CN113396458B - Conductive paste, electronic component, and multilayer ceramic capacitor - Google Patents
Conductive paste, electronic component, and multilayer ceramic capacitor Download PDFInfo
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- CN113396458B CN113396458B CN202080012624.9A CN202080012624A CN113396458B CN 113396458 B CN113396458 B CN 113396458B CN 202080012624 A CN202080012624 A CN 202080012624A CN 113396458 B CN113396458 B CN 113396458B
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- 239000003985 ceramic capacitor Substances 0.000 title claims description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 111
- 239000000843 powder Substances 0.000 claims abstract description 92
- 239000000919 ceramic Substances 0.000 claims abstract description 44
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 32
- -1 alkyl phosphate compound Chemical class 0.000 claims abstract description 30
- 150000001413 amino acids Chemical class 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 22
- 239000010452 phosphate Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000006353 oxyethylene group Chemical group 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000000956 alloy Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 1
- 229920002678 cellulose Polymers 0.000 claims 1
- 239000001913 cellulose Substances 0.000 claims 1
- 238000010304 firing Methods 0.000 abstract description 19
- 239000010408 film Substances 0.000 description 59
- 239000010410 layer Substances 0.000 description 52
- 239000007789 gas Substances 0.000 description 27
- 230000003746 surface roughness Effects 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 230000032798 delamination Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 6
- 229910002113 barium titanate Inorganic materials 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 5
- 125000005702 oxyalkylene group Chemical group 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 229940116411 terpineol Drugs 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 4
- 125000001302 tertiary amino group Chemical group 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 3
- 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 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000012461 cellulose resin Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000007847 structural defect Effects 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000004840 adhesive resin Substances 0.000 description 2
- 229920006223 adhesive resin Polymers 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 239000011882 ultra-fine particle Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- LAVARTIQQDZFNT-UHFFFAOYSA-N 1-(1-methoxypropan-2-yloxy)propan-2-yl acetate Chemical compound COCC(C)OCC(C)OC(C)=O LAVARTIQQDZFNT-UHFFFAOYSA-N 0.000 description 1
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920000896 Ethulose Polymers 0.000 description 1
- 239000001859 Ethyl hydroxyethyl cellulose Substances 0.000 description 1
- KRKIAJBQOUBNSE-GYSYKLTISA-N Isobornyl isobutyrate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(C)C)C[C@@H]1C2(C)C KRKIAJBQOUBNSE-GYSYKLTISA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- DIOYAVUHUXAUPX-KHPPLWFESA-N Oleoyl sarcosine Chemical group CCCCCCCC\C=C/CCCCCCCC(=O)N(C)CC(O)=O DIOYAVUHUXAUPX-KHPPLWFESA-N 0.000 description 1
- FAFMZORPAAGQFV-BREBYQMCSA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] propanoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)CC)C[C@@H]1C2(C)C FAFMZORPAAGQFV-BREBYQMCSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000002003 electrode paste Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 235000019326 ethyl hydroxyethyl cellulose Nutrition 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- DIICMQCJAQLQPI-UHFFFAOYSA-N isobornyl propionate Natural products CCC(=O)C1CC2CCC1(C)C2(C)C DIICMQCJAQLQPI-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000005341 toughened glass Substances 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01G4/018—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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
Provided is a conductive paste which has excellent dispersibility of conductive powder, is more excellent in viscosity stability, and has a small amount of gas generation at a low temperature at the start of firing. The conductive paste comprises a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein the dispersant comprises an amino acid dispersant, an amine dispersant, and an alkyl phosphate compound, the dispersant comprises 0.03 to 0.3 mass% of the amino acid dispersant, 0.2 to 0.05 mass% of the amine dispersant, the alkyl phosphate compound is contained, the total content of the amino acid dispersant and the amine dispersant is 0.5 mass% or less, and the total content of the amino acid dispersant, the amine dispersant, and the alkyl phosphate compound is 0.7 mass% or less.
Description
Technical Field
The invention relates to a conductive paste, an electronic component and a laminated ceramic capacitor.
Background
With miniaturization and higher performance of electronic devices such as mobile phones and digital devices, miniaturization and higher capacity are also desired for electronic components including multilayer ceramic capacitors and the like. The multilayer ceramic capacitor has a structure in which a plurality of dielectric layers and a plurality of internal electrode layers are alternately laminated, and the dielectric layers and the internal electrode layers are thinned, thereby achieving miniaturization and high capacity.
For example, a laminated ceramic capacitor can be manufactured as follows. First, a conductive paste for internal electrodes is printed (coated) in a predetermined electrode pattern on the surface of a green sheet containing dielectric powder such as barium titanate (BaTiO 3) and a binder resin, and dried to form a dry film. Next, the dried film and the green sheet are stacked alternately, and heat-press bonded to form a laminate in an integrated state. The laminate is cut, subjected to an organic binder removal treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip. Next, the paste for external electrodes is applied to both end portions of the fired chip, and after firing, nickel plating or the like is applied to the surface of the external electrode, thereby obtaining a multilayer ceramic capacitor.
In general, the conductive paste for forming the internal electrode layers contains conductive powder, ceramic powder, binder resin, and organic solvent. In addition, in order to improve dispersibility of the conductive powder or the like, the conductive paste sometimes contains a dispersant. With the recent thinning of the internal electrode layers, the conductive powder tends to have a smaller particle size. When the particle diameter of the conductive powder is small, the specific surface area of the particle surface increases, and therefore the surface activity of the conductive powder (metal powder) increases, and there are cases where dispersibility decreases and viscosity characteristics decrease.
Therefore, attempts have been made to improve the viscosity characteristics of the conductive paste over time. For example, patent document 1 discloses a conductive paste containing at least a metal component, an oxide, a dispersant and a binder resin, wherein the metal component is a Ni powder having a specific composition ratio in terms of its surface composition, the acid point amount of the dispersant is 500 to 2000 μmol/g, and the acid point amount of the binder resin is 15 to 100 μmol/g. Further, according to patent document 1, the conductive paste has good dispersibility and viscosity stability.
