CN113396458A - Conductive paste, electronic component, and multilayer ceramic capacitor - Google Patents
Conductive paste, electronic component, and multilayer ceramic capacitor Download PDFInfo
- Publication number
- CN113396458A CN113396458A CN202080012624.9A CN202080012624A CN113396458A CN 113396458 A CN113396458 A CN 113396458A CN 202080012624 A CN202080012624 A CN 202080012624A CN 113396458 A CN113396458 A CN 113396458A
- Authority
- CN
- China
- Prior art keywords
- conductive paste
- dispersant
- mass
- powder
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003985 ceramic capacitor Substances 0.000 title claims description 32
- 239000002270 dispersing agent Substances 0.000 claims abstract description 115
- 239000000843 powder Substances 0.000 claims abstract description 92
- 239000000919 ceramic Substances 0.000 claims abstract description 41
- 229920005989 resin Polymers 0.000 claims abstract description 39
- 239000011347 resin Substances 0.000 claims abstract description 39
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- -1 alkyl phosphate compound Chemical class 0.000 claims abstract description 30
- 150000001413 amino acids Chemical class 0.000 claims abstract description 30
- 150000001412 amines Chemical class 0.000 claims abstract description 29
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 21
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 239000010452 phosphate 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
- 239000000956 alloy Substances 0.000 claims description 7
- 229910045601 alloy Inorganic materials 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
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- 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 25
- 239000010408 film Substances 0.000 description 55
- 239000010410 layer Substances 0.000 description 52
- 239000007789 gas Substances 0.000 description 24
- 230000003746 surface roughness Effects 0.000 description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 238000000354 decomposition reaction Methods 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011229 interlayer Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000002411 thermogravimetry Methods 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
- 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
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000203 mixture Substances 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
- 239000010949 copper Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000007639 printing Methods 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
- 125000003277 amino group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000012461 cellulose resin Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002003 electrode paste Substances 0.000 description 3
- 229920001249 ethyl cellulose Polymers 0.000 description 3
- 235000019325 ethyl cellulose Nutrition 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000007847 structural defect Effects 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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000032798 delamination Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 238000004898 kneading 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 description 2
- 239000010944 silver (metal) Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 239000010409 thin film Substances 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
- 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
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 229910010059 TiBaO3 Inorganic materials 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
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 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
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium 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
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000003628 erosive effect Effects 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 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
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
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 OR LIGHT-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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
Abstract
Provided is a conductive paste which has excellent dispersibility of a conductive powder, has more excellent viscosity stability, and generates a small amount of gas 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 contains an amino acid-based dispersant, an amine-based dispersant and an alkyl phosphate compound, contains 0.03 to 0.3 mass% of the amino acid-based dispersant, contains 0.2 to 0 mass% of the amine-based dispersant, contains 0.05 mass% of the alkyl phosphate compound, has a total content of the amino acid-based dispersant and the amine-based dispersant of 0.5 mass% or less, and has a total content of the amino acid-based dispersant, the amine-based dispersant and the alkyl phosphate compound of 0.7 mass% or less.
Description
Technical Field
The invention relates to a conductive paste, an electronic component and a multilayer ceramic capacitor.
Background
With the miniaturization and high performance of electronic devices such as mobile phones and digital devices, miniaturization and high capacity are also demanded 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 can be reduced in size and increased in capacity by making the dielectric layers and the internal electrode layers thin.
For example, a laminated ceramic capacitor can be manufactured as follows. Firstly, barium titanate (BaTiO) is added3) The conductive paste for internal electrodes is printed (applied) on the surface of the green sheet of the dielectric powder and the binder resin in a predetermined electrode pattern, and dried to form a dry film. Next, the dried film and the green sheet are alternately stacked, and are heated and pressure-bonded to form a laminate in an integrated state. The laminate is cut, subjected to a binder removal treatment in an oxidizing atmosphere or an inert atmosphere, and then fired to obtain a fired chip. Next, an external electrode paste is applied to both ends of the fired chip, and after firing, nickel plating or the like is applied to the surface of the external electrode, thereby obtaining a multilayer ceramic capacitor.
In general, a conductive paste for forming the internal electrode layer contains conductive powder, ceramic powder, a binder resin, and an organic solvent. In addition, the conductive paste may contain a dispersant in order to improve dispersibility of the conductive powder and the like. With the recent reduction in the thickness of the internal electrode layer, 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 is large, and therefore the surface activity of the conductive powder (metal powder) is high, and dispersibility may be reduced, and viscosity characteristics may be reduced.
Therefore, attempts have been made to improve the viscosity characteristics of the conductive paste with time. For example, patent document 1 describes a conductive paste containing at least a metal component, an oxide, a dispersant and a binder resin, wherein the metal component is Ni powder having a surface composition with a specific composition ratio, the acid site amount of the dispersant is 500 to 2000 μmol/g, and the acid site 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 describes a conductive paste for internal electrodes, which is composed of a conductive powder, a resin, an organic solvent, and TiBaO3Mainly ceramic powder, 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 conductive paste for internal electrodes suppresses aggregation of the common material components, has excellent long-term storage properties, and can realize a thin film of a multilayer ceramic capacitor.
