WO2023033163A1 - Pâte conductrice pour héliogravure, composant électronique et condensateur céramique multicouche - Google Patents

Pâte conductrice pour héliogravure, composant électronique et condensateur céramique multicouche Download PDF

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Publication number
WO2023033163A1
WO2023033163A1 PCT/JP2022/033197 JP2022033197W WO2023033163A1 WO 2023033163 A1 WO2023033163 A1 WO 2023033163A1 JP 2022033197 W JP2022033197 W JP 2022033197W WO 2023033163 A1 WO2023033163 A1 WO 2023033163A1
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Prior art keywords
conductive paste
gravure printing
dispersant
mass
less
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PCT/JP2022/033197
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English (en)
Japanese (ja)
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健二 福田
尚史 吉田
純平 山田
清 高野
徹 安藤
卓哉 河村
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住友金属鉱山株式会社
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Priority to KR1020247008662A priority Critical patent/KR20240049576A/ko
Priority to CN202280059331.5A priority patent/CN117897781A/zh
Publication of WO2023033163A1 publication Critical patent/WO2023033163A1/fr

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    • 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
    • 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
    • H01G4/002—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
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H01G4/1227—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates based on alkaline earth titanates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Definitions

  • the present invention relates to a conductive paste for gravure printing, electronic components, and laminated ceramic capacitors.
  • Multilayer ceramic capacitors have a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated. By thinning these dielectric layers and internal electrode layers, miniaturization and high capacity can be achieved. can be planned.
  • a laminated ceramic capacitor is manufactured, for example, as follows. First, on the surface of a dielectric green sheet containing dielectric powder such as barium titanate (BaTiO 3 ) and binder resin, an internal electrode paste (conductive paste) is printed in a predetermined electrode pattern, and the dried films are stacked in multiple layers to obtain a laminate in which the dried films and the dielectric green sheets are stacked in multiple layers. Next, this laminated body is thermocompression-bonded to be integrated to form a compression-bonded body. This compressed body is cut, subjected to organic binder removal treatment in an oxidizing atmosphere or inert atmosphere, and then fired to obtain fired chips in which internal electrode layers and dielectric layers are alternately laminated. Next, an external electrode paste is applied to both ends of the fired chip, and after firing, nickel plating or the like is applied to the surfaces of the external electrodes to obtain a multilayer ceramic capacitor.
  • dielectric green sheet containing dielectric powder such as barium titanate (BaTiO 3 ) and binder resin
  • screen printing has been commonly used as a printing method for printing conductive paste on dielectric green sheets. Therefore, it is required to print a finer electrode pattern with high productivity.
  • gravure is a continuous printing method in which the conductive paste is filled into the depressions provided in the plate making, and the conductive paste is transferred from the plate by pressing it against the surface to be printed.
  • a printing method has been proposed.
  • the gravure printing method has a high printing speed and excellent productivity.
  • a conductive paste used for forming the internal conductor film in a laminated ceramic electronic component comprising a plurality of ceramic layers and an internal conductor film extending along a specific interface between the ceramic layers by gravure printing 30 to 70% by weight of a solid component containing metal powder, 1 to 10% by weight of an ethyl cellulose resin component having an ethoxy group content of 49.6% or more, and 0.05 to 5% by weight of a dispersant and a solvent component as the remainder, the viscosity ⁇ 0.1 at a shear rate of 0.1 (s -1 ) is 1 Pa s or more, and the viscosity at a shear rate of 0.02 (s -1 ) Conductive pastes are described which are thixotropic fluids with ⁇ 0.02 satisfying a specific formula.
  • Patent Document 2 a conductive paste used for forming by gravure printing in the same manner as in Patent Document 1, 30 to 70% by weight solid component containing metal powder, 1 to 10% by weight A thixotropic fluid containing a resin component, 0.05 to 5% by weight of a dispersant, and the balance of a solvent component, and having a viscosity of 1 Pa s or more at a shear rate of 0.1 (s -1 ), It describes a conductive paste having a viscosity change rate of 50% or more at a shear rate of 10 (s -1 ) based on the viscosity at a shear rate of 0.1 (s -1 ).
  • these conductive pastes are thixotropic fluids having a viscosity of 1 Pa s or more at a shear rate of 0.1 (s -1 ), and are stable at high speed in gravure printing. It is said that continuous printability can be obtained, and multilayer ceramic electronic components such as multilayer ceramic capacitors can be manufactured with good production efficiency.
  • Patent Document 3 discloses a conductive powder for internal electrodes of a multilayer ceramic capacitor containing conductive powder (A), organic resin (B), organic solvent (C), additive (D), and dielectric powder (E).
  • organic resin (B) is polyvinyl butyral with a degree of polymerization of 10000 or more and 50000 or less, and ethyl cellulose with a weight average molecular weight of 10000 or more and 100000 or less
  • the organic solvent (C) is propylene glycol monobutyl ether, Alternatively, it consists of either a mixed solvent of propylene glycol monobutyl ether and propylene glycol methyl ether acetate, or a mixed solvent of propylene glycol monobutyl ether and mineral spirits
  • the additive (D) is a gravure printing agent consisting of a separation inhibitor and a dispersant.
  • a conductive paste is described. According to Patent Document 3, this conductive paste has a viscosity suitable for gravure printing and is said to have good
  • a conductive paste for gravure printing is required to have a low viscosity.
