CN110506083B - Conductive paste - Google Patents
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- CN110506083B CN110506083B CN201880022499.2A CN201880022499A CN110506083B CN 110506083 B CN110506083 B CN 110506083B CN 201880022499 A CN201880022499 A CN 201880022499A CN 110506083 B CN110506083 B CN 110506083B
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- 239000000843 powder Substances 0.000 claims abstract description 118
- 239000002270 dispersing agent Substances 0.000 claims abstract description 48
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 238000007646 gravure printing Methods 0.000 claims abstract description 38
- 239000000654 additive Substances 0.000 claims abstract description 26
- 230000000996 additive effect Effects 0.000 claims abstract description 25
- 239000003960 organic solvent Substances 0.000 claims abstract description 24
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 20
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 20
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 17
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 17
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 17
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims abstract description 15
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229940116411 terpineol Drugs 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000003985 ceramic capacitor Substances 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910002113 barium titanate Inorganic materials 0.000 claims description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 4
- 238000007639 printing Methods 0.000 abstract description 42
- 238000003860 storage Methods 0.000 abstract description 15
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 9
- 230000007774 longterm Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 238000010008 shearing Methods 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 4
- 238000007650 screen-printing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 3
- 230000007847 structural defect Effects 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- FFQALBCXGPYQGT-UHFFFAOYSA-N 2,4-difluoro-5-(trifluoromethyl)aniline Chemical compound NC1=CC(C(F)(F)F)=C(F)C=C1F FFQALBCXGPYQGT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000008012 organic excipient Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Chemical group 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M1/00—Inking and printing with a printer's forme
- B41M1/10—Intaglio printing ; Gravure printing
-
- 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
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention provides a conductive paste, which is especially useful for internal electrodes of multilayer ceramic capacitors, has low viscosity suitable for gravure printing, can inhibit the reaggregation of conductive metal powder after printing and storage after manufacturing, is not easy to deform and is not easy to separate. A conductive paste for internal electrodes of multilayer ceramic capacitors, which contains a conductive powder (A), an organic resin (B), an organic solvent (C), an additive (D) and a dielectric powder (E), wherein the organic resin (B) is composed of ethyl cellulose alone, the organic solvent (C) is composed of terpineol alone, the additive (D) is composed of a composition containing an unsaturated carboxylic acid-based dispersant and an oleylamine-based dispersant, the content of the unsaturated carboxylic acid-based dispersant in the additive (D) is 0.2 to 1.2 mass% based on the total amount of the conductive paste, and the content of the oleylamine-based dispersant is 0.3 to 2.0 mass%.
Description
Technical Field
The present invention relates to a conductive paste, more particularly, to a conductive paste for internal electrodes of a multilayer ceramic capacitor, and even more particularly, to a conductive paste for gravure printing.
Background
With the miniaturization of electronic devices such as mobile phones and digital devices, multilayer Ceramic capacitors (hereinafter referred to as "MLCCs") as chip components have been also miniaturized, increased in capacity, and increased in performance. The most effective means for achieving this is to thin the internal electrode layers and the dielectric layers to achieve multilayering.
The MLCC is generally manufactured as follows. To form the dielectric layer, barium titanate (BaTiO) is first used3) And an organic resin binder such as polyvinyl butyral, and then dried to produce a dielectric green sheet. A conductive paste, which is obtained by dispersing a conductive powder as a main component in a vehicle containing an organic resin binder and a solvent, is printed on the obtained green sheet in a predetermined pattern, and the solvent is dried to remove the solvent, thereby forming a dry film as an internal electrode. Next, the dielectric green sheet is pressed in a state where a plurality of dielectric green sheets each having a dry film formed thereon as an internal electrode are stacked, and is bonded and integrated, and then cut, and the organic resin binder is removed by heat treatment at a temperature of 500 ℃ or lower in an oxidizing atmosphere or an inert atmosphere, and then the internal electrode and the dielectric are integrally sintered by heating and firing at about 1300 ℃ in a reducing atmosphere so that the internal electrode is not oxidized. Next, both ends of the fired chip are polished to expose the internal electrodes, and then an external electrode paste is applied to the end faces and fired to form external electrodes, and then nickel plating or the like is applied to the external electrodes to produce the MLCC.
