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WO2020067363A1 - Pâte conductrice, composant électronique et condensateur à base de céramique multicouche - Google Patents

Pâte conductrice, composant électronique et condensateur à base de céramique multicouche Download PDF

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Publication number
WO2020067363A1
WO2020067363A1 PCT/JP2019/038006 JP2019038006W WO2020067363A1 WO 2020067363 A1 WO2020067363 A1 WO 2020067363A1 JP 2019038006 W JP2019038006 W JP 2019038006W WO 2020067363 A1 WO2020067363 A1 WO 2020067363A1
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WIPO (PCT)
Prior art keywords
conductive paste
dispersant
mass
powder
conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2019/038006
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English (en)
Japanese (ja)
Inventor
剛 川島
勝彦 高木
祐伺 舘
純平 山田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Metal Mining Co Ltd
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Sumitomo Metal Mining Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sumitomo Metal Mining Co Ltd filed Critical Sumitomo Metal Mining Co Ltd
Priority to KR1020207035841A priority Critical patent/KR102731211B1/ko
Priority to CN201980040128.1A priority patent/CN112334995B/zh
Priority to JP2020549399A priority patent/JP7420076B2/ja
Priority to MYPI2021001664A priority patent/MY208390A/en
Publication of WO2020067363A1 publication Critical patent/WO2020067363A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • H01B1/14—Conductive material dispersed in non-conductive inorganic material
    • H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
    • 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
    • H01G4/012—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors

Definitions

  • the present invention relates to a conductive paste, an electronic component, and a multilayer ceramic capacitor.
  • a multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately stacked, and by reducing the thickness of these dielectric layers and internal electrode layers, miniaturization and high capacitance can be achieved. Can be planned.
  • the multilayer ceramic capacitor is manufactured, for example, as follows. First, on the surface of a dielectric green sheet containing a dielectric powder such as barium titanate (BaTiO 3 ) and a binder resin, a paste for an internal electrode containing a conductive powder, a binder resin, and an organic solvent (conductive The paste) is printed in a predetermined electrode pattern and stacked in multiple layers to obtain a multilayer body in which internal electrodes and dielectric green sheets are stacked in multiple layers. Next, the laminated body is integrated by heating and pressing to form a pressed body. The pressed body is cut, subjected to a deorganizing binder treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip. Next, an external electrode paste is applied to both ends of the fired chip, and after firing, the external electrode surface is plated with nickel or the like to obtain a multilayer ceramic capacitor.
  • a dielectric powder such as barium titanate (BaTiO 3 ) and a binder
  • screen printing has been generally used as a printing method for printing a conductive paste on a dielectric green sheet.
  • gravure is a continuous printing method in which a conductive paste is filled in a concave portion provided in a plate making and the conductive paste is transferred from the plate making by pressing the conductive paste onto a printing surface.
  • Printing methods have been proposed.
  • the gravure printing method has a high printing speed and excellent productivity.
  • it is necessary to appropriately select a binder resin, a dispersant, a solvent, and the like in the conductive paste and adjust characteristics such as viscosity to a range suitable for gravure printing.
  • a conductive paste used for forming the internal conductor film by gravure printing in a multilayer ceramic electronic component including a plurality of ceramic layers and an internal conductor film extending along a specific interface between the ceramic layers 30 to 70% by weight of a solid component containing a metal powder, 1 to 10% by weight of an ethylcellulose 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 a balance, 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 )
  • a conductive paste, which is a thixotropic fluid, in which ⁇ 0.02 satisfies a condition represented by a specific formula, is described.
  • Patent Document 2 discloses a conductive paste used for forming by gravure printing, similar to Patent Document 1, wherein 30 to 70% by weight of a solid component containing a metal powder and 1 to 10% by weight.
  • a thixotropic fluid comprising a resin component, 0.05 to 5% by weight of a dispersant, and a balance of a solvent component, and has a viscosity of 1 Pa ⁇ s or more at a shear rate of 0.1 (s ⁇ 1 ),
  • a conductive paste is described in which the rate of change in viscosity at a shear rate of 10 (s -1 ) is 50% or more 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 described that a multilayer ceramic electronic component such as a multilayer ceramic capacitor can be manufactured with continuous printability and good production efficiency.
  • Patent Document 3 discloses a conductive material for an internal electrode of a multilayer ceramic capacitor including a conductive powder (A), an organic resin (B), an organic solvent (C), an additive (D), and a dielectric powder (E).