  • a ceramic powder such as barium titanate and a conductive powder such as Ni are added, these powders.
  • the sedimentation velocity difference due to the difference in specific gravity has a more pronounced effect, and the conductive powder and the ceramic powder are easily separated.
  • a phenomenon called "whitening" may occur in which a white separation layer containing ceramic powder is generated at the top when the conductive paste is produced.
  • the conductive paste for gravure printing has a lower viscosity than the conductive paste for screen printing, etc.
  • the ratio of the viscosity after long-term storage to the viscosity immediately after production is It was found that the calculated thickening ratio over time tends to be high.
  • the appropriate viscosity range for gravure printing is narrower, and accurate viscosity control is required for the paste to be applied. There is a problem that the printing process is complicated.
  • the present invention provides a conductive paste that has a low paste viscosity suitable for gravure printing stably over a long period of time and can suppress separation between the conductive powder and the ceramic powder. intended to provide
  • a conductive paste for gravure printing containing a conductive powder, a ceramic powder, a dispersant, a binder resin and an organic solvent, wherein the dispersant is a carboxylic acid having a weight average molecular weight of 5000 or more
  • the dispersant is a carboxylic acid having a weight average molecular weight of 5000 or more
  • a conductive paste for gravure printing containing a polymer dispersant and a carboxylic acid polymer dispersant in an amount of 0.01% by mass or more and less than 2.0% by mass with respect to the entire conductive paste.
  • the acid value of the carboxylic acid polymer dispersant is preferably 50 mgKOH/g or more and 250 mgKOH/g or less.
  • the carboxylic acid-based polymer dispersant preferably contains a polymer-based dispersant having a comb structure and/or a block polymer structure. Further, it is preferable that the polymeric dispersant having a comb structure has a graft chain containing an alkylene oxide polymer.
  • the organic solvent is dihydroterpineol (DHT), dihydroterpinyl acetate (DHTA), terpineol (TPO), propylene glycol monobutyl ether (PNB), diethylene glycol monobutyl ether acetate (BCA), and the group consisting of diisobutyl ketone (DIBK) It is preferable to include one or more selected types.
  • the content of the carboxylic acid polymer dispersant may be 60% by mass or more with respect to the total amount of the dispersant.
  • the dispersant may contain a carboxylic acid-based dispersant having a molecular weight of less than 5,000 in an amount of 0% by mass or more and 60% by mass or less based on the total amount of the dispersant.
  • the conductive powder preferably contains one or more metal powders selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof. Also, the conductive powder preferably has an average particle size of 0.05 ⁇ m or more and 1.0 ⁇ m or less. Also, the ceramic powder preferably contains barium titanate. Also, the ceramic powder preferably has an average particle size of 0.01 ⁇ m or more and 0.5 ⁇ m or less. Moreover, it is preferable that the ceramic powder is contained in an amount of 1% by mass or more and 20% by mass or less with respect to the entire conductive paste. Moreover, it is preferable that the binder resin contains a cellulose-based resin.
  • the conductive paste for gravure printing is preferably for internal electrodes of laminated ceramic parts. Further, the conductive paste for gravure printing preferably has a viscosity of 1.2 Pa ⁇ S or less at a shear rate of 100 sec ⁇ 1 .
  • a second aspect of the present invention provides an electronic component formed using the above conductive paste for gravure printing.
  • a laminated ceramic capacitor having at least a laminated body in which a dielectric layer and an internal electrode layer are laminated, wherein the internal electrode layer is a laminated ceramic capacitor formed using the above conductive paste for gravure printing provided.
  • the conductive paste of the present invention has viscosity characteristics suitable for gravure printing, and can suppress separation between the conductive powder and the ceramic powder even in a low-viscosity paste.
  • the conductive paste of the present invention has good viscosity stability over a long period of time, so viscosity adjustment during printing becomes unnecessary, contributing to simplification of the printing process.
  • FIG. 1A and 1B are a perspective view (FIG. 1A) and a cross-sectional view (FIG. 1B) showing a laminated ceramic capacitor according to an embodiment.
  • the conductive paste of this embodiment contains conductive powder, ceramic powder, dispersant, binder resin and organic solvent. Each component will be described in detail below.
  • the conductive powder is not particularly limited, and metal powder can be used.
  • one or more powders selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof can be used.
  • powder of Ni or its alloy Ni alloy
  • Ni alloy Ni alloy
  • the Ni alloy for example, an alloy of Ni and at least one element selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt and Pd can be used. can.
  • the content of Ni in the Ni alloy is, for example, 50% by mass or more, preferably 80% by mass or more.
  • the Ni powder may contain about several hundred ppm of the element S in order to suppress sudden gas generation due to partial thermal decomposition of the binder resin during the binder removal treatment.
  • the average particle size of the conductive powder is preferably 0.05 ⁇ m or more and 1.0 ⁇ m or less, more preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less.
  • the average particle size is a value obtained from observation with a scanning electron microscope (SEM), and is obtained by measuring the particle size of each of a plurality of particles from an image observed with a SEM at a magnification of 10,000. is the average value (SEM average particle size) obtained.
  • the content of the conductive powder is preferably 30% by mass or more and less than 70% by mass, more preferably 40% by mass or more and 60% by mass or less with respect to the entire conductive paste.
  • the conductivity and dispersibility are excellent.