However, in this firing step, since the temperature at which the dielectric layer starts to sinter is about 1200 ℃ and higher than the temperature at which the conductive powder such as nickel starts to sinter and shrink, structural defects such as delamination (interlayer peeling) and cracks may occur. In particular, as the number of stacked layers increases or the thickness of the dielectric layer decreases with the size reduction and the capacity increase, the occurrence of structural defects becomes remarkable.
Therefore, in general, in order to control sintering/shrinkage of the conductive powder up to a temperature near the temperature at which the dielectric layer starts sintering/shrinkage, ceramic powder containing a perovskite oxide such as barium titanate-based or strontium zirconate-based oxide as a main component similar to the composition of the dielectric layer is added to the nickel paste for internal electrodes. By controlling the sintering behavior of the nickel powder by these ceramic powders, it is possible to reduce the mismatch of the sintering shrinkage behavior of the internal electrode layers and the dielectric layers. Further, if a ceramic powder having a composition similar to that of the dielectric layer is added, there is an effect of reducing dielectric loss caused by a difference between the constituent elements of the main component of the dielectric layer and the constituent elements of the dielectric powder contained in the internal electrode conductive paste.
However, the conductive paste for the internal electrode for the MLCC has been used for screen printing in many cases. However, since cost reduction and productivity improvement are required, gravure printing, which has a higher printing speed than screen printing and is expected to improve productivity, is attracting attention, and conductive pastes that can be used in gravure printing are increasingly required.
Since the printing speed of gravure printing is faster than that of screen printing, in order to perform printing in accordance with the printing speed, the viscosity of the paste for gravure printing at the time of printing needs to be lower than that of the paste for screen printing. On the other hand, if the viscosity is lowered after printing and during storage, the paste tends to flow, and separation of the conductive powder having a different specific gravity from the dielectric powder as the sintering control agent tends to occur. In order to obtain sufficient characteristics in gravure printing, a conductive paste having a low viscosity at the time of printing, being not easily deformed after printing, and having a viscosity that does not allow separation of the conductive powder from the dielectric powder at the time of storage is required.
For example, patent document 1 discloses an intaglio electrode ink containing a base metal powder containing nickel as a main component, wherein the resin is 1 part by weight or more and 15 parts by weight or less, the organic solvent is 20 parts by weight or more and 150 parts by weight or less, the viscosity is 10 poise or less, and aggregates having a size of 10 μm or more are removed, relative to 100 parts by weight of the metal powder.
Further, patent document 2 discloses a conductive paste for gravure printing, which is characterized by containing a conductive powder (a), an organic resin (B), and an organic solvent (C), the conductive paste for the internal electrode of a multilayer ceramic capacitor comprises an additive (D) and a dielectric powder (E), wherein the organic resin (B) is composed of polyvinyl butyral having a polymerization degree of 10000 to 50000 inclusive and ethyl cellulose having a weight average molecular weight of 10000 to 100000 inclusive, the organic solvent (C) is composed of propylene glycol monobutyl ether, 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, and the additive (D) is composed of a separation inhibitor and a dispersant, and the separation inhibitor is composed of a composition containing a polycarboxylic acid polymer or a salt of a polycarboxylic acid.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 10-335167
Patent document 2: japanese laid-open patent publication No. 2012-174797
Disclosure of Invention
Problems to be solved by the invention
The technique described in patent document 1 can produce a conductive paste for gravure printing that has a low viscosity during printing and does not cause separation of metal powder, but since dielectric powder is not contained as a sintering regulator, sintering of metal powder cannot be synchronized with sintering timing of dielectric, and structural defects may occur.
The technique described in patent document 2 uses a mixed organic resin or a mixed organic solvent having a specific polymerization degree and a specific weight average molecular weight in a conductive paste containing a dielectric powder, thereby providing a conductive paste having a low viscosity suitable for gravure printing, but may cause separation of metal powder due to long-term storage.
The present invention has been made in view of the above-described problems of the prior art, and an object of the present invention is to provide a conductive paste which is useful for internal electrodes of a multilayer ceramic capacitor, has a low viscosity suitable for gravure printing at the time of printing, is capable of suppressing re-aggregation of conductive metal powder at the time of storage after printing and after manufacturing, is not easily deformed, and is not easily separated.
