WO2021210455A1 - PÂTE DE Ni ET CONDENSATEUR CÉRAMIQUE MULTICOUCHE - Google Patents

PÂTE DE Ni ET CONDENSATEUR CÉRAMIQUE MULTICOUCHE Download PDF

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WO2021210455A1
WO2021210455A1 PCT/JP2021/014652 JP2021014652W WO2021210455A1 WO 2021210455 A1 WO2021210455 A1 WO 2021210455A1 JP 2021014652 W JP2021014652 W JP 2021014652W WO 2021210455 A1 WO2021210455 A1 WO 2021210455A1
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mass
parts
paste
range
ceramic
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PCT/JP2021/014652
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English (en)
Japanese (ja)
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寛志 岡村
隼人 立野
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昭栄化学工業株式会社
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    • 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
    • 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 multilayer ceramic capacitor, and a multilayer ceramic capacitor manufactured by using the Ni paste.
  • the dielectric layer constituting the multilayer 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 multilayer 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, 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 monolithic 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 describes 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 that can improve the high temperature load life without lowering the continuity of the electrode film.
  • Another object of the present invention is to provide a multilayer 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.
  • At least one selected from the group consisting of D2) Nb-containing additives, (D3) stabilized zirconia (SZ), and (D4) Al-containing additives is a conductive powder mainly containing (A) Ni.
  • the crystal structure of zirconia is stabilized by a stabilizer in the range of 0.05 ⁇ 10 -2 to 2.20 ⁇ 10 -2 mol per 100 g of the conductive powder mainly containing (A) Ni. Stabilized zirconia (SZ) and (D4) (A) Ni-based conductive powder per 100.0 parts by mass, within the range of 0.10 to 5.50 parts by mass in terms of Al 2 O 3. Containing at least one selected from the group consisting of additives containing Al, To provide a Ni paste characterized by.
  • the additive containing (D1) Ta when the additive containing (D1) Ta is contained, the additive containing (D1) Ta is added to the conductive powder containing (A) Ni as the main component by 100.0 mass. It provides the Ni paste of (1), which is characterized by containing in the range of 0.025 to 0.80 parts by mass in terms of Ta 2 O 5 per part.
  • the additive containing (D2) Nb when the additive containing (D2) Nb is contained, the additive containing (D2) Nb is added to the conductive powder containing (A) Ni as the main component by 100.0 mass. It provides the Ni paste of (1), which is characterized by containing in the range of 0.010 to 0.50 parts by mass in terms of Nb 2 O 5 per part.
  • the present invention when containing the (D3) stabilized zirconia (SZ), said stabilizing agent, Y 2 O 3, CaO, at least one selected from MgO and Sc 2 O 3 It provides the Ni paste of (1), which is characterized by being present.
  • SZ stabilized zirconia
  • the (D3) stabilized zirconia (SZ) when the (D3) stabilized zirconia (SZ) is contained, the (D3) stabilized zirconia (SZ) is more than 0.0 mol% and 45.0 mol% or less. It provides the Ni paste of (4), which is characterized by containing the stabilizer in a range.
  • the (D3) stabilized zirconia (SZ) when the (D3) stabilized zirconia (SZ) is contained, the (D3) stabilized zirconia (SZ) is stable in the range of 8.0 to 25.0 mol%. It provides the Ni paste of (4), which is characterized by containing an agent.
  • the (D3) stabilized zirconia (SZ) when the (D3) stabilized zirconia (SZ) is contained, the (D3) stabilized zirconia (SZ) is used per 100 g of the conductive powder mainly containing (A) Ni. , (1), (4) to (6), any of the Ni pastes, which are contained in the range of 0.05 ⁇ 10 ⁇ 2 to 1.40 ⁇ 10 ⁇ 2 mol.
  • the additive containing (D4) Al when the additive containing (D4) Al is contained, the additive containing (D4) Al is added to the conductive powder containing (A) Ni as the main component by 100.0 mass. It provides the Ni paste of (1), which is characterized by containing in the range of 0.10 to 2.30 parts by mass in terms of Al 2 O 3 per part.
  • the present invention (9) is characterized in that the content of the conductive powder mainly containing (A) Ni is 30.0 to 95.0% by mass, any of (1) to (8).
  • the Ni paste is provided.
  • the present invention (10) 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 With The ceramic laminate (D1) Ta, which is in the range of 0.025 to 2.50 parts by mass in terms of Ta 2 O 5 per 100.0 parts by mass of the conductive component containing (A) Ni.
  • (D2) Nb in the range of 0.010 to 1.80 parts by mass in terms of Nb 2 O 5 per 100.0 parts by mass of the conductive component containing (A) Ni
  • Al in the range of 0.10 to 5.50 parts by mass in terms of Al 2 O 3 per 100.0 parts by mass of the conductive component containing Containing at least one selected from the group consisting of Provided is a monolithic ceramic capacitor characterized by the above.