  • the organic resin (B) is composed of polyvinyl butyral having a degree of polymerization of 10,000 or more and 50,000 or less and ethyl cellulose having a weight average molecular weight of 10,000 or more and 100,000 or less.
  • the organic solvent (C) is propylene glycol monobutyl ether
  • the additive (D) comprises 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 spirit
  • the additive (D) comprises a separation inhibitor and a dispersant.
  • Polycarboxylic acid polymers as inhibitors Or gravure printing conductive paste made from a composition comprising a salt of a polycarboxylic acid. According to Patent Document 3, the conductive paste has a viscosity suitable for gravure printing, improves the uniformity and stability of the paste, and has good drying properties.
  • the conductive powder also tends to be reduced in particle size.
  • the particle size of the conductive powder is small, the specific surface area of the particle surface increases, so that the surface activity of the conductive powder (metal powder) increases, and the dispersibility of the conductive paste may decrease.
  • a conductive paste having dispersibility There is a demand for a conductive paste having dispersibility.
  • an object of the present invention is to provide a conductive paste having a paste viscosity suitable for gravure printing, and having excellent paste dispersibility and productivity.
  • a conductive paste containing a conductive powder, a ceramic powder, a dispersant, a binder resin and an organic solvent, wherein the dispersant has an average molecular weight of more than 500 and not more than 2000.
  • the acid-based dispersant has at least one branched chain comprising a hydrocarbon group with respect to the main chain
  • the binder resin includes an acetal-based resin
  • the organic solvent includes a glycol ether-based solvent
  • the acid-based dispersant is preferably an acid-based dispersant having a carboxyl group, and more preferably a hydrocarbon-based graft copolymer having a polycarboxylic acid as a main chain. Further, the acid-based dispersant is preferably contained in an amount of 0.4 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the conductive powder. Also, the conductive powder preferably contains at least one metal powder selected from Ni, Pd, Pt, Au, Ag, Cu and alloys thereof. The conductive powder preferably has an average particle size of 0.05 ⁇ m or more and 1.0 ⁇ m or less. Further, the ceramic powder preferably contains a perovskite oxide.
  • the ceramic powder preferably has an average particle size of 0.01 ⁇ m or more and 0.5 ⁇ m or less.
  • the binder resin preferably contains a butyral resin.
  • the conductive paste is for an internal electrode of a multilayer ceramic component.
  • the conductive paste preferably has a viscosity of 0.8 Pa ⁇ S or less at a shear rate of 100 sec ⁇ 1 and a viscosity of 0.18 Pa ⁇ S or less at a shear rate of 10,000 sec ⁇ 1 .
  • an electronic component formed using the conductive paste.
  • a multilayer ceramic capacitor including at least a laminate in which a dielectric layer and an internal electrode are laminated, wherein the internal electrode is formed using the conductive paste.
  • the conductive paste of the present invention has a viscosity suitable for gravure printing, and has excellent dispersibility and productivity of the paste. Further, the electrode pattern of an electronic component such as a multilayer ceramic capacitor formed using the conductive paste of the present invention is excellent in printability of the conductive paste even when a thinned electrode is formed, and has a uniform thickness.
  • FIGS. 1A and 1B are a perspective view and a cross-sectional view illustrating a multilayer ceramic capacitor according to an embodiment.
  • the conductive paste of the present embodiment includes a conductive powder, a dispersant, a binder resin, and an organic solvent.
  • a conductive powder a conductive powder, a dispersant, a binder resin, and an organic solvent.
  • the conductive powder is not particularly limited, and a metal powder can be used.
  • a metal powder can be used.
  • one or more powders selected from Ni, Pd, Pt, Au, Ag, Cu, and an alloy thereof can be used.
  • Ni powder powder of Ni or an alloy thereof (hereinafter, may be referred to as “Ni powder”).
  • Ni powder for example, an alloy of Ni and at least one or more elements selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt, and Pd may be used. it can.
  • the content of Ni in the Ni alloy is, for example, 50% by mass or more, and preferably 80% by mass or more.
  • the Ni powder may contain about several hundred ppm of element S in order to suppress rapid gas generation due to partial thermal decomposition of the binder resin at the time of 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, and more preferably 0.1 ⁇ m or more and 0.5 ⁇ m or less.
