KR20160013809A - Conductive paste for internal electrode of multi-layer ceramic capacitor and production method thereof, and multi-layer ceramic capacitor - Google Patents
Conductive paste for internal electrode of multi-layer ceramic capacitor and production method thereof, and multi-layer ceramic capacitor Download PDFInfo
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- KR20160013809A KR20160013809A KR1020150101687A KR20150101687A KR20160013809A KR 20160013809 A KR20160013809 A KR 20160013809A KR 1020150101687 A KR1020150101687 A KR 1020150101687A KR 20150101687 A KR20150101687 A KR 20150101687A KR 20160013809 A KR20160013809 A KR 20160013809A
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- conductive paste
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- 239000003985 ceramic capacitor Substances 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000843 powder Substances 0.000 claims abstract description 78
- 239000004952 Polyamide Substances 0.000 claims abstract description 9
- 229920002647 polyamide Polymers 0.000 claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 9
- 239000004814 polyurethane Substances 0.000 claims abstract description 9
- 239000004254 Ammonium phosphate Substances 0.000 claims abstract description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims abstract description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims abstract description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003209 petroleum derivative Substances 0.000 claims abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 78
- 239000000654 additive Substances 0.000 claims description 54
- 230000002401 inhibitory effect Effects 0.000 claims description 41
- 230000000996 additive effect Effects 0.000 claims description 40
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- 239000000956 alloy Substances 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 14
- 239000004034 viscosity adjusting agent Substances 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 30
- 238000000197 pyrolysis Methods 0.000 abstract description 22
- 230000007847 structural defect Effects 0.000 abstract description 11
- 230000032798 delamination Effects 0.000 abstract description 5
- 238000005245 sintering Methods 0.000 abstract description 4
- 238000003860 storage Methods 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 59
- 239000011230 binding agent Substances 0.000 description 31
- 239000010410 layer Substances 0.000 description 24
- 230000003197 catalytic effect Effects 0.000 description 16
- 239000001856 Ethyl cellulose Substances 0.000 description 14
- 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 14
- 235000019325 ethyl cellulose Nutrition 0.000 description 14
- 229920001249 ethyl cellulose Polymers 0.000 description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- 238000010304 firing Methods 0.000 description 9
- 238000000354 decomposition reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 3
- 229910002113 barium titanate Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- -1 triazine thiol Chemical class 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 229920006318 anionic polymer Polymers 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 125000004427 diamine group Chemical group 0.000 description 1
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005211 surface analysis Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/005—Electrodes
- H01G4/008—Selection of materials
-
- 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
- H01G4/30—Stacked capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Conductive Materials (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Ceramic Capacitors (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
Abstract
Description
The present invention relates to a conductive paste used for forming internal electrodes of a multilayer ceramic capacitor and a method of manufacturing the same. The present invention also relates to a multilayer ceramic capacitor using the conductive paste.
A multilayer ceramic capacitor (MLCC) has a structure in which ceramic dielectric layers and internal electrode layers are alternately stacked and integrated. Conventionally, noble metal powders such as palladium have been used as conductive powders for forming internal electrodes of the multilayer ceramic capacitor. However, at present, from the viewpoint of low cost, it is mainstream to use a nickel powder or an alloy powder containing nickel as a main component instead of a noble metal powder.
In such a multilayer ceramic capacitor, an electrically conductive paste in which a conductive powder is dispersed in a vehicle is printed on a ceramic green sheet, and the multilayer ceramic capacitor is integrated by heating and pressing in a multilayered state, To remove the binder (debinding process), and firing the internal electrode in a reducing atmosphere so as not to oxidize the internal electrode (firing process).
In recent years, along with miniaturization of electronic devices, miniaturization of various electronic parts is progressing rapidly, and multilayer ceramic capacitors are also being made smaller and higher in capacity. Specifically, multilayer ceramic capacitor capacitors and internal electrode layers have become thinner. However, when nickel powder is used as the conductive powder, there arises a problem that structural defects such as delamination and cracking, in which the internal electrode layer and the ceramic dielectric layer are peeled off, become present with the multilayered and thinned layers.