  • the present invention (11) 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 With At the interface between the adjacent internal electrode layer and the ceramic dielectric layer and its vicinity, a diffusion region of at least one element selected from the group consisting of Ta, Nb, Zr, a metal element in a stabilizer and Al.
  • a monolithic ceramic capacitor characterized by the above.
  • the present invention (12) also provides the multilayer ceramic capacitor (11), wherein the metal element in the stabilizer is one or more selected from Y, Ca, Mg and Sc. Is.
  • the present invention (13) 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 With The internal electrode layer is formed of a fired product obtained by firing any of the Ni pastes (1) to (9) at 900 to 1400 ° C.
  • a monolithic ceramic capacitor characterized by the above.
  • Ni paste for an internal electrode that can improve the high temperature load life without lowering 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 (A) Conductive powder mainly composed of Ni and (B) Binder resin and (C) Organic solvent and Contains, In addition (D1) Additive containing Ta in the range of 0.025 to 2.50 parts by mass in terms of Ta 2 O 5 per 100.0 parts by mass of the conductive powder mainly containing Ni (A). (D2) Additive containing Nb in the range of 0.010 to 1.80 parts by mass in terms of Nb 2 O 5 per 100.0 parts by mass of the conductive powder mainly containing (A) Ni.
  • the crystal structure of zirconia is stabilized by a stabilizer in the range of 0.05 ⁇ 10 -2 to 2.20 ⁇ 10 -2 mol per 100 g of the conductive powder mainly containing (A) Ni. Stabilized zirconia (SZ) and (D4) (A) Ni-based conductive powder per 100.0 parts by mass, within the range of 0.10 to 5.50 parts by mass in terms of Al 2 O 3. Containing at least one selected from the group consisting of additives containing Al, It is a Ni paste characterized by.
  • the Ni paste of the present invention contains (A) a conductive powder mainly containing Ni, (B) a binder resin, and (C) an organic solvent, and further (D1) the above (A).
  • the Ni paste of the present invention contains (A) a conductive powder mainly containing Ni, (B) a binder resin, and (C) an organic solvent, and further (D2) the above (A).
  • the Ni paste of the present invention contains (A) a conductive powder mainly containing Ni, (B) a binder resin, and (C) an organic solvent, and further (D3) the above (A).
  • the Ni paste of the present invention contains (A) a conductive powder mainly containing Ni, (B) a binder resin, and (C) an organic solvent, and further (D4) the above (A).
  • 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 multilayer ceramic actuators.
  • 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, and "an additive containing (D1) Ta, (D2) Nb. At least one selected from the group consisting of additives containing (D3) stabilized zirconia (SZ) and (D4) Al. That is, 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, and (D1) an additive containing Ta, (D2). It contains any one or more of an additive containing Nb, (D3) stabilized zirconia (SZ), and an additive containing (D4) Al.
  • 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.
  • the conductive powder (A) mainly composed of Ni include a powder composed of only metallic Ni.
  • a composite powder of Ni and another compound, a mixed powder of Ni and another compound, and Ni and other compounds are used as the conductive powder mainly containing (A) Ni. Examples include alloy powder with metal.
  • Examples of 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 a surface of the Ni powder. Examples thereof include composite powders surface-treated with organic metal compounds, surfactants, fatty acids and the like. Examples of the mixed powder of Ni and other compounds include a mixed powder of Ni powder and an oxide powder. Further, as 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 may be any amount, 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 Ni paste of the present invention contains (A) a conductive powder mainly containing Ni, (B) a binder resin and (C) an organic solvent, (D1) an additive containing Ta, and (D2) an additive containing Nb. , (D3) Stabilized Zirconia (SZ), and (D4) Al contains at least one selected from the group consisting of additives.
  • the component (D1) according to the Ni paste of the present invention is an additive containing Ta.
  • the additive containing Ta is not particularly limited as long as Ta 2 O 5 can be obtained after firing the Ni paste, but as an example, in addition to pure metal (Ta), an oxide containing Ta (Ta 2) is used. It may be an inorganic compound such as O 5 , TaO 2 ), a sulfide (TaS 2 ), a halide (TaF 5, etc.), a boride (TaB), or an organic compound such as a metal carbonyl, a metal alkoxide, or a metal resinate. It may be a metal compound. In the present invention, Ta 2 O 5 is particularly preferable as the additive containing Ta.
  • the Ni paste of the present invention contains an additive containing (D1) Ta
  • the Ni paste of the present invention has (A) Ni when Ta in the additive containing Ta is converted into Ta 2 O 5.