Patent document 2 discloses a conductive paste for internal electrodes, which comprises a blend of conductive powder, resin, an organic solvent, and ceramic powder mainly of TiBaO 3 and an aggregation inhibitor, wherein the content of the aggregation inhibitor is 0.1 wt% to 5 wt%, and the aggregation inhibitor is a tertiary amine or a secondary amine represented by a specific structural formula. According to patent document 2, the electroconductive paste for internal electrodes suppresses aggregation of the common material components, is excellent in long-term storage property, and can realize thinning of the multilayer ceramic capacitor.
On the other hand, in the case of thinning the internal electrode layer, a dry film obtained by printing and drying a conductive paste for internal electrodes on the surface of a green sheet is required to have a high density. For example, patent document 3 proposes a metal ultrafine powder slurry containing an organic solvent, a surfactant, and metal ultrafine particles, wherein the surfactant is oleoyl sarcosine, and the metal ultrafine powder slurry contains 70 mass% to 95 mass% of the metal ultrafine powder, and contains more than 0.05 mass parts and less than 2.0 mass parts of the surfactant, based on 100 mass parts of the metal ultrafine powder. According to patent document 3, by preventing aggregation of ultrafine particles, a metal ultrafine powder slurry excellent in dispersibility and dry film density without the presence of aggregated particles can be obtained.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2015-216244
Patent document 2: japanese patent application laid-open No. 2013-149757
Patent document 3: japanese patent laid-open No. 2006-063441
Disclosure of Invention
Problems to be solved by the invention
However, with recent thinning of electrode patterns, further improvement of viscosity characteristics over time and improvement of surface smoothness of a dried film after coating have been demanded. In addition, due to the thinning of the electrode pattern, shrinkage mismatch occurs at the interface between the internal electrode layer and the dielectric layer when the laminate is fired, and structural defects such as cracks and interlayer peeling are more likely to occur.
The inventors of the present invention found that at a low temperature at the start of firing of the laminate, a decomposed gas derived from a component contained in the conductive paste is generated, and this gas becomes one of causes of cracking and delamination. That is, when the laminate is fired at a temperature lower than the temperature at which the dielectric layers (green sheets) start to sinter, if a certain amount of gas is generated from the dried film, the gas stagnates between the dielectric layers to generate voids, which causes cracking and delamination.
Even in the case of the conductive paste in which problems such as cracking and delamination have not been reported in the past, when the electrode pattern is further thinned, a trace amount of gas may be generated at a low temperature at the start of firing, which may cause cracking and delamination.
In view of such a situation, an object of the present invention is to provide a conductive paste having high surface smoothness of a dried film and high density of the dried film, excellent dispersibility of conductive powder, very little change in viscosity with time, more excellent viscosity stability, and less gas generation at a low temperature at the start of firing.
Means for solving the problems
In a first aspect of the present invention, there is provided a conductive paste comprising a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein the dispersant comprises an amino acid dispersant represented by the following general formula (1), an amine dispersant represented by the following general formula (2), and an alkyl phosphate compound, the total content of the amino acid dispersant, the amine dispersant, and the alkyl phosphate compound is 0.03 mass% or more and 0.3 mass% or less relative to the entire conductive paste, the amine dispersant is 0.2 mass% or more and 0.05 mass% or more relative to the entire conductive paste, and the total content of the amino acid dispersant and the amine dispersant is 0.5 mass% or less relative to the entire conductive paste.
[ Chemical 1]
(Wherein, in the formula (1), R 1 represents a chain hydrocarbon group having 10 to 20 carbon atoms.)
[ Chemical 2]
( Wherein in the formula (2), R 2 represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms, R 3 represents an oxyethylene group, an oxypropylene group or a methylene group, R 4 represents an oxyethylene group or an oxypropylene group, and R 3 and R 4 may be the same or different. The N atom in formula (2) is not directly bonded to the O atom in R 3 and R 4, Y is a number of 0 to 2, and Z is a number of 1 to 2. )
In general formula (1), R 1 preferably represents a linear hydrocarbon group having 10 to 20 carbon atoms. In addition, the conductive powder preferably contains at least one metal powder selected from Ni, pd, pt, au, ag, cu and an alloy thereof. The conductive powder is preferably contained in an amount of 40 to 60 mass% based on the entire conductive paste. The average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less. The ceramic powder preferably contains a perovskite oxide. The average particle diameter of the ceramic powder is preferably 0.01 μm or more and 0.5 μm or less. The binder resin preferably contains at least one of a cellulose resin, an acrylic resin, and a butyral resin. The amino acid-based dispersant is preferably contained in an amount of 0.05 to 0.3 mass% based on the entire conductive paste. The conductive paste is preferably used for the internal electrode of a multilayer ceramic capacitor.
In a second aspect of the present invention, there is provided an electronic component formed using the conductive paste.
In a third aspect of the present invention, there is provided a multilayer ceramic capacitor comprising a laminate of an internal electrode layer formed using the conductive paste and a dielectric layer.
Effects of the invention
The conductive paste of the present invention has very small viscosity change with time, more excellent viscosity stability, and excellent dispersibility of conductive powder, and has high surface smoothness and high dry film density in a dry film after coating. In addition, the conductive paste of the present invention has a small amount of gas generated at a low temperature at the start of firing, and therefore can suppress the occurrence of cracks and delamination.
The electrode pattern of an electronic component such as a multilayer ceramic capacitor formed by using the conductive paste of the present invention is excellent in adhesion of the conductive paste even when a thin-film electrode is formed, and has a uniform width and thickness with good accuracy.
Drawings
Fig. 1 is a perspective view and a cross-sectional view showing a multilayer ceramic capacitor according to the present embodiment.
Detailed Description
[ Conductive paste ]
The conductive paste of the present embodiment contains a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent. The components are described in detail below.
