WO1994010697A1 - Electrically conductive resin pastes and multilayer ceramic capacitors having a terminal electrode comprised of the same - Google Patents
Electrically conductive resin pastes and multilayer ceramic capacitors having a terminal electrode comprised of the same Download PDFInfo
- Publication number
- WO1994010697A1 WO1994010697A1 PCT/US1993/010325 US9310325W WO9410697A1 WO 1994010697 A1 WO1994010697 A1 WO 1994010697A1 US 9310325 W US9310325 W US 9310325W WO 9410697 A1 WO9410697 A1 WO 9410697A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- resin
- electrically conductive
- terminal electrode
- multilayer ceramic
- paste
- Prior art date
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- 229920005989 resin Polymers 0.000 title claims abstract description 52
- 239000011347 resin Substances 0.000 title claims abstract description 52
- 239000003985 ceramic capacitor Substances 0.000 title description 2
- 239000003990 capacitor Substances 0.000 claims abstract description 33
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000000919 ceramic Substances 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 11
- 239000011231 conductive filler Substances 0.000 claims abstract description 10
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 11
- 238000010030 laminating Methods 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 abstract description 8
- 238000001723 curing Methods 0.000 description 20
- 239000000758 substrate Substances 0.000 description 9
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- -1 acryl Chemical group 0.000 description 5
- 229920000768 polyamine Polymers 0.000 description 5
- 238000005476 soldering Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 239000013034 phenoxy resin Substances 0.000 description 4
- 229920006287 phenoxy resin Polymers 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- NCHBYORVPVDWBJ-UHFFFAOYSA-N 2-(3-methylbutoxy)ethanol Chemical compound CC(C)CCOCCO NCHBYORVPVDWBJ-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- 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 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N cis-p-Menthan-1,8-diol Natural products CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 description 1
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N methyl pentane Natural products CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229930006948 p-menthane-3,8-diol Natural products 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- RBNWAMSGVWEHFP-WAAGHKOSSA-N terpin Chemical compound CC(C)(O)[C@H]1CC[C@@](C)(O)CC1 RBNWAMSGVWEHFP-WAAGHKOSSA-N 0.000 description 1
- 229950010257 terpin Drugs 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
- H01G4/2325—Terminals electrically connecting two or more layers of a stacked or rolled capacitor characterised by the material of the terminals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/228—Terminals
- H01G4/232—Terminals electrically connecting two or more layers of a stacked or rolled capacitor
Definitions
- This invention relates to an electrically conductive resin composition and in particular to such composition useful as a terminal for multilayer ceramic chi capacitors .
- Electrically conductive compositions for the formation of a terminal electrode for multilayer ceramic chip capacitor are prepared in the form of pastes having suitable consistency and rheology, which are formed by admixing metal powders of gold, silver, palladium or alloys thereof, glass frits, inert organic vehicles and resins and dispersing them by a mechanical mixing.
- Such electrically conductive resin pastes are coated onto the opposing surfaces for taking out an inner electrode in MLC element, dried and fired at a high temperature of about 700 to 860°C to form a terminal electrode.
- This firing causes glass frits in the paste to disperse into a dielectric layer constituting the MLC element, thus effecting fused binding of the particles.
- fused metal powders in the paste permit mechanical, electrical connection and fixing of the termina electrode comprised of electrically conductive compositions and the MLC element .
- soldering is employed in attaching such chip type of circuit board to the patterned surface.
- fused solder is applied to a round area in a circuit patter on which a terminal for tip parts is situated, to effect a prolonged fixing of a copper-clad laminate for circuit boar thereto.
- a stress occurs in a joint between a terminal electrode and a capacitor element, in particular a capacitor element area corresponding to the periphery of th terminal electrode due to a sinter shrinkage of metal powders in the paste, diffusion of a glass component in the paste into a dielectric constituting a capacitor element an diffusion of metal powders in the paste into an inner electrode of a capacitor element.