  • the additive containing Ta is contained in a proportion of 0.025 to 2.50 parts by mass, preferably 0.025 to 0.80 parts by mass, per 100.0 parts by mass of the conductive powder mainly composed of.
  • the component (D2) according to the Ni paste of the present invention is an additive containing Nb.
  • the additive containing Nb is not particularly limited as long as Nb 2 O 5 can be obtained after firing the Ni paste, but as an example, in addition to pure metal (Nb), an oxide containing Nb (Nb 2) It may be an inorganic compound such as O 5 , NbO 2 ), a sulfide (NbS 2 ), a halide (NbF 5, etc.), a boride (NbB), or an organic compound such as a metal carbonyl, a metal alkoxide, or a metal resinate. It may be a metal compound. In the present invention, Nb 2 O 5 is particularly preferable as the additive containing Nb.
  • the Ni paste of the present invention contains an additive containing (D2) Nb
  • the Ni paste of the present invention has (A) Ni when Nb in the additive containing Nb is converted into Nb 2 O 5.
  • the additive containing Nb is contained in a proportion of 0.010 to 1.80 parts by mass, preferably 0.010 to 0.50 parts by mass, per 100.0 parts by mass of the conductive powder mainly composed of.
  • the component (D3) in the Ni paste of the present invention is stabilized zirconia (SZ) in which the crystal structure of zirconia is stabilized by a stabilizer.
  • Stabilized zirconia (SZ) has a crystal structure of zirconia (ZrO 2 ) by dissolving a stabilizer in zirconia (ZrO 2 ) and adding a divalent or trivalent metal element to the tetravalent Zr site. It is stabilized so that it does not change due to temperature changes.
  • the stabilizer is not particularly limited as long as it stabilizes zirconia (ZrO 2 ), but is an oxide of an alkaline earth metal such as MgO, CaO, SrO, BaO; Sc 2 O 3 , Y 2 O. 3 , La 2 O 3 , CeO 2 , Pr 2 O 3 , Nd 2 O 3 , Sm 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Tb 2 O 3 , Dy 2 O 3 , Er 2 O 3 , Oxides of rare earth elements such as Tm 2 O 3 and Yb 2 O 3 ; one or more oxides selected from Bi 2 O 3 and In 2 O 3 and the like can be mentioned.
  • ZrO 2 zirconia
  • the mixture is stabilized by one or more selected from yttria (Y 2 O 3 ), calcia (CaO), magnesia (MgO) and scandia (Sc 2 O 3).
  • the stabilizer used for stabilized zirconia (SZ) may be one kind or a combination of two or more kinds.
  • the stabilized zirconia when the intention of the stabilized zirconia in general which does not specify a stabilizer, the stabilized zirconia may be referred to as "SZ".
  • SZ stabilizing zirconia using yttria (Y 2 O 3 ), calcia (CaO), magnesia (MgO) and scandia (Sc 2 O 3 ) as stabilizers is intended, “YSZ” and “CSZ”, respectively. , “MSZ” and “ScSZ”.
  • stabilized zirconia (SZ) containing an X (mol%) stabilizer may be referred to as "X-SZ”.
  • "3.0-YSZ” means stabilized zirconia (YSZ) stabilized with 3.0 mol% yttria (Y 2 O 3).
  • the content of the stabilizer in the stabilized zirconia (SZ) is not particularly limited, but is preferably more than 0.0 mol% and 45.0 mol% or less, and more preferably more than 0.0 mol% and 40. It is 0.0 mol% or less, particularly preferably 8.0 to 25.0 mol%.
  • the content (X mol%) of the stabilizer in the stabilized zirconia (SZ) is obtained by converting Zr in the stabilized zirconia (SZ) and the metal element in the stabilizer into oxides, respectively.
  • Oxide-equivalent moles of metal elements in stabilizers Percentage of oxide-equivalent moles of metal elements in stabilizers to total oxide-equivalent moles of Zr and metal elements in stabilizers ((Oxide-equivalent moles of metal elements in stabilizers) / (Oxide-equivalent number of moles of metal element in stabilizer + Zr oxide-equivalent mole number in stabilized zirconia (SZ)) x 100).
  • oxide conversion for example, Zr is converted to ZrO 2 , Y is converted to Y 2 O 3 , Ca is converted to Ca O, Mg is converted to Mg O, and Sc is converted to Sc 2 O 3 , and the number of moles is calculated.
  • each metal element in the two or more kinds of stabilizers is converted into an oxide, and the total molar amount of the oxides is converted.
  • Let the number be the number of moles of the metal element in the stabilizer in terms of oxide.
  • the content of (D3) stabilized zirconia (SZ) in the Ni paste of the present invention is conductive mainly containing (A) Ni.
  • the amount is 0.05 ⁇ 10 -2 to 2.20 ⁇ 10-2 mol, preferably 0.05 ⁇ 10 -2 to 1.40 ⁇ 10 -2 mol, per 100.0 g of the sex powder.