  • the conductive powder can be suitably used as a paste for an internal electrode of a multilayer ceramic capacitor (multilayer ceramic component) having a reduced thickness. improves.
  • the average particle diameter is a value obtained by observation with a scanning electron microscope (SEM). The average particle diameter is obtained by measuring the particle diameter of each of a plurality of particles from an image observed with a SEM at a magnification of 10,000 times. Average value (SEM average particle size).
  • 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 based on the total amount of the conductive paste.
  • the conductivity and the dispersibility are excellent.
  • the conductive paste may include a ceramic powder.
  • the ceramic powder is not particularly limited.
  • a known ceramic powder is appropriately selected depending on the type of the multilayer ceramic capacitor to be applied.
  • the ceramic powder include a perovskite oxide containing Ba and Ti, and preferably barium titanate (BaTiO 3 ).
  • a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent may be used.
  • the oxide include oxides of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and one or more rare earth elements.
  • a ceramic powder for example, a perovskite-type oxide ferroelectric ceramic powder in which Ba atom or Ti atom of barium titanate (BaTiO 3 ) is replaced with another atom, for example, Sn, Pb, Zr, or the like.
  • the ceramic powder When used as an internal electrode paste, the ceramic powder may be a powder having the same composition as the dielectric ceramic powder constituting the green sheet of the multilayer ceramic capacitor (electronic component). This suppresses the occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering step.
  • a ceramic powder other than the above include, for example, ZnO, ferrite, PZT, BaO, Al 2 O 3 , Bi 2 O 3 , R (rare earth element) 2 O 3 , TiO 2 , Nd 2 O 3 and the like. Oxides.
  • 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, and preferably 0.01 ⁇ m or more and 0.3 ⁇ m or less.
  • the average particle size is a value obtained from observation with a scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the average particle size is obtained by measuring the particle size of each of a plurality of particles from an image observed at a magnification of 50,000 by SEM. Average value (SEM average particle size).
  • 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.
  • 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 20% by mass or less based on the total amount of the conductive paste.
  • the content of the conductive powder is in the above range, the conductivity and the dispersibility are excellent.
  • the binder resin includes an acetal-based resin.
  • a butyral resin such as polyvinyl butyral is preferable.
  • the binder resin may contain, for example, an acetal-based resin in an amount of 20% by mass or more, 30% by mass or more, or may be composed of only the acetal-based resin based on the entire binder resin. Further, even when the content of the acetal-based resin is less than 40% by mass based on the entire binder resin, it is possible to have a low paste viscosity and a sufficient adhesive strength.
  • the content of the acetal-based resin is preferably 1 part by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less based on 100 parts by mass of the conductive powder.
  • the binder resin may include other resins below the acetal resin.
  • the other resin is not particularly limited, and a known resin can be used.
  • other resins include, for example, cellulose resins such as methyl cellulose, ethyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, acrylic resins, and the like. Resins are preferred, and ethyl cellulose is more preferred.
  • the molecular weight of the binder resin is, for example, about 20,000 to 200,000.
  • the content of the binder resin is preferably from 1 part by mass to 10 parts by mass, more preferably from 1 part by mass to 8 parts by mass, based on 100 parts by mass of the conductive powder.
  • the content of the binder resin is preferably 0.5% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more and 6% by mass or less based on the total amount of the conductive paste.
  • the conductivity and the dispersibility are excellent.
  • the organic solvent includes a glycol ether-based solvent, and may further include an acetate-based solvent.
  • glycol ether solvents 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.
  • examples include propylene glycol monoalkyl ethers such as monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether (PNB).
  • propylene glycol monoalkyl ethers are preferred, and propylene glycol monobutyl ether (PNB) is more preferred.
  • the organic solvent contains a glycol ether-based solvent, the organic solvent is excellent in compatibility with the above-described binder resin and excellent in drying property.
  • the organic solvent may contain, for example, a glycol ether-based solvent in an amount of 25% by mass or more, 50% by mass or more based on the entire organic solvent, or may be composed of only the glycol ether-based solvent.
  • the glycol ether solvents may be used alone or in combination of two or more.
  • acetate-based solvent examples include dihydroterpinyl acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, and ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether.
  • Glycol ether acetates such as acetate, 3-methoxy-3-methylbutyl acetate, 1-methoxypropyl-2-acetate and the like can be mentioned.