Means for solving the problems
In order to achieve the above object, a conductive paste for internal electrodes of multilayer ceramic capacitors according to the present invention is a conductive paste for internal electrodes of multilayer ceramic capacitors, which contains a conductive powder (a), an organic resin (B), an organic solvent (C), an additive (D), and a dielectric powder (E), wherein the organic resin (B) is composed of only ethyl cellulose, the organic solvent (C) is composed of only terpineol, the additive (D) is composed of a composition containing an unsaturated carboxylic acid-based dispersant and an oleylamine-based dispersant, and the content of the unsaturated carboxylic acid-based dispersant in the additive (D) is 0.2 mass% or more and 1.2 mass% or less with respect to the total amount of the conductive paste, and the content of the oleylamine-based dispersant is 0.3 mass% or more and 2.0 mass% or less.
In the conductive paste for gravure printing of the present invention, the content of the conductive powder (a) is preferably 40 mass% or more and 60 mass% or less with respect to the total paste.
In the conductive paste for gravure printing of the present invention, the content of the organic resin (B) is preferably 1.5 mass% or more and 6 mass% or less with respect to the entire conductive paste.
In the conductive paste for gravure printing of the present invention, it is preferable that the dielectric powder (E) is BaTiO3。
In the conductive paste for gravure printing of the present invention, the content of the dielectric powder (E) is preferably 2 mass% or more and 15 mass% or less with respect to the total amount of the paste.
In the conductive paste for gravure printing of the present invention, the shear rate at room temperature is preferably 10000s-1The viscosity is 0.05 Pa.s or more and 10 Pa.s or less, and the shear rate is 10s-1The viscosity is 0.5 pas or more.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, by containing a predetermined amount of an unsaturated carboxylic acid-based dispersant and a predetermined amount of an oleyl amine-based dispersant together with a predetermined amount of an organic solvent composed of terpineol only and an organic resin composed of ethylcellulose only, a conductive paste for gravure printing having a shear rate of 10000s can be obtained-1Viscosity at printing confirmed by viscosity at high shear of (2) is low viscosity and the shear rate is 10s-1The viscosity after printing and during storage confirmed by the viscosity at low-speed shearing of (2) also has a value capable of maintaining a dispersed state for a long period of time, and the conductive powder can be prevented from beingThe separation from the dielectric powder allows normal use without change in viscosity, and does not cause unevenness in a printed film or deterioration in film smoothness even after long-term storage.
Detailed Description
The conductive paste for gravure printing of the present invention will be described in detail below.
The conductive paste for gravure printing is formed from a conductive powder, an organic resin composed only of ethyl cellulose, an organic solvent composed only of terpineol, an additive composed of an unsaturated carboxylic acid-based dispersant and an oleyl amine-based dispersant, and a dielectric powder.
The present inventors have conducted extensive studies and as a result, found that, in a conductive paste having excellent dispersibility, in which only ethyl cellulose is used as an organic resin and only terpineol is used as an organic solvent, when a prescribed amount of an unsaturated carboxylic acid-based dispersant and an oleylamine-based dispersant are contained as an acid-based dispersant and an amine-based dispersant which have been added so far for dispersing a conductive powder in an organic resin binder, respectively, a shear rate at room temperature of 10000s is obtained-1The viscosity of the conductive paste is more than 0.05 Pa.s and less than 10 Pa.s, and the shear rate at normal temperature is 10s-1The viscosity of the conductive paste is 0.5 pas or more, and the conductive paste is suitable for both formation of a printed film during high-speed printing in gravure printing and maintenance of the shape of a printed matter after printing, and can prevent separation of the conductive powder and the dielectric powder in a short time. The conductive paste for gravure printing and the constituent materials thereof of the present invention will be described in further detail below.
< conductive powder >
As the conductive powder used in the conductive paste for gravure printing of the present invention, a silver powder, a palladium powder, or the like may be used in addition to a nickel powder and a copper powder, and a nickel powder is preferably used.
With the miniaturization of electronic devices such as MLCCs, it is necessary to improve the smoothness and dry film density of the dry coating film to form a smaller and thinner conductor such as an internal electrode. Therefore, the particle diameter of the conductive powder is preferably 0.05 μm or more and 0.5 μm or less.
