WO2022114121A1 - Pâte conductrice et condensateur céramique multicouche - Google Patents

Pâte conductrice et condensateur céramique multicouche Download PDF

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Publication number
WO2022114121A1
WO2022114121A1 PCT/JP2021/043372 JP2021043372W WO2022114121A1 WO 2022114121 A1 WO2022114121 A1 WO 2022114121A1 JP 2021043372 W JP2021043372 W JP 2021043372W WO 2022114121 A1 WO2022114121 A1 WO 2022114121A1
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conductive paste
powder
conductive
mass
dispersant
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PCT/JP2021/043372
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English (en)
Japanese (ja)
Inventor
伸寿 鈴木
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住友金属鉱山株式会社
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Priority to CN202180078301.4A priority Critical patent/CN116569293A/zh
Priority to KR1020237009229A priority patent/KR20230110244A/ko
Publication of WO2022114121A1 publication Critical patent/WO2022114121A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • 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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
    • 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
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/008—Selection of materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/005—Electrodes
    • H01G4/012—Form of non-self-supporting electrodes
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/15—Nickel or cobalt

Definitions

  • the present invention relates to a conductive paste and a monolithic ceramic capacitor.
  • Multilayer ceramic capacitors have a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated, and by thinning these dielectric layers and internal electrode layers, the size and capacity can be increased. Can be planned.
  • Multilayer ceramic capacitors are manufactured, for example, as follows. First, a conductive paste for an internal electrode is printed (applied) with a predetermined electrode pattern on the surface of a dielectric powder containing barium titanate (BaTIO 3 ) and a dielectric green sheet containing a binder resin. Dry to form a dry film. Next, the dried film and the green sheet are laminated so as to be alternately overlapped to obtain a laminated body. Next, this laminated body is heat-bonded and integrated to form a pressure-bonded body. This crimped body is cut and subjected to a deorganizing binder treatment in an oxidizing atmosphere or an inert atmosphere, and then calcined to obtain a calcined chip. Next, the paste for the external electrode is applied to both ends of the fired chip, and after firing, the surface of the external electrode is nickel-plated or the like to obtain a laminated ceramic capacitor.
  • a conductive paste for an internal electrode is printed (applied) with a predetermined electrode pattern on the surface of
  • the conductive paste used for forming the internal electrode layer contains, for example, a conductive powder, a ceramic powder, a binder resin and an organic solvent.
  • the conductive paste may contain a dispersant in order to improve the dispersibility of the conductive powder or the like.
  • the conductive powder contained in the conductive paste also tends to have a smaller particle size (micronization).
  • particle size of the conductive powder becomes smaller, the surface area per unit volume increases, so that the properties of the particle surface become dominant.
  • the particles constituting the conductive powder are at the submicron level, the particles are likely to adhere to each other by a force such as an intramolecular force or an electrostatic force to form a coarse agglomerate.
  • aggregates are present in the conductive powder, they form convex portions on the surface of the internal electrode layer during the manufacture of the laminated ceramic capacitor, and in some cases, break through the ceramic dielectric layer to cause a short circuit between the internal electrode layers. May cause.
  • the conductive paste is produced, for example, by containing other materials such as conductive powder in an organic vehicle in which a binder resin is dissolved in an organic solvent, and kneading and dispersing the paste.
  • a kneading method in the conventional conductive paste manufacturing process for example, an apparatus such as a high-speed shear mixer or a planetary mixer having two or more axes is used, and an inorganic powder such as a conductive powder and a ceramic powder is contained in an organic vehicle. , Dispersants, organic solvents, etc. are mixed (kneaded).
  • the organic vehicle may not be sufficiently mixed, or the surface of the conductive powder or the ceramic powder may not be sufficiently wet. Further, even when the dispersion treatment is performed by a three-roll mill or the like after kneading, problems such as poor dispersion of the conductive powder (metal fine powder) and flakes may occur.
  • the conductive powder produced by the wet production method which is one of the general methods for producing fine metal particles, tends to promote the aggregation of the conductive powder at the stage of the drying step of the wet production method, and is conductive.
  • the powder is kneaded into the organic vehicle, many aggregates (secondary particles) have already been formed, and the above problems are likely to occur.
  • inorganic powder When focusing on the dispersion process of conductive powder and ceramic powder (hereinafter collectively referred to as "inorganic powder") in the process of manufacturing a conductive paste containing a dispersant, the particles constituting the inorganic powder are contained in the paste.
  • the dispersion process is divided into the following steps, for example.
  • Step of "wetting" the surface of the particles (including secondary particles) constituting the inorganic powder Step of crushing the secondary particles and dispersing the crushed particles in the paste (3) Step to suppress “reaggregation” of particles after crushing
  • the above (1) wetting process is a step in which the organic vehicle / organic solvent adheres to the surface of the particles constituting the conductive powder and the ceramic powder, and in the case of the conductive paste containing a dispersant, the secondary particles are in this step.