  • the organic solvent contains an acetate-based solvent
  • an acetate-based solvent for example, at least one acetate-based solvent selected from dihydroterpinyl acetate, isobornyl acetate, isobornyl propionate, isobornyl butyrate, and isobornyl isobutyrate It may contain a solvent (A). Of these, isobornyl acetate is more preferred.
  • the acetate-based solvent is contained in an amount of 0% by mass or more and 80% by mass or less, preferably 10% by mass or more and 60% by mass or less, more preferably 20% by mass or more and 40% by mass or less based on the whole organic solvent. .
  • the organic solvent contains an acetate solvent
  • the above-mentioned acetate solvent (A) and at least one acetate solvent (B) selected from ethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate May be included.
  • the viscosity of the conductive paste can be easily adjusted, and the drying speed of the conductive paste can be increased.
  • the organic solvent preferably contains the acetate-based solvent (A) in an amount of 50% by mass or more and 90% by mass or less based on the entire amount of the acetate-based solvent. And more preferably 60% by mass or more and 80% by mass or less.
  • the organic solvent preferably contains the acetate solvent (B) in an amount of 10% by mass to 50% by mass, more preferably 20% by mass to 40% by mass, based on 100% by mass of the total amount of the acetate solvent. % Or less.
  • the organic solvent may include an organic solvent other than the glycol ether-based solvent and the acetate-based solvent.
  • the other organic solvent is not particularly limited, and a known organic solvent that can dissolve the binder resin can be used.
  • organic solvents for example, ethyl acetate, propyl acetate, isobutyl acetate, acetate solvents such as butyl acetate, methyl ethyl ketone, ketone solvents such as methyl isobutyl ketone, terpineol, terpene solvents such as dihydroterpineol, tridecane
  • Examples include aliphatic hydrocarbon solvents such as nonane and cyclohexane. Above all, aliphatic hydrocarbon solvents are preferable, and mineral spirits are more preferable among the aliphatic hydrocarbon solvents.
  • one type may be used for another organic solvent, and two or more types may be used.
  • the organic solvent may include, for example, a glycol ether solvent as a main solvent and an aliphatic hydrocarbon solvent as a secondary solvent.
  • the glycol ether solvent is preferably contained in an amount of 30 parts by mass or more and 50 parts by mass or less, more preferably 40 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the conductive powder. Is preferably 20 to 80 parts by mass, more preferably 20 to 40 parts by mass with respect to 100 parts by mass of the conductive powder.
  • 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 conductivity and the dispersibility are excellent.
  • the content of the organic solvent is preferably from 20% by mass to 50% by mass, more preferably from 25% by mass to 45% by mass, based on the total amount of the conductive paste.
  • the conductivity and the dispersibility are excellent.
  • the present inventors have studied various dispersants for the dispersant used for the conductive paste.
  • the dispersant has one or more, preferably a plurality of, branched chains composed of a hydrocarbon group with respect to the main chain, and has an average
  • a dispersant containing an acid-based dispersant having a molecular weight of more than 500 and not more than 2,000 the dispersibility of conductive powder or ceramic powder, which is a powder material contained in the conductive paste, is excellent, and drying after coating is performed. It has been found that the electrode surface has excellent smoothness.
  • the dispersant has a branch consisting of a hydrocarbon group, thereby effectively forming a steric hindrance, preventing agglomeration of the powder material, and reducing the molecular weight to an appropriate size. It is thought that by having the compound, the viscosity and the dispersibility suitable for the conductive paste can be maintained.
  • the dispersant of the present invention will be described in more detail.
  • the acid-based dispersant used in the present embodiment preferably has a carboxyl group, and is more preferably a hydrocarbon-based graft copolymer having a polycarboxylic acid as a main chain. Further, the polycarboxylic acid preferably has an ester structure. Further, the hydrocarbon group preferably has a chain structure.
  • the molecular weight of the acid-based dispersant is more than 500 and 2,000 or less. When the molecular weight is within the above range, the dispersibility of the conductive powder and the ceramic powder is excellent, and the density and smoothness of the dried electrode surface after application are excellent.
  • the acid-based dispersant for example, a commercially available product that satisfies the above characteristics can be used.
  • the acid-based dispersant may be manufactured using a conventionally known manufacturing method so as to satisfy the above characteristics.
  • the hydrocarbon group may be an alkyl group.
