CN112470236B - Conductive paste, electronic component, and multilayer ceramic capacitor - Google Patents
Conductive paste, electronic component, and multilayer ceramic capacitor Download PDFInfo
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- CN112470236B CN112470236B CN201980048675.4A CN201980048675A CN112470236B CN 112470236 B CN112470236 B CN 112470236B CN 201980048675 A CN201980048675 A CN 201980048675A CN 112470236 B CN112470236 B CN 112470236B
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- 239000003985 ceramic capacitor Substances 0.000 title claims description 33
- 239000002270 dispersing agent Substances 0.000 claims abstract description 120
- 239000000843 powder Substances 0.000 claims abstract description 95
- 239000000919 ceramic Substances 0.000 claims abstract description 45
- 150000001412 amines Chemical class 0.000 claims abstract description 42
- 150000001413 amino acids Chemical class 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 36
- 239000011230 binding agent Substances 0.000 claims abstract description 34
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 11
- -1 oxyethylene, oxypropylene Chemical group 0.000 claims description 9
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 9
- 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
- 125000006353 oxyethylene group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 3
- 239000012461 cellulose resin Substances 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 18
- 239000010408 film Substances 0.000 description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 150000002430 hydrocarbons Chemical group 0.000 description 14
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- 238000000034 method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
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- 239000002904 solvent Substances 0.000 description 7
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 239000012298 atmosphere Substances 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
- 238000002156 mixing Methods 0.000 description 6
- 125000005702 oxyalkylene group Chemical group 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
- 125000004429 atom Chemical group 0.000 description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
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- 239000002253 acid Substances 0.000 description 4
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 4
- 150000003335 secondary amines Chemical class 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
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- 238000000576 coating method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002003 electrode paste Substances 0.000 description 2
- 239000007789 gas Substances 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
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 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
- 230000009467 reduction Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003512 tertiary amines 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 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
- 229910017493 Nd 2 O 3 Inorganic materials 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
- 229910010413 TiO 2 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
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 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
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 230000003628 erosive effect Effects 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
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 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
- 238000003475 lamination Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
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- 238000010405 reoxidation reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 125000001302 tertiary amino group Chemical group 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
- 229910052727 yttrium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/30—Stacked capacitors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/02—Cellulose; Modified cellulose
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
- C08L29/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Ceramic Capacitors (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
Abstract
The invention provides a conductive paste which has high surface smoothness and high density of a dry film, has excellent dispersibility of conductive powder, has high adhesiveness when forming a laminated body, has very small viscosity change along with time and has more excellent viscosity stability. The conductive paste contains 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 general formula (1) described in the specification and an amine-based dispersant represented by general formula (2) described in the specification, the ratio of the amino acid-based dispersant to the amine-based dispersant (amino acid-based dispersant/amine-based dispersant) is in the range of 1/4 to 1/2 by mass, and the total content of the amino acid-based dispersant and the amine-based dispersant is 0.7 to 1.2 mass% relative to the total amount of the conductive paste.
Description
Technical Field
The invention relates to a conductive paste, an electronic component and a laminated 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 added 3 ) 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 films and the green sheets are alternately stacked, and then heated and pressure-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, 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.
Generally, a conductive paste for forming the internal electrode layers contains a conductive powder, a 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 specific surface composition, the dispersant has an acid site amount of 500 to 2000 μmol/g, and the binder resin has an acid site amount of 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 TiBaO 3 Mainly 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 laid-open patent publication No. 2015-216244
Patent document 2: japanese laid-open patent publication No. 2013-149457
Patent document 3: japanese patent laid-open No. 2006-063441
Disclosure of Invention
Problems to be solved by the invention
However, with the recent reduction in the thickness of electrode patterns, further improvements in viscosity characteristics over time and improvements in surface smoothness of dried films after application have been demanded.
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 high adhesiveness when a laminate is formed, has a very small change in viscosity with time, and is further excellent in viscosity stability.
Means for solving the problems
A first aspect of the present invention provides a conductive paste containing 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 general formula (1) and an amine-based dispersant represented by general formula (2), the ratio of the amino acid-based dispersant to the amine-based dispersant (amino acid-based dispersant/amine-based dispersant) is in the range of 1/4 to 1/2 by mass, and the total content of the amino acid-based dispersant and the amine-based dispersant is 0.7 to 1.2 mass% relative to the total amount of the conductive paste.