  • the ceramic powder is not particularly limited, and for example, in the case of a paste for internal electrodes of a laminated ceramic capacitor, a known ceramic powder is appropriately selected depending on the type of laminated ceramic capacitor to be applied.
  • a perovskite-type oxide containing Ba and Ti can be used, preferably containing barium titanate (BaTiO 3 ).
  • a ceramic powder containing barium titanate as a main component and an oxide as an auxiliary component may be used.
  • the oxides include one or more oxides selected from Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb and rare earth elements.
  • a ceramic powder for example, there is a perovskite-type oxide ferroelectric ceramic powder in which Ba atoms or Ti atoms of barium titanate (BaTiO 3 ) are replaced with other atoms such as Sn, Pb, Zr, or the like. mentioned.
  • the ceramic powder used in the conductive paste for the internal electrodes may have the same composition as the dielectric ceramic powder forming the green sheets of the multilayer ceramic capacitor (electronic component). As a result, the occurrence of cracks due to shrinkage mismatch at the interfaces between the dielectric layers and the internal electrode layers in the sintering process is suppressed.
  • ceramic powder include ZnO, ferrite, PZT, BaO, Al 2 O 3 , Bi 2 O 3 , R (rare earth element) 2 O 3 , in addition to the perovskite oxide containing Ba and Ti. Oxides such as TiO 2 and Nd 2 O 3 can be mentioned.
  • One type of ceramic powder may be used, or two or more types may be used.
  • the average particle size of the ceramic powder is, for example, 0.01 ⁇ m or more and 0.5 ⁇ m or less, preferably 0.01 ⁇ m or more and 0.3 ⁇ m or less. Since the average particle size of the ceramic powder is within the above range, when it is used as an internal electrode paste, sufficiently fine and thin uniform internal electrodes can be formed.
  • the average particle size is a value obtained from observation with a scanning electron microscope (SEM), and is obtained by measuring the particle size of each of a plurality of particles from an image observed with a SEM at a magnification of 50,000. is the average value (SEM average particle size) obtained.
  • the content of the ceramic powder is preferably 1% by mass or more and 20% by mass or less, more preferably 3% by mass or more and 15% by mass or less, relative to the entire conductive paste. When the content of the ceramic powder is within the above range, excellent dispersibility and sinterability are obtained.
  • the content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the conductive powder.
  • binder resin is not particularly limited, and known resins can be used.
  • binder resins include cellulose resins such as methyl cellulose, ethyl cellulose, ethylhydroxyethyl cellulose, and nitrocellulose, acrylic resins, and acetal resins including butyral resins such as polyvinyl butyral.
  • cellulose resins such as methyl cellulose, ethyl cellulose, ethylhydroxyethyl cellulose, and nitrocellulose
  • acrylic resins and acetal resins including butyral resins such as polyvinyl butyral.
  • it preferably contains a cellulose-based resin, and more preferably contains ethyl cellulose.
  • When used as an internal electrode paste it may contain an acetal resin or may be used alone from the viewpoint of improving the adhesive strength with the green sheet.
  • the binder resin may contain, for example, both a cellulose-based resin and an acetal-based resin.
  • the binder resin may contain, for example, 20% by mass or more, or 30% by mass or more of the acetal-based resin with respect to the entire binder resin.
  • the binder resin may contain 50% by mass or less of the acetal-based resin with respect to the entire binder resin.
  • the degree of polymerization and weight average molecular weight of the binder resin can be appropriately adjusted within the above ranges according to the required viscosity of the conductive paste.
  • the content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 7% by mass or less, relative to the entire conductive paste.
  • the conductivity and dispersibility are excellent.
  • the content of the binder resin is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 14 parts by mass or less with respect to 100 parts by mass of the conductive powder.
  • Organic solvent is not particularly limited, and any known organic solvent capable of dissolving the binder resin can be used.
  • organic solvents include terpene-based solvents, glycol ether-based solvents, acetate-based solvents, acetic ester-based solvents, ketone-based solvents, and hydrocarbon solvents.
  • One type of organic solvent may be used, or two or more types may be used.
  • Terpene-based solvents include terpineol (TPO), dihydroterpineol (DHT), dihydroterpinyl acetate (DHTA), etc. Among them, dihydroterpineol (DHT) is preferred.
  • glycol ether solvents examples include (di)ethylene glycol ethers such as diethylene glycol mono-2-ethylhexyl ether, ethylene glycol mono-2-ethylhexyl ether, diethylene glycol monohexyl ether, ethylene glycol monohexyl ether, and propylene glycol.
  • propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether (PNB); Among them, propylene glycol monoalkyl ethers are preferred, and propylene glycol monobutyl ether (PNB) is more preferred.
  • the organic solvent contains a glycol ether-based solvent, it has excellent compatibility with the above-mentioned binder resin and excellent drying properties.
  • Acetate solvents include, for example, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether acetate (butyl carbitol acetate: BCA), dipropylene glycol methyl ether acetate, 3-methoxy-3-methylbutyl acetate, 1-methoxypropyl-2- Glycol ether acetates such as acetate, and isobornyl acetate, isobornyl propinate, isobornyl butyrate, isobornyl isobutyrate and the like.
  • acetate solvent examples include ethyl acetate, propyl acetate, isobutyl acetate, and butyl acetate.
  • ketone-based solvents examples include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone (DIBK), and the like.
  • hydrocarbon solvents examples include aliphatic hydrocarbon solvents such as tridecane, nonane, cyclohexane, naphthenic solvents and mineral spirits (MA), and aromatic hydrocarbon solvents such as toluene and xylene.