- a crack occurs due to a rapid temperature change when soldering a chip capacitor to a circuit substrate and "deflection" occurs in the circuit due to the external bending force exerted on the substrate.
- a terminal of a chip type has less degree of freedom and the strength of an inner electrode and a capacitor element formed of a dielectric is lower than that of the substrate comprised of e.g., a glass fabric based epoxy resin. Therefore, "deflection" or forced bending in the circuit substrate produces a crack in a chip capacitor body after package, thus giving no sufficient terminal strength.
- it has been extensively performed to connect and fix a chip part to both surfaces of the substrate made of alumina, glass fabric or epoxy resin for the purpose of increasing a package density. In such, a both surface package, the occurrence of crack in the capacitor element becomes an important issue.
- a technical approach has been demanded to form a terminal electrode without a high temperature firing.
- the present invention provides an electrically conductive resin composition for the formation of a terminal electrode for a multilayer ceramic chip capacitor with no need of a high temperature firing and a multilayer ceramic chip capacitor formed of the same.
- the electrically conductive resin composition of the invention is paste, comprising an admixture of an electrically conductive filler consisting of a noble metal powder, a resin under, and a curing agent dispersed in an organic medium, the resin binder comprising a mixture of at least two resins of an epoxy resin and a thermosetting or thermoplastic resin and the weight ratio of the noble metal powder to the thermosetting resin being about 100:5 to 100:45.
- the present invention also provides a multilayer ceramic chip capacitor formed from the electrically conductive resin paste serving as a terminal electrode for the multilayer ceramic chip capacitor.
- the multilayer ceramic chip capacitor is formed by laminating alternately a plurality of dielectric sheets having an electrically conductive inner electrode adhered thereon in such manner that the areas for taking out the inner electrode are arranged oppositely, laminating the outmost layer with a dielectric sheet for a protective layer to integrate them, applying the electrically conductive resin paste for the multilayer ceramic chip capacitor to said areas in the integrated laminate and.fixing it to form a terminal electrode.
- the electrically conductive fillers used in the invention can be any of noble metal powders.
- all metals referred to as noble metals can be used, but gold, silver, platinum, palladium, rhodium, the mixtures thereof and the alloys thereof are particularly used.
- the resin binders constituting the conductive resin pastes of the invention comprise a mixture of at least two resins of an epoxy resin and a thermosetting or thermoplastic resin.
- An epoxy resin which is one component of the resin binder refers to that consisting of a compound containing two or more epoxy groups in the molecule which cures by the action of a curing agent or a catalyst.
- the epoxy resins can include bisphenol A type epoxy resins, i.e., glycidyl etherified compounds of bisphenol A or its analogous compounds, diglycidyl ester type resins, novolak epoxy resins, glycidyl amine type resins, cycloaliphatic epoxy resins or the like. Those epoxy resins are capable of curing with the curing agents described later on.
- thermosetting resin which is another component of the resin binder can include phenol resins, melamine resins, alkyd resins, unsaturated polyester resins, diarylphthalate resins or the like.
- Other components of the resin binder may be a thermoplastic resin which can include phenoxy resins, acryl resins or the like.
- the ratio of resin solid component in the dispersions to conductive filler can vary considerably. As a matter of course, larger amount of resin solid component provides improved mechanical strength, improved adhesion strength of the coated film and improved resistance to wear, but gives an adverse effect on capacitance and dissipation factor which are important among characteristics of capacitor, capacitance being a constant of proportionality between an electrical charge and an applied voltage and dissipation factor being the tangent of the angle ( ⁇ ) at which current lags from 90° vector relative to voltage and expressed as 100 x tan ⁇ .
- the elastic modulus of the terminal electrode for a multilayer ceramic chip capacitor fabricated from the compositions of the invention is measured in the range of 2.5-3.0 x 10 ⁇ MPa. On the other hand, it was confirmed by measurement that the elastic modulus of the prior terminal electrode for the same capacitor is more than the above range, which is fabricated by coating a paste composition having silver powder and glass frit dispersed in an inert organic solvent, drying and baking at high temperature.