On the other hand, when the internal electrode layer is made thin, a dried 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, the metal ultrafine powder slurry contains 70 to 95 mass% of the metal ultrafine powder, and the surfactant is contained in an amount of more than 0.05 parts by mass and less than 2.0 parts by mass based on 100 parts by mass of the metal ultrafine powder. According to patent document 3, by preventing aggregation of ultrafine particles, a metal ultrafine powder slurry having excellent dispersibility and dry film density without aggregated particles can be obtained.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2015-216244
Patent document 2: japanese patent laid-open publication No. 2013-149457
Patent document 3: japanese patent laid-open No. 2006 and 063441
Disclosure of Invention
Problems to be solved by the invention
However, with recent reduction in the thickness of electrode patterns, further improvement in viscosity characteristics over time and improvement in surface smoothness of a dried film after coating have been demanded. Further, since the electrode pattern is made thin, when the laminate is fired, a mismatch in shrinkage occurs at the interface between the internal electrode layer and the dielectric layer, and structural defects such as cracks and interlayer peeling are more likely to occur.
The present inventors have found that generation of decomposition gas derived from components contained in the conductive paste at a low temperature at the start of firing of the laminate causes cracking and interlayer peeling. That is, when a certain amount of gas is generated from the dried film at a temperature lower than the temperature at which the dielectric layers (green sheets) start to be sintered at the time of firing the laminate, the gas is likely to remain between the dielectric layers to generate voids, thereby causing cracks and interlayer peeling.
Even in a conventional conductive paste which has not reported problems such as cracking and interlayer peeling, when an electrode pattern is further thinned, generation of a trace amount of gas at a low temperature at the start of firing may cause cracking and interlayer peeling.
In view of such circumstances, an object of the present invention is to provide a conductive paste which has high surface smoothness of a dried film and high density of the dried film, is excellent in dispersibility of a conductive powder, has very little change in viscosity with time, is further excellent in viscosity stability, and generates a small amount of gas 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 contains an amino acid-based dispersant represented by the following general formula (1), an amine-based dispersant represented by the following general formula (2), and an alkyl phosphate compound, and the dispersant contains 0.03 to 0.3 mass% of the amino acid-based dispersant, 0.2 to 0.2 mass% of the amine-based dispersant, 0.05 to 0.5 mass% of the alkyl phosphate compound, and the total content of the amino acid-based dispersant and the amine-based dispersant, and 0.7 mass% or less of the amino acid-based dispersant, the amine-based dispersant, and the alkyl phosphate compound, respectively, relative to the entire conductive paste.
[ solution 1]
(wherein, in the formula (1), R1Represents a chain-like hydrocarbon group having 10 to 20 carbon atoms. )
[ solution 2]
(wherein, in the formula (2), R2Represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms, R3Represents an oxyethylene group, oxypropylene group or methylene group, R4Represents an oxyethylene group or an oxypropylene group, R3And R4May be the same or may be different. In addition, the N atom in the formula (2) is not bound to R3And R4Wherein O atom is directly bonded, Y is a number of 0 to 2, and Z is a number of 1 to 2. )
In the general formula (1), R1Preferably, the hydrocarbon group is a linear hydrocarbon group having 10 to 20 carbon atoms. The conductive powder preferably contains at least one metal powder selected from the group consisting of Ni, Pd, Pt, Au, Ag, Cu, and alloys 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. In addition, ceramicsThe powder preferably contains a perovskite-type 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 internal electrodes of multilayer ceramic capacitors.
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 having a multilayer body in which internal electrode layers and dielectric layers formed using the conductive paste are laminated.
Effects of the invention
The conductive paste of the present invention has very little change in viscosity with time, is more excellent in viscosity stability, is excellent in dispersibility of the conductive powder, and has high surface smoothness and high dry film density in a dried film after coating. In addition, since the conductive paste of the present invention generates a small amount of gas at a low temperature at the start of firing, the generation of cracks and delamination can be suppressed.
The electrode pattern of an electronic component such as a multilayer ceramic capacitor formed using the conductive paste of the present invention is excellent in adhesion of the conductive paste when forming a thin-film electrode, 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. Hereinafter, each component will be described in detail.
(conductive powder)
The conductive powder is not particularly limited, and a metal powder may be used, and for example, at least one powder selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof may be used. Among them, Ni or an alloy thereof is preferably used as the powder in terms of conductivity, corrosion resistance, and cost. As the Ni alloy, for example, an alloy (Ni alloy) of Ni and at least one element selected from the group consisting of Mn, Cr, Co, Al, Fe, Cu, Zn, Ag, Au, Pt, and Pd can be used. The Ni content in the Ni alloy is, for example, 50 mass% or more, preferably 80 mass% or more. In addition, the Ni powder may contain S in the order of several hundred ppm in order to suppress the generation of a violent gas due to the thermal decomposition of the binder resin portion during the binder removal treatment.