It is considered that the cause of such a problem is the catalytic action of nickel in the binder removal process. That is, the thermal decomposition temperature of the resin component (binder) contained in the vehicle is lowered due to the catalytic action of nickel at the surface and in the vicinity of the nickel powder, so that the decomposition reaction gas is abruptly generated in the debinding process. For example, in the case of using ethyl cellulose as the binder, the thermal decomposition which is originally carried out at around 355 DEG C is lowered to about 290 DEG C, accompanied by a rapid generation of decomposition product gas. On the other hand, since the catalytic action of the resin component of the ceramic dielectric layer is insufficient, pyrolysis does not proceed at this point. As a result, the decomposition product gas is trapped in the vicinity of the surface of the nickel powder, and voids are formed between the internal electrode layer and the ceramic dielectric layer, and it is considered that structural defects such as interlayer peeling and cracks are caused through the subsequent firing process. Particularly, in order to make the internal electrode layer thinner, it is necessary to use a nickel powder having a small particle size, whereby the catalytic action of nickel is activated, and structural defects are more likely to occur.
To solve such a problem, it has been attempted to add a component for suppressing the catalytic action of nickel to the conductive paste and a component for delaying the sintering of nickel to the conductive paste in the binder removing step.
For example, Japanese Patent Laid-Open Publication No. 2011-18898 discloses a nickel paste for use in an internal electrode of a multilayer ceramic capacitor, which comprises, in addition to nickel powder, a binder and a solvent, a sulfur-containing titanium compound in which barium titanate powder is mixed with sulfur A technique of adding barium oxide is disclosed. According to this technique, the generation of the rapid decomposition product gas is suppressed by the effect of suppressing the catalytic action of nickel by sulfur and the effect of suppressing the sintering of barium titanate, so that occurrence of structural defects during firing can be sufficiently suppressed It is thought to be possible. However, in this technique, since a step of adding sulfur to barium titanate is required before each component is kneaded, a cost increase due to an increase in the number of steps can not be avoided. In addition, an inorganic component other than the nickel powder is present in the nickel paste, which may adversely affect the reliability of the electronic component.
On the other hand, Japanese Patent Application Laid-Open No. 2008-223068 discloses a nickel powder having an average particle diameter of 0.05 to 1.0 탆, which contains nickel particles containing a sulfur oxide and a surface oxidation layer as the conductive powder. The nickel powder has a sulfur content of 100 ppm to 2000 ppm with respect to the total weight of the powder. In the surface analysis of the nickel particles by ESCA (X-ray photoelectron spectroscopy), the intensity of the peak which is returned to the sulfur atom bonded to the nickel atom, And its intensity is maximized at a position deeper than 3 nm from the surface of the particle. Japanese Patent Application Laid-Open No. 2008-223068 discloses that nickel powder containing sulfur dispersed in a non-oxidizing gas atmosphere is brought into contact with an oxidizing gas at a temperature ranging from 300 ° C. to 800 ° C. have.
Japanese Patent Laid-Open Publication No. 2013-87355 discloses a conductive powder which is obtained by hydrothermally treating the conductive powder at a temperature in the range of more than 100 占 폚 and not more than 300 占 폚 in the presence of a sulfur compound such as sodium thiosulfate or thiourea, Containing nickel fine particles containing sulfur in an amount of 1.0% by mass or less.
In these techniques, it is considered that the reliability of the electronic parts is not adversely affected because inorganic components other than the nickel powder are not present in the conductive paste. However, in any of these techniques, it is necessary to contain sulfur in the nickel powder, and the cost increase due to the increase in the number of steps can not be avoided.