- the organic media used for the conductive resin paste of the invention are added in order to reduce the viscosity rising during the milling of the binder and the conductive filler and provide improved workability. It is important to select those having the solubility according to kinds of the binder.
- the media free from the solubility produces an agglomeration of resin which results in no formation of chain combination of conductive filler, making the electrical conductivity unstable and losing physical and chemical stability of the coated film.
- the organic media which can be used for the conductive resin paste include'aliphatic alcohols, e.g., ethanol, i-propanol, n-propanol, butanol; esters of these alcohols, e.g., their acetate and propionate; caritol solvents, e.g., methyl carbitol, ethyl carbitol, butyl carbitol, butyl carbitol acetate; cellosolve solvents, e.g., cellosolve, butyl cellosolve, isoamyl cellosolve, hexyl cellosolve, butyl cellosolve acetate; ketone solvents, e.g., acetone, methyl ethyl ketone, 2-pentanone, 3-pentanone, cyclohexanone and hydrocarbon solvents, e.g., benzene, toluene, xylene,
- compositions of the invention can be used including: polyamide curing agents, aliphatic polyamine curing agents, cycloaliphatic polyamine curing agents, aromatic polyamine curing agents, dicyandiamide or the like.
- the curing agents which initiate a curing reaction at a temperature below 40°C are used.
- Preferable low-temperature curing agents in the present invention are aliphatic polyamine curing agents and dicyandiamide.
- high-temperature curing agents can also be used, example of which include those which do not react at ordinary temperature, e.g., aromatic polyamine curing agents, HY 932, HT 972, HY 974, HT 976, NX 11014 (available from Ciba Geigy) ; acid anhydride curing agents, HY 920 (available from Ciba Geigy) and amide curing agents or the like.
- the electrically conductive resin pastes are coated in one layer onto the opposing surfaces for taking out an inner electrode in MLC element to form a terminal electrode area.
- th terminal electrode area having a multilayer structure of coated films is thought to form.
- the ratio of the conductive filler component to the resin solid component can be varied.
- directly bonding to the surfaces for taking out th ⁇ inner electrode in MLC element electrode bonding layer
- there is ensured good electrical connection of the chip capacitor element to the inner electrode is ensured and there is inhibited a deterioration of the characteristics such as capacitance an dissipation factor which are important electrical characteristics for capacitor.
- the proportion of the resin solid component in the paste is reduced so as to provide the range of 100:5 to 100:35 by the weight ratio to noble metal powder as described previously.
- the proportion of the resin solid component is increased in the paste for the coating formation of the soldering layer.
- the range of 100:20 to 100:40 by the weight ratio to noble metal powder is preferable.
- the composition is formed in the form of paste by mixing and milling a conductive filler component consisting of a noble metal powder, a resin binder, a curing agent, and other additives with an inert organic solvent.
- a conductive filler component consisting of a noble metal powder, a resin binder, a curing agent, and other additives with an inert organic solvent.
- the conductive resin paste thus produced, can be applied to the area for taking out the inner electrode in MLC, for example by coating, screen-printing or dipping.
- defoaming is preferably performed by applying vacuum during or after the step of depositing the conductive resin paste. Reducing the air gaps by defoaming can prevent the penetration of a plating solution which may be occurred in the subsequent plating treatment.
- a cured surface of the terminal electrode tailored by depositing the conductive resin paste may contain a large number of voids, since it is not a sintered body. Depending upon a plating condition to the surface, the plating solution may penetrate into those voids. This surface can be polished for the removal of the voids. This polishing extends the metal on the surface, which results in good plate adhesion. As a polishing method may be employed a barrel polish with a small rubber ball.
- the resultant conductive resin paste was adjusted to a viscosity suitable for the application of dipping.
- the silver powder used herein has a particle diameter of 0.2-10 ⁇ m.