  • the dispersant is adsorbed on the surface of the (aggregate)
  • the air existing in the voids inside the secondary particles is replaced by the organic solvent containing the dispersant, and the dispersant is adsorbed on the inner wall of the secondary particles.
  • the step of getting wet is, specifically, a step of kneading and stirring using an apparatus such as the above-mentioned mixer, and is also called a pretreatment step.
  • the degree of "wetting" of the conductive and ceramic powders affects the processing time in the next dispersion step.
  • the above (2) dispersion step is a step that greatly affects the dispersibility of the conductive powder and the ceramic powder (inorganic powder) in the conductive paste.
  • a disperser such as a three-roll machine is used.
  • the secondary particles (aggregates) of the inorganic powder are crushed to disperse the crushed particles (eg, single primary particles or secondary particles in which a small number of primary particles are aggregated) in an organic vehicle. It is a process.
  • the various characteristics of the conductive paste vary widely, and the surface smoothness of the dry film is caused by the coarse particles caused by the secondary particles that are insufficiently crushed. Will worsen.
  • the above (3) step of suppressing reaggregation is a step of suppressing "reaggregation" of the particles after crushing by adsorbing the dispersant on the new surface of the particle surface newly appeared by crushing.
  • the above (2) dispersion step if an appropriate treatment time is not provided for the dispersion treatment, there may be a portion where the dispersant is not adsorbed on the new surface of the particle surface after crushing, and (3) the step of suppressing reaggregation. In some cases, the particles after crushing may reaggregate and the dispersion stability of the conductive paste may decrease.
  • the above-mentioned (2) dispersion step and (3) reaggregation suppression step may proceed at the same time.
  • Patent Document 1 As a method for improving the dispersion stability of the conductive paste, for example, in Patent Document 1, as a conductive paste having excellent dispersion stability, specific metal fine particles are added to an organic solvent having a dielectric constant in the range of 4 to 24. Dispersing techniques are disclosed.
  • Patent Document 1 can improve the dispersion stability to some extent, the effect of improving the crushability of the formed secondary particles in the above (2) dispersion step is insufficient, and the crushing is insufficient. However, it may contain coarse particles due to insufficient secondary particles, and it is difficult to use it suitably for small products whose thinning progresses.
  • the present inventor improves "wetting" on the surface of the particles constituting the inorganic powder, thereby improving the "wetting" of the secondary particles in the above (2) dispersion step.
  • the dispersant can be easily crushed and high dispersibility can be obtained, and in the step (3) of suppressing reaggregation, the dispersant is easily adsorbed on the new surface of the crushed particle surface. It has been found that since "reaggregation" of particles can be prevented, the dispersion stability of the conductive paste can be maintained even after long-term storage, and the viscosity stability is also excellent.
  • the present invention has high dispersibility and viscosity in a conductive paste using a conductive powder or a ceramic powder that has been miniaturized for miniaturization and thinning of a laminated ceramic electronic component. It is an object of the present invention to provide a conductive paste having excellent stability.
  • the amount of H 2 O adsorbed per unit area is 0.30 mg / m 2 or more and 0.70 mg / m 2 or less, the dispersant has a relative permittivity of 10 or more, and (1) has an acid group.
  • a conductive paste containing at least one compound selected from the group consisting of a compound and (2) a compound having an amine group.
  • the compound having an acid group is a compound containing at least one of a carboxyl group and a phosphoric acid group.
  • the binder resin contains at least one selected from the group consisting of cellulosic resins and butyral resins. Further, the content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less with respect to 100% by mass of the conductive paste.
  • the conductive powder contains one or more metal powders selected from the group consisting of Ni, Cu, Ag, Pd, Au, Pt powders and alloy powders thereof. Further, the conductive powder is preferably nickel powder.
  • NiO is 20 mol% or more and 90 mol% or less.
  • the content of the conductive powder is preferably 30% by mass or more and 70% by mass or less with respect to 100% by mass of the conductive paste.
  • the ceramic powder is at least one selected from the group consisting of barium titanate and strontium zirconate.
  • the conductive paste was allowed to stand at 25 ° C. for 30 days after production, and the rate of change in the viscosity of the conductive paste when measured with a Brookfield viscometer under the conditions of 25 ° C. and 10 rpm was 8 hours after production. It is preferably ⁇ 10% or less with respect to the viscosity of the conductive paste.
  • the second aspect of the present invention there is at least a laminate in which a dielectric layer and an internal electrode layer are laminated, and the internal electrode layer is provided by a laminated ceramic capacitor formed by using the above-mentioned conductive paste. Will be done.
  • the conductive paste of the present invention has high dispersibility and excellent viscosity stability over time. Therefore, the conductive paste of the present invention can be suitably used, for example, for an electrode whose thinning progresses, and particularly preferably for an electrode of a laminated ceramic electronic component whose miniaturization progresses.
  • FIG. 1 is a perspective view and a cross-sectional view showing a multilayer ceramic capacitor according to an embodiment.
  • the conductive paste according to the present invention contains a conductive powder, a ceramic powder, a binder resin, an organic solvent and a dispersant.