On the other hand, Japanese Patent Application Laid-Open No. 2006-24539 discloses a technique of suppressing the catalytic action of nickel by adding a sulfur-containing organic compound to the conductive paste. Specifically, there is disclosed a technique of dispersing a nickel powder in a vehicle in which a binder is dissolved in a solvent and containing a triazine thiol, a sulfur-containing compound, or the like. According to this technique, since the catalytic action of nickel can be suppressed by sulfur, without increasing the number of process steps, it is considered that the above problem can be solved at a low cost.
However, the triazine thiol or sulfuric acid-containing compound exemplified in Japanese Patent Application Laid-Open No. 2006-24539 has a remarkably low solubility in a petroleum solvent and tends to be swollen when made into a paste. As a result, the viscosity of the conductive paste varies with time, which may cause gelation. Particularly, when this conductive paste is stored for a long period of time, the viscosity remarkably increases, and it becomes very difficult to form a desired internal electrode layer.
As a means for improving the stability of the viscosity of the conductive paste, JP-A-2001-6434 discloses a technique of adding an amine-based surfactant and an anionic polymeric dispersant to a conductive paste containing a conductive powder and an organic vehicle . However, the amine surfactant and the anionic polymer dispersant do not have the effect of retarding the catalytic action of nickel or retarding the sintering, and can not suppress the occurrence of structural defects in the debindering process and the firing process.
It is an object of the present invention to provide a multilayer ceramic capacitor which is capable of preventing the occurrence of structural defects such as delamination during the debindering process and subsequent firing process and also has a small viscosity change even when stored for a long period of time, It is an object of the present invention to provide a conductive paste. It is another object of the present invention to provide a production method capable of producing such a conductive paste at low cost. Another object of the present invention is to provide a multilayer ceramic capacitor including an internal electrode layer formed by using the conductive paste.
The present invention relates to a conductive paste comprising a conductive powder, a vehicle, a viscosity adjusting agent comprising a petroleum hydrocarbon, and a thermal decomposition inhibiting additive.
Particularly, the conductive paste of the present invention contains at least one compound selected from the group consisting of modified polyurethane, modified polyamide and ammonium phosphate as the thermal decomposition inhibiting additive, and the content of the thermal decomposition inhibiting additive is 100 parts by mass By mass to 1 part by mass with respect to 100 parts by mass of water.
The thermal decomposition inhibiting additive is preferably a modified polyamide.
It is preferable that the viscosity adjuster has a boiling point of 150 캜 to 260 캜.
The average particle diameter of the conductive powder is preferably 1 m or less.
The conductive powder is preferably at least one selected from the group consisting of Ni powder, Pd powder, alloy powder containing Ni, and alloy powder containing Pd. Among them, Ni powder is more preferable.
The conductive paste of the present invention can be produced by adding the conductive powder, the viscosity adjusting agent and the thermal decomposition inhibiting additive to the vehicle, and kneading the mixture.
Further, the conductive paste of the present invention can be suitably used when forming the internal electrode layers of the multilayer ceramic capacitor.
According to the present invention, by adding a specific thermal decomposition inhibiting additive, it is possible to suppress the thermal decomposition of the binder generated on the surface of the nickel powder in the conductive paste and the generation of abrupt gas accompanied therewith in the debindering process at the time of production of the multilayer ceramic capacitor And it is possible to effectively prevent occurrence of structural defects such as delamination in the subsequent firing process. Further, according to the present invention, stability of the viscosity of the conductive paste can be improved without adding an additive other than the thermal decomposition inhibiting additive, so that the internal electrode layer of the multilayer ceramic capacitor is formed stably even after a long period of time after the production of the conductive face can do. According to the present invention, since the conductive paste having such characteristics can be realized only by adding a very small amount of a specific thermal decomposition inhibiting additive without controlling the shape and the particle diameter of the conductive powder, it is easy to manufacture, There is almost no increase in cost due to the addition of additives. As a result, the industrial significance of the present invention is very large.