(Conductive powder)
The conductive powder is not particularly limited, and a metal powder may be used, and for example, one or more kinds of powder selected from Ni, pd, pt, au, ag, cu and an alloy thereof may be used. Among them, ni or its alloy powder is preferable from the viewpoints of conductivity, corrosion resistance and cost. As the Ni alloy, for example, an alloy (Ni 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 can be used. The Ni content in the Ni alloy is, for example, 50 mass% or more, and preferably 80 mass% or more. In addition, the Ni powder may contain S in the order of several hundred ppm in order to suppress severe gas generation due to thermal decomposition of a portion of the binder resin at the time of binder removal treatment.
The average particle diameter of the conductive powder is preferably 0.05 μm or more and 1.0 μm or less, more preferably 0.1 μm or more and 0.5 μm or less. When the average particle diameter of the conductive powder is within the above range, the conductive powder can be suitably used as a slurry for internal electrodes of a laminated ceramic capacitor, and for example, the smoothness and dry film density of a dry film can be improved. The average particle diameter is a value obtained by observation with a Scanning Electron Microscope (SEM), and is an average value obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observation with the SEM at a magnification of 10,000.
The content of the conductive powder is preferably 30 mass% or more and less than 70 mass%, more preferably 40 mass% or more and 60 mass% or less, relative to the entire conductive paste. When the content of the conductive powder is within the above range, the conductive property and dispersibility are excellent.
(Ceramic powder)
The ceramic powder is not particularly limited, and for example, in the case of being a paste for an internal electrode of a multilayer ceramic capacitor, a known ceramic powder may be appropriately selected according to the type of the multilayer ceramic capacitor to be used. The ceramic powder is, for example, a perovskite oxide containing Ba and Ti, and preferably barium titanate (BaTiO 3).
As the ceramic powder, a ceramic powder containing barium titanate as a main component and an oxide as a subcomponent can be used. The oxide includes Mn, cr, si, ca, ba, mg, V, W, ta, nb and oxides of one or more rare earth elements. Examples of the ceramic powder include perovskite oxide ferroelectric ceramic powder obtained by replacing Ba atoms and Ti atoms of barium titanate (BaTiO 3) with other atoms such as Sn, pb, zr, and the like.
In the internal electrode paste, a powder having the same composition as the dielectric ceramic powder constituting the green sheet of the multilayer ceramic capacitor can be used. Thereby, occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the sintering process can be suppressed. Examples of such ceramic powders include oxides such as ZnO, ferrite, PZT, baO, al 2O3、Bi2O3, and R (rare earth element) 2O3、TiO2、Nd2O3, in addition to the above. In addition, one kind of ceramic powder may be used, or two or more kinds may be used.
The average particle diameter of the ceramic powder is, for example, in the range of 0.01 μm to 0.5 μm, preferably 0.01 μm to 0.3 μm. When the average particle diameter of the ceramic powder is within the above range, a sufficiently thin and uniform internal electrode can be formed when the ceramic powder is used as a slurry for internal electrodes. The average particle diameter is a value obtained by observation with a Scanning Electron Microscope (SEM), and is an average value obtained by measuring the particle diameters of a plurality of particles one by one from an image obtained by observation with the SEM at a magnification of 50,000.
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, based on 100 parts by mass of the conductive powder.
The content of the ceramic powder is preferably 1 mass% or more and 20 mass% or less, and more preferably 5 mass% or more and 20 mass% or less, with respect to the entire conductive paste. When the content of the ceramic powder is within the above range, the electrical conductivity and dispersibility are excellent.
(Adhesive resin)
The binder resin is not particularly limited, and a known resin can be used. Examples of the binder resin include cellulose resins such as methyl cellulose, ethyl hydroxyethyl cellulose, and nitrocellulose, butyral resins such as acrylic resins, and polyvinyl butyral resins. Among them, ethylcellulose is preferably contained from the viewpoints of solubility in solvents, combustion degradability, and the like. In addition, in the case of being used as a paste for internal electrodes, a butyral resin may be contained or may be used alone from the viewpoint of improving the adhesive strength with a green sheet. One kind of binder resin may be used, or two or more kinds may be used. As the binder resin, for example, a cellulose resin and a butyral resin can be used. The molecular weight of the binder resin is, for example, 20000 to 200000.
The content of the binder 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 content of the binder resin is preferably 0.5 mass% or more and 10 mass% or less, and more preferably 1 mass% or more and 6 mass% or less, with respect to the entire conductive paste. When the content of the binder resin is within the above range, the electrical conductivity and dispersibility are excellent.
(Organic solvent)
The organic solvent is not particularly limited, and a known organic solvent capable of dissolving the binder resin may be used. Examples of the organic solvent include acetate solvents such as dihydroterpineol acetate, isobornyl propionate, isobornyl butyrate, isobornyl isobutyrate, ethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, terpene solvents such as terpineol and dihydroterpineol, hydrocarbon solvents such as tridecane, nonane and cyclohexane, and the like. In addition, one kind of organic solvent may be used, or two or more kinds may be used.
The content of the organic solvent is preferably 40 parts by mass or more and 100 parts by mass or less, more preferably 65 parts by mass or more and 95 parts by mass or less, based on 100 parts by mass of the conductive powder. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
The content of the organic solvent is preferably 20 mass% or more and 60 mass% or less, more preferably 35 mass% or more and 55 mass% or less, with respect to the entire conductive paste. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
(Dispersant)
The conductive paste of the present embodiment contains a dispersant. The dispersant includes an amino acid dispersant (amino acid surfactant) represented by the general formula (1), an amine dispersant represented by the general formula (2), and an alkyl phosphate compound. The alkyl phosphate compound is an acid dispersant. The dispersant may contain other than the above 3 kinds of dispersants.
As a result of the studies of the inventors of the present invention on various dispersants for use in a conductive paste, it was found that by combining the above 3 dispersants in a specific blending amount, the viscosity stability of the conductive paste was very excellent, the surface smoothness and the dry film density were high in the dry film after coating, the dispersibility of the conductive powder was excellent, and the gas generation amount was small at a low temperature at the start of firing, and the occurrence of cracks and interlayer peeling was suppressed. The dispersant used in the present embodiment will be described below.