  • Zr in stabilized zirconia (SZ) and the metal element in the stabilizer are converted into oxides, respectively, and Zr and stabilized.
  • the stabilized zirconia (SZ) in the Ni paste Calculate the content.
  • the component (D4) according to the Ni paste of the present invention is an additive containing Al.
  • the additive containing Al is not particularly limited as long as Al 2 O 3 can be obtained after firing Ni paste, but as an example, in addition to pure metal (Al), an oxide containing Al (Al 2).
  • Al 2 O 3 sulfide (Al 2 S 3), the halide (AlF 3, etc.), borides (AlB 2), nitride (AlN), carbide (Al 4 C 3), hydroxide (Al (OH) It may be an inorganic compound such as 3), a phosphate (AlPO 4 ), a sulfate (Al 2 (SO 4 ) 3 ), or an organic metal compound such as a metal alkoxide or a metal resinate. In the present invention, Al 2 O 3 is particularly preferable as the additive containing Al.
  • the Ni paste of the present invention contains an additive containing (D4) Al
  • the Ni paste of the present invention has (A) Ni when Al in the additive containing Al is converted into Al 2 O 3.
  • the additive containing Al is contained in a proportion of 0.10 to 5.50 parts by mass, preferably 0.10 to 2.30 parts by mass, per 100.0 parts by mass of the conductive powder mainly composed of.
  • the Ni paste of the present invention contains a combination of an additive containing (D1) Ta, an additive containing (D2) Nb, an additive containing (D3) stabilized zirconia (SZ), and (D4) Al. May be good.
  • the Ni paste of the present invention is selected from the group consisting of (D1) Ta-containing additives, (D2) Nb-containing additives, (D3) stabilized zirconia (SZ), and (D4) Al-containing additives.
  • the mechanism by which the above-mentioned effects of the present invention can be obtained by containing at least one of these in the above-mentioned content ratio is not clear. However, according to tests and studies by the present inventor, most of the Ta component, Nb component, stabilized zirconia (SZ) component or Al component contained in the Ni paste is ceramic dielectric during firing of the paste.
  • 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, and from the interface to the internal electrode. It shall refer to the region up to 1/2 of the internal electrode layer thickness on the layer side.
  • the present inventor reduces the speed of movement of oxygen vacancies to the cathode side that occurs in the ceramic dielectric layer during the high temperature load life test, leading to an improvement in life. I'm guessing that there is.
  • the composition of the co-material powder is the same as or similar to that of the ceramic dielectric layer even when the co-material powder containing Zr is used. Therefore, even if it diffuses from the internal electrode layer to the ceramic dielectric layer side during firing, the element concentration distribution of Zr in the ceramic dielectric layer is hardly changed.
  • the formation of the diffusion region (diffusion layer) containing a high concentration of Zr and the metal element in the stabilizer observed at the interface between the ceramic dielectric layer and the internal electrode layer and its vicinity is separate from the co-material powder. It is considered that this is due to the stabilized zirconia (SZ) contained in the Ni paste. Moreover, stabilized zirconia (SZ) is obtained by introducing oxygen vacancies into zirconia (ZrO 2 ), and the more stabilizer there is, the larger the amount of oxygen vacancies. Therefore, stabilized zirconia (SZ) is added to the Ni paste.
  • the oxygen vacancy concentration in the vicinity of the interface can be increased as compared with the case where zirconia (ZrO 2) which is not stabilized is contained.
  • ZrO 2 zirconia
  • the oxygen vacancies inside the dielectric layer are less likely to move to the electrode interface (cathode) side, and the high temperature load life can be further improved, but the amount of stabilizer is excessive. If this is the case, the oxygen vacancies concentration becomes too high, and it is considered that the high temperature load life characteristic drops sharply due to this.
  • the content of the Ta component, the Nb component, the stabilized zirconia (SZ) component, or the Al component in the internal electrode layer after firing does not lower the melting point of Ni, and thus adversely affects the continuity of the electrode film. There is no such thing. However, if the concentration of the Ta component, Nb component, stabilized zirconia (SZ) component, or Al component in the diffusion layer in the ceramic dielectric layer becomes too large, the wettability with Ni decreases and the electrode film is continuous. May adversely affect sexuality.
  • the content of is less than the above range, the effect of improving the high temperature load life cannot be obtained, and if it exceeds the above range, the Ta component, the Nb component, and the stabilized zirconia (SZ) diffused in the ceramic dielectric layer are obtained.
  • Component or Al component causes crystal grain growth, which reduces the high temperature load life.
  • the Ni paste of the present invention can further contain a co-material powder that is usually added to the Ni paste for forming internal electrodes.