If the particle diameter of the conductive powder is less than 0.05 μm, the specific surface area of the particles becomes too large, and the surface activity of the conductive powder is excessively increased, which is not only a bad influence on drying and binder removal properties, but also a difficulty in obtaining appropriate viscosity properties, and a possibility of deterioration in long-term storage of the conductive paste occurs, and thus it is not preferable.
Further, if the particle size exceeds 0.5 μm, the film forming property when the coating film of the paste is made thin is poor, it is difficult to obtain a predetermined capacitance, the smoothness of the dried film becomes insufficient, the filling of the conductive powder becomes insufficient, and a desired dry film density cannot be secured, so that it is difficult to form a sufficiently small and thin uniform internal electrode, which is not preferable. The preferable particle diameter of the conductive powder is 0.1 μm or more and 0.4 μm or less.
In the present invention, the particle diameter of the conductive powder is, unless otherwise specified, a particle diameter calculated from a specific surface area value obtained by a BET method. The calculation formula is shown in equation 1.
(number formula 1)
The particle size of the conductive powder is 6/(SA1 × ρ 1)
SA 1: specific surface area value of conductive powder (BET method)
ρ 1: true Density of conductive powder (e.g. 8.9 for Nickel)
The content of the conductive powder with respect to the total amount of the conductive paste is preferably 40 mass% or more and 60 mass% or less. If the content of the conductive powder is less than 40%, the thickness of the electrode after firing becomes too thin, an electrode film cannot be sufficiently formed, the resistance value increases, or the conductivity is lost, and the desired capacitance may not be obtained. On the other hand, if the content of the conductive powder exceeds 60%, it may be difficult to make the electrode film thinner.
< organic resin >
Only ethyl cellulose was used as the organic resin. Ethyl cellulose has been an organic resin component which is excellent in solubility in a solvent, printability, combustion decomposability, and the like, and is suitably used for a conductive paste for an internal electrode of an MLCC and the like. While various other organic resins are used in conventional conductive pastes, the conductive paste for gravure printing of the present invention is required to be uniformly printed without variation even in high-speed printing in terms of its characteristics, and the use of only ethyl cellulose as an organic resin can minimize variation in high-speed printing.
The content of the organic resin using only ethyl cellulose with respect to the total amount of the conductive paste is preferably 1.5 mass% or more and 6 mass% or less. If the amount is less than 1.5% by mass, the strength of the dried film may be reduced, the adhesion between the conductive film formed of the conductive paste and the dielectric sheet may be deteriorated, or the conductive film may be easily peeled off from the dielectric sheet. As a result of repeated experiments by the present inventors, a conductive paste comprising a conductive powder, an organic resin composed of only ethyl cellulose, an organic solvent composed of only terpineol, an additive composed of an unsaturated carboxylic acid-based dispersant and an oleylamine-based dispersant, and a dielectric powder was obtained, and thus a conductive paste having no deterioration in the binder removal property was obtained even when the content of the organic resin exceeded 5 mass%. However, if the content of the organic resin exceeds 6 mass%, the binder removal property may be deteriorated due to an increase in the content of the organic resin.
< organic solvent >
Only terpineol was used as the organic solvent. Terpineol is also an organic solvent that has been used conventionally, like ethyl cellulose, has good affinity with the conductive metal powder, can produce a conductive paste in a short time, and has the effect of facilitating uniform dispersion of the conductive metal powder and the dielectric powder. The gravure printing of the present invention requires a conductive paste having a better dispersibility than conventional conductive pastes, and requires only terpineol as an organic solvent, thereby making it possible to obtain a conductive paste having a better dispersibility.
The content of the organic solvent using only terpineol is adjusted to be contained so that the viscosity of the conductive paste is suitable for gravure printing during printing, and the conductive paste has a viscosity capable of maintaining a shape after printing and a long-term dispersion state during storage after production and preventing separation of the conductive powder and the dielectric powder.
Height suitable for gravure printingViscosity of conductive paste for fast printing has shear rate of 10000s at normal temperature-1When the amount is 0.05 pas or more and 10 pas or less.