  • a conductive powder a conductive powder, a ceramic powder, a binder resin, an organic solvent and a dispersant.
  • Conductive powder The material of the conductive powder is not particularly limited, and a known metal powder or the like can be appropriately selected and used according to the required characteristics. Further, these conductive powders may be used alone or in combination.
  • the conductive powder is selected from the group consisting of, for example, nickel (Ni), copper (Cu), silver (Ag), palladium (Pd), gold (Au), platinum (Pt), and alloys thereof1. More than one kind of metal powder can be used, and among these, Ni, Cu, and one or more kinds of metal powders among these alloys are preferable from the viewpoint of conductivity, corrosion resistance, price, etc. Among them, Ni metal powder (nickel powder) is more preferable. Further, the nickel powder may contain sulfur (S) of about several hundred ppm in order to suppress rapid gas generation due to partial thermal decomposition of the binder resin during the debinder treatment.
  • S sulfur
  • the method for producing the conductive powder is not particularly limited, and for example, a method of directly precipitating chloride vapor from the gas phase in hydrogen gas, an atomizing method from a molten metal, a spray thermal decomposition method using an aqueous solution, and a metal as a raw material.
  • a wet method or the like in which a salt is reduced in an aqueous solution can be applied.
  • the average particle size of the conductive powder is not particularly limited and may be selected according to the size of the electronic component to be used.
  • the average particle size of the conductive powder is preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less, for example, for a multilayer ceramic capacitor whose thinning progresses. If the average particle size exceeds 5 ⁇ m, the surface of the internal electrode becomes uneven, which may deteriorate the electrical characteristics of the capacitor, which is not preferable.
  • the lower limit of the average particle size of the conductive powder is not particularly limited, but is, for example, 0.05 ⁇ m or more. If the average particle size is smaller than 0.05 ⁇ m, handling becomes extremely difficult and a risk of spontaneous combustion or the like is likely to occur.
  • the average particle size of the conductive powder is a particle size calculated by using the specific surface area based on the BET method unless otherwise specified.
  • the calculation formula for obtaining the average particle size of nickel powder is as follows (1).
  • the wettability with the solvent and the vehicle changes, and in particular, it greatly affects the crushing and dispersibility of the agglomerates of the fine powder, which is becoming finer.
  • the strength of hydrophilicity and hydrophobicity of the surface of the conductive powder can be evaluated by the amount of H2O adsorbed.
  • the hydrophilicity may become too strong and the viscosity stability may deteriorate. It is considered that this is because the relative permittivity of the conductive powder becomes too high, and the hydrophobic group of the dispersant adsorbed on the conductive powder does not extend, so that it becomes difficult to be compatible with the solvent.
  • the proportion of NiO is preferably 20 mol% or more and 90 mol% or less in the surface composition thereof.
  • the adsorbed state of the dispersant on the surface of the conductive powder may not be appropriate, or the conductive powder may react with the binder resin. If the dispersant is not sufficiently adsorbed on the surface of the conductive powder, the wettability with an organic solvent or an organic vehicle deteriorates, and the aggregates (secondary particles) of the conductive powder are crushed or the crushed particles (1).
  • the suppression of reaggregation of secondary particles, etc.) may be insufficient (that is, the dispersion of the conductive powder may be insufficient), the viscosity stability of the conductive paste may be lowered, or the surface smoothness of the dried film may be poor. be.
  • the proportion of NiO in the surface composition of the nickel powder may be 50 mol% or more within the above range. It may be 60 mol% or more, 70 mol% or more, or 80 mol% or more. The larger the proportion of NiO in the above range, the more a conductive paste having high dispersibility can be obtained even if the amount of the dispersant described later is small.
  • the proportion of NiO in the surface composition of the nickel powder can be measured by using X-ray photoelectron spectroscopy (XPS). For example, when the Ni2p spectrum on the surface of nickel powder is analyzed using XPS and a Ni peak, a Ni (OH) 2 peak, and a NiO peak are detected, the NiO peak with respect to the total peak area of these three components. From the area ratio, the ratio of NiO (mol%) can be measured.
  • XPS X-ray photoelectron spectroscopy
  • the content ratio of the conductive powder is preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the conductive paste. If the proportion of the conductive powder is less than 30% by mass, the thickness of the electrode after firing becomes extremely thin and the resistance value rises, or the formation of the electrode film is insufficient and the conductivity is lost, so that the desired capacitance can be obtained. It is not preferable because it may not be available. If it exceeds 70% by mass, it becomes difficult to thin the electrode film, which is not preferable.
  • the ratio of the conductive powder to the entire paste is more preferably 40% by mass or more and 60% by mass or less.
  • the ceramic powder is not particularly limited, and for example, in the case of a paste for an internal electrode of a laminated ceramic capacitor, a known ceramic powder can be appropriately selected depending on the type of the laminated ceramic capacitor to be applied.
  • the ceramic powder preferably contains, for example, at least one oxide powder selected from the group consisting of barium titanate and strontium zirconate, and among these, barium titanate (BaTIO 3 , hereinafter, "BT". It is preferable to contain the powder of).