  • the optionally contained co-material powder 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, but is the same as that of the ceramic dielectric. It is desirable to select so that the change in the characteristics of the capacitor due to the reaction of 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.
  • Hf for example, perovskite-type oxide powders such as barium titanate, strontium zirconium, calcium zirconium, and those to which various additives are added. Is preferable.
  • the co-material powder those 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 are preferable.
  • the co-material powder may be attached 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 in the Ni paste of the present invention is (A) per 100.0 parts by mass of the conductive powder mainly containing Ni.
  • the total ratio is 30.0 parts by mass or less.
  • 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 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.
  • CaO, ZrO 2 , Y 2 O 3 , Ti 4 O 7 Even if compounds such as TiO 2 , Co 3 O 4 , Fe 2 O 3 , La 2 O 3 , Li 2 O, MgO, MoO 3 , SrO, V 2 O 5 , WO 3 , CuO, etc. are added for various purposes. good.
  • 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.
  • the additive containing (D1) Ta and (D2) Nb are used. It may be used in combination with an additive containing (D3) stabilized zirconia (SZ) or an additive containing (D4) Al.
  • 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 contains the above-mentioned (A) Ni-based conductive powder, (B) binder resin, (C) organic solvent, "(D1) Ta-containing additive, and (D2) Nb-containing additive. "At least one selected from the group consisting of additives, (D3) stabilized zirconia (SZ), and (D4) Al-containing additives", and other co-material powders and various additives added as needed. Is 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 zircone strontium, or some of the metal elements constituting these are used.
  • a powder containing a normal perovskite-type oxide as a main component is used, such as those substituted with the metal element of. If necessary, various additives for adjusting the capacitor characteristics are added to these raw material powders.
  • 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.
  • the obtained laminated body is cut into a predetermined shape and then fired at a high temperature, and the dielectric layer and the electrode layer are sintered at the same time to obtain a laminated ceramic capacitor element.
  • 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 With The ceramic laminate (D1) Ta, which is in the range of 0.025 to 2.50 parts by mass in terms of Ta 2 O 5 per 100.0 parts by mass of the conductive component containing (A) Ni.
  • (D2) Nb in the range of 0.010 to 1.80 parts by mass in terms of Nb 2 O 5 per 100.0 parts by mass of the conductive component containing (A) Ni, and (D4) the above (A) Ni.
  • Al in the range of 0.10 to 5.50 parts by mass in terms of Al 2 O 3 per 100.0 parts by mass of the conductive component containing Containing at least one selected from the group consisting of It is a monolithic ceramic capacitor characterized by.
  • 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 With Up to 1/16 of the thickness of the ceramic dielectric layer from the interface between the adjacent internal electrode layer and the ceramic dielectric layer and its vicinity, that is, from the interface between the ceramic dielectric layer and the internal electrode layer to the dielectric layer side. From the region to any portion of the region from the interface to the region up to 1/2 of the thickness of the internal electrode layer on the internal electrode layer side, from Ta, Nb, Zr, the metal element in the stabilizer, and Al.
  • a diffusion region having a concentration peak of at least one element selected from the group consisting of It is a monolithic ceramic capacitor characterized by.
  • the concentration of at least one element selected from the group consisting of Ta, Nb, Zr, a metal element in the stabilizer, and Al is transferred from the internal electrode layer side to the ceramic dielectric layer side. It is a region having a concentration distribution that increases in the direction toward the direction, reaches a concentration peak, and then decreases.
  • the metal element in the stabilizer is preferably one or more selected from Y, Ca, Mg and Sc.
  • the ceramic dielectric layer according to the multilayer ceramic capacitor of the present invention is a perovskite-type oxide such as barium titanate, strontium zirconate, or calcium zircone strontium as a dielectric ceramic raw material powder, or a metal element constituting these.
  • 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 is 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 firing. Most of the Ta component, Nb component, stable zirconia (SZ) component, or Al component contained in the Ni paste moves from the internal electrode layer to the ceramic dielectric layer side during firing as described above, and is inside. At the interface between the electrode layer and the ceramic dielectric layer and its vicinity, a diffusion region (diffusion layer) containing a high concentration of the metal element in Ta, Nb, Zr and the stabilizer, or Al is formed.
  • a diffusion region diffusion layer
  • the concentration distribution of Ta, Nb, Zr and the metal element in the stabilizer or Al in the diffusion region (diffusion layer) is not uniform, and the metal element or Al in Ta, Nb, Zr and the stabilizer is not uniform.
  • the concentration of zirconium 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, the concentration peak is presumed to be near the interface, but its position has not been accurately identified. That is, 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 Ta component diffuses from the internal electrode layer toward the dielectric layer and the dielectric is said.