[ CHEM 1]
(wherein, in the formula (1), R 1 Represents a chain hydrocarbon group having 10 to 20 carbon atoms. )
[ CHEM 2]
(wherein, in the formula (2), R 2 Represents an alkyl, alkenyl or alkynyl group having 8 to 16 carbon atoms, R 3 Represents an oxyethylene group, oxypropylene group or methylene group, R 4 Represents an oxyethylene group or an oxypropylene group, R 3 And R 4 May be the same or may be different. The N atom in formula (2) is not bound to R 3 And R 4 Wherein the 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), R 1 Preferably a straight chain having 10 to 20 carbon atomsA hydrocarbyl group. The conductive powder preferably contains at least one metal powder selected from the group consisting of Ni, pd, pt, au, ag, cu, and alloys of the above elements. The conductive powder is preferably contained in an amount of 40 to 60 mass% based on the total amount of the 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-based resin, an acrylic resin, and a butyral-based resin. The conductive paste is preferably used for internal electrodes of multilayer ceramic capacitors.
A second aspect of the present invention provides an electronic component formed using the conductive paste.
A third aspect of the present invention provides a multilayer ceramic capacitor including 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, when forming a thin-film electrode, the electrode pattern of an electronic device such as a multilayer ceramic capacitor formed using the conductive paste of the present invention is excellent in adhesion of the conductive paste, has good precision, and has a uniform width and thickness.
Drawings
Fig. 1 a is a perspective view showing the multilayer ceramic capacitor according to the present embodiment, and fig. 1B is a cross-sectional view showing the multilayer ceramic capacitor according to the present embodiment.
Detailed Description
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 an alloy of the above elements may be used. Among them, ni or its alloy powder is preferable from the viewpoint 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 severe gas generation caused by partial thermal decomposition of the binder resin during the binder removal process.
The average particle diameter of the conductive powder is preferably 0.05 μm to 1.0 μm, and 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 determined by observation with a Scanning Electron Microscope (SEM), and is an average value obtained by measuring particle diameters of a plurality of particles one by one from an image observed with the 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 total amount of the 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 an internal electrode paste for a multilayer ceramic capacitor, a known ceramic powder can be appropriately selected according to the type of multilayer ceramic capacitor to be used. The ceramic powder may be, for example, a perovskite-type 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 an accessory component can be used. 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 a ceramic powder, for example, barium titanate (BaTiO) is cited 3 ) 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 slurry, a powder having the same composition as the dielectric ceramic powder constituting the multilayer ceramic capacitor green sheet 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 Al 2 O 3 、Bi 2 O 3 R (rare earth element) 2 O 3 、TiO 2 、Nd 2 O 3 And the like. One kind of 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 total amount of the conductive paste. When the content of the ceramic powder is within the above range, the electrical conductivity and the 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 properties, and the like. When used as a paste for internal electrodes, a butyral resin may be contained or used alone from the viewpoint of improving the adhesive strength with the green sheets. One or two or more kinds of binder resins 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, 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%, with respect to the total amount of the 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.
The content of the organic solvent is preferably 20 mass% to 60 mass%, and more preferably 35 mass% to 55 mass%, with respect to the total amount of the 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 contains an amino acid-based dispersant (amino acid-based surfactant) represented by general formula (1) and an amine-based dispersant represented by general formula (2). The dispersant may contain a dispersant other than the amino acid-based dispersant represented by the general formula (1) and the amine-based dispersant represented by the general formula (2).
As a result of studies on various dispersants for a dispersant used in a conductive paste, the inventors of the present invention found that: by combining the two dispersants in a specific ratio, the conductive paste shows a small change in viscosity with time, is excellent in viscosity stability, and has excellent dispersibility of the conductive powder, high surface smoothness and high dry film density in a dried film after coating.
The inventors of the present invention have also found that by combining the two dispersants at a specific ratio and setting the ratio of the total content of the two dispersants to a specific amount, the viscosity stability and dispersibility of the conductive paste can be further improved, and that the conductive paste is excellent in adhesion when formed into a laminate.