  • barium titanate-based oxide powder for example, a powder containing barium titanate (BT) as a main component and other oxides as a sub-component can be used.
  • BT barium titanate
  • other oxides as auxiliary components include manganese (Mn), chromium (Cr), silicon (Si), calcium (Ca), barium (Ba), magnesium (Mg), vanadium (V), and tungsten (tungsten). W), tantalum (Ta), niobium (Nb), and one or more oxides selected from rare earth elements can be mentioned.
  • barium titanate-based oxide powder As the barium titanate-based oxide powder, the Ba atom and / or Ti atom of barium titanate (BaTIO 3 ) was replaced with another atom, tin (Sn), lead (Pb), zirconium (Zr), or the like. A powder of a perovskite-type oxide strong dielectric such as above may be used.
  • the ceramic powder may contain other powders other than the barium titanate-based and strontium zirconate-based oxide powders, for example, zinc oxide (ZnO), which is a ceramic powder forming a green sheet of a laminated ceramic device.
  • ZnO zinc oxide
  • the average particle size of the ceramic powder may be selected according to the size of the electronic component to be used, etc., but for example, for laminated electronic components whose thinning is progressing, the range of 0.01 ⁇ m or more and 0.5 ⁇ m or less is preferable. .. If it exceeds 0.5 ⁇ m, the unevenness of the film surface after coating and drying becomes severe, and if it is smaller than 0.01 ⁇ m, handling becomes extremely difficult and there is a risk of spontaneous combustion, which is not preferable.
  • the content of the ceramic powder is, for example, 1% by mass or more and 20% by mass or less, more preferably 5% by mass or more and 20% by mass or less, based on the total mass of the conductive paste.
  • Binder Resin The binder resin exhibits appropriate viscous property and adhesiveness when printing a conductive paste, improves printability, and also has an effect of improving drying characteristics and the like.
  • the binder resin is not particularly limited, and a known material can be used depending on the required properties.
  • a cellulosic resin a butyral resin, and an acrylic resin.
  • Examples of the cellulosic resin include acetyl cellulose, methyl cellulose, ethyl cellulose, butyl cellulose, nitrocellulose, and partially etherified celluloses.
  • Examples of the butyral resin include polyvinyl butyral and the like.
  • the butyral resin When used for laminated electronic components, the butyral resin may be contained or the butyral resin may be used alone from the viewpoint of improving the adhesive strength with the green sheet.
  • One kind of binder resin may be used, or two or more kinds may be used.
  • the content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1 from the viewpoint of film strength, debinderability, printability, and viscosity with respect to the total mass of the conductive paste. It is by mass% or more and 5% by mass or less.
  • the content of the binder resin is smaller than the above range, the strength of the dry film may be lowered, or the adhesion between the electrode pattern portion of the conductive paste and the dielectric sheet may be deteriorated at the time of laminating, and it may be easily peeled off.
  • the content of the binder resin exceeds the above range, the content of the binder resin becomes too large, so that the debinder property deteriorates and a part of the binder resin may remain.
  • Organic solvent is not particularly limited, the binder resin can be dissolved, the conductive powder can be dispersed, the viscosity of the conductive paste can be adjusted, and appropriate fluidity and printability can be adjusted.
  • a known organic solvent that can impart drying characteristics and the like can be used.
  • various known organic solvents such as organic solvents having a boiling point of about 150 ° C. to 250 ° C., terpene solvents, aliphatic hydrocarbon solvents, alcohols and the like can be used. ..
  • Examples of the terpene-based solvent include tarpineol, dihydroterpineol, and dihydroterpinyl acetate.
  • Examples of the aliphatic hydrocarbon solvent include decane and tridecane.
  • Examples of alcohols include decanol and tridecanol.
  • Examples of the organic solvent having a boiling point of about 150 ° C. to 250 ° C. other than the above include isobornyl acetate, butyl carbitol acetate, diethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether and the like.
  • the content of the organic solvent is preferably 30% by mass or more and 70% by mass or less, preferably 40% by mass or more and 60% by mass, based on the total mass of the conductive paste, from the viewpoints of evaporation amount, viscosity, compatibility with the binder resin, and printability. More preferably, it is by mass or less.
  • the order in which the materials are mixed is not particularly limited, but the above binder resin is dissolved in a part of the organic solvent in advance to prepare an organic vehicle, and then the organic vehicle and others. It is preferable to mix the material of the above and the remaining organic solvent (for adjusting the viscosity).
  • the blending amount of the binder resin contained in the organic vehicle is not particularly limited, but is 1% by mass with respect to the total mass of the organic vehicle from the viewpoint of making the conductive paste used for electronic parts, which are becoming smaller and smaller, have an appropriate viscosity. It is preferably 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less.
  • Dispersant The role of the dispersant is to adsorb to the surface of the inorganic powder (conductive powder and ceramic powder), suppress the aggregation of the inorganic powders, and improve the wettability with the organic vehicle in the conductive paste. It is to disperse to. Dispersants (surfactants) are generally classified into cationic dispersants, anionic dispersants, nonionic dispersants and amphoteric dispersants.