- the viscosity of the paste deposited in the terminal by the application of dipping is preferably in the range of 6 to 9 at 16-30 PA.S. 0.5/10 rpm (viscosity ratio) at 10 rpm when Brookfield rotational viscometer (spindle No. 14) was used. Table 1
- Silver Powder 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Epoxy resin 6.75 9 11.25 3.7 4.9 6.1 7.4 8.6 8.8
- Each of the conductive resin pastes thus prepared was coated onto a capacitor chip using a Palomer machine manufactured by Palomer Co., Ltd. After coating those pastes onto a capacitor chip, the pastes of Examples 1-4 were cured at 250°C for 60 minutes. The pastes of Examples 5-10 were cured at 200°C for 60 minutes or 230°C for 60 minutes or 250°C for 60 minutes. The pastes of Comparative Examples 11-12 as described later were cured at 200°C for 60 minutes and the paste of Example 13 was fired at 850°C.
- Capacitance and Dissipation Factor, tan ⁇ (%) of the resultant capacitors were measured in the following manner.
- capacitance can be calculated from the formula
- C 4d in which K is dielectric constant, A is a play area in cm ⁇ and d is thickness of dielectric layer in cm.
- Capacitance is measured at a frequency of 120 or 1 KHz and IV (A.C.) using a general radioautomatic RLC bridge model 1683. Capacitance was measured between the cathode coating generally soldered to an anode lead. In some case, the lead was soldered to cathode and used for the measurement .
- Dissipation Factor is the tangent of the angle ( ⁇ ) of the current lugged from a 90° vector relative to voltage, which is expressed herein as % DF (100 x tan ⁇ ) .
- DF was measured using the same general radioautomatic bridge as mentioned above for the capacitance. Further, the post strength and elasticity modulus of the cured film were measured. The post strength refers to a force requied for bringing down a post after the conductive resin paste was coated on an aluminum substrate and a small disc with a grasp (post) was placed on a coated surface which was in turn cured.
- the conductive pastes were prepared by mixing silver powders, phenoxy resin and solvent in the proportions indicated in Table 1 and milling the mixture by the similar procedure as in Examples 1-10.
- the paste used in Example 13 is a firing type of paste.
- composition of the pastes is shown in Table 1.
- the curing condition and the electrical properties of the product are shown in Table 2.
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Ceramic Capacitors (AREA)
Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1019950701759A KR950704801A (en) | 1992-11-04 | 1993-11-03 | Electrically Conductive Resin Pastes and Multilayer Ceramic Capacitors Having a Terminal Electrode Comprised of the Same |
EP94900411A EP0667031A1 (en) | 1992-11-04 | 1993-11-03 | Electrically conductive resin pastes and multilayer ceramic capacitors having a terminal electrode comprised of the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP4/294893 | 1992-11-04 | ||
JP4294893A JPH06267784A (en) | 1992-11-04 | 1992-11-04 | Conductive resin paste and laminated ceramic chip capacitor with terminal electrode consisting of same |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1994010697A1 true WO1994010697A1 (en) | 1994-05-11 |
Family
ID=17813618
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1993/010325 WO1994010697A1 (en) | 1992-11-04 | 1993-11-03 | Electrically conductive resin pastes and multilayer ceramic capacitors having a terminal electrode comprised of the same |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP0667031A1 (en) |
JP (1) | JPH06267784A (en) |
KR (1) | KR950704801A (en) |
CN (1) | CN1038370C (en) |