The average particle diameter of the conductive powder is preferably 0.05 μm to 1.0 μm, more preferably 0.1 μm to 0.5 μm. 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 to be made thin, and for example, the smoothness and density of a dried 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 a SEM at a magnification of 10,000 times.
The content of the conductive powder is preferably 30 mass% or more and less than 70 mass%, and more preferably 40 mass% or more and 60 mass% or less with respect to the entire conductive paste. When the content of the conductive powder is within the above range, the conductivity and dispersibility are excellent.
(ceramic powder)
The ceramic powder is not particularly limited, and for example, in the case of the internal electrode paste for a multilayer ceramic capacitor, a known ceramic powder can be appropriately selected depending on the type of multilayer ceramic capacitor to be used. The ceramic powder includes, for example, a perovskite-type oxide containing Ba and Ti, preferably barium titanate (BaTiO)3)。
The ceramic powder may contain barium titanate as a main component andceramic powder containing oxides as a subcomponent. Examples of the oxide include oxides of Mn, Cr, Si, Ca, Ba, Mg, V, W, Ta, Nb, and one or more rare earth elements. As such ceramic powder, for example, barium titanate (BaTiO) is cited3) The ceramic powder of a perovskite oxide ferroelectric material in which Ba atoms and Ti atoms are substituted with other atoms such as Sn, Pb, and Zr.
In the internal electrode paste, a powder having the same composition as the dielectric ceramic powder of the green sheet constituting the multilayer ceramic capacitor can be used. This can suppress the occurrence of cracks due to shrinkage mismatch at the interface between the dielectric layer and the internal electrode layer in the firing step. Examples of such ceramic powders include, in addition to the above, ZnO, ferrite, PZT, BaO, and Al2O3、Bi2O3R (rare earth element)2O3、TiO2、Nd2O3And the like. One kind of the ceramic powder may be used, or two or more kinds may be used.
The average particle size of the ceramic powder is, for example, in the range of 0.01 to 0.5. mu.m, preferably in the range of 0.01 to 0.3. mu.m. 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 a SEM at a magnification of 50,000 times.
The content of the ceramic powder is preferably 1 part by mass or more and 30 parts by mass or less, and 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% to 20 mass%, more preferably 5 mass% to 20 mass%, with respect to the entire conductive paste. When the content of the conductive powder is within the above range, the conductivity and dispersibility are excellent.
(Binder 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, acrylic resins, and butyral resins such as polyvinyl butyral. Among them, ethyl cellulose is preferably contained from the viewpoint of solubility in a solvent, combustion decomposition property, and the like. When used as a paste for internal electrodes, the paste may contain a butyral based resin or may use a butyral based resin alone, from the viewpoint of improving the adhesion strength with green sheets. One kind of the binder resin may be used, or two or more kinds thereof may be used. Examples of the binder resin include cellulose resins and butyral resins. 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, and 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% to 10 mass%, more preferably 1 mass% to 6 mass%, based on 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 can 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, and dipropylene glycol methyl ether acetate, terpene solvents such as terpineol and dihydroterpineol, and hydrocarbon solvents such as tridecane, nonane, and cyclohexane. One or two or more kinds of organic solvents may be used.
The content of the organic solvent is preferably 40 parts by mass or more and 100 parts by mass or less, and 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% to 60 mass%, and more preferably 35 mass% to 55 mass% of the entire conductive paste. When the content of the organic solvent is within the above range, the conductivity and dispersibility are excellent.
(dispersing agent)
The conductive paste of the present embodiment contains a dispersant. The dispersant includes an amino acid-based dispersant (amino acid-based surfactant) represented by general formula (1), an amine-based dispersant represented by general formula (2), and an alkyl phosphate compound. The alkyl phosphate compound is an acid dispersant. The dispersant may contain other than the above-mentioned 3 kinds.
The inventors of the present invention have studied various dispersants for a dispersant used in a conductive paste, and as a result, have found that by combining the above-mentioned 3 dispersants in a specific mixing amount, the conductive paste is extremely excellent in viscosity stability, has high surface smoothness and high dry film density in a dry film after application, is excellent in dispersibility of a conductive powder, and is capable of suppressing generation of cracks and interlayer peeling due to a small amount of gas generation at a low temperature at the start of firing. The dispersant used in the present embodiment will be described below.
The amino acid-based dispersant used in the present embodiment has an N-acyl amino acid skeleton and has a chain hydrocarbon group having 10 to 20 carbon atoms, as shown by the following general formula (1).
[ solution 3]
(wherein, in the formula (1), R1Represents a chain-like hydrocarbon group having 10 to 20 carbon atoms. )
In the above formula (1), R1Represents a chain hydrocarbon group having 10 to 20 carbon atoms. R1The number of carbon atoms of (2) is preferably 15 to 20. The chain hydrocarbon group may be a straight-chain hydrocarbon group or a branched-chain hydrocarbon group. The chain hydrocarbon group may be an alkyl group, an alkenyl group, or an alkynyl group. R1The hydrocarbon group is preferably a linear hydrocarbon group, and more preferably a linear alkenyl group having a double bond.