  • the alkyl group may be composed of only carbon and hydrogen, or a part of hydrogen constituting the alkyl group may be substituted with a substituent.
  • the main chain and the hydrocarbon group preferably do not have a ring structure.
  • the acid dispersant is preferably contained in an amount of 0.01 part by mass or more and 5 parts by mass or less, more preferably 0.05 part by mass or more and 3 parts by mass or less, more preferably 100 parts by mass of the conductive powder. Is contained in an amount of 0.4 to 3 parts by mass.
  • the content of the acid-based dispersant is within the above range, the dispersibility of the conductive powder or the ceramic powder and the smoothness of the dried electrode surface after application are excellent, and the viscosity of the conductive paste is adjusted to an appropriate range. In addition, it is possible to suppress sheet attacks and poor peeling of the green sheet.
  • the conductive paste according to the present embodiment can have high dispersibility even when the content of the entire acid-based dispersant is 2 parts by mass or less.
  • the acid-based dispersant is preferably contained in an amount of 3% by mass or less based on the total amount of the conductive paste.
  • the upper limit of the content of the acid dispersant is preferably 2% by mass or less, more preferably 1% by mass or less.
  • the lower limit of the content of the acid dispersant is not particularly limited, but is, for example, 0.01% by mass or more, and preferably 0.05% by mass or more.
  • the conductive paste may contain a dispersant other than the above-mentioned acid-based dispersant as long as the effects of the present invention are not impaired.
  • Other dispersants include, for example, higher fatty acids, acid-based dispersants including polymer surfactants, base-based dispersants, amphoteric surfactants, and may include polymer-based dispersants and the like. It is more preferable to include a system dispersant. These dispersants may be used alone or in combination of two or more.
  • the content (total content) of the entire dispersant, combined with the acid-based dispersant to be mainly added, is based on 100 parts by mass of the conductive powder.
  • the amount may be from 0.01 to 5 parts by mass, and preferably from 0.01 to 3 parts by mass.
  • the conductive paste according to the present embodiment can have high dispersibility even when the content (total content) of the entire dispersant is 2 parts by mass or less.
  • the conductive paste of the present embodiment may include other components other than the above components as necessary.
  • additives such as an antifoaming agent, a dispersant, a plasticizer, a surfactant, and a thickener can be used.
  • the method for producing the conductive paste of the present embodiment is not particularly limited, and a conventionally known method can be used.
  • the conductive paste can be produced, for example, by stirring and kneading the above components with a three-roll mill, a ball mill, a mixer, or the like. At this time, if the dispersant is applied to the surface of the conductive powder in advance, the conductive powder is sufficiently loosened without agglomeration, and the dispersant spreads over the surface, so that a uniform conductive paste can be easily obtained.
  • the conductive paste may be prepared by stirring and kneading.
  • the conductive paste has a viscosity of preferably 100 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. If it exceeds the above range, the viscosity may be too high to be suitable for gravure printing.
  • the lower limit of the viscosity at a shear rate of 100 sec ⁇ 1 is not particularly limited, but is, for example, 0.2 Pa ⁇ S or more.
  • the conductive paste has a viscosity at a shear rate of 10,000 sec -1 of preferably 0.18 Pa ⁇ S or less.
  • the viscosity at a shear rate of 10,000 sec -1 is within the above range, it can be suitably used as a conductive paste for gravure printing. Even when it exceeds the above range, the viscosity may be too high and may not be suitable for gravure printing.
  • the lower limit of the viscosity at a shear rate of 10,000 sec -1 is not particularly limited, but is, for example, 0.05 Pa ⁇ S or more.
  • the dried film density (DFD) of the dried film obtained by printing and drying the conductive paste is preferably higher than 5.0 g / cm 3, and may be higher than 5.2 g / cm 3 .
  • the surface roughness Ra (arithmetic average roughness) of a 20 mm square dried film having a film thickness of 1 to 3 ⁇ m is reduced to 0 by printing a conductive paste and drying the film at 120 ° C. for 1 hour in the air. .2 ⁇ m or less, and may be 0.16 ⁇ m or less.
  • the lower limit of the surface roughness Ra is preferably not particularly limited, but the surface is preferably flat, but a value exceeding 0 and a smaller value is more preferable.
  • the conductive paste can be suitably used for electronic components such as multilayer ceramic capacitors.
  • the multilayer ceramic capacitor has a dielectric layer formed using a dielectric green sheet and an internal electrode layer formed using a conductive paste.