  • Group hydrocarbon solvents are preferred, and mineral spirits (MA) are more preferred.
  • the mineral spirit (MA) may contain a chain saturated hydrocarbon as a main component, and may contain 20% by mass or more of the saturated chain hydrocarbon with respect to the entire mineral spirit.
  • the organic solvent consists of dihydroterpineol (DHT), dihydroterpinyl acetate (DHTA), terpineol (TPO), propylene glycol monobutyl ether (PNB), diethylene glycol monobutyl ether acetate (BCA), and diisobutyl ketone (DIBK). It is preferable to include one or more selected from the group. By using these solvents, it is possible to achieve both an appropriate viscosity and a drying speed.
  • DHT dihydroterpineol
  • DHTA dihydroterpinyl acetate
  • TPO terpineol
  • PPB propylene glycol monobutyl ether
  • BCA diethylene glycol monobutyl ether acetate
  • DIBK diisobutyl ketone
  • the organic solvent includes one or more terpene solvents (a) selected from the group consisting of dihydroterpineol (DHT), dihydroterpinyl acetate (DHTA), and terpineol (TPO), and propylene glycol monobutyl ether (PNB). , diethylene glycol monobutyl ether acetate (BCA), and a hydrocarbon solvent.
  • a terpene solvents
  • the organic solvent includes one or more terpene-based solvents (a) selected from the group consisting of dihydroterpineol (DHT), dihydroterpinyl acetate (DHTA), and terpineol (TPO), and propylene glycol monobutyl ether ( PNB), one or more solvents (b) selected from the group consisting of diethylene glycol monobutyl ether acetate (BCA), a hydrocarbon solvent, and diisobutyl ketone (DIBK).
  • DHT dihydroterpineol
  • DHTA dihydroterpinyl acetate
  • TPO terpineol
  • PNB propylene glycol monobutyl ether
  • solvents b
  • DIBK diisobutyl ketone
  • the content of the organic solvent is preferably 20% by mass or more and 50% by mass or less, more preferably 25% by mass or more and 45% by mass or less, relative to the total amount of the conductive paste.
  • the content of the organic solvent is within the above range, the electroconductivity and dispersibility are excellent.
  • the content of the organic solvent is preferably 50 parts by mass or more and 130 parts by mass or less, more preferably 60 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the conductive powder.
  • the content of the organic solvent is within the above range, the electroconductivity and dispersibility are excellent.
  • the terpene-based solvent may be 5% by mass or more and 40% by mass or less, or 10% by mass or more and 30% by mass or less with respect to the total amount of the conductive paste. 12% by mass or more and 25% by mass or less.
  • the conductive paste contains a solvent (b) such as propylene glycol monobutyl ether (PNB), the content of the solvent (b) may be 3% by mass or 20% by mass or less with respect to the total amount of the conductive paste. , 5% by mass or more and 20% by mass or less.
  • a solvent (b) such as propylene glycol monobutyl ether (PNB)
  • the content of the solvent (b) may be 3% by mass or 20% by mass or less with respect to the total amount of the conductive paste. , 5% by mass or more and 20% by mass or less.
  • the hydrocarbon solvent may be 1% by mass or more and 20% by mass or less, or 3% by mass or more and 15% by mass or less with respect to the total amount of the conductive paste. It may be 5% by mass or more and 10% by mass or less.
  • the content of diisobutyl ketone (DIBK) is preferably 1% by mass or more and 20% by mass or less, and 3% by mass or more and 15% by mass. % by mass or less, or 3% by mass or more and 10% by mass or less.
  • the conductive paste according to this embodiment contains a carboxylic acid polymer dispersant having a molecular weight of 5000 or more.
  • the present inventor stably has a viscosity suitable for gravure printing by including a specific amount of a carboxylic acid polymer dispersant having a molecular weight of 5000 or more in a conductive paste for gravure printing, and It has been found that the separation between the conductive powder and the ceramic powder can be suppressed.
  • a carboxylic acid-based polymer dispersant is a polymer-based dispersant (surfactant) having a carboxylic acid group as an adsorption group.
  • the carboxylic acid-based polymeric dispersant may be, for example, a polymer (copolymer) produced by polymerizing two or more types of monomers including a carboxylic acid-containing monomer and a hydrophobic monomer. Moreover, this polymer may be synthesized by methods such as random polymerization, block polymerization, and graft polymerization.
  • carboxylic acid-based polymer dispersants include random polymers in which carboxylic acid-containing monomers and hydrophobic monomers are randomly arranged, and block polymers in which carboxylic acid group-containing monomers and hydrophobic monomers are arranged in blocks.
  • Examples include polymer-based dispersants having a structure, a comb-like structure, and the like.
  • a polymeric dispersant having a comb-shaped structure is obtained, for example, by polymerizing a carboxylic acid-containing monomer, a macromonomer, a hydrophobic monomer, or the like, and may have a graft chain.
  • the carboxylic acid polymer dispersant preferably contains a carboxylic acid polymer dispersant having a comb structure and/or a block polymer structure, and more preferably contains a carboxylic acid polymer dispersant having a comb structure.
  • the polymeric dispersant having a comb structure preferably has a graft chain, and the graft chain preferably contains an alkylene oxide polymer. Examples of the alkylene oxide polymer contained in the graft chain include ethylene oxide polymer, propylene oxide polymer, butylene oxide polymer, etc., and may include ethylene oxide polymer.