The amino acid-based dispersant represented by the above formula (1) can be selected from commercially available products, for example, amino acid-based dispersants satisfying the above characteristics. The amino acid-based dispersant may be produced by a conventionally known production method so as to satisfy the above characteristics.
The amine-based dispersant used in the present embodiment is a tertiary amine or a secondary amine having a structure in which an amino group is bonded to one or two oxyalkylene groups, as shown by the following general formula (2).
[ solution 4]
(wherein, in the formula (2), R2Represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms, R3Represents an oxyethylene group, oxypropylene group or methylene group, R4Represents an oxyethylene group or an oxypropylene group, R3And R4May be the same or may be different. In addition, the N atom in the formula (2) is not bound to R3And R4Wherein O atom is directly bonded, Y is a number of 0 to 2, and Z is a number of 1 to 2. )
In the above formula (2), R2Represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms. At R2When the number of carbon atoms of (b) is within the above range, the powder in the conductive paste has sufficient dispersibility and is excellent in solubility in a solvent. Furthermore, R2Preferably a linear hydrocarbon group.
In the above formula (2), R3Represents an oxyethylene group, oxypropylene group or methylene group, R4Represents an oxyethylene group or an oxypropylene group, R3And R4May be the same or may be different. In addition, the N atom in the formula (2) is not bound to R3And R4Wherein O atom is directly bonded, Y is a number of 0 to 2, and Z is a number of 1 to 2.
For example, in the above formula (2), R3Is an oxyalkylene group represented by-AO-, and when Y is 1 to 2, the sum of O atoms and (R) in the oxyalkylene group at the terminal part3)YAdjacent H atoms are bonded. In addition, when R is3In the case of methylene, (R)3)YFrom- (CH)2)YWhen Y is 1 to 2, it is bonded to an adjacent H element to form a methyl group (-CH)3) Or ethyl (-CH)2-CH3). In addition, when R is4When the oxyalkylene group is represented by-AO-, the sum of the O atom and the (R) in the oxyalkylene group at the terminal part4)ZAdjacent H atoms are bonded.
In the above formula (2), when Y is 0, the amine-based dispersant has the formula-R2A hydrogen radical and- (R)4)zSecondary amine of H. For example, when Y is 0 and Z is 2, the amine-based dispersant is composed of an alkyl group, alkenyl group or alkynyl group having 8 to 16 carbon atoms, a hydrogen group, and- (R)4)2H, said- (R) is a secondary amine4)2H is- (AO) formed by bonding any one of ethylene dioxide group or propylene dioxide group and H element2H。
In the formula (2), when Y is 1, the amine-based dispersant has the formula-R2、-R3H and- (R)4)zH, a tertiary amine. When Y is 2, the amine dispersant is a compound having the formula-R2、-(R3)2H. And- (R)4)zTertiary amine of H, - (R)3)2H is- (AO) formed by bonding any one of ethylene dioxide group, propylene dioxide group or ethylene group and H element2H or-C2H5。
The amine-based dispersant represented by the above formula (2) can be selected from commercially available amine-based dispersants satisfying the above characteristics. The amine-based dispersant may be produced by a conventionally known production method so as to satisfy the above characteristics.
Further, in the present embodiment, an alkyl phosphate ester compound is used as the acid-based dispersant. The alkyl phosphate ester compound is a phosphate ester having an alkyl group, preferably having a polyoxyalkylene structure, and may be a phosphoric acid alkyl polyoxyalkylene compound.
The inventors of the present invention have studied various dispersants for the dispersant used in the conductive paste, and as a result, have found that by adding an alkyl phosphate compound to the dispersant used in the conductive paste in addition to the amino acid-based dispersant and the amine-based dispersant, generation of decomposition gas derived from components contained in the conductive paste is delayed when the laminate is fired, and thus generation of structural defects such as cracks and interlayer peeling can be suppressed. The contents of the respective components used as the dispersant are described below.
The amino acid-based dispersant is contained in an amount of 0.03 to 0.3 mass% based on the entire conductive paste. When the amino acid-based dispersant is less than 0.03% by mass, the conductive paste may not have sufficient dispersibility. When the content of the amino acid-based dispersant exceeds 0.3% by mass, the amount of decomposed gas generated from the conductive paste at the time of firing initiation is large, and the dispersant removal property may be insufficient. From the viewpoint of further improving the dispersibility, the amino acid-based dispersant may be contained in an amount of 0.05 to 0.3 mass% or less, or may be contained in an amount of 0.10 to 0.3 mass% or less, based on the entire conductive paste.
The amine-based dispersant is contained in an amount of 0.2% by mass or more based on the whole conductive paste. When the amine dispersant is less than 0.2% by mass, the conductive paste may not have sufficient viscosity stability and dispersibility.