  • the dielectric ceramic powder contained in the dielectric green sheet and the ceramic powder contained in the conductive paste have the same composition.
  • the multilayer ceramic device manufactured using the conductive paste of the present embodiment even when the thickness of the dielectric green sheet is, for example, 3 ⁇ m or less, sheet attack and poor peeling of the green sheet are suppressed.
  • FIGS. 1A and 1B are views showing a multilayer ceramic capacitor 1 which is an example of an electronic component according to an embodiment.
  • the multilayer ceramic capacitor 1 includes a multilayer body 10 in which dielectric layers 12 and internal electrode layers 11 are alternately stacked, and external electrodes 20.
  • an internal electrode layer 11 made of a conductive paste is formed on a dielectric layer 12 made of a ceramic green sheet by a printing method, and a plurality of dielectric layers having the internal electrode layer on the upper surface are laminated by pressure bonding.
  • the laminate 10 is obtained, the laminate 10 is fired and integrated to produce a fired multilayer ceramic body (not shown) that becomes a ceramic capacitor body.
  • the multilayer ceramic capacitor 1 is manufactured by forming a pair of external electrodes at both ends of the ceramic capacitor body. The details will be described below.
  • a ceramic green sheet which is an unfired ceramic sheet is prepared.
  • the ceramic green sheet for example, a dielectric layer paste obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a raw material powder of a predetermined ceramic such as barium titanate, a PET film or the like. Examples thereof include those coated on a support film in a sheet form and dried to remove the solvent.
  • the thickness of the dielectric layer formed 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 demand for miniaturization of the multilayer ceramic capacitor.
  • the above-mentioned conductive paste is printed and applied to one surface of the ceramic green sheet by using a gravure printing method, and a plurality of sheets each having the internal electrode layer 11 made of the conductive paste are prepared.
  • the thickness of the internal electrode layer 11 made of a conductive paste is preferably 1 ⁇ m or less after drying from the viewpoint of a demand for thinning the internal electrode layer 11.
  • the ceramic green sheets were peeled off from the support film, and the dielectric layers 12 composed of the ceramic green sheets and the internal electrode layers 11 composed of the conductive paste formed on one side thereof were laminated alternately.
  • the laminate 10 is obtained by a heating / pressurizing treatment. Note that a configuration may be adopted in which ceramic green sheets for protection, to which the conductive paste is not applied, are further disposed on both surfaces of the laminate 10.
  • the green chip is subjected to a binder removal treatment and fired in a reducing atmosphere to produce a fired multilayer ceramic body.
  • the atmosphere in the binder removal treatment is preferably air or an N 2 gas atmosphere.
  • the temperature at the time of performing the binder removal treatment is, for example, 200 ° C. or more and 400 ° C. or less.
  • the holding time of the above-mentioned temperature when performing the binder removal 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.
  • the firing temperature of the stacked body is, for example, 1000 ° C. or more and 1350 ° C. or less.
  • the temperature holding time at the time of performing 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 internal electrode layer 11 is removed, and the nickel powder or the alloy powder containing nickel as a main component is sintered or melted and integrated to form an internal electrode.
  • a multilayer ceramic fired body in which a plurality of layers 11 are alternately stacked is formed.
  • the fired multilayer ceramic fired body may be annealed from the viewpoint of improving reliability by taking oxygen into the dielectric layer and suppressing re-oxidation of the internal electrode.
  • the multilayer ceramic capacitor 1 is manufactured by providing a pair of external electrodes 20 to the manufactured multilayer ceramic fired body.
  • the external electrode 20 includes an external electrode layer 21 and a plating layer 22.
  • External electrode layer 21 is electrically connected to internal electrode layer 11.
  • a material of the external electrode 20 for example, copper, nickel, or an alloy thereof can be preferably used.
  • electronic components other than the multilayer ceramic capacitor can be used as the electronic components.
  • Viscosity of conductive paste The viscosity after production of the conductive paste was measured using a rheometer (Rheometer MCR302, manufactured by Anton Paar Japan). Viscosity, a cone angle of 1 °, by using a cone plate with a diameter of 25 mm, a shear rate (shear rate) 100 sec -1, and, using the value when measured under the conditions of 10000 sec -1.