If the shear rate at normal temperature is 10000s-1If the viscosity of the conductive paste is less than 0.05 pas, the viscosity becomes too low, and problems such as bleeding occur at the time of high-speed printing. On the other hand, if the shear rate at ordinary temperature is 10000s-1When the viscosity of the conductive paste exceeds 10Pa · s, the viscosity becomes too high, and a problem such as white blur occurs at the time of high-speed printing.
Further, the shear rate of the viscosity of the conductive paste at room temperature, which can maintain the shape after printing and the long-term dispersion state during storage after production and can prevent the separation of the conductive powder from the dielectric powder, is 10s-1When the pressure is higher than 0.5 pas.
If the shear rate at normal temperature is 10s-1If the viscosity of the conductive paste is less than 0.5Pa · s, the shape after printing and the long-term dispersion state during storage after production cannot be maintained, and the conductive powder and the dielectric powder are likely to be separated.
< additives >
The additive is a composition containing an unsaturated carboxylic acid-based dispersant and an oleylamine-based dispersant. The conductive paste for gravure printing of the present invention is required to be a conductive paste having excellent dispersibility while minimizing various variations due to high-speed printing, and the improvement of dispersibility due to the ethyl cellulose and terpineol is not sufficient. However, the present inventors have found that when a composition containing an unsaturated carboxylic acid-based dispersant and an oleylamine-based dispersant is added as an additive, the dispersibility can be further improved, and an excellent conductive paste for gravure printing can be obtained.
The content of the unsaturated carboxylic acid dispersant is 0.2 to 1.2 mass% relative to the total amount of the conductive paste, and the content of the oleylamine dispersant is 0.3 to 2.0 mass%. When each dispersant is less than the above range, the viscosity is out of the range suitable for maintaining the shape after printing and the long-term dispersion state during storage after production (shear rate at room temperature 10 s)-1Viscosity range of (2):
0.5Pas or more), the dispersion effect cannot be sufficiently exhibited, and a separation phenomenon between the conductive powder and the dielectric powder occurs. When the respective dispersants exceed the above ranges, the dispersing effect is exhibited, but the viscosity of the conductive paste is deteriorated by the additive present in excess, and the shear rate at room temperature is 10000s for gravure printing applications, which is out of the range of viscosity suitable for high-speed printing-1The viscosity at that time is less than 0.05 pas.
The conductive paste of the present invention can maintain the shear rate at room temperature of 10000s as an additive in addition to the dispersant-1Viscosity characteristics and shear rate of 10s-1The separation inhibitor is added within the range of viscosity characteristics.
< dielectric powder >
BaTiO used in a common conductive paste can be used as the dielectric powder3And the like. Further, the BaTiO compound may be contained3The powder containing as a main component Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb and an oxide of a rare earth element as a subcomponent may be BaTiO3A powder of a perovskite oxide ferroelectric material in which Ba atoms and Ti atoms are replaced with other atoms, Sn, Pb, Zr, or the like. Further, when powders for forming the MLCC green sheet are selected, ZnO (zinc oxide), ferrite, PZT (lead zirconate titanate), BaO (barium oxide), and Al are used2O3(aluminum oxide) Bi2O3(bismuth oxide), R2O3(rare earth oxide: R ═ rare earth element), TiO2(titanium oxide) and Nd2O3An oxide such as (neodymium oxide) may be more preferable because it may reduce dielectric loss.
The particle diameter of the dielectric powder is preferably in the range of 0.01 μm to 0.5 μm. If the particle diameter of the dielectric powder is less than 0.01 μm, the specific surface area of the particles is excessively increased, and the surface activity of the dielectric powder is excessively increased, which is not only disadvantageous in drying and binder removal properties but also makes it difficult to obtain appropriate viscosity properties, and thus the conductive paste may be deteriorated during long-term storage, which is not preferable.
Further, if the particle size of the dielectric powder exceeds 0.5 μm, the film forming property when a coating film of the paste is made thin is poor, filling of the dielectric powder becomes insufficient, smoothness becomes insufficient when a dry film is formed, a desired dry film density cannot be secured, it is difficult to form a sufficiently small and thin uniform internal electrode, and a predetermined capacitance cannot be obtained in some cases, which is not preferable. The more preferable particle diameter of the dielectric powder is 0.01 μm or more and 0.3 μm or less.