The alkyl phosphate compound is contained in an amount of 0.05% by mass or more based on the whole conductive paste. When the content of the alkyl phosphate compound is less than 0.05% by mass, the conductive paste may not have sufficient viscosity stability, and decomposition gas may be generated at a low temperature at the start of firing, causing cracks and delamination.
The total content of the amine-based dispersant and the amino acid-based dispersant is 0.5% by mass or less with respect to the entire conductive paste. When the total amount of the 2 dispersants exceeds the above range, generation of decomposition gas derived from the components contained in the conductive paste may occur at a lower temperature during firing of the laminate, and voids, peeling failure of green sheets, 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% by mass or less based on the entire conductive paste. When the content of the 3 dispersant exceeds 0.7% by mass, the dispersant is not sufficiently removed and remains in part during firing of the laminate, and structural defects such as cracks, voids, and peeling failure of the green sheet, and sheet corrosion may occur.
The conductive paste may contain a dispersant other than the amino acid-based dispersant, the amine-based dispersant, and the alkyl phosphate compound, within a range not to impair the effects of the present invention. Examples of the dispersant other than the above-mentioned dispersants include acid dispersants including higher fatty acids and polymeric surfactants, cationic dispersants other than the acid dispersants, nonionic dispersants, amphoteric surfactants, and polymeric dispersants. These dispersants may be used singly or in combination.
(conductive paste)
The method for producing the conductive paste of the present embodiment is not particularly limited, and conventionally known methods 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, when the dispersant is applied to the surface of the conductive powder in advance, the conductive powder is dispersed sufficiently without being aggregated, and the dispersant is distributed over the surface of the conductive powder, so that a uniform conductive paste can be easily obtained. Alternatively, the conductive paste may be prepared by dissolving the binder resin in an organic solvent for the carrier to prepare an organic vehicle, adding the conductive powder, the ceramic powder, the organic vehicle, and the dispersant to an organic solvent for the paste, and then stirring and kneading the mixture.
When the viscosity of the conductive paste after 24 hours from the production of the conductive paste is defined 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 (using a B-type viscometer manufactured by Brookfield corporation at 10rpm (shear rate 4 sec.)-1) The conditions of (1) and the like).
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 can be measured using a surface roughness meter for the dried film having a film thickness of 3 μm, which is prepared by applying a conductive paste on a glass substrate using an applicator (gap thickness of 10 μm) and then drying the conductive paste at 120 ℃ for 5 minutes in air. The surface roughness is preferably 0.05 μm or less, and more preferably 0.04 μm or less.
In addition, after printing the conductive paste, the dry film obtained by drying preferably has a Dry Film Density (DFD) of 5.45g/cm3Above, more preferably more than 5.45g/cm3More preferably, it is more than 5.5g/cm3。
Further, the conductive paste preferably has a mass change amount (Δ TG) at 250 ℃ when heated at a temperature rise rate of 5 ℃/min in a nitrogen atmosphere to measure the weight of heat (TG) to be less than 0.0020%/s, more preferably 0.0015%/s or less. When the amount of mass change is within the above range, the dispersant removal performance during firing can be improved.
The conductive paste can be suitably used for electronic components such as multilayer ceramic capacitors. The multilayer ceramic capacitor has dielectric layers formed using green sheets and internal electrode layers 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 ]
Embodiments of electronic components and the like according to the present invention will be described below with reference to the drawings. In the drawings, the drawings are schematically illustrated and the scale may be changed as appropriate. The position, direction, and the like of the member will be described with reference to the XYZ rectangular coordinate system shown in fig. 1 and the like as appropriate. In the XYZ rectangular coordinate system, the X direction and the Y direction are horizontal directions, and the Z direction is a vertical direction (vertical direction).
Fig. 1 a and 1B are views showing a multilayer ceramic capacitor 1 as an example of an electronic component according to an embodiment. The multilayer ceramic capacitor 1 includes a multilayer body 10 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated, and external electrodes 20.
A method for manufacturing a multilayer ceramic capacitor using the conductive paste will be described below. 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 in which the internal electrode layers 11 and the dielectric layers 12 are alternately laminated is prepared by laminating and pressure-bonding a plurality of dielectric layers having the dry film on the upper surface to obtain a laminate, and then firing the laminate to integrate it. Then, a pair of external electrodes 20 is formed on both end portions of the ceramic laminate 10, thereby producing the multilayer ceramic capacitor 1. Hereinafter, the description will be made in more detail.
First, green sheets, which are unfired ceramic sheets using a dielectric material, are prepared. Examples of the green sheet include a green sheet formed by applying a dielectric layer slurry 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 in a sheet form, and drying the sheet 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 on one surface of the green sheet, on which the conductive paste is printed (applied) by a known method such as a screen printing method and dried, are prepared, and a dried film is formed. In addition, from the viewpoint of the requirement for making the internal electrode layer 11 thinner, the thickness of the conductive paste after printing is preferably such that the thickness of the dried film after drying is 1 μm or less.