Brief Description of the Drawings Fig. 1 is a view for explaining an effect obtained by adding a pyrolysis inhibiting additive to a vehicle. Fig.
The inventors of the present invention have conducted intensive studies on the conductive paste used for forming the multilayer ceramic capacitor. As a result, by adding a specific compound such as a modified polyurethane, a modified polyamide or ammonium phosphate as a thermal decomposition inhibiting additive in the conductive paste, Can be solved at the same time. The present invention has been completed on the basis of this finding.
1. Components
Hereinafter, the conductive paste of the present invention will be described separately for each constituent component.
(1) Conductive powder
As the conductive powder constituting the conductive paste of the present invention, at least one selected from the group consisting of nickel (Ni) powder, palladium (Pd) powder, alloy powder containing Ni and alloy powder containing Pd is used . Of these, it is preferable to use a low-cost Ni powder.
As the alloy powder containing Ni, for example, an alloy powder containing Ni and at least one metal selected from chromium (Cr), cobalt (Co), copper (Cu) As the alloy powder containing Pd, an alloy powder containing Pd and a metal containing at least one kind selected from silver (Ag) and platinum (Pt) can be suitably used. In these alloy powders, the content of Ni or Pd is preferably 50 mass% or more, more preferably 80 mass% or more.
The conductive paste of the present invention is not limited by the average particle diameter and the like of the conductive powder as described above. However, in order to make the internal electrode layer thinner, it is important to use a conductive powder having a smaller particle diameter than the thickness thereof. Concretely, it is preferable to use conductive powder of 1 탆 or less, more preferably 0.4 탆 or less. Since such a catalytic action is activated in such a small-particle-diameter conductive powder, the effect obtained by the present invention becomes more remarkable. On the other hand, in the conductive powder having an average particle diameter exceeding 1 탆, the ratio of coarse particles is increased, which is not disadvantageous for making the multilayer ceramic capacitor thinner. In addition, the coarse particles in the internal electrode layers pass electrically through the ceramic dielectric layer, The capacity may be insufficient.
(2) Vehicle
The vehicle constituting the conductive paste of the present invention is not particularly limited, and a solvent and a binder may be uniformly mixed as in the prior art. For example, as the solvent, terpineol, butyl carbitol acetate, butyl carbitol, dihydroterpineol, dihydroterpineol acetate and the like can be used. As the binder, cellulose such as ethyl cellulose and polyvinyl butyral can be used.
The content of the binder in the vehicle is not particularly limited and should be appropriately selected according to its use and desired characteristics. It is preferable to adjust the content of the binder to 1 part by mass to 7 parts by mass with respect to 100 parts by mass of the conductive powder , And more preferably 1.5 parts by mass to 6 parts by mass.
(3) Viscosity adjusting agent
The viscosity adjusting agent is a component added to adjust the viscosity of the conductive paste so as to be satisfactorily printed on an object such as a ceramic green sheet.
As such a viscosity adjuster, it is necessary to use a petroleum hydrocarbon as a main component from the viewpoint of imparting adequate drying and solubility to the conductive paste. In particular, the boiling point is preferably in the range of 150 to 260 캜, more preferably 160 to 200 캜. When the boiling point of the viscosity adjusting agent is less than 150 캜, the drying time is very short, and the viscosity of the conductive paste increases sharply during printing, making it difficult to form a desired internal electrode layer. On the other hand, when the boiling point exceeds 260 캜, the dry composition is markedly deteriorated, requiring a long time for drying after printing, and the productivity is markedly deteriorated.
As the viscosity adjuster satisfying the above-mentioned conditions, for example, one containing as a main component methyl ethylbenzene, trimethylbenzene, tridecane, nonane, cyclohexane and the like, specifically, A solvent of JX Nikkoseki Energy Co., (Trade name, boiling point: 160 占 폚 to 195 占 폚) and LS solvent (trade name, boiling point: 200 占 폚 to 260 占 폚) manufactured by JX Nikkoseki Energy Co., .