The content of the dielectric powder in the conductive paste of the present invention is preferably 2 mass% or more and 15 mass% or less. If the content of the dielectric powder is less than 2 mass%, the shrinkage of the electrode may not be sufficiently suppressed, while if the content of the dielectric powder exceeds 15 mass%, the electrode may become too thick or the electrode may be broken due to a decrease in the metal content.
< conductive paste >
The conductive paste of the present invention is obtained by first dissolving an organic resin in an organic solvent to prepare an organic vehicle, and then adding a conductive powder, a dispersant as an additive, and a dielectric powder to the organic vehicle to disperse the conductive powder in the organic vehicle.
The organic excipient is obtained by adding an organic resin consisting only of ethyl cellulose to an organic solvent consisting only of terpineol heated to 50 ℃ or higher and 60 ℃ or lower, and mixing and stirring the mixture.
Subsequently, predetermined amounts of the conductive powder, the dielectric powder, the prepared organic vehicle, and the additive composed of the composition containing the unsaturated carboxylic acid-based dispersant and the oleylamine-based dispersant were weighed, put into a mixer, stirred, and uniformly dispersed and mixed in the organic vehicle by a three-roll mill to obtain a conductive paste.
The shear rate of the conductive paste of the invention at normal temperature is 10000s-1The viscosity is 0.05 pas or more and 10 pas or less. Shear rate at normal temperature 10000s-1When the viscosity of the conductive paste is less than 0.05 pas, the printing width cannot be maintained when the conductive paste is printed at high speed, and bleeding occurs after printing, and it is not possible to ensureThe required film thickness is ensured. On the other hand, if the shear rate at ordinary temperature is 10000s-1If the viscosity of the conductive paste exceeds 10Pa · s, the following properties cannot be sufficiently exhibited when printing is performed at high speed, and the following disadvantages occur: the conductive paste cannot be sufficiently filled in a cylinder for gravure printing to cause defects in a printing portion, or the conductive paste cannot be entirely transferred from a concave portion of the cylinder during printing to contaminate a printed matter or cause shading variation. It should be noted that if the shear rate at room temperature is 10000s-1The viscosity of the conductive paste in the case of using the conductive paste is preferably 0.05Pa · s or more and 0.3Pa · s or less because the viscosity is sufficiently low to sufficiently cope with high-speed printing.
Further, the shear rate of the conductive paste of the present invention at normal temperature was 10s-1The viscosity is 0.5 pas or more. Shear rate at Normal temperature 10s-1If the viscosity of the conductive paste is less than 0.5Pa · s, it becomes difficult to maintain the shape of a printed material such as a wiring after printing the conductive paste, and a desired wiring width and thickness cannot be obtained. Note that, if the shear rate at normal temperature is 10s-1When the viscosity of the conductive paste is 1Pa · s or more, the shape of the wiring formed as a printed material is not substantially deformed, and therefore, it is preferable.
In addition, the conductive paste of the present invention does not cause separation of the conductive powder from the dielectric powder and the like after standing for 30 days. If the conductive paste is separated, the separated and aggregated conductive powder or the like is aggregated, and the aggregation cannot be improved by only slightly kneading before printing, so that the dispersibility is poor, and the shape of the printed film and the smoothness of the surface of the printed film are poor.
Examples
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the examples at all.
(1) Composition of conductive paste
As the conductive powder (A), a spherical Ni powder having a particle diameter of 0.3 μm was contained. The organic vehicle contains a mixture of ethyl cellulose as an organic resin (B) as a binder and terpineol as an organic solvent (C) heated to 60 ℃. As the additive (D), an acid dispersant and a base dispersant were mixed in accordance with the kind and formulation shown in Table 1. The dielectric powder (E) contained spherical barium titanate having a particle diameter of 70 nm. The composition of the conductive paste of each sample is shown in table 1.
The content of the organic resin (B) in the organic vehicle was based on the amount of 1/10 in the conductive powder (a), and in order to confirm the effect of the organic resin (B), the content of the conductive powder (a) was kept constant and only the content of the organic resin (B) was changed for samples 22 to 25. The content of the organic solvent (C) is the balance when a predetermined amount of other materials is contained with respect to 100 mass% of the conductive paste.