Next, the green sheet was peeled off from the support film, and a dielectric layer made of the green sheet and a dry film formed on one surface of the dielectric layer were stacked so as to be alternately arranged, followed by heating and pressing to obtain a stacked body. Further, a protective green sheet to which no conductive paste is applied may be further disposed on both surfaces of the laminate.
Next, the ceramic laminate 10 is manufactured by cutting the laminate into a predetermined size to form green chips, then subjecting the green chips to a debinding treatment, and firing the green chips in a reducing atmosphere. Further, the atmosphere in the binder removal treatment is preferably air or N2A gas atmosphere. The temperature at which the binder removal treatment is performed is, for example, 200 ℃ to 400 ℃. The holding time at the temperature when the binder removal treatment is performed is preferably 0.5 hours or more and 24 hours or less. The firing is performed in a reducing atmosphere in order to suppress oxidation of the metal used for the internal electrode layer, and the temperature at which the firing is performed for the laminate is, for example, 1000 ℃ to 1350 ℃ inclusive, and the holding time at which the firing is performed is, for example, 0.5 hour to 8 hours inclusive.
By firing the green chip, the organic binder in the green sheet is completely removed, and the ceramic raw material powder is fired to form the ceramic dielectric layer 12. The organic vehicle in the 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 to form the internal electrode layer 11, and further, a multilayer ceramic fired body in which the dielectric layers 12 and the internal electrode layer 11 are alternately stacked in a plurality of layers is formed. In addition, from the viewpoint of bringing oxygen into the dielectric layers to improve reliability and suppressing reoxidation of the internal electrodes, the fired multilayer ceramic body after firing may be subjected to annealing treatment.
Then, the multilayer ceramic capacitor 1 is manufactured by providing the prepared multilayer 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 layers 21 are electrically connected to the internal electrode layers 11. Further, as the material of the external electrode 20, for example, copper, nickel, or an alloy thereof can be preferably used. The electronic component is not limited to the multilayer ceramic capacitor, and may be an electronic component other than the multilayer ceramic capacitor.
Examples
The present invention will be described in detail below based on examples and comparative examples, but the present invention is not limited to the examples at all.
[ materials used ]
(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) was used3(ii) a SEM average particle diameter of 0.05 μm).
(Binder resin)
As the binder resin, an ethyl cellulose resin and a polyvinyl butyral resin (PVB resin) are used. In addition, as the binder resin, a binder resin prepared as a carrier dissolved in terpineol was used.
(dispersing agent)
(1) As the amino acid-based dispersant, R in the above general formula (1) is used1＝C17H33(linear hydrocarbon group) or the like.
(2) As the amine-based dispersant, R in the above general formula (2) is used2＝C12H25、R3＝C2H4O、R4＝C2H4O, Y-1 and Z-1.
(3) As the alkyl phosphate ester compound, a dispersant C composed of an alkyl polyoxyalkylene phosphate compound was used.
(organic solvent)
As the organic solvent, terpineol was used.
[ example 1]
A conductive paste was prepared by mixing 48 mass% of Ni powder, 5 mass% of ceramic powder, 3 mass% in total of binder resin (composed of ethyl cellulose resin and polyvinyl butyral resin) in a carrier, 0.2 mass% of amino acid-based dispersant, 0.6 mass% of amine-based dispersant, and terpineol (organic solvent) as the balance, to 100 mass% as a whole. The viscosity stability, dispersibility (dry film density, surface roughness of the dry film), and dispersant removal property of the prepared conductive paste were evaluated by the following methods. The evaluation results are shown in table 1.
[ evaluation method ]
(1) Viscosity stability: change amount of viscosity of conductive paste
The viscosity of each sample after standing at room temperature (25 ℃) for 28 days from the reference time was measured by the following method, with the reference time being set at 24 hours from the production of the conductive paste. Then, a value representing the amount of change in viscosity of the sample after standing for 28 days in percentage (%) with the viscosity after 24 hours from the time of production (reference time) as a reference (0%) ([ (viscosity after standing for 28 days-viscosity after 24 hours from the time of production)/viscosity after 24 hours from the time of production]X 100) as the amount of change in viscosity. A type B viscometer manufactured by Brookfield corporation was used at 10rpm (shear rate 4 sec)-1) The viscosity of the conductive paste was measured under the conditions of (1). The smaller the amount of change in the viscosity of the conductive paste, the more preferable. The change in viscosity of the conductive paste after the paste was left to stand for 28 days was 10% or less and was marked as "O", and the change in viscosity was more than 10%The viscosity stability of the conductive paste was evaluated by "Δ" when the viscosity was less than 40% and "x" when the viscosity was 40% or more.
(2) Dispersibility: surface roughness of dry film and dry film density
< surface roughness >
The prepared conductive paste was screen-printed on a heat-resistant tempered glass of 2.54cm (1 inch) square, and dried at 120 ℃ for 1 hour in the atmosphere, thereby preparing a dried film of 20mm square and a film thickness of about 3 μm. 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 becomes rough, resulting in a decrease in surface smoothness. Here, the dry film was measured for surface protrusions 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 corporation). The smaller the value of the surface roughness Ra, the smoother the surface of the dried film.