  • the prepared conductive paste was placed on a PET film and stretched to about 100 mm in length with an applicator having a width of 50 mm and a gap of 125 ⁇ m. After drying the obtained PET film at 120 ° C. for 40 minutes to form a dried body, the dried body was cut into four pieces of 2.54 cm (1 inch) square, and the PET film was peeled off. The thickness and weight of the dry films were measured to calculate the dry film density (average value).
  • the prepared conductive paste was printed on a 2.54 cm (1 inch) square heat-resistant tempered glass, and dried at 120 ° C. for 1 hour in the air to prepare a 20 mm square dried film having a thickness of 1 to 3 ⁇ m.
  • the surface roughness Ra (arithmetic mean roughness) of the produced dried film was measured based on the standard of JIS B0601-2001.
  • Ceramic powder As the ceramic powder, barium titanate (BaTiO 3 ; SEM average particle size 0.10 ⁇ m) was used.
  • Binder resin As the binder resin, polyvinyl butyral resin (PVB) and ethyl cellulose (EC) were used.
  • an acid-based dispersant A having a hydrocarbon-based graft copolymer having a polycarboxylic acid main chain and having an average molecular weight of 1500 was used.
  • a phosphoric acid-based dispersant used in a conventional conductive paste was used.
  • organic solvent propylene glycol monobutyl ether (PNB), mineral spirit (MA), and terpineol (TPO) were used.
  • PNB propylene glycol monobutyl ether
  • MA mineral spirit
  • TPO terpineol
  • Example 1 25 parts by mass of ceramic powder, 3.00 parts by mass of acid dispersant A as a dispersant, 2 parts by mass of PVB and 4 parts by mass of EC as a binder resin, 100 parts by mass of Ni powder, which is a conductive powder, and an organic solvent was mixed with 48 parts by mass of PNB (acetal-based solvent) and 21 parts by mass of MA to prepare a conductive paste.
  • the viscosity of the prepared conductive paste, the dry film density of the paste, and the surface roughness were evaluated by the above methods.
  • Table 1 shows the content of the conductive paste such as a dispersant
  • Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Example 2 A conductive paste was prepared and evaluated in the same manner as in Example 1, except that the content of the acid-based dispersant A was 1.74 parts by mass as the dispersant.
  • Table 1 shows the content of the conductive paste such as a dispersant, and Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Example 3 A conductive paste was prepared and evaluated in the same manner as in Example 1, except that the content of the acid-based dispersant A was 1.24 parts by mass as the dispersant.
  • Table 1 shows the content of the conductive paste such as a dispersant, and Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Example 4 A conductive paste was prepared and evaluated in the same manner as in Example 1, except that the content of the acid-based dispersant A was 0.74 parts by mass as the dispersant.
  • Table 1 shows the content of the conductive paste such as a dispersant, and Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Example 5 A conductive paste was prepared and evaluated in the same manner as in Example 1 except that the content of the acid-based dispersant A was 0.42 parts by mass as the dispersant.
  • Table 1 shows the content of the conductive paste such as a dispersant, and Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Example 1 A conductive paste was prepared and evaluated in the same manner as in Example 1, except that 0.8 parts by mass of a phosphoric acid-based dispersant was used as the dispersant.
  • Table 1 shows the content of the conductive paste such as a dispersant, and Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Example 2 A conductive paste was prepared and evaluated in the same manner as in Example 4, except that only terpineol (TPO) was used as the organic solvent.
  • Table 1 shows the content of the conductive paste such as a dispersant, and Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Table 3 A conductive paste was prepared and evaluated in the same manner as in Example 4, except that only EC was used as the binder resin.
  • Table 1 shows the content of the conductive paste such as a dispersant
  • Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • Example 4 A conductive paste was prepared and evaluated in the same manner as in Example 4, except that only EC was used as the binder resin and only terpineol (TPO) was used as the organic solvent.
  • Table 1 shows the content of the conductive paste such as a dispersant, and Table 2 shows the evaluation results of the viscosity, the dry film density, and the surface roughness of the conductive paste.
  • the conductive paste of the example has a lower viscosity than the conductive pastes of Comparative Example 1 using a phosphoric acid-based dispersant and Comparative Examples 2 to 4 having different binder resins and organic solvents, and is suitable for gravure printing. It was confirmed that the composition had excellent viscosity, a high dry film density, a smooth dry film surface, and excellent dispersibility.