The content of the viscosity adjuster in the conductive paste is preferably 10 parts by mass to 50 parts by mass, more preferably 10 parts by mass to 40 parts by mass, based on 100 parts by mass of the conductive powder. When the content of the viscosity modifier is less than 10 parts by mass, the above-mentioned effects can not be sufficiently obtained. On the other hand, when the content of the viscosity modifier exceeds 50 parts by mass, the viscosity is remarkably lowered, and the conductive paste is spread during printing or it becomes difficult to control the thickness of the internal electrode layer to a desired range.
(4) Pyrolysis inhibiting additive
In the conductive paste of the present invention, in addition to the above-mentioned components, at least one compound selected from modified polyurethane, modified polyamide and ammonium phosphate as a thermal decomposition inhibiting additive is contained in an amount of 0.1 part by mass to 1 part by mass with respect to 100 parts by mass of the conductive powder .
In the conductive paste of the present invention, by adding these thermal decomposition inhibiting additives, it is possible to suppress the catalytic function of the conductive powder in the binder removal step and to prevent the generation of abrupt decomposition products accompanied therewith. The reason why such an effect is obtained is not clear, but the modified polyurethane or modified polyamide does not contain S in its structure, but the functional groups of molecules constituting the thermal decomposition inhibiting additive are adsorbed on the surface of the conductive powder, It is considered that the contact of the binder is inhibited and rapid thermal decomposition is suppressed. On the other hand, with respect to the polyphosphoric acid ester, it is considered that the functional group including phosphorus is decomposed upon heating to form a film, and the contact between the binder and the conductive powder is likewise inhibited, so that partial thermal decomposition of the binder is suppressed.
Further, these pyrolysis inhibiting additives are hardly swollen even when they are mixed with the above-described viscosity regulator containing petroleum hydrocarbon as a main component, so that the mixed state can be maintained for a long period of time. Therefore, even when the conductive paste of the present invention is stored for a long time after fabrication, viscosity change is small, and a desired internal electrode layer can be easily formed.
Among the above-mentioned pyrolysis inhibiting additives, examples of the modified polyurethane include urea-modified polyurethanes that introduce a diamine skeleton through a urea bond into a urethane bond. However, polyurethane modified by an imide bond, amide bond, amide bond or the like Lt; / RTI > Specifically, EFKA4046 (trade name) and EFKA4047 (trade name) manufactured by Ciba Specialty Chemicals may be suitably used.
As the modified polyamide, there can be mentioned, for example, a compound obtained by substituting at least a part of hydrogen atoms of an amide bond with a functional group such as a methoxymethyl group. Specifically, Disuron DA-1401 (trade name) manufactured by Kusumoto Kasei Co., Ltd. can be suitably used.
Examples of the ammonium phosphate include ammonium dihydrogen phosphate, ammonium type I polyphosphate and ammonium type II polyphosphate. Specific examples thereof include Taien K (trade name) and Taien C = II (trade name) manufactured by Taihei Kagaku Kogyo K.K. (Trade name) may be appropriately used.
The content of the thermal decomposition inhibiting additive is 0.1 parts by mass to 1 part by mass, preferably 0.2 parts by mass to 0.8 parts by mass, more preferably 0.4 parts by mass to 0.6 parts by mass relative to 100 parts by mass of the conductive powder. When the content of the thermal decomposition inhibiting additive is less than 0.1 part by mass, the effect of suppressing thermal decomposition of the binder can not be sufficiently obtained. On the other hand, if the content of the thermal decomposition inhibiting additive exceeds 1 part by mass, the effect of suppressing thermal decomposition of the binder can be obtained, but the properties of the electronic parts may be adversely affected. In addition, the stability of the viscosity of the conductive paste may deteriorate when stored for a long period of time, and the cost may increase.