The amino acid dispersant used in the present embodiment has an N-acyl amino acid skeleton and a chain hydrocarbon group having 10 to 20 carbon atoms, as shown in the following general formula (1).
[ Chemical 3]
(Wherein, in the formula (1), R 1 represents a chain hydrocarbon group having 10 to 20 carbon atoms.)
In the above formula (1), R 1 represents a chain hydrocarbon group having 10 to 20 carbon atoms. The number of carbon atoms of R 1 is preferably 15 to 20. The chain hydrocarbon group may be a straight chain hydrocarbon group or a branched hydrocarbon group. In addition, the chain hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group. R 1 is preferably a linear hydrocarbon group, more preferably a linear alkenyl group, and has a double bond.
The amino acid-based dispersant represented by the above formula (1) may be, for example, an amino acid-based dispersant satisfying the above characteristics among commercially available products. The amino acid-based dispersant may be produced by a conventionally known production method so as to satisfy the above-described characteristics.
The amine dispersant used in the present embodiment is a tertiary amine or a secondary amine, and has a structure in which an amino group is bonded to one or two oxyalkylene groups, as shown in the following general formula (2).
[ Chemical 4]
( Wherein in the formula (2), R 2 represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms, R 3 represents an oxyethylene group, an oxypropylene group or a methylene group, R 4 represents an oxyethylene group or an oxypropylene group, and R 3 and R 4 may be the same or different. The N atom in formula (2) is not directly bonded to the O atom in R 3 and R 4, Y is a number of 0 to 2, and Z is a number of 1 to 2. )
In the above formula (2), R 2 represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms. When the number of carbon atoms of R 2 is within the above range, the powder in the conductive paste has sufficient dispersibility and is excellent in solubility with respect to the solvent. Further, R 2 is preferably a linear hydrocarbon group.
In the above formula (2), R 3 represents an oxyethylene group, oxypropylene group or methylene group, R 4 represents an oxyethylene group or oxypropylene group, and R 3 and R 4 may be the same or different. In addition, the N atom in formula (2) is not directly bonded to the O atom in R 3 and R 4, Y is a number of 0 to 2, and Z is a number of 1 to 2.
For example, in the above formula (2), R 3 is an oxyalkylene group represented by-AO-, when Y is 1 to 2, an O atom in the oxyalkylene group at the terminal end and an H atom adjacent to (R 3)Y) are bonded, when R 3 is a methylene group, (R 3)Y is represented by- (CH 2)Y) -, when Y is 1 to 2, it is bonded to an adjacent H element to form a methyl group (-CH 3) or an ethyl group (-CH 2-CH3) and when R 4 is an oxyalkylene group represented by-AO-, an O atom in the oxyalkylene group at the terminal portion is bonded to an H atom adjacent to (R 4)Z).
In the above formula (2), when Y is 0, the amine-based dispersant is a secondary amine having-R 2, one hydrogen group and- (R 4)z H): for example, when Y is 0 and Z is 2, the amine dispersant is a secondary amine composed of an alkyl group, alkenyl group or alkynyl group having 8 to 16 carbon atoms, a hydrogen group, and- (R 4)2 H), wherein- (R 4)2 H is- (AO) 2 H in which either one of a vinyl dioxide group and a propenyl dioxide group is bonded to an H element.
In the formula (2), when Y is 1, the amine-based dispersant is a tertiary amine having-R 2、-R3 H and- (R 4)z H), and when Y is 2, the amine dispersant is a tertiary amine having-R 2、-(R3)2 H and- (R 4)z H, wherein- (R 3)2 H is- (AO) 2 H or-C 2H5 in which any one of a vinyl dioxide group, a propylene dioxide group and an ethylene group is bonded to an H element.
The amine-based dispersant represented by the above formula (2) may be, for example, one which satisfies the above characteristics in a commercially available product. The amine-based dispersant may be produced by a conventionally known production method so as to satisfy the above-described characteristics.
Further, in the present embodiment, an alkyl phosphate compound is used as an acid-based dispersant. The alkyl phosphate compound is a phosphate having an alkyl group, preferably having a polyoxyalkylene structure, and may be an alkyl phosphate polyoxyalkylene compound.
As a result of the studies of various dispersants for use in the conductive paste, the inventors of the present invention have found that the use of a dispersant for use in the conductive paste can suppress the occurrence of structural defects such as cracks and delamination by delaying the occurrence of decomposition gas derived from components contained in the conductive paste when firing the laminate by containing an alkyl phosphate compound in addition to the amino acid-based dispersant and the amine-based dispersant. Hereinafter, the content of each component used as a dispersant will be described.
The above-mentioned amino acid dispersant is contained in an amount of 0.03 to 0.3 mass% based on the entire conductive paste. When the amount of the amino acid-based dispersant is less than 0.03 mass%, the conductive paste may not have sufficient dispersibility. When the content of the amino acid-based dispersant exceeds 0.3 mass%, the amount of the decomposed gas generated from the conductive paste at the start of firing is large, and the dispersibility and removability may be insufficient. From the viewpoint of further improving dispersibility, the amino acid-based dispersant may be contained in an amount of 0.05 to 0.3 mass% or more and 0.10 to 0.3 mass% or less, based on the entire conductive paste.
The amine dispersant is contained in an amount of 0.2 mass% or more based on the entire conductive paste. When the amount of the amine-based dispersant is less than 0.2% by mass, the conductive paste may not have sufficient viscosity stability and insufficient dispersibility.
The conductive paste contains 0.05 mass% or more of an alkyl phosphate compound relative to the entire conductive paste. When the content of the alkyl phosphate compound is less than 0.05 mass%, the conductive paste may not have sufficient viscosity stability, and may generate decomposition gas at a low temperature at the start of sintering, thereby causing cracks and delamination.
The total content of the amine-based dispersant and the amino acid-based dispersant is 0.5 mass% or less with respect to the entire conductive paste. When the total amount of the 2 kinds of dispersants exceeds the above range, generation of decomposition gas derived from the components contained in the conductive paste may occur at a lower temperature when the laminate is fired, and voids, peeling failure of the green sheet, and the like may occur.