  • an anionic dispersant for example, an acid-based dispersant such as a carboxylic acid-based dispersant, a phosphoric acid-based dispersant, or a phosphate-based dispersant
  • an acid-based dispersant such as a carboxylic acid-based dispersant, a phosphoric acid-based dispersant, or a phosphate-based dispersant
  • the inorganic powder may not be sufficiently dispersed even if an anionic dispersant is used.
  • the relative permittivity is 10 or more, and an acid group and / or an amine group is used. It has been found that dispersibility can be improved by using a dispersant containing a compound having. Since such a dispersant has a large adsorption force on the surface of the inorganic powder and the wettability between the inorganic powder and the organic vehicle is improved ((1) "wetting" step), the surface modifying action of the dispersant makes the inorganic powder. It is considered that it contributes to the improvement of dispersibility by promoting the crushing of the above ((2) dispersal step) and suppressing reaggregation ((3) "reaggregation” suppressing step). ..
  • the relative permittivity of the dispersant may be 10 or more, 11 or more, or 12 or more.
  • the relative permittivity of the dispersant used in the present specification indicates the relative permittivity at 20 ° C. Further, the relative permittivity can be measured by putting an evaluation sample (dispersant used) in an electrode cell for a liquid sample.
  • the upper limit of the relative permittivity of the dispersant is not particularly limited, but is, for example, about 15 or less.
  • the dispersant contains at least one compound selected from the group consisting of (1) a compound having an acid group and (2) a compound having an amine group.
  • the dispersant is a compound corresponding to both (1) a compound having an acid group and (2) a compound having an amine group, that is, (3) a compound having an acid group and an amine group in the same molecule. It may be a mixture containing both (1) a compound having an acid group and (2) a compound having an amine group.
  • the compound having an acid group a compound containing at least one of a carboxyl group and a phosphoric acid group is preferable.
  • the compound having an amine group includes a primary amine, a secondary amine, and a tertiary amine.
  • the dispersant contains a dispersant having an amine value of 100 or more.
  • a dispersant having an amine value of 100 or more is used, the dispersibility of the conductive paste can be further improved, and the smoothness of the surface of the dried film after coating can be further improved.
  • the acid value of the dispersant having an acid group may be 30 or more and 300 or less, or 30 or more and 200 or less.
  • the content of the dispersant is preferably 0.1% by mass or more and 2.0% by mass or less, and more preferably 0.3% by mass or more and 1.0% by mass or less with respect to the total mass of the conductive paste. If the content of the dispersant is less than 0.1% by mass, the content of the dispersant may be too small to obtain the effect of suppressing crushing and reaggregation. On the other hand, if the content of the dispersant is more than 2.0% by mass, the paste characteristics such as printability may be significantly changed, which is not desirable.
  • the conductive paste of the present invention contains, if necessary, a defoaming agent, a plasticizer, a thickener, a chelating agent, and a dispersant other than the above-mentioned dispersant, within the range not deviating from the gist of the present invention.
  • a defoaming agent such as a plasticizer, a thickener, a chelating agent, and a dispersant other than the above-mentioned dispersant, within the range not deviating from the gist of the present invention.
  • One or more known additives such as a dispersant and a thickening agent may be added.
  • the method for producing the conductive paste according to the present embodiment is not particularly limited, and the conductive paste can be produced by using a known method.
  • the conductive paste is produced by kneading and dispersing each of the above materials with an apparatus such as a mixer, a ball mill, a kneader, and a roll mill to form a slurry.
  • the conductive paste according to this embodiment is left to stand at 25 ° C. for 30 days after production, and the rate of change in viscosity ( ⁇ 30 ) when measured with a Brookfield viscometer at 25 ° C. and 10 rpm is the production rate. It is preferably ⁇ 10% or less with respect to the viscosity ( ⁇ 0 ) after 8 hours. When the rate of change in the viscosity of the conductive paste is within the above range, the dispersibility of the conductive paste is excellent.
  • the rate of change in viscosity of the conductive paste after standing for 30 days can be calculated by the following formula (2).
  • Viscosity change rate (%) ( ⁇ 30 - ⁇ 0 ) / ⁇ 0 ⁇ 100 ... (2) ⁇ 30 : 10 rpm viscosity after 30 days ⁇ 0 : 10 rpm viscosity after 8 hours of manufacture (initial viscosity)
  • the glossiness of the dried film of the conductive paste according to the present embodiment is preferably 10 or more, preferably 15 or more, and further preferably 20 or more. The higher the glossiness of the dried film, the less diffused reflection on the entire surface of the dried film, indicating that a smoother surface is obtained.
  • the dry film for evaluation is obtained, for example, by printing a conductive paste on a PET film with an area of 5 ⁇ 10 cm and a film thickness of 30 ⁇ m, and then drying the film at 120 ° C. for 40 minutes in the air. Can be done.
  • FIGS. 1A and 1B are diagrams showing a multilayer ceramic capacitor 1 which is an example of an electronic component according to an embodiment.