  • a diffusion layer having a steep concentration gradient (concentration peak) in which Ta is unevenly distributed only at a position extremely close to the interface with the internal electrode layer in the body layer was formed.
  • a relatively broad Ta concentration gradient (concentration peak) is provided in the dielectric layer. A diffusion layer was formed.
  • the multilayer ceramic capacitor of the present invention has a Ta 2 O 5 conversion per 100.0 parts by mass of a conductive component containing (D1) and (A) Ni in a ceramic laminate in which a dielectric and an internal electrode layer are combined.
  • Al per 100.0 parts by mass of the conductive component containing Nb in the range of 0.010 to 1.80 parts by mass, preferably 0.010 to 0.50 parts by mass, and (D4) (A) Ni.
  • 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 With Diffusion of at least one element selected from the group consisting of Ta, Nb, Zr, a metal element in a stabilizer, and Al at the interface between the adjacent internal electrode layer and the ceramic dielectric layer and its vicinity. It is characterized by having a region (diffusion layer).
  • the metal element in the stabilizer is preferably one or more selected from Y, Ca, Mg and Sc.
  • the multilayer ceramic capacitor of the present invention has the above-mentioned characteristics and thus has an improved high-temperature load life. Therefore, even if the dielectric layer is further thinned and a voltage with a high electric field strength is applied, excellent reliability is achieved. show.
  • the dielectric layer and the internal electrode layer contain a Ta component, an Nb component, a stabilized zirconia (SZ) component, or an Al component, and they are higher in the direction from the internal electrode layer side to the ceramic dielectric layer side.
  • Having a diffusion region (diffusion layer) with a low concentration distribution after reaching a concentration peak means that SEM (scanning electron microscope), TEM (transmission electron microscope), or STEM (scanning transmission electron microscope) )
  • an element analysis method such as EDS (energy dispersion type X-ray spectroscopy), WDS (wavelength dispersion 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 1100-1300 ° 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 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 1100-1300 ° C., and the firing atmosphere is a reducing atmosphere. That is, the internal electrode layer is formed of a fired product of the Ni paste of the present invention at 900 to 1400 ° C, preferably 1100 to 1300 ° C.
  • a Ni paste was prepared by kneading using a 3-roll mill. Next, a polyvinyl butyral-based binder, ethanol, and an additive for adjusting the capacitor characteristics were added to BaTiO 3 powder having an average particle size of 0.2 ⁇ m, which is the main component of the ceramic green sheet, and wet-mixed with a media mill to prepare a ceramic slurry. bottom. This ceramic slurry was sheet-molded by the die coater method to prepare a ceramic green sheet having a thickness of 5.5 ⁇ m. Subsequently, 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-bonded and molded by applying a pressure of 1250 kg / cm 2 at 90 ° C. 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.
  • 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 .
  • Each multilayer ceramic capacitor (samples in Tables 1 and 2) produced as described above is subjected to a high-temperature load test by the method described below, the continuity of the internal electrode layer is evaluated, and the ceramic dielectric layer is evaluated.
  • the diffusion region (diffusion layer) in which the concentration of Ta or Nb increases in the direction from the internal electrode layer side toward the ceramic dielectric layer side, reaches a concentration peak, and then decreases. was confirmed to be formed.
  • (1) High-temperature load test Fifteen samples are sampled from each sample, and the high-temperature load test is performed under the conditions of 180 ° C. and 60 V. 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. bottom.
  • Ta 2 O 5 or Nb 2 O 5 with respect to samples not mixed a defined range of Ta 2 O 5 or Nb 2 O 5 in the present invention MTTF increased in all the samples mixed in (Sample Nos. 2A-10A and 12A-20A).
  • the continuity of the internal electrodes was 90% or more for sample numbers 2A to 7A and 12A to 16A, and 80 to 90% for sample numbers 8A to 10A and 17A to 20A.
  • the sample mixture of Ta 2 O 5 or Nb 2 O 5 is in the sample (Sample No.
  • Example 2 and Comparative Example 1 ⁇ Manufacturing of Ni paste and multilayer ceramic capacitors> (Making Ni paste) As Comparative Example 1, ZrO 2 was prepared at a ratio of the number of moles shown in Table 3 with respect to 100.0 g of spherical nickel powder having an average particle size of 0.3 ⁇ m, and further, an average particle size of 0.05 ⁇ m as a co-material powder.
  • BaTiO 3 powder is mixed at a ratio of 10.0 g, ethyl cellulose (binder resin) 6.0 g, surfactant 2.0 g, plasticizer 1.0 g, and dihydroterpineol acetate (organic solvent) 100.0 g, and 3
  • a Ni paste was prepared by kneading using this roll mill. Further, as Example 2, in the same manner as in Comparative Example 1 except that 3.0 mol% yttria-stabilized zirconia (3.0-YSZ) was used instead of ZrO 2 at a ratio of the number of moles shown in Table 4. A Ni paste was prepared.