(2) Evaluation of separability
For the evaluation of the separability of the conductive paste, 100g of the conductive paste of this sample was put into a 100ml container and left at 25 ℃ for 30 days to visually confirm the presence or absence of the separation of the conductive powder and the dielectric powder. The state in which the dielectric powder (E) contained in the conductive paste was separated and a white supernatant portion could be confirmed was determined as x, and the state in which no white supernatant portion was present and separation of the dielectric powder (E) was not confirmed was determined as o. The evaluation results are shown in Table 1.
(3) Measurement of viscosity
The viscosity of the conductive paste was measured using a rheometer. Shear rate 10000s-1The viscosity at the time of high-speed shearing of (1) is 0.05 pas or more and 0.3 pas or less is judged as "good", the viscosity exceeding 0.3 pas and 10 pas or less is judged as "delta", and the viscosity exceeding 10 pas is judged as "x". Further, the shear rate was adjusted to 10s-1The viscosity at the time of low-speed shearing of (1) is judged as "good", the viscosity at the time of low-speed shearing of (0.5) to less than 1Pa · s is judged as "Δ", and the viscosity at the time of less than 0.5Pa · s is judged as "x". The measurement results of each are shown in table 1.
[ Table 1]
From the results of table 1, it is understood that the content of the unsaturated carboxylic acid-based dispersant and the oleylamine-based dispersant which contain the conductive powder (a) and the dielectric powder (E) and are the additive (D) within the range of the present invention, and that the samples 3 to 6, 10 to 12, and 18 to 29 which contain only ethylcellulose as the organic resin (B) and terpineol as the organic solvent (C) within the range of the present invention do not separate the conductive powder (a) from the dielectric powder (E) even when they are left in a container for 30 days, and have a viscosity suitable for gravure printing.
Of these samples, samples 3 to 6, 10 to 12, 19, 20, 23, 24, 27, and 28, which respectively contain the conductive powder (a), the organic resin (B), and the dielectric powder (E) in the preferred ranges of the present invention, have viscosities that are very suitable for forming a printed film during high-speed printing of gravure printing and maintaining the shape of a printed matter after printing.
In addition, in sample 18 in which the content of the conductive powder (a) is lower than the lower limit of the preferable range of the present invention, sample 22 in which the content of the organic resin (B) is lower than the lower limit of the preferable range of the present invention, and sample 26 in which the content of the dielectric powder (E) is lower than the lower limit of the preferable range of the present invention, the viscosity at the time of low-speed shearing for maintaining the shape of the printed matter after printing by gravure printing is slightly lower than in samples 3 to 6, 10 to 12, 19 to 21, 23 to 25, and 27 to 29, but has a viscosity suitable for forming a printed film at the time of high-speed printing.
In addition, in the case of sample 21 in which the content of each of the conductive powder (a) and the organic resin (B) exceeds the upper limit of the preferable range of the present invention, sample 25 in which the content of the organic resin (B) exceeds the upper limit of the preferable range of the present invention, and sample 29 in which the content of the dielectric powder (E) exceeds the upper limit of the preferable range of the present invention, the viscosity at the time of high-speed shearing for forming a printed film in high-speed printing of gravure printing is slightly higher than that of samples 3 to 6, 10 to 12, 18 to 20, 22 to 24, and 26 to 28, but has a viscosity suitable for maintaining the shape of a printed matter after printing.
On the other hand, with respect to samples 1 and 2 in which at least one of the unsaturated carboxylic acid-based dispersant and the oleylamine-based dispersant as the additive (D) is contained in an amount lower than the range of the present invention or the unsaturated carboxylic acid-based dispersant and the oleylamine-based dispersant are not contained,8.9, the conductive powder (a) and the dielectric powder (E) were separated from each other during 30 days of storage. In addition, in sample 7 in which the content of the unsaturated carboxylic acid-based dispersant as the additive (D) exceeds the upper limit of the present invention (1.2 mass%) and sample 13 in which the content of the oleylamine-based dispersant as the additive (D) exceeds the upper limit of the present invention (2.0 mass%), the shear rate was 10000s although the conductive powder (a) and the dielectric powder (E) were not separated from each other-1The viscosity of (3) is too high at the time of high-speed shearing, and therefore, blooming occurs at the time of high-speed printing in gravure printing. Furthermore, in samples 14 to 17 containing a substance other than the unsaturated carboxylic acid-based dispersant or the oleylamine-based dispersant as the additive (D) in place of at least one of the unsaturated carboxylic acid-based dispersant and the oleylamine-based dispersant, separation of the conductive powder (a) and the dielectric powder (E) was not suppressed when the samples were left in a container for 30 days.