  • the laminated ceramic capacitor 1 includes a ceramic laminated body 10 in which a dielectric layer 12 and an internal electrode layer 11 are alternately laminated, and an external electrode 20.
  • a method for manufacturing a multilayer ceramic capacitor using the above conductive paste will be described.
  • a conductive paste is printed on a ceramic green sheet and dried to form a dry film.
  • a plurality of ceramic green sheets having the dried film on the upper surface are laminated by pressure bonding to obtain a laminated body, and then the laminated body is fired to be integrated, whereby the internal electrode layer 11 and the dielectric layer 12 alternate.
  • the ceramic laminate 10 laminated to the above is produced.
  • the multilayer ceramic capacitor 1 is manufactured by forming a pair of external electrodes at both ends of the ceramic laminate 10. It will be described in more detail below.
  • a ceramic green sheet which is an unfired ceramic sheet.
  • a paste for a dielectric layer obtained by adding an organic binder such as polyvinyl butyral and a solvent such as tarpineol to a predetermined ceramic raw material powder such as barium titanate is used as a PET film or the like.
  • examples thereof include those coated on a support film in the form of a sheet and dried to remove the solvent.
  • the thickness of the dielectric layer made of the ceramic green sheet is not particularly limited, but is preferably 0.05 ⁇ m or more and 3 ⁇ m or less from the viewpoint of requesting miniaturization of the laminated ceramic capacitor.
  • a plurality of ceramic green sheets having a dry film formed on one side of the ceramic green sheet were prepared by printing and applying the above-mentioned conductive paste on one side of the ceramic green sheet using a gravure printing method. do.
  • the thickness of the dried film formed from the conductive paste is preferably 1 ⁇ m or less after drying from the viewpoint of requesting thinning of the internal electrode layer 11.
  • the ceramic green sheet is peeled off from the support film, and the ceramic green sheet and the dry film formed on one side thereof are laminated so as to be alternately arranged, and then a laminated body is obtained by heat and pressure treatment.
  • a protective ceramic green sheet to which the conductive paste is not applied may be further arranged on both sides of the laminated body.
  • the green chip is subjected to a debinder treatment and fired in a reducing atmosphere to produce a laminated ceramic fired body (ceramic laminate 10). do.
  • the atmosphere in the debinder treatment is preferably an atmosphere or an N2 gas atmosphere.
  • the temperature at which the debindering treatment is performed is, for example, 200 ° C. or higher and 400 ° C. or lower. Further, it is preferable that the holding time of the above temperature during the debindering treatment is 0.5 hours or more and 24 hours or less.
  • the firing is performed in a reducing atmosphere in order to suppress the oxidation of the metal used for the internal electrode layer, and the temperature at which the laminated body is fired is, for example, 1000 ° C. or higher and 1350 ° C. or lower, and the firing is performed.
  • the temperature holding time is, for example, 0.5 hours or more and 8 hours or less.
  • the organic binder in the ceramic green sheet is completely removed, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12. Further, the organic vehicle in the dry film is removed, and nickel powder or an alloy powder containing nickel as a main component is sintered or melted and integrated to form an internal electrode layer 11, and the dielectric layer 12 and the internal electrode are formed.
  • a laminated ceramic fired body in which a plurality of layers 11 are alternately laminated is formed. From the viewpoint of taking oxygen into the inside of the dielectric layer to improve reliability and suppressing reoxidation of the internal electrode, the laminated ceramic fired body after firing may be annealed.
  • the laminated ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 with respect to the produced laminated ceramic fired body.
  • the external electrode 20 includes an external electrode layer 21 and a plating layer 22.
  • the external electrode layer 21 is electrically connected to the internal electrode layer 11.
  • the material of the external electrode 20 for example, copper, nickel, or an alloy thereof can be preferably used.
  • the electronic component an electronic component other than the monolithic ceramic capacitor can also be used.
  • Rate of change in viscosity of conductive paste over time is determined by first determining the viscosity of the conductive paste after 8 hours of production as the initial viscosity ( ⁇ 0 ). ), Then the viscosity ( ⁇ x ) of the conductive paste after being allowed to stand at room temperature (25 ° C) for 1 day, 10 days and 30 days, respectively, and then the viscosity after being allowed to stand for each number of days. It is expressed as a percentage (%) obtained by dividing the amount of change in the initial viscosity ( ⁇ 0 ). By measuring not only the viscosity change rate after 30 days but also the viscosity change rate after 1 day and 10 days, the tendency of the viscosity change was confirmed.
  • Viscosity change rate (%) ( ⁇ x ⁇ 0 ) / ⁇ 0 ⁇ 100 ⁇ ⁇ ⁇ (2) ⁇ x : 10 rpm viscosity after X days ⁇ 0 : 10 rpm viscosity after 8 hours of manufacture (initial viscosity)
  • the conductive paste is printed on a PET film with an area of 5 ⁇ 10 cm and a film thickness of 30 ⁇ m, and then dried in air at 120 ° C. for 40 minutes to form a dried film (dried conductive paste). Obtained.