(5) Other additives
In the conductive paste of the present invention, in addition to the above-mentioned additives, additives such as dispersants, flame retardants, and anti-settling agents (hereinafter referred to as " other additives " These other additives preferably have a decomposition temperature in the range of 150 캜 to 350 캜. When the decomposition temperature is less than 150 ° C, the compound is easily decomposed at the time of mixing or kneading, and the effect of adding other additives may not be obtained. On the other hand, if the decomposition temperature exceeds 350 DEG C, there is a fear that structural defects such as cracks and interlayer delamination described above may occur due to the gas generated by the thermal decomposition of these other additives in the firing process.
The content of other additives is preferably 1.0 part by mass or less, more preferably 0.5 parts by mass or less based on 100 parts by mass of the conductive powder. If the content of the other additive exceeds 1.0 part by mass, the effect of the present invention may not be obtained due to the other constituent components.
2. Conductive paste
(1) Method of producing conductive paste
The conductive paste of the present invention can be produced by a method similar to that of the conventional art as long as the above-described components can be uniformly dispersed. For example, the above-described respective components can be manufactured by uniformly kneading them by a three-roll mill mill.
The timing of adding the thermal decomposition inhibiting additive is not particularly limited and may be dispersed in advance in the vehicle, but it is preferable to mix the conductive powder in the step of dispersing the conductive powder in the vehicle.
The timing of addition of the above-mentioned other additives is not particularly limited, and may be added at any timing. However, depending on the kind of the other additive, it may be considered that the affinity with the conductive powder is high, thereby preventing the thermal decomposition-inhibiting additive from being adsorbed on the surface of the conductive powder. In this case, it is necessary to appropriately adjust the order of addition of the thermal decomposition inhibiting additive and other additives.
(2) Characteristics of conductive paste
As described above, according to the conductive paste of the present invention, since the catalytic action of the conductive powder in the binder removal step is suppressed, the thermal decomposition temperature of the binder in the paste can be prevented from being excessively lowered. Therefore, when the internal electrode layer of the multilayer ceramic capacitor is formed by using the conductive paste of the present invention, occurrence of structural defects such as interlayer peeling and cracking can be effectively prevented.
The thermal decomposition inhibiting effect of the binder can be judged by measuring the pyrolysis peak intensity of the binder in the vehicle and the pyrolysis peak intensity of the binder contained in the conductive paste using a differential thermogravimetric analyzer.
Fig. 1 schematically shows the amount of change ΔTG (thermal decomposition peak strength) of the thermal weight TG of the vehicle and the conductive paste with respect to the temperature. In the
On the other hand, in the
Therefore, the pyrolysis peak temperature T 3 of the binder in the vehicle 3 and the pyrolysis peak temperature T 1 of the binder in the
Thermal decomposition intensity ratio:? =? TG1a/? TG3 (a)
In addition, the conductive paste of the present invention is excellent in viscosity stability and hardly increases in viscosity even when stored for a long period after fabrication. Specifically, the rate of increase in viscosity in a case where the conductive paste viscosity η 1, at the time of a lapse of 24 hours after production of the conductive paste 20 days storage under a constant temperature of 25 ℃ and the viscosity η 2 after the lapse of this period, That is, the rate of increase? Of the viscosity calculated based on the following formula (b) can be made less than 20%, preferably less than 15%.
Increase rate of viscosity:? = (? 2- ? 1 ) /? 1 × 100 (b)
The conductive paste of the present invention can be suitably used for forming internal electrodes of a multilayer ceramic capacitor. The method of manufacturing the multilayer ceramic capacitor of the present invention is the same as that of the conventional art except that the conductive paste of the present invention is used.
<Examples>
Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. In the following examples and comparative examples, the present invention will be described by taking as an example the case of using Ni powder having particularly high catalytic action among the above-mentioned conductive powders. However, the present invention is not limited to this, and the same can be applied to the case of using Pd powder, alloy powder containing Ni, and alloy powder containing Pd.