The total content of the amino acid-based dispersant, the amine-based dispersant, and the alkyl phosphate compound is 0.7 mass% or less with respect to the entire conductive paste. When the content of the 3 kinds of dispersants exceeds 0.7 mass%, the dispersants are not sufficiently removed and remain partially at the time of firing the laminate, and structural defects such as cracks, voids, peeling failure of green sheets, and sheet erosion may occur.
The conductive paste may contain a dispersant other than the amino acid dispersant, the amine dispersant, and the alkyl phosphate compound within a range that does not inhibit the effect of the present invention. Examples of the dispersant other than the above include an acid-based dispersant including a higher fatty acid and a polymer surfactant, a cationic dispersant other than the acid-based dispersant, a nonionic dispersant, an amphoteric surfactant, and a polymer dispersant. In addition, one or a combination of two or more of these dispersants may be used.
(Conductive paste)
The method for producing the conductive paste of the present embodiment is not particularly limited, and a conventionally known method can be used. For example, the conductive paste can be produced by stirring and kneading the above components by a three-roll mill, a ball mill, or a mixer. In this case, if the dispersant is applied in advance to the surface of the conductive powder, the conductive powder is not aggregated, and can be sufficiently dispersed, and the dispersant is spread over the surface of the conductive powder, so that a uniform conductive paste can be easily obtained. The conductive paste may be prepared by dissolving the binder resin in an organic solvent for a carrier to prepare an organic carrier, adding the conductive powder, ceramic powder, organic carrier and dispersant to the organic solvent for paste, and stirring and kneading the mixture.
When the viscosity after 24 hours from the production of the conductive paste is used as a reference (0%), the viscosity of the conductive paste after standing for 28 days from the reference day is preferably within ±10%. The viscosity of the conductive paste can be measured, for example, by the method described in examples (a method of measuring at 10rpm (shear rate=4sec -1) using a B-type viscometer manufactured by Brookfield corporation).
The surface smoothness of the dried film formed by printing the conductive paste can be evaluated by the surface roughness. The surface roughness of the conductive paste can be measured, for example, using a surface roughness meter. Specifically, the surface roughness of the dried film was measured using a surface roughness meter for the dried film having a film thickness of 3 μm, which was obtained by applying the conductive paste on a glass substrate using an applicator (gap thickness of 10 μm) and then drying at 120℃for 5 minutes in air. Such surface roughness is preferably 0.05 μm or less, more preferably 0.04 μm or less.
Further, the Dry Film Density (DFD) of the dry film obtained by drying after printing the conductive paste is preferably 5.45g/cm 3 or more, more preferably more than 5.45g/cm 3, and still more preferably more than 5.5g/cm 3.
The mass change amount (Δtg) of the conductive paste at 250 ℃ when the conductive paste is heated at a temperature rise rate of 5 ℃/min in a nitrogen atmosphere and subjected to thermal weight measurement (TG) is preferably less than 0.0020%/s, more preferably 0.0015%/s or less. When the mass change amount is within the above range, the dispersant removability at the time of firing can be made good.
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 green sheet and an internal electrode layer formed using a conductive paste.
In the multilayer ceramic capacitor, the dielectric ceramic powder contained in the green sheet and the ceramic powder contained in the conductive paste are preferably powders having the same composition. The multilayer ceramic capacitor manufactured using the conductive paste of the present embodiment can suppress sheet erosion and peeling failure of the green sheet even when the thickness of the green sheet is, for example, 3 μm or less.
[ Electronic component ]
Hereinafter, embodiments of an electronic component and the like according to the present invention will be described with reference to the drawings. In the drawings, the drawings may be schematically represented or may be represented by changing the scale. The position, direction, and the like of the member will be described with reference to an XYZ orthogonal coordinate system shown in fig. 1 and the like as appropriate. In the XYZ orthogonal coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is vertical direction (vertical direction).
A in fig. 1 and B in fig. 1 are diagrams showing a multilayer ceramic capacitor 1 as an example of an electronic component according to the embodiment. The multilayer ceramic capacitor 1 has a laminate 10 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated, and external electrodes 20.
Hereinafter, a method for manufacturing a multilayer ceramic capacitor using the above conductive paste will be described. First, a conductive paste is printed on a dielectric layer made of a green sheet and dried to form a dried film. The ceramic laminate 10 is produced by laminating and bonding a plurality of dielectric layers having the dry film on the upper surface, and then firing and integrating the laminate, thereby alternately laminating the internal electrode layers 11 and the dielectric layers 12. Thereafter, a pair of external electrodes 20 are formed at both end portions of the ceramic laminate 10 to produce the laminated ceramic capacitor 1. Hereinafter, the present invention will be described in more detail.
First, a green sheet is prepared as an unfired ceramic sheet using a dielectric material. Examples of the green sheet include a green sheet formed by applying a slurry for a dielectric layer, which is obtained by adding an organic binder such as polyvinyl butyral and a solvent such as terpineol to a predetermined ceramic raw material powder such as barium titanate, onto a support film such as a PET film, and drying the support film to remove the solvent. The thickness of the dielectric layer formed of the green sheet is not particularly limited, but is preferably 0.05 μm or more and 3 μm or less from the viewpoint of the demand for downsizing of the multilayer ceramic capacitor.
Next, a plurality of sheets are prepared, each of which has a dry film formed by printing (coating) the conductive paste on one surface of the green sheet by a known method such as a screen printing method, and drying the printed conductive paste. In view of the requirement for thinning the internal electrode layer 11, the thickness of the printed conductive paste is preferably such that the thickness of the dried film after drying is 1 μm or less.
Next, the green sheet is peeled from the support film, and laminated so that the dielectric layer made of the green sheet and the dry film formed on one surface of the dielectric layer are alternately arranged, and then the laminate is obtained by heating and pressurizing. The protective green sheet to which the conductive paste is not applied may be further disposed on both sides of the laminate.