  • the glossiness of the obtained dried film at an incident angle of 60 ° was measured with a glossiness meter (Gloss Checker manufactured by HORIBA, Ltd .; IG-320). The higher the glossiness, the less diffused reflection is, indicating that a smoother surface is obtained.
  • Ratio of NiO on the surface of nickel powder The surface of the nickel powder used as the conductive powder was measured by X-ray photoelectron spectroscopy (XPS), and nickel hydroxide (Ni (OH) 2 ) and nickel oxide (NiO) were measured. The peaks of nickel and metallic nickel attributed to NiO were detected, and the ratio of NiO (mol%) was calculated from the respective abundance ratios.
  • Example 1 As a conductive powder, nickel powder ( H2O adsorption amount 0.31 mg / m 2 , NiO surface abundance ratio 34 mol%, particle size 0.4 ⁇ m) was 47% by mass, and as a ceramic powder, barium titanate (particle size 0). .05 ⁇ m) was added in an amount of 4.7% by mass, an organic vehicle was added in an amount of 26.67% by mass, a dispersant was added in an amount of 0.4% by mass, and the balance of an organic solvent was added in an amount of 21.23% by mass.
  • the organic vehicle used was prepared by blending 13% by mass of ethyl cellulose as a binder resin and 87% by mass of tarpineol as an organic solvent and heating and mixing at 60 ° C.
  • an amine-based dispersant having a relative permittivity of 12.5, an acid value of 58, and an amine value of 110 (a mixture of a compound having an acid group and a compound having an amine group) was used.
  • Tarpineol was used as the organic solvent.
  • Table 1 shows the types and contents of each material used, and Table 2 shows the measurement results and calculation results.
  • Example 2 As the conductive powder, nickel powder having an H2O adsorption amount of 0.53 mg / m 2 , a NiO surface presence ratio of 26 mol%, and a particle size of 0.2 ⁇ m was used, and the dispersant content was 0.6% by mass.
  • a conductive paste was prepared in the same manner as in Example 1 except that the organic solvent was dihydroterpinyl acetate and the residual content was 21.03% by mass. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 3 Nickel powder having an H2O adsorption amount of 0.42 mg / m 2 , a surface presence ratio of NiO of 45 mol%, and a particle size of 0.08 ⁇ m was used as the conductive powder, and BT having a particle size of 0.02 ⁇ m was used as the ceramic powder.
  • a conductive paste was prepared in the same manner as in Example 2 except that the content of the dispersant was 1.5% by mass and the residual content of the organic solvent was 20.13% by mass. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 4 A conductive paste was prepared in the same manner as in Example 2 except that an acid-based dispersant having a carboxyl group having a relative permittivity of 11.4 and an acid value of 129 was used as the dispersant. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 5 Nickel powder having an H2O adsorption amount of 0.42 mg / m 2 , a surface presence ratio of NiO of 45 mol%, and a particle size of 0.08 ⁇ m was used as the conductive powder, and BT having a particle size of 0.02 ⁇ m was used as the ceramic powder.
  • a conductive paste was prepared in the same manner as in Example 4 except that the content of the dispersant was 1.5% by mass and the residual content of the organic solvent was 20.13% by mass. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 6 A conductive paste was prepared in the same manner as in Example 2 except that the content of the dispersant was 1.5% by mass and the residual content of the organic solvent was 20.13% by mass. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2. [Example 7] As the conductive powder, the conductive paste was used in the same manner as in Example 6 except that nickel powder having an H2O adsorption amount of 0.34 mg / m 2 , a surface presence ratio of NiO of 79 mol%, and a particle size of 0.2 ⁇ m was used. Was produced.
  • Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 8 As the conductive powder, the conductive paste was used in the same manner as in Example 2 except that nickel powder having an H2O adsorption amount of 0.38 mg / m 2 , a surface abundance ratio of NiO of 89 mol%, and a particle size of 0.2 ⁇ m was used. Was produced. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 1 Same as Example 2 except that a dispersant having an amine group having a specific dielectric constant of 3.0, an acid value of 53, and an amine value of 48 (a mixture of a compound having an acid group and a compound having an amine group) was used as the dispersant.
  • a conductive paste To prepare a conductive paste. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 2 Same as Example 2 except that a dispersant having an amine group having a specific dielectric constant of 8.5, an acid value of 60, and an amine value of 60 (a mixture of a compound having an acid group and a compound having an amine group) was used as the dispersant.
  • a conductive paste To prepare a conductive paste. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 3 As the conductive powder, the conductive paste was used in the same manner as in Example 2 except that nickel powder having an H2O adsorption amount of 0.29 mg / m 2 , a surface abundance ratio of NiO of 49 mol%, and a particle size of 0.2 ⁇ m was used. Was produced. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 4 As the conductive powder, the conductive paste was used in the same manner as in Example 6 except that nickel powder having an H2O adsorption amount of 0.29 mg / m 2 , a surface abundance ratio of NiO of 49 mol%, and a particle size of 0.2 ⁇ m was used. Was produced. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • Example 5 As the conductive powder, the conductive paste was used in the same manner as in Example 2 except that nickel powder having an H2O adsorption amount of 0.71 mg / m 2 , a NiO surface presence ratio of 42 mol%, and a particle size of 0.2 ⁇ m was used. Was produced. Table 1 shows the types and contents of each material used. Further, with respect to the obtained conductive paste, the viscosity change rate and the glossiness were determined in the same manner as in Example 1. The results are shown in Table 2.