  • 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-bonded and molded by applying a pressure of 1250 kg / cm 2 at 90 ° C. 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.
  • the samples marked with * in the sample numbers are comparative examples that do not satisfy the requirements of the present invention.
  • 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 .
  • Each multilayer ceramic capacitor (sample in Table 3 or Table 4) produced as described above is subjected to a high-temperature load test by the method described below, the continuity of the internal electrode layer is evaluated, and the ceramic dielectric layer is evaluated.
  • the concentration of Y which is a metal element in Zr and / or the stabilizer, increases in the direction from the internal electrode layer side toward the ceramic dielectric layer side, and reaches a concentration peak. After that, it was confirmed that a lower diffusion region (diffusion layer) was formed.
  • MTTF increased in all samples (Samples 12B-20B) in which zirconia (3.0-YSZ) was mixed within the range specified in the present invention. Further, all the samples (Sample 12B) in which stabilized zirconia (3.0-YSZ) was mixed within the range specified in the present invention were also mixed with the samples (Samples 2B to 10B) to which the same molar amount of zirconia (ZrO 2) was added. MTTF increased in ⁇ 20B).
  • the continuity of the internal electrodes was 90% or more in the samples 12B to 18B, and 80 to 90% in the samples 19B to 20B.
  • the MTTF is lower than that of the sample (Sample 11B) in which zirconia (ZrO 2) is mixed.
  • the continuity of the internal electrodes was less than 80%. From the above, by mixing 0.05 ⁇ 10-2 to 2.20 ⁇ 10-2 mol of stabilized zirconia (3.0-YSZ) per 100 g of spherical nickel powder, no additives and zirconia (ZrO 2) were added.
  • High temperature load life can be improved compared to the case of addition, and if it is within the range of 0.05 ⁇ 10 -2 to 1.40 ⁇ 10 -2 mol, it is high without impairing the continuity of the internal electrodes. It becomes possible to further improve the load life.
  • Example 3 ⁇ Manufacturing of Ni paste and multilayer ceramic capacitors> (Preparation of Ni paste) Against the spherical nickel powder 100.0g of an average particle diameter of 0.3 [mu] m, the content (X mole%) of yttria (Y 2 O 3) stabilized with stabilized zirconia (X-YSZ) powder shown in Table 6 Prepared at a ratio of 0.80 ⁇ 10-2 mol, 10.0 g of BaTiO 3 powder having an average particle size of 0.05 ⁇ m as a co-material powder, 6.0 g of ethyl cellulose (binder resin), 2.0 g of surfactant, A Ni paste was prepared by mixing 1.0 g of a plasticizer and 100.0 g of dihydroterpineol acetate (organic solvent) and kneading using a three-roll mill.
  • X-YSZ stabilized zirconia
  • MTTF (Sample 16B, 22B-28B) of similarly stabilized zirconia (X-YSZ) to MTTF (Sample 6B) to which the same amount of zirconia (ZrO 2) was added, that is, MTTF (X-YSZ). / MTTF (ZrO 2 ) is indicated by a square (vertical axis is on the right side) in FIG.
  • X refers to the molar% of Y 2 O 3 contained in stabilized zirconia (YSZ). 2) Ratio of MTTF of each sample to MTTF of sample 1B (additive-free) (MTTF of each sample / MTTF of sample 1B) 3) Ratio of MTTF of each sample to sample 6B to which the same mole of ZrO 2 was added (MTTF of each sample / MTTF of sample 6B)
  • the content of the stabilizer (Y 2 O 3 ) is in the range of more than 0.0 mol% and 45.0 mol% or less.
  • the range of more than 0.0 mol% and 40.0 mol% or less is preferable, and the range of 8.0 to 25.0 mol% is particularly preferable.
  • Example 4 ⁇ Manufacturing of Ni paste and multilayer ceramic capacitors> (Preparation of Ni paste) 0.80 of stabilized zirconia (10.0-SZ) powder containing 10.0 mol% of the stabilizers of the types shown in Table 7 with respect to 100.0 g of spherical nickel powder having an average particle size of 0.3 ⁇ m. Prepared at a ratio of ⁇ 10-2 mol, and 10.0 g of BaTiO 3 powder having an average particle size of 0.05 ⁇ m, 6.0 g of ethyl cellulose (binder resin), 2.0 g of surfactant, and 1 plasticizer as co-material powder. A Ni paste was prepared by mixing at a ratio of 0.0 g and 100.0 g of dihydroterpineol acetate (organic solvent) and kneading using a three-roll mill.