Next, the laminate is cut into a predetermined size to form green chips, and then the green chips are subjected to binder removal treatment and fired in a reducing atmosphere to produce the ceramic laminate 10. The atmosphere in the binder removal treatment is preferably an atmosphere of air or N 2 gas. The temperature at which the binder removal treatment is performed is, for example, 200 ℃ to 400 ℃. The holding time at the temperature at the time of the binder removal treatment is preferably 0.5 hours to 24 hours. In addition, the firing is performed in a reducing atmosphere in order to suppress oxidation of the metal used in the internal electrode layer, and the temperature at which the laminate is fired is, for example, 1000 ℃ to 1350 ℃, and the holding time of the temperature at which the firing is performed is, for example, 0.5 hours to 8 hours.
By firing the green chip, the organic binder in the green chip is completely removed, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12. The organic carrier in the dried film is removed, and the nickel powder or the alloy powder containing nickel as a main component is sintered or melted to be integrated, thereby forming the internal electrode layers 11, and further forming a multilayer ceramic fired body in which the dielectric layers 12 and the internal electrode layers 11 are alternately laminated in layers. In addition, from the viewpoints of improving reliability by introducing oxygen into the dielectric layer and suppressing reoxidation of the internal electrode, the fired laminated ceramic fired body may be subjected to an annealing treatment.
Then, the laminated ceramic capacitor 1 is manufactured by providing the prepared laminated ceramic fired body with a pair of external electrodes 20. For example, the external electrode 20 includes an external electrode layer 21 and a plating layer 22. The external electrode layer 21 is electrically connected to the internal electrode layer 11. Further, as a material of the external electrode 20, copper, nickel, or an alloy thereof, for example, can be preferably used. The electronic component is not limited to the monolithic ceramic capacitor, and may be an electronic component other than the monolithic ceramic capacitor.
Examples
Hereinafter, the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to the examples.
[ Use of materials ]
(Conductive powder)
As the conductive powder, ni powder (SEM average particle diameter of 0.2 μm) was used.
(Ceramic powder)
As the ceramic powder, barium titanate (BaTiO 3; SEM average particle size 0.05 μm) was used.
(Adhesive resin)
As the binder resin, an ethylcellulose resin and a polyvinyl butyral resin (PVB resin) were used. The binder resin prepared as a carrier dissolved in terpineol is used.
(Dispersant)
(1) As the amino acid-based dispersant, dispersant A represented by R 1＝C17H33 (linear hydrocarbon group) in the above general formula (1) was used.
(2) As the amine-based dispersant, dispersant B represented by the above general formula (2) R2＝C12H25、R3＝C2H4O、R4＝C2H4O、Y＝1、Z＝1 was used.
(3) As the alkyl phosphate compound, a dispersant C composed of an alkyl phosphate polyoxyalkylene compound is used.
(Organic solvent)
As the organic solvent, terpineol was used.
Example 1
48 Mass% of Ni powder, 5 mass% of ceramic powder, a binder resin (composed of an ethyl cellulose resin and a polyvinyl butyral resin) in a carrier, 0.10 mass% of an amino acid-based dispersant, 0.26 mass% of an amine-based dispersant, 0.10 mass% of a dispersant composed of an alkyl polyoxyalkylene phosphate compound, and terpineol (an organic solvent) as the balance were blended so as to be 100 mass% as a whole, and these materials were mixed to prepare a conductive paste. The viscosity stability, dispersibility (dry film density, surface roughness of the dry film) and dispersant removability of the prepared conductive paste were evaluated by the following methods. The evaluation results are shown in table 1.
[ Evaluation method ]
(1) Viscosity stability: variation of viscosity of conductive paste
The viscosity of each sample was measured at the reference time, after 24 hours from the reference time at room temperature (25 ℃) and after 28 days from the reference time, by the following method, using the reference time after 24 hours from the production of the conductive paste. Then, a value ([ (viscosity after 28 days of standing-viscosity after 24 hours of production)/viscosity after 24 hours of production ] ×100) representing the amount of change in viscosity of the sample after 28 days of standing in percent (%) was obtained with the viscosity after 24 hours of production (reference time) as a reference (0%), and used as the amount of change in viscosity. The viscosity of the conductive paste was measured using a B-type viscometer manufactured by Brookfield company at 10rpm (shear rate=4sec -1). Further, the smaller the amount of change in the viscosity of the conductive paste, the more desirable. The viscosity stability of the conductive paste was evaluated by referring to "o" when the amount of change in the viscosity of the conductive paste after 28 days of standing was 10% or less, referring to "Δ" when it was more than 10% and less than 40%, and referring to "x" when it was 40% or more.
(2) Dispersibility: surface roughness of dried film, dried film density
Surface roughness >
The prepared conductive paste was screen-printed on heat-resistant tempered glass having a square of 2.54cm (1 inch), and dried at 120℃in the atmosphere for 1 hour, thereby preparing a dried film having a square of 20mm and a film thickness of about 3. Mu.m. When the dispersibility of the conductive paste is good, the surface of the dried film becomes a smooth film. If the dispersibility is poor, aggregation occurs in the conductive paste, and the surface of the dried film is roughened, and the surface smoothness is lowered. In this case, the protrusions on the surface of the dry film were measured by a contact surface roughness meter. Specifically, the surface roughness Ra of the dried film was measured using a surface roughness measuring device (SURFCOM 480 manufactured by tokyo precision co.). The smaller the value of the surface roughness Ra, the smoother the surface of the dried film.
< Dry film Density (DFD: DRY FILM DENSITY) >
The prepared conductive paste was placed on a PET film and extended to a length of about 100mm by an applicator having a width of 50mm and a gap of 125. Mu.m. After the obtained PET film was dried at 120 ℃ for 40 minutes to form a dried body, the dried body was cut into 4 squares of 2.54cm (1 inch), and after the PET film was peeled off, the thickness and mass of the 4 dried films were measured, respectively, to calculate the dried film density (average value). If the dispersibility of the conductive paste is low and the conductive powder is aggregated, the dry film density may be lowered, and the electrical characteristics and the like may be poor. The higher the dry film density, the better the dispersibility.