  • the conductive paste of the example containing the dispersant having a relative permittivity of 10 or more has a higher glossiness on the surface of the dried film and is excellent in smoothness as compared with the conductive paste of the comparative example having a relative permittivity of less than 10. You can see that there is. In addition, since the rate of change in viscosity is small, it can be seen that the improvement in dispersibility due to the adsorption of the dispersant is maintained for a long period of time.
  • Examples 4 and 5 using a dispersant having no amine value (amine group) and only an acid value (acid group) have a slightly lower glossiness than the other examples, but are comparative examples. By comparison, it shows a sufficiently high glossiness and a small rate of change in viscosity. Therefore, from the viewpoint of improving the smoothness of the entire surface of the dried film, it is preferable to use a dispersant having an amine value of 100 or more.
  • the conductive pastes of Comparative Examples 1 and 2 containing a dispersant having a relative permittivity of less than 10 have a very low glossiness on the surface of the dried film and are inferior in smoothness. This is because the dispersant does not satisfy the predetermined characteristics, so that the wettability to the particle surface is poor, and the dispersant is not sufficiently adsorbed to the particle surface, so that the crushing and reaggregation of the particles cannot be sufficiently suppressed. It is considered that the dispersibility of the conductive paste is poor, the material is biased, and the smoothness of the dry film surface is inferior. Further, it is considered that the dispersant has poor adsorptivity, so that the dispersion stability is poor and the aggregation of each material increases with time, and therefore the viscosity change rate increases with time.
  • Comparative Examples 3 to 5 in which the amount of H 2 O adsorbed per unit area is outside the scope of the invention although the smoothness is low to some extent, the surface condition of the conductive powder is not appropriate in any of them, so that when they are made into a paste, they are made into a paste. It is considered that the dispersion stability is poor, the aggregation of the conductive powders increases with time, and the viscosity change rate also increases with time.
  • Multilayer ceramic capacitor 10 Ceramic laminate 11 Internal electrode layer 12 Dielectric layer 20 External electrode 21 External electrode layer 22 Plating layer

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Abstract

La présente invention concerne une pâte conductrice qui présente une dispersibilité élevée, tout en présentant une excellente stabilité de viscosité à long terme.　Une pâte conductrice qui contient une poudre conductrice, une poudre céramique, une résine liante, un solvant organique et un dispersant, dans laquelle : la poudre conductrice a une adsorption H2O par unité de surface de 0,30 mg/m2 à 0,70 mg/m2 à une pression relative P/P0 de 0,5 ; et le dispersant a une constante diélectrique relative supérieure ou égale à 10, tout en contenant au moins un composé qui est choisi dans le groupe constitué par (1) des composés ayant un groupe acide et (2) des composés ayant un groupe amine.
PCT/JP2021/043372 2020-11-26 2021-11-26 Pâte conductrice et condensateur céramique multicouche WO2022114121A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000299016A (ja) * 1999-04-15 2000-10-24 Koichi Niihara 変形導電性エラストマー及びその製造方法
JP2001214201A (ja) * 1999-11-22 2001-08-07 Mitsui Mining & Smelting Co Ltd ニッケル粉、その製造方法及び電子部品電極形成用ペースト
JP2016076627A (ja) * 2014-10-07 2016-05-12 住友金属鉱山株式会社 積層セラミックコンデンサ用内部電極材料
WO2020144746A1 (fr) * 2019-01-08 2020-07-16 住友金属鉱山株式会社 Pâte de nickel pour condensateur en céramique stratifié
WO2020166361A1 (fr) * 2019-02-12 2020-08-20 住友金属鉱山株式会社 Pâte électroconductrice, composant électronique et condensateur céramique multicouche

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4801958B2 (ja) 2005-09-29 2011-10-26 東海ゴム工業株式会社 導電性ペースト

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000299016A (ja) * 1999-04-15 2000-10-24 Koichi Niihara 変形導電性エラストマー及びその製造方法
JP2001214201A (ja) * 1999-11-22 2001-08-07 Mitsui Mining & Smelting Co Ltd ニッケル粉、その製造方法及び電子部品電極形成用ペースト
JP2016076627A (ja) * 2014-10-07 2016-05-12 住友金属鉱山株式会社 積層セラミックコンデンサ用内部電極材料
WO2020144746A1 (fr) * 2019-01-08 2020-07-16 住友金属鉱山株式会社 Pâte de nickel pour condensateur en céramique stratifié
WO2020166361A1 (fr) * 2019-02-12 2020-08-20 住友金属鉱山株式会社 Pâte électroconductrice, composant électronique et condensateur céramique multicouche

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