  • the conductive paste of the present invention has a viscosity suitable for gravure printing, has a high dry film density after application, has excellent dry film surface smoothness, and has excellent dispersibility. Therefore, the conductive paste of the present invention can be suitably used as a raw material for an internal electrode of a multilayer ceramic capacitor, which is a chip component (electronic component) used in electronic devices such as mobile phones and digital devices, which are increasingly miniaturized. In particular, it can be suitably used as a conductive paste for gravure printing.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Physics & Mathematics (AREA)
  • Conductive Materials (AREA)
  • Ceramic Capacitors (AREA)
  • Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne une pâte conductrice affichant une excellente dispersibilité. La pâte conductrice comprend une poudre conductrice, une poudre céramique, un agent dispersant, une résine liante et un solvant organique, l'agent dispersant comprenant un agent dispersant à base d'acide ayant un poids moléculaire supérieur à 500 et inférieur à 2 000, l'agent dispersant à base d'acide comportant une chaîne principale et au moins une chaîne ramifiée comprenant un groupe hydrocarbure, la résine liante comprenant une résine à base d'acétal et le solvant organique comprenant un solvant à base d'éther glycolique.
PCT/JP2019/038006 2018-09-27 2019-09-26 Pâte conductrice, composant électronique et condensateur à base de céramique multicouche Ceased WO2020067363A1 (fr)

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KR1020207035841A KR102731211B1 (ko) 2018-09-27 2019-09-26 도전성 페이스트, 전자 부품, 및 적층 세라믹 콘덴서
CN201980040128.1A CN112334995B (zh) 2018-09-27 2019-09-26 导电性浆料、电子部件以及叠层陶瓷电容器
JP2020549399A JP7420076B2 (ja) 2018-09-27 2019-09-26 導電性ペースト、電子部品、及び積層セラミックコンデンサ
MYPI2021001664A MY208390A (en) 2018-09-27 2019-09-26 Conductive paste, electronic component, and laminated ceramic capacitor

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JP2018182502 2018-09-27

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WO2022092045A1 (fr) * 2020-10-27 2022-05-05 住友金属鉱山株式会社 Pâte conductrice pour héliogravure, composant électronique et condensateur céramique stratifié
JP2022070803A (ja) * 2020-10-27 2022-05-13 住友金属鉱山株式会社 グラビア印刷用導電性ペースト、電子部品、及び積層セラミックコンデンサ
WO2022225361A1 (fr) * 2021-04-22 2022-10-27 주식회사 아모텍 Procédé de fabrication de composant électronique en céramique multicouche, et composant électronique en céramique multicouche mis en œuvre à travers celui-ci
WO2022225360A1 (fr) * 2021-04-22 2022-10-27 주식회사 아모텍 Procédé de fabrication d'un composant électronique céramique multicouche et composant électronique céramique multicouche mis en œuvre à l'aide de celui-ci

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CN111627699A (zh) * 2020-06-08 2020-09-04 江苏国瓷泓源光电科技有限公司 一种用于mlcc的高分散性内电极浆料的制作工艺
CN111627699B (zh) * 2020-06-08 2022-03-18 江苏国瓷泓源光电科技有限公司 一种用于mlcc的高分散性内电极浆料的制作工艺
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JP2022070803A (ja) * 2020-10-27 2022-05-13 住友金属鉱山株式会社 グラビア印刷用導電性ペースト、電子部品、及び積層セラミックコンデンサ
CN116113671A (zh) * 2020-10-27 2023-05-12 住友金属矿山株式会社 凹版印刷用导电性浆料、电子部件以及叠层陶瓷电容器
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WO2022225361A1 (fr) * 2021-04-22 2022-10-27 주식회사 아모텍 Procédé de fabrication de composant électronique en céramique multicouche, et composant électronique en céramique multicouche mis en œuvre à travers celui-ci
WO2022225360A1 (fr) * 2021-04-22 2022-10-27 주식회사 아모텍 Procédé de fabrication d'un composant électronique céramique multicouche et composant électronique céramique multicouche mis en œuvre à l'aide de celui-ci

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TWI814910B (zh) 2023-09-11
CN112334995A (zh) 2021-02-05
JPWO2020067363A1 (ja) 2021-09-02
JP7420076B2 (ja) 2024-01-23
KR102731211B1 (ko) 2024-11-18
KR20210056952A (ko) 2021-05-20
TW202025178A (zh) 2020-07-01
MY208390A (en) 2025-05-06

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