< Evaluation of dispersibility >
The dispersibility was evaluated by marking the surface roughness Ra of the dried film as "o" when the surface roughness Ra of the dried film was 0.04 μm or less and the dried film density DFD was 5.45g/cm 3 or more, marking the surface roughness Ra (arithmetic average height) of the dried film as more than 0.04 μm and 0.05 μm or less and the dried film density DFD as 5.45g/cm 3 or more as "Δj" when either the surface roughness Ra of the dried film was more than 0.05 μm or the dried film density DFD was less than 5.45g/cm 3 was satisfied.
(3) Evaluation of dispersant removability
The prepared conductive paste was heated at a heating rate of 5 ℃/min in a nitrogen atmosphere to perform Thermogravimetry (TG), and the decomposition behavior due to the difference in dispersant was analyzed, thereby evaluating the dispersant removability. Specifically, a curve of the mass change amount (Δtg) with respect to temperature was prepared, and the evaluation was performed by the mass change amount (Δtg) at 250 ℃. The larger the mass change amount (Δtg) at 250 ℃, the larger the amount of the decomposed gas generated from the conductive paste at the start of firing can be determined.
250 ℃ Is the temperature at which sintering of the dielectric layer begins. When the dielectric layer starts to sinter, a gap is formed in the dielectric layer, and a certain amount of decomposed gas generated from the components contained in the conductive paste can be discharged from the gap. On the other hand, when a certain amount of decomposed gas is generated before firing of the dielectric layers is started, since there is no gap in the dielectric layers, the gas is not discharged to the outside and is easily trapped between the dielectric layers to generate voids. Therefore, by measuring the mass change amount of the conductive paste at the time of heat treatment at 250 ℃, it can be judged whether the gas generated by decomposition at the start of firing of the laminate can be discharged through the dielectric layers (good dispersant removability) or is retained between the dielectric layers to be a main cause of void generation (poor dispersant removability).
In the evaluation of the dispersant removability, the gas generation amount was sufficiently small when the mass change amount was 0.0015%/s or less, and thus it was marked as "good", and the gas generation amount was larger than 0.0015%/s and smaller than 0.0020%/s, but the gas generation amount was a certain amount, and it was marked as "Δ" (good) because the gas was able to be discharged through the dielectric layer, and the gas generation amount was not able to be discharged to the outside and remained in many cases when the mass change amount was 0.0020%/s or more, and thus it was marked as "×" (bad).
Examples 2 to 6 and comparative examples 1 to 9
A conductive paste was prepared under the same conditions as in example 1, except that the proportions of the dispersants were changed by changing the contents of the dispersants a, B and C to the amounts shown in table 1. The viscosity stability, dispersibility (dry film density, surface roughness of the dry film) and dispersant removability of the prepared conductive paste were evaluated by the above-described method. The evaluation results are shown in table 1.
[ Evaluation results ]
As shown in table 1, the viscosity stability of the conductive paste of examples was good. The conductive paste of the example had a dry film density of 5.45g/cm 3 or more and a surface roughness Ra of 0.05 μm or less, and exhibited good dispersibility. Further, the conductive paste of the example has a small weight change at 250 ℃ and a small amount of decomposed gas generated at a low temperature at the start of firing, and there is no concern that voids are generated due to the residue of decomposed gas.
On the other hand, the conductive paste of the comparative example having the content of the dispersant out of the range of the present invention was found to have poor viscosity stability and low dispersibility.
Industrial applicability
The conductive paste according to the present embodiment is excellent in dispersibility in addition to excellent in viscosity stability with time, and thus the smoothness and dry film density of the dried film after coating are excellent. Further, the conductive paste according to the present embodiment can suppress the generation of decomposition gas at 250 ℃, and thus suppress the generation of cracks and interlayer peeling due to the generation of voids or the like. Therefore, the conductive paste according to the present embodiment can be used particularly suitably as a raw material for internal electrodes of a monolithic ceramic capacitor used as a chip component (electronic component) of electronic devices such as mobile phones and digital devices.
The technical scope of the present invention is not limited to the embodiments described in the above embodiments and the like. One or more of the elements described in the above embodiments and the like may be omitted. The elements described in the above embodiments and the like may be appropriately combined. In addition, the disclosures of all documents cited in the above embodiments and the like are incorporated by reference as part of the description herein, whenever allowed by law. In addition, the contents of Japanese patent application No. 2019-022906, which is Japanese patent application, are incorporated by reference as if allowed by law and as part of the description herein.
Description of the reference numerals
1. Multilayer ceramic capacitor
10. Ceramic laminate
11. Internal electrode layer
12. Dielectric layer
20. External electrode
21. External electrode layer
22. Electroplated layer
Claims (12)
1. A conductive paste comprising a conductive powder, a ceramic powder, a dispersant, a binder resin, and an organic solvent, wherein,
The dispersant comprises an amino acid dispersant represented by the following general formula (1), an amine dispersant represented by the following general formula (2) and an alkyl phosphate compound,
The above-mentioned amino acid dispersant is contained in an amount of 0.03 to 0.3 mass% based on the whole conductive paste,
The amine dispersant is contained in an amount of 0.2 mass% or more relative to the entire conductive paste,
The above alkyl phosphate compound is contained in an amount of 0.05 mass% or more relative to the entire conductive paste,
The total content of the amino acid-based dispersant and the amine-based dispersant is 0.5 mass% or less with respect to the whole conductive paste,
The total content of the amino acid-based dispersant, the amine-based dispersant and the alkyl phosphate compound is 0.7 mass% or less with respect to the whole conductive paste,
[ Chemical 1]
Wherein in formula (1), R 1 represents a chain hydrocarbon group having 10 to 20 carbon atoms,
[ Chemical 2]
Wherein in formula (2), R 2 represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms, R 3 represents an oxyethylene group, an oxypropylene group or a methylene group, R 4 represents an oxyethylene group or an oxypropylene group, R 3 and R 4 may be the same or different, and in addition, the N atom in formula (2) is not directly bonded to the O atom in R 3 and R 4, Y is a number of 0to 2, and Z is a number of 1 to 2.
2. The conductive paste according to claim 1, wherein in the general formula (1), R 1 represents a linear hydrocarbon group having 10 to 20 carbon atoms.
3. The conductive paste according to claim 1 or 2, wherein the conductive powder comprises a metal powder selected from at least one of Ni, pd, pt, au, ag, cu and an alloy thereof.
4. The conductive paste according to claim 1 or 2, wherein the conductive powder is contained in an amount of 40 mass% to 60 mass% with respect to the entire conductive paste.
5. The conductive paste according to claim 1 or 2, wherein the conductive powder has an average particle diameter of 0.05 μm or more and 1.0 μm or less.
6. The electroconductive paste according to claim 1 or 2, wherein the ceramic powder contains perovskite-type oxides.
7. The electroconductive paste according to claim 1 or 2, wherein the ceramic powder has an average particle diameter of 0.01 μm or more and 0.5 μm or less.
8. The conductive paste according to claim 1 or 2, wherein the binder resin contains at least one of a cellulose-based resin, an acrylic-based resin, and a butyral-based resin.
9. The conductive paste according to claim 1 or 2, wherein the amino acid-based dispersant is contained in an amount of 0.05 to 0.3 mass% based on the entire conductive paste.
10. The electroconductive paste according to claim 1 or 2, wherein the electroconductive paste is used for internal electrodes of a laminated ceramic capacitor.
11. An electronic component formed using the electroconductive paste according to any one of claims 1 to 9.
12. A laminated ceramic capacitor comprising a laminate of an internal electrode layer formed using the electroconductive paste according to claim 10 and a dielectric layer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2019-022906 | 2019-02-12 | ||
| JP2019022906 | 2019-02-12 | ||
| PCT/JP2020/003531 WO2020166361A1 (en) | 2019-02-12 | 2020-01-30 | Electroconductive paste, electronic component, and laminated ceramic capacitor |
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| CN113396458A CN113396458A (en) | 2021-09-14 |
| CN113396458B true CN113396458B (en) | 2024-07-09 |
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| CN202080012624.9A Active CN113396458B (en) | 2019-02-12 | 2020-01-30 | Conductive paste, electronic component, and multilayer ceramic capacitor |
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| JP (1) | JP7517156B2 (en) |
| KR (1) | KR20210120006A (en) |
| CN (1) | CN113396458B (en) |
| TW (1) | TWI819190B (en) |
| WO (1) | WO2020166361A1 (en) |
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| JP2022084400A (en) * | 2020-11-26 | 2022-06-07 | 住友金属鉱山株式会社 | Conductive paste and laminated ceramic capacitor |
| KR20230119946A (en) | 2022-02-08 | 2023-08-16 | 삼성전기주식회사 | Method for manufacturing conductive paste and method for manufacturing multilayer ceramic electronic component |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1896082A (en) * | 2005-07-15 | 2007-01-17 | 三星电机株式会社 | Phosphate dispersant, paste composition and dispersion method using the same |
| JP2018198202A (en) * | 2017-05-23 | 2018-12-13 | 住友金属鉱山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05242724A (en) * | 1992-02-27 | 1993-09-21 | Taiyo Yuden Co Ltd | Conductive paste |
| JP2005002070A (en) * | 2003-06-16 | 2005-01-06 | Q P Corp | Method for producing water dispersion composition of phospholipid and aqueous cosmetic |
| JP4495644B2 (en) | 2004-07-30 | 2010-07-07 | Ｊｆｅミネラル株式会社 | Metal super fine slurry |
| JP2010177084A (en) * | 2009-01-30 | 2010-08-12 | Mitsuboshi Belting Ltd | Metal nanoparticle paste and conductive base material |
| WO2012147955A1 (en) * | 2011-04-28 | 2012-11-01 | 富士フイルム株式会社 | Conductive member, method for producing same, touch panel, and solar cell |
| JP5772621B2 (en) | 2012-01-19 | 2015-09-02 | 住友金属鉱山株式会社 | Conductive paste for internal electrodes |
| JP6292014B2 (en) | 2014-05-12 | 2018-03-14 | 株式会社村田製作所 | Conductive paste and ceramic electronic components |
| JP7013731B2 (en) | 2017-08-30 | 2022-02-01 | 住友金属鉱山株式会社 | Method for manufacturing conductive paste, electronic components and multilayer ceramic capacitors |
| JP2019046782A (en) | 2017-08-30 | 2019-03-22 | 住友金属鉱山株式会社 | Conductive paste and methods for manufacturing electronic component and multilayer ceramic capacitor |
| JP2019046783A (en) | 2017-08-30 | 2019-03-22 | 住友金属鉱山株式会社 | Conductive paste and methods for manufacturing electronic component and multilayer ceramic capacitor |
| JP2019046781A (en) | 2017-08-30 | 2019-03-22 | 住友金属鉱山株式会社 | Conductive paste and methods for manufacturing electronic component and multilayer ceramic capacitor |
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- 2020-01-30 JP JP2020572162A patent/JP7517156B2/en active Active
- 2020-01-30 CN CN202080012624.9A patent/CN113396458B/en active Active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1896082A (en) * | 2005-07-15 | 2007-01-17 | 三星电机株式会社 | Phosphate dispersant, paste composition and dispersion method using the same |
| JP2018198202A (en) * | 2017-05-23 | 2018-12-13 | 住友金属鉱山株式会社 | Conductive paste, electronic component, and multilayer ceramic capacitor |
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| KR20210120006A (en) | 2021-10-06 |
| TWI819190B (en) | 2023-10-21 |
| TW202042252A (en) | 2020-11-16 |
| JP7517156B2 (en) | 2024-07-17 |
| JPWO2020166361A1 (en) | 2021-12-16 |
| WO2020166361A1 (en) | 2020-08-20 |
| CN113396458A (en) | 2021-09-14 |
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