< Dry Film Density >
The prepared conductive paste was placed on a PET film and extended to a length of about 100mm using an applicator having a width of 50mm and a gap of 125 μm. After the obtained PET film was dried at 120 ℃ for 40 minutes to form a dried body, the dried body was cut into 4 pieces of 2.54cm (1 inch) square, the thickness and mass of each of the 4 pieces of dried film were measured after the PET film was peeled, and the density (average value) of the dried film was calculated. When 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 may be deteriorated. The higher the dry film density, the better the dispersibility.
< evaluation of dispersibility >
The surface roughness Ra of the dried film is 0.04 μm or less, and the density DFD of the dried film is 5.45g/cm3The above-mentioned case was marked as "O", and the surface roughness Ra (arithmetic mean height) of the dried film was set to be more than 0.04 μm and 0.05 μm or less, and driedThe film density DFD was 5.45g/cm3The above-mentioned case is denoted by "Δ", and the case where the surface roughness Ra of the dried film exceeds 0.05 μm or the density DFD of the dried film is less than 5.45g/cm3In any case, the dispersion was evaluated by marking as "x".
(3) Evaluation of dispersant removability
The prepared conductive paste was heated at a temperature increase rate of 5 ℃/min in a nitrogen atmosphere to perform Thermogravimetry (TG) and the dispersant removal was evaluated by analyzing the decomposition behavior due to the difference in dispersant. Specifically, a curve of the amount of change in mass (Δ TG) with respect to temperature was prepared, and the amount of change in mass (Δ TG) at 250 ℃ was evaluated. The larger the mass change amount (Δ TG) at 250 ℃, the larger the amount of decomposition gas generated from the conductive paste at the start of firing can be determined.
250 c is the temperature at which sintering of the dielectric layer begins. When the dielectric layer starts to be sintered, a gap is formed in the dielectric layer, and a certain amount of decomposition 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 decomposition gas is generated before the start of firing of the dielectric layers, since there is no gap in the dielectric layers, the decomposition gas is not discharged to the outside and easily stays between the dielectric layers to generate a gap. Therefore, by measuring the amount of change in the mass of the conductive paste during the heat treatment at 250 ℃, it can be determined whether the gas generated by decomposition at the start of firing of the laminate can be discharged through the dielectric layers (good dispersant removal performance) or remains between the dielectric layers to cause voids (poor dispersant removal performance).
In the evaluation of the dispersant removability, when the mass change amount is 0.0015%/s or less, the gas generation amount is sufficiently small, and therefore, it is indicated as "o" (very good), when the mass change amount is more than 0.0015%/s and less than 0.0020%/s, although a certain amount of gas is generated, it is an amount that can be discharged through the dielectric layer, and therefore, it is indicated as "Δ" (good), and when the mass change amount is 0.0020%/s or more, a large amount of generated gas cannot be discharged to the outside and remains, and therefore, it is indicated as "x" (bad).
Examples 2 to 6 and comparative examples 1 to 9
Conductive pastes were prepared under the same conditions as in example 1, except that the mixing ratio of the dispersant was changed by setting the contents of the dispersant a, the dispersant B, and the dispersant 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 methods. The evaluation results are shown in table 1.
[ evaluation results ]
As shown in table 1, the conductive pastes of the examples had good viscosity stability. In addition, the conductive paste of the example had a dry film density of 5.45g/cm3As described above, the surface roughness Ra was 0.05 μm or less, and good dispersibility was exhibited. Further, the conductive paste of the examples had a small amount of weight change at 250 ℃, and at a low temperature at the start of firing, the amount of decomposition gas generated was small, and there was no concern that voids were generated due to the remaining decomposition gas.
In contrast, the conductive paste of the comparative example in which the content of the dispersant is 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 viscosity stability with time and also excellent in dispersibility, and thus the dried film after coating is excellent in smoothness and dried film density. 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 caused by the generation of voids and the like. Therefore, the conductive paste according to the present embodiment can be suitably used as a raw material for an internal electrode of a multilayer ceramic capacitor, which is a chip component (electronic component) of an electronic device such as a mobile phone and a digital device.
The technical scope of the present invention is not limited to the embodiments described above. One or more of the elements described in the above embodiments may be omitted. In addition, the elements described in the above embodiments and the like can be combined as appropriate. 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, as far as the law permits. In addition, the contents of Japanese patent application No. 2019-022906 are incorporated by reference as part of the disclosure herein, as far as the law permits.