  • the average molecular weight of the carboxylic acid-based polymer dispersant is 5,000 or more, may be 10,000 or more, may be 20,000 or more, or may be 40,000 or more.
  • the average molecular weight of the carboxylic acid polymer dispersant affects the initial viscosity of the paste and the increase in viscosity over time. When the average molecular weight is 5000 or more, a stable dispersing effect can be exhibited, and thickening over time can be sufficiently suppressed.
  • the upper limit of the average molecular weight is not particularly limited from the viewpoint of suppressing thickening over time, if the average molecular weight is too large, the initial viscosity of the paste itself increases and may not be suitable for gravure printing. It may be 10,000 or less.
  • the average molecular weight is weight average molecular weight, and can be measured by GPC (gel permeation chromatography), for example.
  • the acid value of the carboxylic acid polymer dispersant is preferably 50 mgKOH/g or more and 250 mgKOH/g or less, and may be 50 mgKOH/g or more and 200 mgKOH/g or less. By setting the acid value within this range, a sufficient dispersing effect can be obtained.
  • the acid value (mgKOH/g) can be determined, for example, by potentiometric titration according to JIS K0070.
  • the carboxylic acid-based polymer dispersant is contained in an amount of 0.01% by mass or more and less than 2.0% by mass, preferably 0.01% by mass or more and 1.0% by mass or less, and more The content is preferably 0.03% by mass or more and 0.5% by mass or less.
  • a viscosity suitable for gravure printing can be stably maintained for a long period of time, and separation between the conductive powder and the ceramic powder can be suppressed.
  • the dispersant may consist only of a carboxylic acid-based polymer dispersant, but may also contain a dispersant other than a carboxylic acid-based polymer dispersant, as described later.
  • a dispersant other than a carboxylic acid-based polymer dispersant is included, the content of the carboxylic acid-based polymer dispersant may be, for example, 40% by mass or more, preferably 60% by mass, based on the total amount of the dispersant. or more, more preferably 80% by mass or more. As the content of the carboxylic acid-based polymer dispersant relative to the total amount of the dispersant increases, the effect of suppressing separation between the conductive powder and the ceramic powder is improved.
  • the conductive paste of the present embodiment may further contain an acid-based dispersant (a dispersant having an acidic adsorptive group) other than the carboxylic acid-based polymer dispersant.
  • an acid-based dispersant a dispersant having an acidic adsorptive group
  • the acid-based dispersant include carboxylic acid-based dispersants having an average molecular weight of less than 5,000, phosphoric acid-based dispersants, and other acidic polymer surfactants. mentioned. These acid dispersants may be used singly or in combination of two or more.
  • carboxylic acid-based dispersants having an average molecular weight of less than 5,000 include higher fatty acids, dicarboxylic acids, polycarboxylic acid-based dispersants, and alkylmonoamine salt-type carboxylic acid-based dispersants.
  • the conductive paste contains a carboxylic acid-based dispersant having an average molecular weight of less than 5000 together with the carboxylic acid-based polymer dispersant, the dispersibility of ceramic powder such as barium titanate may be further improved.
  • the average molecular weight of the carboxylic acid-based dispersant having an average molecular weight of less than 5,000 may be 2,000 or less, or may be 1,000 or less.
  • the higher fatty acid may be either an unsaturated carboxylic acid or a saturated carboxylic acid, and is not particularly limited, and includes stearic acid, oleic acid, myristic acid, palmitic acid, linoleic acid, lauric acid, linolenic acid, etc., having 11 or more carbon atoms. are listed. Among them, oleic acid or stearic acid is preferable as the higher fatty acid.
  • alkyl monoamine salt types include oleoyl sarcosine, which is a compound of glycine and oleic acid, and stearic acid amide and lauryloyl, which are amide compounds using higher fatty acids such as stearic acid or lauric acid instead of oleic acid. Sarcosine is preferred.
  • the content of the carboxylic acid-based dispersant having an average molecular weight of less than 5,000 is too large, there is a concern that it may have an adverse effect such as inhibiting the adsorption of the carboxylic acid-based polymer dispersant to the metal powder material (filler). Therefore, when used in combination, it is preferable to appropriately adjust the content.
  • the content of the carboxylic dispersant having an average molecular weight of less than 5000 may be 60% by mass or less, preferably 40% by mass or less, more preferably 20% by mass, relative to the total amount of the dispersant. It is below.
  • the lower limit of the content of the carboxylic acid-based dispersant having an average molecular weight of less than 5,000 is 0% by mass.
  • the dispersant may or may not contain a dispersant other than an acid-based dispersant.
  • Dispersants other than acid dispersants include basic dispersants, nonionic dispersants, and amphoteric dispersants. These dispersants may be used singly or in combination of two or more.
  • Examples of basic dispersants include aliphatic amines such as laurylamine, rosinamine, cetylamine, myristylamine, stearylamine, and oleylamine.
  • the content of the basic dispersant may be, for example, 10% by mass or less or 5% by mass or less relative to the total amount of the dispersant.
  • the content of the dispersant (total) is preferably less than 3.0% by mass with respect to the entire conductive paste. Also, the content of the dispersant (total) may be 2% by mass or less, or may be 1.5% by mass or less with respect to the entire conductive paste. If the content of the carboxylic acid-based polymer dispersant or the total dispersant is too large, drying becomes insufficient in the printing and drying processes, and the internal electrode layers become soft. Misalignment may occur. In addition, the dispersing agent remaining during firing may be vaporized, and the vaporized gas component may generate internal stress or cause structural destruction of the laminate.