Industrial applicability
As described above, the conductive paste of the present invention has a low viscosity suitable for gravure printing and excellent long-term storage stability, and can be suitably used as a material for internal electrodes of multilayer ceramic capacitors, which are chip components of electronic devices, such as mobile phones and digital devices, for which miniaturization is advanced.
Claims (1)
1. A conductive paste for gravure printing used for internal electrodes of a multilayer ceramic capacitor, characterized in that it is a conductive paste for gravure printing used for internal electrodes of a multilayer ceramic capacitor containing a conductive powder (A), an organic resin (B), an organic solvent (C), an additive (D) and a dielectric powder (E),
the conductive powder (A) is composed of nickel powder, the content of the conductive powder (A) is more than 40% by mass and less than 60% by mass relative to the total amount of the conductive paste,
the organic resin (B) is composed of only ethyl cellulose, the content of the organic resin (B) is more than 1.5 mass percent and less than 6 mass percent relative to the total mass of the conductive paste,
the organic solvent (C) consists of terpineol only,
the additive (D) is composed of a composition containing an unsaturated carboxylic acid dispersant and an oleylamine dispersant, wherein the content of the unsaturated carboxylic acid dispersant in the additive (D) is 0.2 to 1.2 mass% relative to the total amount of the conductive paste, and the content of the oleylamine dispersant is 0.3 to 0.5 mass% relative to the total amount of the conductive paste,
the dielectric powder (E) is composed of barium titanate, the content of the dielectric powder (E) is more than 2 mass percent and less than 15 mass percent relative to the total amount of the conductive paste,
the conductive paste for gravure printing of internal electrodes of a multilayer ceramic capacitor has a characteristic that the conductive powder (A) and the dielectric powder (E) are maintained in a non-separated state when the conductive paste is added to a container and left at a temperature of 25 ℃ for 30 days, and
shear rate at normal temperature 10000s-1A viscosity of 0.05 to 0.3 pas and a shear rate of 10s-1The viscosity is 1 pas or more.
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| JP2017065321A JP6939015B2 (en) | 2017-03-29 | 2017-03-29 | Conductive paste for gravure printing for internal electrodes of multilayer ceramic capacitors |
| JP2017-065321 | 2017-03-29 | ||
| PCT/JP2018/006313 WO2018180048A1 (en) | 2017-03-29 | 2018-02-21 | Electroconductive paste |
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| KR (1) | KR102501339B1 (en) |
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| WO2020090415A1 (en) * | 2018-10-31 | 2020-05-07 | 昭栄化学工業株式会社 | Ni paste and layered ceramic capacitor |
| WO2020137289A1 (en) * | 2018-12-25 | 2020-07-02 | 住友金属鉱山株式会社 | Conductive paste, electronic component, and laminated ceramic capacitor |
| JP7053527B2 (en) * | 2019-03-29 | 2022-04-12 | 株式会社ノリタケカンパニーリミテド | Conductive paste |
| KR20220145326A (en) * | 2020-03-04 | 2022-10-28 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive pastes, electronic components and multilayer ceramic capacitors |
| WO2022168446A1 (en) | 2021-02-02 | 2022-08-11 | 株式会社村田製作所 | Inorganic particle-containing paste, inorganic particle-containing film, and laminate |
| JPWO2022168445A1 (en) | 2021-02-02 | 2022-08-11 | ||
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| JP6939015B2 (en) | 2021-09-22 |
| JP2018168238A (en) | 2018-11-01 |
| TWI762596B (en) | 2022-05-01 |
| WO2018180048A1 (en) | 2018-10-04 |
| KR20190129980A (en) | 2019-11-20 |
| CN110506083A (en) | 2019-11-26 |
| TW201840756A (en) | 2018-11-16 |
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