WO (1) | WO1994010697A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0855724A2 (en) * | 1997-01-22 | 1998-07-29 | Taiyo Yuden Co., Ltd. | Electronic parts and manufacturing method thereof |
EP1482524A1 (en) * | 2002-03-07 | 2004-12-01 | TDK Corporation | Laminate type electronic component |
EP1826786A1 (en) * | 2006-02-28 | 2007-08-29 | TDK Corporation | External electrode with an electroconductive resin layer for electronic component |
US8587923B2 (en) | 2009-06-01 | 2013-11-19 | Murata Manufacturing Co., Ltd. | Laminated electronic component including water repellant and manufacturing method therefor |
US20150068794A1 (en) * | 2013-09-12 | 2015-03-12 | Samsung Electro-Mechanics Co., Ltd. | Multilayer ceramic capacitor, manufacturing method thereof and board for mounting the same thereon |
US10242802B2 (en) | 2015-10-09 | 2019-03-26 | Murata Manufacturing Co., Ltd. | Electronic component with an external electrode including a conductive material-containing resin layer |
US20190148074A1 (en) * | 2017-11-15 | 2019-05-16 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor |
Families Citing this family (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100225928B1 (en) * | 1992-03-12 | 1999-10-15 | 정윤이 | Method of manufacturing sealed terminal and cell manufactured by it |
US7152291B2 (en) | 2002-04-15 | 2006-12-26 | Avx Corporation | Method for forming plated terminations |
AU2003289277A1 (en) | 2002-12-09 | 2004-06-30 | Matsushita Electric Industrial Co., Ltd. | Electronic part with external electrode |
EP1965397B1 (en) | 2005-12-22 | 2019-03-20 | Namics Corporation | Thermosetting conductive paste and multilayer ceramic component having external electrode which is formed by using such thermosetting conductive paste |
JP2007234800A (en) * | 2006-02-28 | 2007-09-13 | Tdk Corp | Electronic component and manufacturing method thereof |
WO2008001542A1 (en) * | 2006-06-28 | 2008-01-03 | Murata Manufacturing Co., Ltd. | Ceramic electronic component and method for manufacturing same |
JP2008255279A (en) * | 2007-04-06 | 2008-10-23 | Walsin Technology Corp | Terminal composition for electric component |
JP2011204849A (en) * | 2010-03-25 | 2011-10-13 | Murata Mfg Co Ltd | Method of manufacturing laminated ceramic electronic component |
JP5708009B2 (en) * | 2011-02-17 | 2015-04-30 | セイコーエプソン株式会社 | Optical module and electronic equipment |
KR102004759B1 (en) | 2012-06-11 | 2019-07-29 | 삼성전기주식회사 | Conductive paste composition for external electrode and multi-layered ceramic electronic parts fabricated by using the same |
JP2014107157A (en) * | 2012-11-28 | 2014-06-09 | Sumitomo Metal Mining Co Ltd | Conductive resin paste and electronic element using the same |
JP2014120382A (en) * | 2012-12-18 | 2014-06-30 | Sumitomo Metal Mining Co Ltd | Conductive resin paste and electronic element using the same |
JP5877239B2 (en) * | 2014-12-24 | 2016-03-02 | ナミックス株式会社 | Conductive paste for external electrode and multilayer ceramic electronic component provided with external electrode formed using the same |
CN104629260B (en) * | 2014-12-29 | 2017-09-15 | 广东风华高新科技股份有限公司 | The end-blocking slurry of chip multilayer ceramic capacitor, chip multilayer ceramic capacitor and preparation method thereof |
JP2017073539A (en) * | 2015-10-09 | 2017-04-13 | 株式会社村田製作所 | Electronic component |
JP6673273B2 (en) * | 2016-09-28 | 2020-03-25 | 株式会社村田製作所 | Electronic components |
JP2020107704A (en) * | 2018-12-27 | 2020-07-09 | Tdk株式会社 | Electronic component |
US10937596B2 (en) * | 2019-02-06 | 2021-03-02 | Tdk Corporation | Electronic component |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0167905A2 (en) * | 1984-07-09 | 1986-01-15 | W.R. Grace & Co.-Conn. | Conductive theromosetting compositions and process for using same |
JPS62164757A (en) * | 1986-01-14 | 1987-07-21 | Shinto Paint Co Ltd | Solderable, electrically conductive composition |