  • the conductive paste of the present embodiment may contain additives other than the above dispersant, if necessary.
  • additives conventionally known additives such as antifoaming agents, plasticizers and thickeners can be used.
  • Patent Document 3 describes a polycarboxylic acid polymer and a salt of a polycarboxylic acid as a separation suppressing agent for suppressing the separation of the conductive powder and the dielectric powder.
  • Separation inhibitors are also broadly included in acid-based dispersants as those that improve the dispersibility of inorganic powder.
  • the method for producing the conductive paste according to this embodiment is not particularly limited, and conventionally known methods can be used.
  • the conductive paste can be produced, for example, by stirring and kneading the above components with a three-roll mill, ball mill, mixer, or the like.
  • the dicarboxylic acid (separation inhibitor) is preferably added after being weighed when stirring and kneading with a mixer or the like, but after stirring and kneading (dispersion) A similar effect can be obtained even if it is added as a separation inhibitor to the material of (1).
  • the conductive paste preferably has a viscosity of 1.2 Pa ⁇ S or less at a shear rate of 100 sec ⁇ 1 .
  • the viscosity at a shear rate of 100 sec ⁇ 1 is within the above range, it can be suitably used as a conductive paste for gravure printing.
  • the viscosity is too high and may not be suitable for gravure printing.
  • the lower limit of the viscosity at a shear rate of 100 sec ⁇ 1 is not particularly limited, it is, for example, 0.2 Pa ⁇ S or more.
  • the thickness of the white layer observed one week after immediately after preparation is preferably less than 8%, and not more than 5%, of the entire thickness of the conductive paste. may be 2% or less.
  • the smaller the thickness of the white layer the more excellent the effect of suppressing separation between the conductive powder and the ceramic powder.
  • the thickness of the whitening layer can be measured by the method described in Examples described later.
  • the conductive paste of the present embodiment can be suitably used for electronic components such as multilayer ceramic capacitors.
  • a multilayer ceramic capacitor has dielectric layers and internal electrode layers formed using dielectric green sheets, and the conductive paste of the present embodiment can be suitably used for forming the internal electrode layers.
  • FIGS. 1A and 1B An example of an electronic component etc. according to the present embodiment will be described below with reference to the drawings. In the drawings, they may be represented schematically or may be represented by changing the scale as appropriate. Also, the positions and directions of the members will be described with reference to the XYZ orthogonal coordinate system shown in FIGS. 1A and 1B. In this XYZ orthogonal coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is the vertical direction (vertical direction).
  • FIGS. 1A and 1B are diagrams showing a laminated ceramic capacitor 1, which is an example of an electronic component.
  • a laminated ceramic capacitor 1 includes a laminate 10 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated, and external electrodes 20 .
  • a conductive paste is gravure-printed on a ceramic green sheet (dielectric green sheet) and dried to form a dry film.
  • a plurality of ceramic green sheets having this dried film on the upper surface are laminated by pressure bonding to obtain a laminated body, and then the laminated body is fired and integrated, so that the internal electrode layers 11 and the dielectric layers 12 are alternately formed.
  • a ceramic laminate 10 is produced by laminating . After that, a pair of external electrodes 20 are formed on both ends of the ceramic laminate 10 to manufacture the laminated ceramic capacitor 1 .
  • a ceramic green sheet which is an unfired ceramic sheet.
  • a dielectric layer paste obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate is used as a PET film or the like.
  • examples include those obtained by coating a support film in the form of a sheet and drying to remove the solvent.
  • the thickness of the ceramic green sheet is not particularly limited, it is preferably 0.05 ⁇ m or more and 3 ⁇ m or less from the viewpoint of the demand for miniaturization of laminated ceramic capacitors.
  • the above-described conductive paste is applied by printing using a gravure printing method, and dried to form a dry film, and a plurality of sheets are prepared.
  • the thickness of the dried film is preferably 1 ⁇ m or less after drying.
  • the ceramic green sheets are peeled off from the support film, and after laminating so that the ceramic green sheets and the dry film formed on one side thereof are alternately arranged, a laminate is obtained by heat and pressure treatment. It should be noted that a configuration may be adopted in which protective ceramic green sheets to which the conductive paste is not applied are further arranged on both sides of the laminate.
  • the green chip is subjected to binder removal treatment and fired in a reducing atmosphere to obtain a laminated ceramic fired body (ceramic laminate 10).
  • the atmosphere in the binder removal treatment is preferably air or N2 gas atmosphere.
  • the temperature at which the binder removal treatment is performed is, for example, 200° C. or higher and 400° C. or lower. In addition, it is preferable that the temperature is maintained for 0.5 hours or more and 24 hours or less when the binder removal treatment is performed.
  • the firing is performed in a reducing atmosphere in order to suppress oxidation of the metal used for the internal electrode layers, and the temperature at which the laminate is fired is, for example, 1000° C. or higher and 1350° C. or lower.
  • the time for which the temperature is maintained is, for example, 0.5 hours or more and 8 hours or less.
  • the organic binder in the green sheet is completely removed, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12 .