In the following Examples and Comparative Examples, ethylcellulose and terpineol were mixed as a vehicle so as to have a mass ratio of 1:19. The pyrolysis temperature of ethyl cellulose in this vehicle, that is, the pyrolysis peak temperature of ethyl cellulose in the absence of catalytic action by the conductive powder, was measured by the following method.
First, this vehicle was applied to the PET film so that the thickness became 100 占 퐉 and dried at 90 占 폚 for 6 hours using an applicator (YBA-2, manufactured by Kodaira Seisakusho Co., Ltd.). After confirming that the vehicle had been completely dried, only the dried film of the vehicle was peeled off from the PET film, and this was pulverized with a mortar and filtered through a sieve having a mesh size of 100 mu m to obtain a vehicle dried powder.
Next, the obtained dried vehicle powder was analyzed by setting a temperature raising rate in a nitrogen stream of 200 ml / min at a rate of 10 占 폚 / min by using a differential thermogravimetric analyzer (TG-DTA2000SA, manufactured by Bruker A.x. , And the change amount? TG 3 with respect to the temperature of the thermogravimetric was calculated from the following equation (c). Based on this result, the pyrolysis peak temperature T 3 of ethyl cellulose was determined to be 355 ° C.
DELTA TG = (amount of change in thermal weight TG) / (heating time) (c)
(Example 1)
Ni powder (manufactured by Sumitomo Chemical Co., Ltd.) having an average particle diameter of 0.2 占 퐉 was prepared as a conductive powder. To the 100 parts by mass of the Ni powder, 60 parts by mass of the above-mentioned vehicle (ethyl cellulose: 3 parts by mass) , 40 parts by mass of a viscosity adjusting agent (trade name: A solvent, manufactured by Idemitsu Kosan Co., Ltd.), and 0.1 part by mass of Dishalone DA-1401 (manufactured by Gusumoto Kasei K.K.) as a thermal decomposition inhibiting additive. Then, these components were simultaneously mixed, and the particle diameter measured by a FOG gauge (particle gauge) was 10 mu m or less using a 3-axis roll mill (43/4 x 11S type roll machine manufactured by Inoue Seisakusho Co., Ltd.) By weight to obtain a conductive paste.
[Evaluation of thermal decomposition property]
The pyrolysis peak temperature of ethyl cellulose contained in the conductive paste is measured in the same manner as the pyrolysis peak temperature of ethylcellulose in the vehicle to determine the pyrolysis peak temperature T 1a and the pyrolysis intensity ratio alpha is calculated by the formula did. On the basis of these results, the thermal decomposition of ethyl cellulose in the conductive paste of Example 1 and the degree of gas generation accompanying it were evaluated.
[Evaluation of stability of viscosity]
Initially, the viscosity? 1 at a point of time 24 hours after the production of the conductive paste was measured using a viscometer (HBT type viscometer, manufactured by Brookfield). Then, this conductive paste was stored at a constant temperature of 25 캜 for 20 days, and the viscosity η 2 after the elapse of this period was similarly measured. Then, the rate of increase? Of the viscosity was calculated from the formula (b). Based on these results, it was evaluated as " good (?) &Quot;, that having a viscosity increase rate? Of less than 15%, as " possible (O) " These results are shown in Table 2.