The reason for this is not clear, but it is considered that the effect is brought about by the action of coordinating the amino group and the carboxyl group present in the molecule of the dispersant to the metal atom of the conductive powder. 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).
[ CHEM 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. R 1 The 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. Further, the chain hydrocarbon group may be an alkyl group, an alkenyl group or an alkynyl group. R is 1 The 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 dispersant is represented by the following general formula (2), and has a structure in which a tertiary amine or a secondary amine is bonded to an amino group and one or two oxyalkylene groups.
[ CHEM 4]
(wherein, in the formula (2), R 2 Represents an alkyl, alkenyl or alkynyl group having 8 to 16 carbon atoms, R 3 Represents an oxyethylene group, oxypropylene group or methylene group, R 4 Represents an oxyethylene group or an oxypropylene group, R 3 And R 4 May be the same or may be different. In addition, the N atom in the formula (2) is not bound to R 3 And R 4 Wherein the 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), R 2 Represents an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms. At R 2 Has the carbon number of the above rangeIn the case of inside, the powder in the conductive paste has sufficient dispersibility and is excellent in solubility in a solvent. Furthermore, R 2 The hydrocarbon group 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, R 3 And R 4 May be the same or may be different. In addition, the N atom in the formula (2) is not bound to R 3 And R 4 Wherein O atom in (A) 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), R 3 Is 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 part 3 ) Y Adjacent H atoms are bonded. In addition, when R is 3 In the case of methylene, (R) 3 ) Y From- (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 ethyl (-CH) 2 -CH 3 ). In addition, when R is 4 When the oxyalkylene group is an oxyalkylene group represented by-AO-, the sum of the O atom and the (R) atom in the oxyalkylene group at the terminal part 4 ) Z Adjacent H atoms are bonded.
In the formula (2), when Y is 0, the amine-based dispersant has the formula 2 A hydrogen radical and- (R) 4 ) z And (c) a secondary amine of H. For example, when Y is 0 and Z is 2, the amine-based dispersant is a mixture of an alkyl group, an alkenyl group or an alkynyl group having 8 to 16 carbon atoms, a hydrogen group, and- (R) 4 ) 2 H, said- (R) is a secondary amine 4 ) 2 H is- (AO) formed by bonding any one of ethylene dioxide group or propylene dioxide group and H element 2 H。
In the formula (2), when Y is 1, the amine-based dispersant has the formula 2 、-R 3 H and- (R) 4 ) z And (c) a tertiary amine of H. When Y is 2, the amine dispersant is a compound having the formula-R 2 、-(R 3 ) 2 H. And- (R) 4 ) z Of H tertAmine of the formula- (R) 3 ) 2 H is- (AO) formed by bonding any one of ethylene dioxide group, propylene dioxide group or ethylene group and H element 2 H or-C 2 H 5 。
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.
The ratio of the amino acid-based dispersant to the amine-based dispersant (amino acid-based dispersant/amine-based dispersant) contained in the conductive paste is in the range of 1/4 to 1/2 by mass. Particularly, when the ratio of the amino acid-based dispersant to the amine-based dispersant is 1/4 to 2/5, the viscosity stability of the conductive paste is very high.
When the lower limit of the blending ratio of the amino acid-based dispersant to the amine-based dispersant is 1/4 or more, the effect of improving the change over time in the viscosity of the conductive paste can be further improved, the dispersibility of the conductive powder can be improved, and the surface smoothness of the dried film and the density of the dried film can be high. In addition, when the upper limit of the mixing ratio of the amino acid-based dispersant and the amine-based dispersant is 1/2 or less, the amine-based dispersant becomes relatively large, and thus the change with time in the viscosity of the conductive paste can be greatly reduced.
The ratio of the total content of the amino acid-based dispersant represented by the above formula (1) and the amine-based dispersant represented by the above formula (2) to the total amount of the conductive paste is 0.7 mass% to 1.2 mass%. When the total content of the amino acid-based dispersant and the amine-based dispersant is within the above range, a dry film having improved dispersibility of the conductive paste, a high dry film density and excellent surface smoothness can be obtained, and sheet corrosion and green sheet peeling failure due to the residual dispersant can be suppressed.
When the lower limit of the ratio of the total content of the amino acid-based dispersant and the amine-based dispersant is 0.7 mass% or more, the dispersibility of the conductive paste containing the amino acid-based dispersant and the amine-based dispersant at the above ratio can be further improved, and the conductive paste can have high dry film smoothness and dry film density, and can further reduce the change in viscosity of the conductive paste with time. When the upper limit of the ratio of the total content of the amino acid-based dispersant and the amine-based dispersant is 1.2 mass% or less, the amount of the dispersant remaining on the surface of the dry film is further reduced, and the occurrence of peeling due to inhibition of adhesion between the surface of the dry film and the surface of the green sheet during lamination and pressure bonding is suppressed.
The conductive paste may contain a dispersant other than the amino acid-based dispersant and the amine-based dispersant as long as the effects of the present invention are not impaired. 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 conductive paste of the present embodiment can be produced by preparing the above components, and stirring and kneading the components with 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 carrier, adding the conductive powder, the ceramic powder, the organic carrier, and the dispersant to the organic solvent for the paste, and stirring and kneading the mixture by a mixer.
Among the organic solvents, the same organic solvent as the organic solvent for the paste for adjusting the viscosity of the conductive paste is preferably used as the organic solvent for the carrier in order to improve the affinity of the organic carrier. The content of the organic solvent for the carrier is, for example, 5 parts by mass or more and 80 parts by mass or less based on 100 parts by mass of the conductive powder. The content of the organic solvent for the carrier is preferably 10 mass% or more and 40 mass% or less with respect to the total amount of the conductive paste.
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).
Further, 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, by a method described in examples (a method of using VK-X120 manufactured by keyence corporation and performing an arithmetic mean height Sa based on the standard of ISO 25178). When the evaluation is made with the arithmetic average height Sa, the surface smoothness of the dried film is preferably 0.17 μm or less.
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 laminated 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 an XYZ rectangular coordinate system shown by a and the like in fig. 1 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 show a multilayer ceramic capacitor 1 as an example of an electronic component according to the embodiment. The multilayer ceramic capacitor 1 includes a ceramic laminate 10 and external electrodes 20 in which dielectric layers 12 and internal electrode layers 11 are alternately laminated.
Hereinafter, a method for manufacturing a multilayer ceramic capacitor using the conductive paste will be described. First, a conductive paste is printed on a green sheet and dried to form a dried film. A ceramic laminate 10 in which internal electrode layers 11 and dielectric layers 12 are alternately laminated is prepared by laminating and pressure bonding a plurality of green sheets having the dry film on the upper surface to obtain a laminate, and then firing the laminate to integrate it. Then, the multilayer ceramic capacitor 1 is manufactured by forming a pair of external electrodes 20 on both end portions of the ceramic laminate 10. 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 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 are prepared, on which the conductive paste is printed (applied) by a known method such as a screen printing method and dried to form a dry film. 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 sheets were peeled off from the supporting film, and laminated so that the green sheets and the dried film formed on one surface of the green sheets were alternately arranged, followed by heating and pressing to obtain a laminate. 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 N 2 A 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 in the internal electrode layer, and the temperature at which the firing is performed is, for example, 1000 ℃ to 1350 ℃, and the holding time at which the firing is performed is, for example, 0.5 hours to 8 hours.
The green chip is fired to completely remove the organic binder in the green sheet, 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 a material of the external electrode 20, for example, copper, nickel, or an alloy of the above elements 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 0.3 μm) was used.
(ceramic powder)
As the ceramic powder, barium titanate (BaTiO) was used 3 (ii) a SEM average particle diameter of 0.06 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 used 1 ＝C 17 H 33 (linear hydrocarbon group).
(2) As the amine-based dispersant, R in the above general formula (2) is used 2 ＝C 12 H 25 、R 3 ＝C 2 H 4 O、R 4 ＝C 2 H 4 And dispersants represented by O, Y =1, and Z = 1.
(organic solvent)
As the organic solvent, terpineol was used.
[ example 1]
A conductive paste was prepared by mixing 46 mass% of Ni powder, 11.5 mass% of ceramic powder, and 3.2 mass% in total of a binder resin (composed of an ethyl cellulose resin and a polyvinyl butyral resin) in a carrier, 0.2 mass% of an amino acid-based dispersant, 0.6 mass% of an amine-based dispersant, and terpineol (organic solvent) as the balance, to 100 mass% in total, and mixing these materials. The prepared conductive paste was evaluated for viscosity stability, dispersibility (dry film density, surface roughness of the dry film), and adhesion by the following methods. The evaluation results are shown in table 1.
[ evaluation method ]
(viscosity stability: amount of change in viscosity of electroconductive paste)
The viscosity of the sample at the reference time after 24 hours from the production of the conductive paste was measured by the following method after the sample was left to stand at room temperature (25 ℃) for 7 days, 14 days, and 28 days from the reference time. Then, a value representing the amount of change in viscosity of each sample after standing in percentage (%) with the viscosity after 24 hours from the time of production (reference time) as a reference (0%) ([ (viscosity after standing-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 B-type 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 viscosity stability of the conductive paste was evaluated by designating a case where the change in viscosity of the conductive paste after standing for 28 days was 10% or less as "a" and a case where the change in viscosity exceeded 10% as "B".
( Dispersibility: surface roughness of dry film and dry film density )
< surface roughness >
The thus-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 air to prepare a dried film of 20mm square and 1 to 3 μm in thickness. 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 surface roughness Sa (arithmetic mean height), sz (maximum height) of the prepared dried film was measured using a laser microscope (VK-X120 manufactured by keyence corporation) based on the standard of ISO 25178. The smaller the value of the surface roughness Sa (arithmetic mean height) or Sz (maximum height), 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 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 Sa (arithmetic mean height) of the dried film is 0.17 μm or less, and the density DFD of the dried film is 5.50g/cm 3 The above case is referred to as "A" and satisfies the case where the surface roughness Sa (arithmetic mean height) of the dried film is more than 0.17 μm and the density DFD of the dried film is less than 5.50g/cm 3 Either or both of the cases (a) and (B) are referred to as "B", and dispersibility is evaluated.
(adhesion property)
The prepared conductive paste was printed (applied) on a green sheet by a screen printing method and dried to prepare a plurality of sheets having a dry film formed on the green sheet. Laminating five layers of the above sheets at 80 deg.C and 100kg/cm 2 The thermocompression bonding treatment was performed for 3 minutes under the pressure of (2) to form a laminate. In the obtained laminate, adhesion was evaluated by designating "x" as a case where adhesion between the surface of the dried film (electrode layer surface) and the bottom surface of the green sheet stacked thereon was weak and peeling occurred at one or more positions and designating "o" as a case where no peeling occurred in addition to this.
Examples 2 and 3, comparative examples 1 and 2
Conductive pastes were prepared under the same conditions as in example 1, except that the mixing ratio of the dispersing agent was changed by setting the contents of the amino acid-based dispersing agent and the amine-based dispersing agent to the amounts shown in table 1. The change amount of the viscosity of the prepared conductive paste, the density of the dried film, the surface roughness of the dried film, and the adhesion were evaluated by the above methods. The evaluation results are shown in table 1.
Examples 4 to 6, comparative examples 3 and 4
Conductive pastes were prepared under the same conditions as in example 1, except that the total content of the dispersant in the conductive paste was changed to the amount shown in table 2 so as to maintain the blending ratio of the dispersant constant. The change amount of the viscosity of the prepared conductive paste, the density of the dried film, the surface roughness of the dried film, and the adhesion were evaluated by the above methods. The evaluation results are shown in table 2.
TABLE 1
TABLE 2
[ evaluation results ]
As shown in tables 1 and 2, the conductive pastes of the examples had a dry film density of 5.5g/cm 3 As described above, the surface roughness Sa (arithmetic mean height) was 0.17 μm or less, and no peeling was observed even in the laminate, and good dispersibility and adhesiveness were exhibited. In the conductive pastes of the examples, the change with time in the viscosity of the conductive paste was 5.4% or less after 28 days, and it was found that the conductive paste had very good viscosity stability.
On the other hand, the conductive paste of comparative example 1, which had a low mixture ratio of the amino acid-based dispersant and the amine-based dispersant and contained a large amount of the amine-based dispersant, had a dry film density of 5.5g/cm, although the viscosity stability was good 3 Hereinafter, the surface roughness Sa exceeds 0.17 μm, and compared with the conductive paste of the example,the dispersibility is low. In addition, the surface roughness Sz (maximum height) also shows a slightly larger value than in the examples. The conductive paste of comparative example 2, which had a high mixture ratio of the amino acid-based dispersant and the amine-based dispersant and contained a large amount of the amino acid-based dispersant, had a change in viscosity of 16.7% or more and a change of 10% or more after 28 days.
In addition, the conductive paste of comparative example 3 in which the total content of the amino acid-based dispersant and the amine-based dispersant was less than 0.7 mass% had lower dispersibility and lower viscosity stability than those of the conductive pastes of examples. In addition, with respect to the conductive paste of comparative example 4 in which the total content of the amino acid-based dispersant and the amine-based dispersant exceeds 1.2 mass%, peeling may occur in the laminate produced using the conductive paste of comparative example 4, and the adhesiveness may be lowered as compared with the conductive paste of example.
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 and the like may be omitted. In addition, the elements described in the above embodiments and the like can be combined as appropriate. In addition, the contents of Japanese patent application No. 2018-139501, which is a Japanese patent application, and all documents cited in this specification are incorporated by reference as far as the law permits.
Industrial applicability
The conductive paste according to the present embodiment is excellent in dispersibility, excellent in smoothness and dry film density of a dried film after application, and excellent in viscosity stability with time, and therefore is particularly suitable as a raw material for an internal electrode of a multilayer ceramic capacitor used as a chip component (electronic component) of an electronic device such as a mobile phone and a digital device.
Description of the reference numerals
1. Laminated ceramic capacitor
10. Ceramic laminate
11. Internal electrode layer
12. Dielectric layer
20. External electrode
21. External electrode layer
22. Electroplated coating
Claims (10)
1. A conductive paste comprising a conductive powder, a ceramic powder, a dispersant, a binder resin and an organic solvent, characterized in that,
the dispersant comprises an amino acid dispersant represented by the following general formula (1) and an amine dispersant represented by the following general formula (2),
the ratio of the amino acid-based dispersant to the amine-based dispersant (amino acid-based dispersant/amine-based dispersant) is in the range of 1/4 to 1/2 by mass,
the ratio of the total content of the amino acid-based dispersant and the amine-based dispersant to the total amount of the conductive paste is 0.7 to 1.2 mass%,
wherein, in the formula (1), R 1 Represents a linear hydrocarbon group having 10 to 20 carbon atoms,
wherein, in the formula (2), R 2 Represents an alkyl, alkenyl or alkynyl group having 8 to 16 carbon atoms, R 3 Represents oxyethylene, oxypropylene or methylene, R 4 Represents an oxyethylene group or oxypropylene group, R 3 And R 4 May be the same or different, and the N atom in the formula (2) is not the same as R 3 And R 4 Wherein the O atom is directly bonded, and 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,
the conductive powder contains at least one metal powder selected from the group consisting of Ni, pd, pt, au, ag, cu, and alloys of the above elements.
3. The electroconductive paste according to claim 1 or 2,
the conductive powder is contained in an amount of 40 to 60 mass% relative to the total amount of the conductive paste.
4. The conductive paste according to claim 1 or 2,
the conductive powder has an average particle diameter of 0.05 to 1.0 [ mu ] m.
5. The electroconductive paste according to claim 1 or 2,
the ceramic powder contains a perovskite-type oxide.
6. The conductive paste according to claim 1 or 2,
the average particle diameter of the ceramic powder is 0.01-0.5 [ mu ] m.
7. The conductive paste according to claim 1 or 2,
the binder resin contains at least one of a cellulose resin, an acrylic resin, and a butyral resin.
8. The conductive paste according to claim 1 or 2,
the conductive paste is used for internal electrodes of a laminated ceramic capacitor.
9. An electronic component formed by using the conductive paste according to any one of claims 1 to 7.
10. 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 8 are laminated.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018139501A JP7206671B2 (en) | 2018-07-25 | 2018-07-25 | Conductive paste, electronic parts and laminated ceramic capacitors |
| JP2018-139501 | 2018-07-25 | ||
| PCT/JP2019/028713 WO2020022291A1 (en) | 2018-07-25 | 2019-07-22 | Conductive paste, electronic component, and laminated ceramic capacitor |
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| Publication Number | Publication Date |
|---|---|
| CN112470236A CN112470236A (en) | 2021-03-09 |
| CN112470236B true CN112470236B (en) | 2023-02-28 |
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| CN201980048675.4A Active CN112470236B (en) | 2018-07-25 | 2019-07-22 | Conductive paste, electronic component, and multilayer ceramic capacitor |
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| Country | Link |
|---|---|
| JP (1) | JP7206671B2 (en) |
| KR (1) | KR20210040290A (en) |
| CN (1) | CN112470236B (en) |
| TW (1) | TWI810336B (en) |
| WO (1) | WO2020022291A1 (en) |
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| JP7215047B2 (en) * | 2018-09-28 | 2023-01-31 | 住友金属鉱山株式会社 | Conductive paste, electronic parts, and laminated ceramic capacitors |
| KR20220145326A (en) * | 2020-03-04 | 2022-10-28 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive pastes, electronic components and multilayer ceramic capacitors |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009200009A (en) * | 2008-02-25 | 2009-09-03 | Sekisui Chem Co Ltd | Conductive paste for electrode inside laminated ceramic capacitor |
| JP2013149457A (en) * | 2012-01-19 | 2013-08-01 | Sumitomo Metal Mining Co Ltd | Conductive paste for internal electrode |
| JP2017143202A (en) * | 2016-02-12 | 2017-08-17 | 住友金属鉱山株式会社 | Paste for internal electrodes, method for manufacturing the same, and multilayer ceramic capacitor |
| WO2017150438A1 (en) * | 2016-02-29 | 2017-09-08 | 住友金属鉱山株式会社 | Electrically conductive paste, electronic component, and laminated ceramic capacitor |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4495644B2 (en) | 2004-07-30 | 2010-07-07 | Ｊｆｅミネラル株式会社 | Metal super fine slurry |
| EP3121829B1 (en) * | 2014-03-20 | 2020-09-16 | Sekisui Chemical Co., Ltd. | Electroconductive paste |
| JP6292014B2 (en) | 2014-05-12 | 2018-03-14 | 株式会社村田製作所 | Conductive paste and ceramic electronic components |
| KR102410080B1 (en) * | 2014-07-31 | 2022-06-16 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Conductive paste |
| JP2018037630A (en) * | 2016-08-25 | 2018-03-08 | 住友金属鉱山株式会社 | Paste for internal electrodes, method for manufacturing the same, and multilayer ceramic capacitor |
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2018
- 2018-07-25 JP JP2018139501A patent/JP7206671B2/en active Active
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2019
- 2019-07-22 WO PCT/JP2019/028713 patent/WO2020022291A1/en active Application Filing
- 2019-07-22 KR KR1020207037657A patent/KR20210040290A/en active Search and Examination
- 2019-07-22 CN CN201980048675.4A patent/CN112470236B/en active Active
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009200009A (en) * | 2008-02-25 | 2009-09-03 | Sekisui Chem Co Ltd | Conductive paste for electrode inside laminated ceramic capacitor |
| JP2013149457A (en) * | 2012-01-19 | 2013-08-01 | Sumitomo Metal Mining Co Ltd | Conductive paste for internal electrode |
| JP2017143202A (en) * | 2016-02-12 | 2017-08-17 | 住友金属鉱山株式会社 | Paste for internal electrodes, method for manufacturing the same, and multilayer ceramic capacitor |
| WO2017150438A1 (en) * | 2016-02-29 | 2017-09-08 | 住友金属鉱山株式会社 | Electrically conductive paste, electronic component, and laminated ceramic capacitor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020022291A1 (en) | 2020-01-30 |
| KR20210040290A (en) | 2021-04-13 |
| CN112470236A (en) | 2021-03-09 |
| JP2020017405A (en) | 2020-01-30 |
| JP7206671B2 (en) | 2023-01-18 |
| TW202008394A (en) | 2020-02-16 |
| TWI810336B (en) | 2023-08-01 |
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