  • a Ni paste was prepared by kneading. Next, a polyvinyl butyral-based binder, ethanol, and an additive for adjusting the capacitor characteristics were added to BaTiO 3 powder having an average particle size of 0.2 ⁇ m, which is the main component of the ceramic green sheet, and wet-mixed with a media mill to prepare a ceramic slurry. bottom.
  • This ceramic slurry was sheet-molded by the die coater method to prepare a ceramic green sheet having a thickness of 5.5 ⁇ m. Subsequently, 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. at 1250 kg / cm 2 to crimp and cut 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.
  • 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 .
  • Each multilayer ceramic capacitor (sample in Table 8) produced as described above is subjected to a high-temperature load test by the method described below, the continuity of the internal electrode layer is evaluated, and the dielectric layer and the internal electrode layer are evaluated. By observing the vicinity of the interface, the concentration of Al increases in the direction from the internal electrode layer side toward the ceramic dielectric layer side, and after reaching the concentration peak, a diffusion region (diffusion layer) is formed. It was confirmed.
  • (1) High-temperature load test Fifteen samples are sampled from each sample, and the high-temperature load test is performed under the conditions of 180 ° C. and 60 V. 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. bottom.

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Abstract

L'invention concerne une pâte de Ni qui est caractérisée en ce qu'elle contient (A) une poudre conductrice qui est composée principalement de Ni, (B) une résine liante et (C) un solvant organique et en ce qu'elle contient en outre au moins une substance qui est choisie dans le groupe constitué par (D1) un additif qui contient du Ta en une proportion dans la plage de 0,025 à 2,50 parties en masse en termes de Ta2O5 pour 100,0 parties en masse de la poudre conductrice (A) qui est composée principalement de Ni, (D2) un additif qui contient du Nb en une proportion dans la plage de 0,010 à 1,80 parties en masse en termes de Nb2O5 pour 100,0 parties en masse de la poudre conductrice (A) qui est composée principalement de Ni, (D3) une zircone stabilisée (SZ) en une proportion dans la plage de 0,05 × 10-2 à 2,20 × 10-2 mole pour 100 g de la poudre conductrice (A) qui est composée principalement de Ni, ladite zircone stabilisée étant obtenue par stabilisation de la structure cristalline de zircone au moyen d'un stabilisant et (D4) un additif qui contient de l'Al en une proportion dans la plage de 0,10 à 5,50 parties en masse en termes d'Al2O3 pour 100,0 parties en masse de la poudre conductrice (A) qui est composée principalement de Ni. La présente invention sert à fournir une pâte de Ni pour des électrodes internes, ladite pâte de Ni permettant d'améliorer la durée de la charge à haute température sans abaisser la continuité d'un film d'électrode.
PCT/JP2021/014652 2020-04-13 2021-04-06 PÂTE DE Ni ET CONDENSATEUR CÉRAMIQUE MULTICOUCHE WO2021210455A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08241828A (ja) * 1995-03-02 1996-09-17 Murata Mfg Co Ltd 積層セラミックコンデンサ
JPH1121644A (ja) * 1997-07-02 1999-01-26 Sumitomo Metal Mining Co Ltd Ｎｉ粉末およびそれを用いたＮｉペースト
JP2000049031A (ja) * 1998-07-30 2000-02-18 Toshiba Corp コンデンサの電極組成物及びそれを用いた電極ペースト
JP2004178866A (ja) * 2002-11-25 2004-06-24 Tdk Corp 導電性組成物とセラミック電子部品
JP2005129425A (ja) * 2003-10-27 2005-05-19 Murata Mfg Co Ltd 導電性ペーストおよび積層セラミック電子部品
WO2006041030A1 (fr) * 2004-10-08 2006-04-20 Mitsui Mining & Smelting Co., Ltd. Encre conductrice
JP2014232850A (ja) * 2013-05-30 2014-12-11 京セラ株式会社 積層型電子部品

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08241828A (ja) * 1995-03-02 1996-09-17 Murata Mfg Co Ltd 積層セラミックコンデンサ
JPH1121644A (ja) * 1997-07-02 1999-01-26 Sumitomo Metal Mining Co Ltd Ｎｉ粉末およびそれを用いたＮｉペースト
JP2000049031A (ja) * 1998-07-30 2000-02-18 Toshiba Corp コンデンサの電極組成物及びそれを用いた電極ペースト
JP2004178866A (ja) * 2002-11-25 2004-06-24 Tdk Corp 導電性組成物とセラミック電子部品
JP2005129425A (ja) * 2003-10-27 2005-05-19 Murata Mfg Co Ltd 導電性ペーストおよび積層セラミック電子部品
WO2006041030A1 (fr) * 2004-10-08 2006-04-20 Mitsui Mining & Smelting Co., Ltd. Encre conductrice
JP2014232850A (ja) * 2013-05-30 2014-12-11 京セラ株式会社 積層型電子部品

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