(Examples 2 to 8)
A conductive paste was prepared in the same manner as in Example 1 except that the kind of the thermal decomposition inhibiting additive and the content thereof were changed as shown in Tables 1 and 2 and the thermal decomposition peak temperature T 1a and the thermal decomposition strength ratio? The thermal decomposition of ethyl cellulose in these conductive pastes and the degree of gas generation accompanying the thermal decomposition were evaluated. In the same manner as in Example 1, the viscosity increase rate? Was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(Examples 9 and 10)
A conductive paste was prepared in the same manner as in Example 2 except that the materials shown in Table 1 and Table 2 were used as the viscosity adjusting agent and the thermal decomposition peak temperature T 1a and the thermal decomposition strength ratio alpha thereof were measured. , The degree of thermal decomposition of ethylcellulose and the degree of gas generation accompanying it were evaluated. In the same manner as in Example 1, the viscosity increase rate? Was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(Comparative Example 1)
A conductive paste was prepared in the same manner as in Example 1 except that the thermal decomposition inhibiting additive was not added and the thermal decomposition peak temperature T 1b and the thermal decomposition strength ratio alpha of the conductive paste were measured and the thermal decomposition of ethylcellulose Performance, and degree of gas generation accompanying it. In the same manner as in Example 1, the viscosity increase rate? Was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(Comparative Examples 2 and 3)
A conductive paste was prepared in the same manner as in Example 1 except that the kind of the thermal decomposition inhibiting additive and the content thereof were changed as shown in Tables 1 and 2 and the thermal decomposition peak temperature T 1a and the thermal decomposition strength ratio? The thermal decomposition of ethyl cellulose in these conductive pastes and the degree of gas generation accompanying the thermal decomposition were evaluated. In the same manner as in Example 1, the viscosity increase rate? Was measured to evaluate the stability of the viscosity. These results are shown in Table 2.
(Comprehensive evaluation)
It can be seen from Tables 1 and 2 that the conductive pastes of Examples 1 to 10 contained in the technical scope of the present invention had a thermal decomposition peak temperature of 300 ° C to 315 ° C and a thermal decomposition strength ratio α of less than 1 , And it was confirmed that thermal decomposition of the binder was suppressed. Also, it was confirmed that the evaluation on the stability of the viscosity was also good. Therefore, it is considered that the multilayer ceramic capacitor in which the internal electrode layers are formed using these conductive pastes can considerably reduce the occurrence of structural defects in the debindering process and the firing process. It is also believed that these conductive pastes can form the internal electrode layers without hindrance even after prolonged lapse of time after production. In Example 10 in which a viscosity adjuster having a boiling point of more than 200 占 폚 was used, the rate of increase? Of viscosity was higher than in the other Examples, but practically no problems were found.
On the other hand, in the conductive pastes of Comparative Examples 1 and 2, it was confirmed that the thermal decomposition peak temperature of ethylene cellulose was lowered to 290 ° C and the thermal decomposition strength ratio? Further, in the conductive paste of Comparative Example 3, the addition amount of the thermal decomposition inhibiting additive was large and the thermal decomposition peak temperature was not lowered. However, it was confirmed that the viscosity increase rate? Was 20% or more and the viscosity stability was low.
1 conductive paste containing a thermal decomposition inhibiting additive
2 conductive paste not containing thermal decomposition inhibiting additive
3 Vehicle
Claims (8)
Wherein the thermal decomposition inhibiting additive comprises at least one compound selected from a modified polyurethane, a modified polyamide and ammonium phosphate, and the content of the thermal decomposition inhibiting additive is 0.1 part by mass to 1 part by mass relative to 100 parts by mass of the conductive powder Paste.
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| CN101872679B (en) * | 2010-05-26 | 2012-09-05 | 广东风华高新科技股份有限公司 | Nickel inner electrode slurry |
| KR101452186B1 (en) * | 2012-12-26 | 2014-10-21 | 주식회사 누리비스타 | Paste for internal electrode and multi-layer ceramic capacitor using the same |
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| CN105321713B (en) | 2018-11-27 |
| JP2016031994A (en) | 2016-03-07 |
| JP6365068B2 (en) | 2018-08-01 |
| KR102042566B1 (en) | 2019-11-11 |
| CN105321713A (en) | 2016-02-10 |
| TW201606825A (en) | 2016-02-16 |
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