  • the organic vehicle in the dry film is removed, and the conductive powder is sintered or melted and integrated to form the internal electrode layer 11, and the dielectric layer 12 and the internal electrode layer 11 are formed into a plurality of sheets, A laminated ceramic sintered body that is alternately laminated is formed. From the viewpoint of taking oxygen into the dielectric layers to improve reliability and suppressing reoxidation of the internal electrodes, the laminated ceramic sintered body after sintering may be annealed.
  • the multilayer ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 to the manufactured multilayer ceramic sintered body.
  • the external electrode 20 comprises an external electrode layer 21 and a plated layer 22 .
  • the external electrode layers 21 are electrically connected to the internal electrode layers 11 .
  • the material of the external electrodes 20 for example, copper, nickel, or alloys thereof can be suitably used.
  • electronic components other than the laminated ceramic capacitor can be used as the electronic component.
  • the viscosity of the conductive paste is measured at 1 day and 1 week after production, the measured value at 1 day is defined as the initial viscosity, and the ratio of the measured value at 1 week to the initial viscosity (1 week at Measured value/measured value at 1 day) was evaluated as the thickening ratio over time.
  • An initial viscosity of 0.2 Pa ⁇ s or more and less than 1.2 Pa ⁇ s was evaluated as " ⁇ ", and a value of 1.2 Pa ⁇ s or more was evaluated as "x”.
  • a viscosity increase ratio over time of less than 1.3 was evaluated as "good” (sufficient viscosity stability), and a time-dependent thickening ratio of 1.3 or more was evaluated as “poor” (insufficient viscosity stability).
  • the ratio (%) of whitening is calculated by (thickness of layer of whitening/thickness of entire amount of paste)*100.
  • the whitening ratio (%) is less than 5% with " ⁇ " (separation suppression effect is good), 5% or more and less than 8% with " ⁇ " (separation suppression effect), 8% or more with "X" ( Insufficient separation suppression effect).
  • Ceramic powder Barium titanate (BaTiO 3 ; SEM average particle size 0.10 ⁇ m) was used as the ceramic powder.
  • binder resin Polyvinyl butyral and ethyl cellulose were used as the binder resin.
  • Carboxylic acid polymer dispersants 1 to 4 Carboxylic acid polymer dispersants 1 to 4, carboxylic acid low molecular dispersants 1 to 2, and amine polymer dispersant 1 having a molecular weight of 5000 or more were used. Details of each dispersant are summarized in Table 1.
  • the carboxylic acid polymer dispersant 4 has a linear block polymer structure (does not have a comb structure).
  • Organic solvents include propylene glycol monobutyl ether (PNB), butyl carbitol (BCA), mineral spirits (MA), terpineol (TPO), dihydroterpineol (DHT), dihydroterpinyl acetate (DHTA), and diisobutyl ketone. (DIBK) was used.
  • PNB propylene glycol monobutyl ether
  • BCA butyl carbitol
  • MA mineral spirits
  • TPO terpineol
  • DHT dihydroterpineol
  • DHTA dihydroterpinyl acetate
  • DIBK diisobutyl ketone
  • Example 1 50% by mass of conductive powder, 12.5% by mass of ceramic powder, 0.05% by mass of dispersant (dispersant type: carboxylic acid polymer dispersant 1), 2.5% by mass of binder resin (polyvinyl butyral resin 1. 7% by mass, ethyl cellulose 0.8% by mass), and an organic solvent as the balance (solvent 1: balance, solvent 2: 9.5% by mass, solvent 3: 7% by mass) to give a total of 100% by mass.
  • a material blended so as to be was prepared.
  • a conductive paste was prepared by mixing and dispersing these materials.
  • solvent 1 is DHT
  • solvent 2 is PNB
  • solvent 3 is MA. Table 1 shows test conditions and evaluation results including details of additives.
  • Examples 2 to 10 Comparative Examples 1 to 3
  • a conductive paste was prepared and evaluated in the same manner as in Example 1, except that the type and amount of dispersant added and the solvents 1 to 3 were changed as shown in Tables 1 and 2.
  • the mixing ratio of the dispersant was adjusted by adjusting the amount of solvent 1 added so that the total amount of the conductive paste was 100% by mass. Details of the dispersant are shown in Table 1, and test conditions and evaluation results are shown in Table 2.
  • Example 11 The composition of the organic solvent was changed to contain four types, and the content of each was set to (solvent 1: balance, solvent 2: 5.3% by mass, solvent 3: 7% by mass, solvent 4: 4.2% by mass). .
  • a conductive paste was prepared and evaluated in the same manner as in Example 2 except that DHT was used as solvent 1, BCA was used as solvent 2, MSA was used as solvent 3, and DIBK was used as solvent 4. Details of the dispersant are shown in Table 1, and test conditions and evaluation results are shown in Table 2.
  • a carboxylic acid-based dispersant with a comb-shaped structure is used.
  • As a conductive paste an unacceptable increase in viscosity has occurred.
  • a low-molecular-weight carboxylic acid-based dispersant is used, and although the viscosity is sufficiently stable, the percentage of whitening exceeds the allowable amount.
  • the conductive paste of Comparative Example 3 uses a polymeric dispersant having a comb-shaped structure, but since the adsorption group is amine, the initial viscosity is high and it is not suitable for gravure printing.
  • Example 2 is a sample in which the content of the comb-shaped carboxylic acid-based polymer dispersant 1 used in Example 1 was increased, and better results were obtained in the initial viscosity, the ratio of thickening over time, and the amount of whitening. ing.