JPH03188180A (en) * | 1989-12-18 | 1991-08-16 | Hitachi Chem Co Ltd | Conductive film adhesive, method for adhesion, semiconductor device, and preparation of semiconductor device |
JPH04239710A (en) * | 1991-01-23 | 1992-08-27 | Nec Corp | Laminated ceramic capacitor |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8921742D0 (en) * | 1989-09-27 | 1989-11-08 | Cookson Group Plc | Conductive polymer composition |
-
1992
- 1992-11-04 JP JP4294893A patent/JPH06267784A/en active Pending
-
1993
- 1993-11-03 KR KR1019950701759A patent/KR950704801A/en not_active Application Discontinuation
- 1993-11-03 WO PCT/US1993/010325 patent/WO1994010697A1/en not_active Application Discontinuation
- 1993-11-03 EP EP94900411A patent/EP0667031A1/en not_active Withdrawn
- 1993-11-04 CN CN93112683A patent/CN1038370C/en not_active Expired - Fee Related
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0167905A2 (en) * | 1984-07-09 | 1986-01-15 | W.R. Grace & Co.-Conn. | Conductive theromosetting compositions and process for using same |
JPS62164757A (en) * | 1986-01-14 | 1987-07-21 | Shinto Paint Co Ltd | Solderable, electrically conductive composition |
JPH03188180A (en) * | 1989-12-18 | 1991-08-16 | Hitachi Chem Co Ltd | Conductive film adhesive, method for adhesion, semiconductor device, and preparation of semiconductor device |
JPH04239710A (en) * | 1991-01-23 | 1992-08-27 | Nec Corp | Laminated ceramic capacitor |
Non-Patent Citations (3)
Title |
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PATENT ABSTRACTS OF JAPAN vol. 12, no. 005 (C - 467) 8 January 1988 (1988-01-08) * |
PATENT ABSTRACTS OF JAPAN vol. 15, no. 445 (C - 0884) 13 November 1991 (1991-11-13) * |
PATENT ABSTRACTS OF JAPAN vol. 17, no. 006 (E - 1302) 7 January 1993 (1993-01-07) * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0855724A2 (en) * | 1997-01-22 | 1998-07-29 | Taiyo Yuden Co., Ltd. | Electronic parts and manufacturing method thereof |
EP0855724A3 (en) * | 1997-01-22 | 2004-08-18 | Taiyo Yuden Co., Ltd. | Electronic parts and manufacturing method thereof |
EP1482524A1 (en) * | 2002-03-07 | 2004-12-01 | TDK Corporation | Laminate type electronic component |
EP1482524A4 (en) * | 2002-03-07 | 2008-08-27 | Tdk Corp | Laminate type electronic component |
EP1826786A1 (en) * | 2006-02-28 | 2007-08-29 | TDK Corporation | External electrode with an electroconductive resin layer for electronic component |
US7505249B2 (en) | 2006-02-28 | 2009-03-17 | Tdk Corporation | Electronic component |
US8587923B2 (en) | 2009-06-01 | 2013-11-19 | Murata Manufacturing Co., Ltd. | Laminated electronic component including water repellant and manufacturing method therefor |
US20150068794A1 (en) * | 2013-09-12 | 2015-03-12 | Samsung Electro-Mechanics Co., Ltd. | Multilayer ceramic capacitor, manufacturing method thereof and board for mounting the same thereon |
US9520234B2 (en) * | 2013-09-12 | 2016-12-13 | Samsung Electro-Mechanics Co., Ltd. | Multilayer ceramic capacitor, manufacturing method thereof and board for mounting the same thereon |
US10242802B2 (en) | 2015-10-09 | 2019-03-26 | Murata Manufacturing Co., Ltd. | Electronic component with an external electrode including a conductive material-containing resin layer |
US20190148074A1 (en) * | 2017-11-15 | 2019-05-16 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor |
US10665392B2 (en) * | 2017-11-15 | 2020-05-26 | Murata Manufacturing Co., Ltd. | Multilayer ceramic capacitor |
Also Published As
Publication number | Publication date |
---|---|
CN1038370C (en) | 1998-05-13 |
JPH06267784A (en) | 1994-09-22 |
EP0667031A1 (en) | 1995-08-16 |
KR950704801A (en) | 1995-11-20 |
CN1091854A (en) | 1994-09-07 |
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