Description of the reference numerals
1 laminated ceramic capacitor
10 ceramic laminate
11 internal electrode layers
12 dielectric layer
20 external electrode
21 external electrode layer
22 plating 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 amino acid-based 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 based on the whole conductive paste,
the alkyl phosphate compound is contained in an amount of 0.05% by mass or more based on the whole conductive paste,
the total content of the amino acid-based dispersant and the amine-based dispersant is 0.5% by mass or less relative to the entire conductive paste,
a total content of the amino acid-based dispersant, the amine-based dispersant, and the alkyl phosphate compound is 0.7% by mass or less with respect to the entire conductive paste,
[ solution 1]
Wherein, in the formula (1), R1Represents a chain-like hydrocarbon group having 10 to 20 carbon atoms,
[ solution 2]
Wherein, in the formula (2), R2Represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms, R3Represents an oxyethylene group, oxypropylene group or methylene group, R4Represents an oxyethylene group or an oxypropylene group, R3And R4May be the same or different, and the N atom in the formula (2) is not the same as R3And R4Wherein O atom is directly bonded, Y is a number of 0 to 2, and Z is a number of 1 to 2.
2. The electroconductive paste according to claim 1, wherein, in said general formula (1), R1Represents a linear hydrocarbon group having 10 to 20 carbon atoms.
3. The electroconductive paste according to claim 1 or 2, wherein the electroconductive powder contains at least one metal powder selected from Ni, Pd, Pt, Au, Ag, Cu, and alloys thereof.
4. The conductive paste according to any one of claims 1 to 3, wherein the conductive powder is contained in an amount of 40 to 60 mass% based on the entire conductive paste.
5. The conductive paste according to any one of claims 1 to 4, wherein the conductive powder has an average particle diameter of 0.05 μm or more and 1.0 μm or less.
6. The conductive paste according to any one of claims 1 to 5, wherein the ceramic powder contains a perovskite oxide.
7. The conductive paste according to any one of claims 1 to 6, wherein the average particle diameter of the ceramic powder is 0.01 μm or more and 0.5 μm or less.
8. The electroconductive paste according to any one of claims 1 to 7, 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 any one of claims 1 to 8, 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 conductive paste according to any one of claims 1 to 9, wherein the conductive paste is used for an internal electrode of a laminated ceramic capacitor.
11. An electronic component formed using the conductive paste according to any one of claims 1 to 9.
12. A multilayer ceramic capacitor comprising a multilayer body in which an internal electrode layer and a dielectric layer formed using the conductive paste according to claim 10 are laminated.
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 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113396458A true CN113396458A (en) | 2021-09-14 |
Family
ID=72044749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202080012624.9A Pending CN113396458A (en) | 2019-02-12 | 2020-01-30 | Conductive paste, electronic component, and multilayer ceramic capacitor |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPWO2020166361A1 (en) |
| KR (1) | KR20210120006A (en) |
| CN (1) | CN113396458A (en) |
| TW (1) | TWI819190B (en) |
| WO (1) | WO2020166361A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005002070A (en) * | 2003-06-16 | 2005-01-06 | Q P Corp | Method for producing water dispersion composition of phospholipid and aqueous cosmetic |
| 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 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05242724A (en) * | 1992-02-27 | 1993-09-21 | Taiyo Yuden Co Ltd | Conductive paste |
| 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 |
-
2020
- 2020-01-30 CN CN202080012624.9A patent/CN113396458A/en active Pending
- 2020-01-30 JP JP2020572162A patent/JPWO2020166361A1/en active Pending
- 2020-01-30 WO PCT/JP2020/003531 patent/WO2020166361A1/en active Application Filing
- 2020-01-30 KR KR1020217024941A patent/KR20210120006A/en active Search and Examination
- 2020-02-07 TW TW109103935A patent/TWI819190B/en active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005002070A (en) * | 2003-06-16 | 2005-01-06 | Q P Corp | Method for producing water dispersion composition of phospholipid and aqueous cosmetic |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI819190B (en) | 2023-10-21 |
| TW202042252A (en) | 2020-11-16 |
| JPWO2020166361A1 (en) | 2021-12-16 |
| WO2020166361A1 (en) | 2020-08-20 |
| KR20210120006A (en) | 2021-10-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112106149B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN113227246B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| WO2021106470A1 (en) | Electroconductive paste for gravure printing, electronic component, and laminated ceramic capacitor | |
| JP7279643B2 (en) | Conductive paste, electronic parts, and laminated ceramic capacitors | |
| JP2024032861A (en) | Conductive paste, electronic components, and multilayer ceramic capacitors | |
| CN113396458A (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN112470236B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN113227233A (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN112368786B (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| CN115210823A (en) | Conductive paste, electronic component, and multilayer ceramic capacitor | |
| WO2024010075A1 (en) | Conductive paste, dried film, internal electrode and layered ceramic capacitor | |
| WO2021060540A1 (en) | Electroconductive composition, electroconductive paste, electronic component, and laminated ceramic capacitor | |
| TW202414441A (en) | Conductive paste, dry film, internal electrodes, and multilayer ceramic capacitors | |
| KR20230093418A (en) | Conductive paste for gravure printing, electronic components, and multilayer ceramic capacitors | |
| JP2021064607A (en) | Conductive paste, electronic component, and laminated ceramic capacitor | |
| JP2021180073A (en) | Conductive paste, electronic component, and multilayer ceramic capacitor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |