni, (B) a binder resin, (C) an organic solvent, (D) a co-material powder, and "(E) Ti.
  • Additives containing and / or additives containing (F) Zr " is, the Ni paste of the present invention has at least (A) a conductive powder mainly containing Ni, (B) a binder resin, (C) an organic solvent, (D) a co-material powder, and (E) Ti. It contains one or both of an additive containing (F) Zr and an additive containing (F) Zr.
  • the conductive powder mainly containing Ni according to the Ni paste of the present invention is used as a conductive powder in the Ni paste for forming an internal electrode and is a powder mainly containing Ni.
  • Examples of the conductive powder mainly composed of Ni include powders composed only of metallic Ni. Further, as the conductive powder mainly containing (A) Ni, as long as the action and effect of the present invention are exhibited, a composite powder of Ni and other compounds, a mixed powder of Ni and other compounds, and Ni and other compounds are used. Examples include alloy powder with metal.
  • the composite powder of Ni and other compounds include a composite powder in which the surface of the Ni powder is coated with a vitreous thin film, a composite powder in which the surface of the Ni powder is coated with an oxide, and the surface of the Ni powder.
  • examples thereof include composite powders surface-treated with organic metal compounds, surfactants, fatty acids and the like.
  • other metals that can be used in the alloy powder a metal that does not easily cause a melting point drop when alloying with Ni, or even a metal that causes a melting point drop does not cause the above-mentioned ball-up phenomenon.
  • the content of the above may be sufficient, and examples thereof include Cu, Ag, Pd, Pt, Rh, Ir, Re, Ru, Os, In, Ga, Zn, Bi, Pb, Fe, V, and Y.
  • the Ni content in the conductive powder mainly containing Ni is not particularly limited as long as the effects of the present invention are exhibited, but is preferably 60.0% by mass or more, particularly preferably 80.0% by mass. As mentioned above, it is more preferably 100.0% by mass.
  • the average particle size of the conductive powder mainly containing Ni is not particularly limited, but is preferably 0.05 to 1.0 ⁇ m.
  • A When the average particle size of the conductive powder mainly containing Ni is within the above range, it is dense and has high smoothness, and a thin internal electrode layer is easily formed.
  • the reference numeral "-" indicating a numerical range indicates a range including the numerical values described before and after the symbol "-" unless otherwise specified. That is, for example, the notation "0.05 to 1.0" is synonymous with "0.05 or more and 1.0 or less” unless otherwise specified.
  • the content of the conductive powder mainly composed of (A) Ni in the Ni paste of the present invention is not particularly limited, and is usually 30. In consideration of the finished viscosity, printability, storage stability, etc. of the Ni paste. It may be appropriately selected in the range of 0 to 95.0% by mass.
  • the binder resin (B) according to the Ni paste of the present invention is not particularly limited as long as it can be used as a conductive paste for forming an internal electrode.
  • the binder resin those generally used as a conductive paste for forming an internal electrode, for example, a cellulose resin such as ethyl cellulose, an acrylic resin, a methacrylic resin, a butyral resin, an epoxy resin, a phenol resin, etc. Examples include rosin.
  • the content ratio of the binder resin (B) in the Ni paste of the present invention is not particularly limited, and is usually 0.1 to 30.0 parts by mass per 100.0 parts by mass of the conductive powder mainly containing (A) Ni.
  • the ratio is preferably 1.0 to 15.0 parts by mass.
  • the (C) organic solvent according to the Ni paste of the present invention is not particularly limited as long as it dissolves the (B) binder resin, and for example, alcohol-based, ether-based, ester-based, hydrocarbon-based solvents and the like. Examples of the mixed solvent of.
  • the (D) co-material powder according to the Ni paste of the present invention is intended to approximate the sintering shrinkage behavior of the internal electrode to the dielectric layer, and the type of the co-material powder is not particularly limited. , It is desirable to select so that the change in the characteristics of the capacitor due to the reaction with the ceramic dielectric is minimized.
  • the co-material powder the general formula: ABO 3 (where A is at least one of Ba, Ca and Sr, and B is Ti, Zr, as is usually used for Ni paste for forming an internal electrode. And at least one of Hf), for example, perovskite-type oxide powders such as barium titanate, strontium zirconate, calcium zirconate, and those to which various additives are added. Is preferable.
  • the co-material powder a powder having the same composition as or similar to that of the dielectric ceramic raw material powder used as the main component of the dielectric layer is preferable. It should be noted that the co-material powder may be adhered to the surface of the conductive powder mainly composed of (A) Ni in advance, and then mixed with other components in the Ni paste.
  • the content ratio of the co-material powder exceeds 0.0 parts by mass and 50.0 parts by mass of the co-material powder in total per 100.0 parts by mass of the conductive powder mainly composed of (A) Ni.
  • the ratio is, preferably 1.0 to 40.0 parts by mass, and particularly preferably 5.0 to 30.0 parts by mass. If the co-material powder is contained in the Ni paste, the effect of the co-material powder can be obtained. On the other hand, when the content ratio of the co-material powder in the Ni paste exceeds the above range, the electrode layer becomes thick, structural defects are likely to occur, and the electrode layer becomes a discontinuous film.
  • the average particle size of the co-material powder is not particularly limited, but (A) 30% or less of the average particle size of the conductive powder mainly composed of Ni is a more excellent effect of suppressing sintering and improving density. It is preferable because it shows. Further, it is preferable that the total specific surface area of the co-material powder in the paste is larger than the total specific surface area of the conductive powder mainly composed of (A) Ni, because the effect of improving the high temperature load life is enhanced. By selecting the average particle size and content of the co-material powder, the total specific surface area of the co-material powder in the paste should be larger than the total specific surface area of the conductive powder mainly composed of (A) Ni. Can be done.
  • the average particle size of the material powder is preferably 0.01 ⁇ m or more.
  • the component (E) according to the Ni paste of the present invention is an additive containing Ti.
  • the additive containing Ti is not particularly limited as long as TiO 2 can be obtained after firing the Ni paste, but as an example, in addition to pure metal (Ti), an oxide containing Ti (TIO 2-x) is used.
  • TiO 2 is particularly preferable as the additive containing Ti.
  • the Ni paste of the present invention contains an additive containing (E) Ti
  • the Ni paste of the present invention mainly contains (A) Ni when Ti in the additive containing Ti is converted into TiO 2.
  • the additive containing Ti is contained in a proportion of 0.05 to 3.50 parts by mass, preferably 0.05 to 1.30 parts by mass, per 100.0 parts by mass of the conductive powder.
  • the component (F) according to the Ni paste of the present invention is an additive containing Zr.
  • the additive containing Zr is not particularly limited as long as ZrO 2 can be obtained after firing the Ni paste, but as an example, in addition to pure metal (Zr), an oxide containing Zr (ZrO 2 ) and the like can be used. halide (ZrCl 2, ZrBr 4, etc.), nitrides (ZrN, etc.), hydrides (ZrH 2, etc.), an oxyacid salt (Zr (NO 3) 4 ⁇ 5H 2 O, Zr (SO 4) 2 , etc.), etc.
  • It may be an inorganic compound of the above, or it may be an organic metal compound such as a metal carbonyl, a metal alkoxide, a metal resinate, or an organic acid salt.
  • ZrO 2 is particularly preferable as the additive containing Zr.
  • the Ni paste of the present invention contains an additive containing (F) Zr
  • the Ni paste of the present invention mainly contains (A) Ni when Zr in the additive containing Zr is converted into ZrO 2.
  • the additive containing Zr is contained in a proportion of 0.05 to 2.80 parts by mass, preferably 0.05 to 1.80 parts by mass, per 100.0 parts by mass of the conductive powder.
  • the Ni paste of the present invention can also contain both an additive containing (E) Ti and an additive containing (F) Zr.
  • the Ti in the additive containing Ti, and Zr in the additive containing Zr, the sum of when converted each to TiO 2 and ZrO 2 is, conductive powder comprising mainly (A) Ni It is preferably in the range of 0.05 to 3.50 parts by mass, and more preferably in the range of 0.05 to 1.80 parts by mass per 100.0 parts by mass.
  • the case where a co-material powder containing the Ti component or Zr component is used is also applicable, but the composition of the co-material powder is the same as or similar to that of the dielectric layer. Therefore, even if it diffuses from the internal electrode layer to the dielectric layer side during firing, the element distribution of Ti or Zr in the dielectric layer is hardly changed. Therefore, the formation of the diffusion region (diffusion layer) containing a high concentration of Ti or Zr observed at the interface with the electrode layer and its vicinity includes (E) Ti present in the Ni paste separately from the co-material powder. It is considered that it is due to the additive or the additive containing (F) Zr.
  • the term "interface and its vicinity” refers to the region from the interface between the ceramic dielectric layer and the internal electrode layer to the dielectric layer side up to 1/16 of the thickness of the ceramic dielectric layer, from the interface to the internal electrode. It refers to the region up to 1/2 of the internal electrode layer thickness on the layer side.
  • the present inventor has improved the life by reducing the speed of movement of oxygen pores to the cathode side in the dielectric layer during the high temperature load life test due to the existence of this diffusion region (diffusion layer). I'm guessing that it might be. Further, since the content of the Ti component and the Zr component in the electrode layer after firing does not lower the melting point of Ni, the continuity of the electrode film is not adversely affected.
  • the concentration of Ti or Zr in the diffusion region (diffusion layer) in the dielectric layer becomes too large, the wettability with Ni may decrease, which may adversely affect the continuity of the electrode film.
  • the content of the additive containing (E) Ti or the content of the additive containing (F) Zr in the Ni paste is less than the above range, the effect of improving the high temperature load life cannot be obtained, and the above If it exceeds the range, crystal grain growth occurs due to the Ti component or Zr component diffused in the ceramic dielectric layer, and the high temperature load life is lowered.
  • the content of the additive containing (E) Ti or the content of the additive containing (F) Zr in the Ni paste is less than the above range, the effect of improving the high temperature load life cannot be obtained, and the effect of improving the high temperature load life cannot be obtained. If it exceeds the above range, the continuity of the electrode film is lowered, and the crystal grain growth due to the Ti component or the Zr component diffused in the dielectric layer becomes remarkable, and the high temperature load life cannot be expected to be improved.
  • the Ni paste of the present invention may contain a known compound containing a metal element other than the above as long as the effect of the present invention is not impaired.
  • a metal element other than the above as long as the effect of the present invention is not impaired.
  • Compounds such as 3 , La 2 O 3 , Li 2 O, MgO, MoO 3 , SrO, V 2 O 5 , WO 3 , Y 2 O 3 and the like may be added for various purposes.
  • the ZrO 2 commercially available ones often contain HfO 2 as an inevitable impurity.
  • the present invention also allows the inclusion of such unavoidable impurities as long as it does not interfere with the action and effect of the present invention.
  • the present invention does not exclude the inclusion of the Sn component. It is considered that Sn is alloyed with Ni during firing to lower the melting point and promote the sintering, so that the above-mentioned ball-up phenomenon occurs. Therefore, a Sn compound that is not alloyed with Ni is used, or if the content is such that a ball-up phenomenon does not occur even if alloyed, an additive containing (E) Ti or (F) Zr. It may be used in combination with an additive containing.
  • the Ni paste of the present invention can contain additives such as plasticizers, dispersants, and surfactants that are usually added to the Ni paste for forming internal electrodes, if necessary. ..
  • the Ni paste of the present invention comprises the above-mentioned (A) Ni-based conductive powder, (B) binder resin, (C) organic solvent, (D) co-material powder, "(E) Ti-containing additives and”. (F) One or both of the additives containing Zr ”and various other additives added as needed are uniformly mixed and dispersed according to a conventional method.
  • the multilayer ceramic capacitor of the present invention is manufactured by the following method using the Ni paste of the present invention.
  • the dielectric ceramic raw material powder is dispersed in a resin binder, and a sheet is formed by a doctor blade method, a die coater method, or the like to prepare a ceramic green sheet containing the dielectric ceramic raw material powder.
  • a sheet is formed by a doctor blade method, a die coater method, or the like to prepare a ceramic green sheet containing the dielectric ceramic raw material powder.
  • perovskite-type oxides such as barium titanate, strontium zirconate, and calcium strontium zirconate, or some of the metal elements constituting these are used.
  • the average particle size of the raw material powder for example, when the thickness of the dielectric ceramic layer is 5.0 ⁇ m or less, the average particle size is preferably about 0.05 to 0.4 ⁇ m.
  • the Ni paste of the present invention is applied onto the obtained ceramic green sheet by a usual method such as screen printing, and dried to remove the solvent to form an internal electrode paste drying film having a predetermined pattern.
  • a predetermined number of ceramic green sheets on which the internal electrode paste film is formed are stacked and heat-bonded to prepare an unfired laminate.
  • terminal electrodes are baked on both end faces of the element body to form the monolithic ceramic capacitor of the present invention.
  • the terminal electrode may be attached before firing the above-mentioned laminated body and fired at the same time as the laminated body.
  • the multilayer ceramic capacitor of the present invention thus obtained comprises a ceramic laminate in which a plurality of ceramic dielectric layers and a plurality of internal electrode layers containing Ni are alternately laminated.
  • An external electrode formed on the outer surface of the ceramic laminate and Equipped with Having a diffusion region of Ti element and / or Zi element at the interface between the adjacent internal electrode layer and the ceramic dielectric layer and its vicinity. It is a monolithic ceramic capacitor characterized by.
  • the ceramic dielectric layer according to the multilayer ceramic capacitor of the present invention is a perovskite-type oxide such as barium titanate-based, strontium zirconate-based, calcium zirconate strontium-based, or a metal element constituting these as a dielectric ceramic raw material powder.
  • These dielectric ceramic raw material powders are sheet-molded using a powder containing a normal perovskite-type oxide as a main component, such as one in which a part of the above is replaced with another metal element, and 900 to 900 in a reducing atmosphere. It was formed by firing at 1400 ° C, preferably 1100 to 1300 ° C.
  • the multilayer ceramic capacitor of the present invention has an internal electrode layer containing Ni formed by using the Ni paste of the present invention, that is, a ceramic green for forming a dielectric layer by printing the Ni paste of the present invention by screen printing or the like. It is formed by molding on a sheet, drying, and baking. Most of the co-material powder contained in the Ni paste moves from the internal electrode layer to the dielectric layer side during firing, but the composition of the co-material powder is the same as or similar to that of the dielectric layer. Therefore, even if it diffuses into the dielectric layer, it hardly changes the element distribution in the dielectric layer.
  • the Ti component or Zr component added to the Ni paste separately from the co-material powder moves from the internal electrode layer to the dielectric layer side while being oxidized during firing as described above, and the internal electrode.
  • a diffusion region (diffusion layer) containing a high concentration of Ti or Zr is formed at the interface between the layer and the ceramic dielectric layer and its vicinity.
  • the concentration of Ti or Zr increases in the direction from the internal electrode layer side toward the dielectric layer side, reaches a concentration peak, and then decreases. According to the research results up to this stage, it is presumed that the concentration peak is near the interface, but the position has not been accurately identified.
  • the thickness of the diffusion layer, the shape of the concentration gradient, and the position of the concentration peak differ depending on the firing profile such as the firing temperature, the firing time, and the rate of temperature rise.
  • the Ti component diffuses from the internal electrode layer toward the dielectric layer, and the dielectric is said to be the same.
  • a diffusion layer having a steep concentration gradient (concentration peak) in which Ti is unevenly distributed only at a position very close to the interface with the internal electrode layer in the body layer was formed.
  • a relatively broad Ti concentration gradient (concentration peak) is observed in the dielectric layer.
  • a diffusion layer was formed.
  • the multilayer ceramic capacitor of the present invention includes a ceramic laminate in which a plurality of ceramic dielectric layers and a plurality of internal electrode layers containing Ni are alternately laminated.
  • An external electrode formed on the outer surface of the ceramic laminate and Equipped with It is characterized by having a diffusion region of Ti element and / or Zi element at and near the interface between the adjacent internal electrode layer and the ceramic dielectric layer.
  • the multilayer ceramic capacitor of the present invention has an improved high-temperature load life due to the above-mentioned characteristics, and therefore has excellent reliability even when the dielectric layer is further thinned and a voltage having a high electric field strength is applied. show.
  • the dielectric layer and the internal electrode layer contain Ti or Zr means that SEM (scanning electron microscope), TEM (transmission electron microscope), EDS (energy dispersion type X-ray spectroscopy), and WDS (wavelength dispersion) It is confirmed by combining element analysis methods such as type X-ray spectroscopy) or EELS (electron energy loss spectroscopy).
  • the internal electrode layer containing Ni according to the multilayer ceramic capacitor of the present invention is formed by firing the Ni paste of the present invention at 900 to 1400 ° C., preferably 1100 to 1300 ° C. in a reducing atmosphere.
  • the external electrode of the multilayer ceramic capacitor of the present invention is not particularly limited as long as it can be used as an external electrode of the multilayer ceramic capacitor.
  • the multilayer ceramic capacitor of the present invention includes a ceramic laminate in which a plurality of ceramic dielectric layers and a plurality of internal electrode layers containing Ni are alternately laminated.
  • An external electrode formed on the outer surface of the ceramic laminate and Equipped with The internal electrode layer is formed of a fired product obtained by firing the Ni paste of the present invention at 900 to 1400 ° C. It is a monolithic ceramic capacitor characterized by.
  • the internal electrode layer is formed by molding the Ni paste of the present invention on a ceramic green sheet for forming a laminated layer by screen printing or the like, drying and firing. ..
  • the firing temperature of the Ni paste of the present invention is 900 to 1400 ° C., preferably 1100 to 1300 ° C., and the firing atmosphere is a reducing atmosphere.
  • Example 1 ⁇ Manufacturing of Ni paste and multilayer ceramic capacitors> (Making Ni paste) To 100.0 g of spherical nickel powder having an average particle size of 0.3 ⁇ m, TiO 2 or ZrO 2 is used as a co-material powder at a ratio of parts by mass shown in Table 1 or Table 2, and BaTiO having an average particle size of 0.05 ⁇ m. 3 powder were mixed 10.0 g, ethyl cellulose (binder resin) 6.0 g, surfactant 2.0 g, plasticizer 1.0 g, and so that the ratio of dihydroterpineol acetate (organic solvent) 100.0 g, 3-roll mill A Ni paste was prepared by kneading using.
  • This ceramic slurry was sheet-molded by the die coater method to prepare a ceramic green sheet with a thickness of 5.5 ⁇ m.
  • a Ni paste was printed on this ceramic green sheet in a rectangular pattern of 1.5 mm ⁇ 3.0 mm, and then dried to form an internal electrode drying film.
  • the thickness of the internal electrode dry film was 1.5 ⁇ m.
  • Ceramic green sheets having an internal electrode dry film were stacked so that the effective dielectric layer was 50 layers, and pressure was applied at 90 ° C. to 1250 kg / cm 2 for pressure bonding and molding to obtain an unfired ceramic laminate. ..
  • the ceramic laminate, N 2 in an atmosphere composed of -0.1% H 2 -H 2 O gas was heated to 700 ° C., after burning a binder, at 1220 ° C. oxygen partial pressure 1 ⁇ 10 - in 8 atm of N 2 -0.1% H 2 -H 2 O gas consists in a reducing atmosphere, the temperature was raised, sintering densification and held for 2 hours at 1220 ° C. at a heating rate of 5 ° C. / min It is allowed, then to obtain a laminated ceramic body by performing re-oxidation treatment for 3 hours at 1000 ° C. in N 2 -H 2 O gas atmosphere in a cooling step.
  • the both end surfaces of the laminated ceramic body is coated with a Cu paste for external electrode formation containing Cu powder and BaO-based glass frit, an N 2 atmosphere, by forming the external electrodes by baking at a temperature of 780 ° C.
  • a monolithic ceramic capacitor was manufactured.
  • the external dimensions of the obtained multilayer ceramic capacitor are width (W): 1.6 mm, length (L): 3.2 mm, thickness (T): 0.7 mm, and the thickness of the internal electrode layer is 1. It was 2 ⁇ m, and the thickness of the ceramic dielectric layer interposed between the internal electrodes was 4.0 ⁇ m. The area of the counter electrode per layer of the dielectric layer was 3.25 mm 2 .
  • High-temperature load test Fifteen samples are sampled from each sample, and a high-temperature load test is performed under the conditions of 180 ° C. and 60V. The time required for the insulation resistance to decrease by an order of magnitude is defined as the failure time of each multilayer ceramic capacitor. did. Then, this failure time was weibull plotted to obtain MTTF (Mean Time Between Failure). The MTTF evaluation results are also shown in Table 1 or Table 2.
  • sample Nos. 1 and 15 samples obtained by mixing TiO 2 or ZrO 2, all except sample No. 14 ( MTTF increased in sample numbers 2-13 and 16-25).
  • the continuity of the internal electrodes showed 90% or more in sample numbers 2 to 9 and 16 to 22, and 80 to 90% in sample numbers 10 to 13 and 23 to 24.
  • Example 2 ⁇ Manufacturing of Ni paste and multilayer ceramic capacitors> (Preparation of Ni paste)
  • 100.0 g of spherical nickel powder having an average particle size of 0.3 ⁇ m 0.50 parts by mass of titanium oxide shown in Table 3 in terms of TiO 2 and BaTiO 3 powder having an average particle size of 0.05 ⁇ m as a co-material powder.
  • a Ni paste was prepared by the above.

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JP2005317432A (ja) * 2004-04-30 2005-11-10 Shoei Chem Ind Co 導電性ペースト及びガラスフリット
JP2006196421A (ja) * 2005-01-17 2006-07-27 Noritake Co Ltd 被覆導体粉末および導体ペースト
WO2020090415A1 (ja) * 2018-10-31 2020-05-07 昭栄化学工業株式会社 Ｎｉペーストおよび積層セラミックコンデンサ

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JP2005317432A (ja) * 2004-04-30 2005-11-10 Shoei Chem Ind Co 導電性ペースト及びガラスフリット
JP2006196421A (ja) * 2005-01-17 2006-07-27 Noritake Co Ltd 被覆導体粉末および導体ペースト
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