  • Examples 3 and 4 are samples using a comb-shaped carboxylic acid (Mw: 10,000 to 30,000) having a smaller average molecular weight than the comb-shaped carboxylic acid (Mw: 50,000) used in Example 2.
  • Mw 10,000 to 30,000
  • Mw comb-shaped carboxylic acid
  • the conductive pastes of Examples 3 and 4 have a slightly increased amount of whitening, and the conductive paste of Example 4 has a higher viscosity increase ratio over time.
  • the conductive paste of Example 5 uses a block polymerization type carboxylic acid-based polymer dispersant, and is added in a larger amount than other examples using a carboxylic acid-based polymer dispersant having a comb-shaped structure. By doing so, the same degree of effect as in other embodiments can be exhibited.
  • the conductive pastes of Examples 6 and 7 are a combination of a carboxylic acid-based comb-type polymer dispersant and a low-molecular-weight carboxylic acid-based dispersant.
  • the conductive pastes of Examples 6 and 7 have a similarly low thickening ratio over time as compared with the conductive paste of Example 2, which uses the same comb-shaped carboxylic acid-based polymer dispersant. The amount of whitening increases slightly.
  • the conductive pastes of Examples 6 and 7 are other examples using a dispersant having a smaller average molecular weight than the comb-shaped carboxylic acid polymer dispersant of Example 2 (Example: Example 4 , 5), the thickening ratio over time is low, but the amount of whitening tends to increase within the allowable range.
  • the conductive pastes of Examples 8, 9, 10 and 11 are samples obtained by changing the type of solvent in the conductive paste of Example 2. Even if the content of the solvent is the same, the viscosity, the time-dependent thickening ratio, and the amount of whitening change slightly by changing the combination of the types of solvents, but they do not change significantly. Therefore, it is possible to finely adjust the viscosity by selecting the type of solvent according to the usage conditions.
  • the conductive paste of the present invention stably has a viscosity suitable for gravure printing over a long period of time, and can sufficiently suppress separation between the conductive powder and the ceramic powder. Therefore, the conductive paste of the present invention can be suitably used as a raw material for internal electrodes of laminated ceramic capacitors, which are chip components of electronic devices such as mobile phones and digital devices, which are becoming increasingly compact. Moreover, the conductive paste of the present invention can be suitably used as a conductive paste for gravure printing.

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  • Chemical & Material Sciences (AREA)
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  • Microelectronics & Electronic Packaging (AREA)
  • Ceramic Engineering (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

La présente invention concerne une pâte conductrice pour héliogravure, la pâte conductrice pouvant être supprimée lors de la séparation entre une poudre conductrice et une poudre céramique, ayant ainsi une bonne stabilité de viscosité dans le temps.　La présente invention concerne une pâte conductrice pour héliogravure, la pâte conductrice contenant une poudre conductrice, une poudre céramique, un dispersant, une résine liante et un solvant organique, le dispersant contenant un dispersant polymère à base d'acide carboxylique qui a un poids moléculaire moyen en poids de 5000 ou plus ; et le dispersant polymère à base d'acide carboxylique est contenu dans une quantité qui n'est pas inférieure à 0,01 % en masse mais inférieure à 2,0 % en masse par rapport à la quantité totale de la pâte conductrice.
PCT/JP2022/033197 2021-09-03 2022-09-02 Pâte conductrice pour héliogravure, composant électronique et condensateur céramique multicouche WO2023033163A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012174797A (ja) * 2011-02-18 2012-09-10 Sumitomo Metal Mining Co Ltd 積層セラミックコンデンサ内部電極に用いられるグラビア印刷用導電性ペースト
WO2019181875A1 (fr) * 2018-03-19 2019-09-26 株式会社ノリタケカンパニーリミテド Pâte conductrice disposant d'une viscosité stable dans le temps
WO2021020557A1 (fr) * 2019-07-31 2021-02-04 住友金属鉱山株式会社 Pâte conductrice pour héliogravure, composant électronique et condensateur céramique stratifié
WO2021059925A1 (fr) * 2019-09-25 2021-04-01 株式会社ノリタケカンパニーリミテド Pâte électroconductrice et procédé de production d'un composant électronique l'utilisant

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JP4389431B2 (ja) 2001-12-13 2009-12-24 株式会社村田製作所 グラビア印刷用導電性ペーストおよびその製造方法、ならびに積層セラミック電子部品
JP2003187638A (ja) 2001-12-20 2003-07-04 Murata Mfg Co Ltd グラビア印刷用導電性ペーストおよびその製造方法、ならびに積層セラミック電子部品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012174797A (ja) * 2011-02-18 2012-09-10 Sumitomo Metal Mining Co Ltd 積層セラミックコンデンサ内部電極に用いられるグラビア印刷用導電性ペースト
WO2019181875A1 (fr) * 2018-03-19 2019-09-26 株式会社ノリタケカンパニーリミテド Pâte conductrice disposant d'une viscosité stable dans le temps
WO2021020557A1 (fr) * 2019-07-31 2021-02-04 住友金属鉱山株式会社 Pâte conductrice pour héliogravure, composant électronique et condensateur céramique stratifié
WO2021059925A1 (fr) * 2019-09-25 2021-04-01 株式会社ノリタケカンパニーリミテド Pâte électroconductrice et procédé de production d'un composant électronique l'utilisant

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