CN108281215A - Low-temperature setting thermoplastic polyimide MLCC silver-colored terminal electrode pastes and preparation method thereof - Google Patents
Low-temperature setting thermoplastic polyimide MLCC silver-colored terminal electrode pastes and preparation method thereof Download PDFInfo
- Publication number
- CN108281215A CN108281215A CN201810069349.9A CN201810069349A CN108281215A CN 108281215 A CN108281215 A CN 108281215A CN 201810069349 A CN201810069349 A CN 201810069349A CN 108281215 A CN108281215 A CN 108281215A
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- China
- Prior art keywords
- silver
- polyamic acid
- acid resin
- mlcc
- terminal electrode
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Links
- 229920006259 thermoplastic polyimide Polymers 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 93
- 229920005989 resin Polymers 0.000 claims abstract description 92
- 239000011347 resin Substances 0.000 claims abstract description 92
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 68
- 239000002245 particle Substances 0.000 claims abstract description 63
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002003 electrode paste Substances 0.000 claims abstract description 17
- 229910052709 silver Inorganic materials 0.000 claims abstract description 13
- 239000004332 silver Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 24
- 241000276425 Xiphophorus maculatus Species 0.000 claims description 23
- 239000012798 spherical particle Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000004014 plasticizer Substances 0.000 claims description 15
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 13
- 150000004985 diamines Chemical class 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 10
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical group C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007822 coupling agent Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 125000001142 dicarboxylic acid group Chemical group 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 1
- 150000001263 acyl chlorides Chemical class 0.000 claims 1
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000011267 electrode slurry Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 14
- 238000007711 solidification Methods 0.000 abstract description 3
- 230000008023 solidification Effects 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 description 33
- 239000002184 metal Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 230000008569 process Effects 0.000 description 13
- 239000000178 monomer Substances 0.000 description 12
- 239000004952 Polyamide Substances 0.000 description 11
- 229920002647 polyamide Polymers 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000001723 curing Methods 0.000 description 7
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 229940113088 dimethylacetamide Drugs 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 238000010422 painting Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001413 amino acids Chemical class 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- NJMOHBDCGXJLNJ-UHFFFAOYSA-N trimellitic anhydride chloride Chemical compound ClC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 NJMOHBDCGXJLNJ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229910052573 porcelain Inorganic materials 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 phenol aldehyde Chemical class 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 1
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010007247 Carbuncle Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- JGGQWILNAAODRS-UHFFFAOYSA-N n-methyl-4-[4-(methylamino)phenyl]aniline Chemical compound C1=CC(NC)=CC=C1C1=CC=C(NC)C=C1 JGGQWILNAAODRS-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/105—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1046—Polyimides containing oxygen in the form of ether bonds in the main chain
- C08G73/1053—Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the tetracarboxylic moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
-
- 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
- H01G4/30—Stacked capacitors
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of low-temperature setting thermoplastic polyimide MLCC silver-colored terminal electrode pastes and preparation method thereof, obtained low-temperature setting thermoplastic polyimide MLCC is made of with silver-colored terminal electrode paste conducting particles and polyamic acid resin, conducting particles and polyamic acid resin therein uniformly mix, and in the silver terminal electrode paste conducting particles mass fraction between 60%~85%.The electrode made by silver-colored terminal electrode paste through the invention, not only mechanical performance is excellent, heat resisting temperature is up to 400 DEG C, it can extensive use in a wider scope, and due to being free of curing agent in the slurry, but imidization is utilized to realize solidification, thus it is longer by the electrode life made by the slurry.
Description
Technical field
The present invention relates to MLCC electrode technical fields more particularly to a kind of low-temperature setting thermoplastic polyimide MLCC to use
Silver-colored terminal electrode paste and preparation method thereof.
Background technology
In recent years, it in the chip-type electronic components such as multilayer ceramic capacitor MLCC, is widely used through coating containing gold
The resin terminal electrode paste of category and make its be sintered and formed resin electrode be used as external electrode.Existing external electrode molding
Mode is generally divided into two classes：
One kind is high temperature sintering type, such sizing material forming process need to pass through low temperature drying and remove slurry internal solvent, then
Resin component in electrode is excluded by high temperature sintering furnace, then into the sintered of row metal within the temperature range of 600~850 DEG C
Journey, makes metal powder and glass powder form fine and close electrode layer, and resin usually selects ethyl cellulose, alkyd resin, acrylic acid tree
Fat, phenolic resin etc., tenor is generally in 60~80wt.%；
Another kind of is low temperature curing type, such slurry is to be coated with one layer of the type slurry in sintering silver electrode surface, at
Then type process forms electricity at 200 DEG C or so it is only necessary to remove slurry internal solvent by low temperature drying by curing reaction
Pole, resin usually select epoxy resin, polyurethane resin, phenol aldehyde modified epoxy resin etc., also add amine, triazole system, imidazoles
System etc. is used as curing agent, silver content generally very high.
Multilayer ceramic capacitor base material usually selects a kind of ceramics and two class ceramics as base material, and two class ceramics are due to dielectric
Constant is larger, therefore to cater to the development trend of multilayer ceramic capacitor small size large capacity, is usually all to select two classes ceramics
Unique shortcoming as base material, but two class porcelain is that its porcelain body intensity is relatively low, by porcelain body crackle can be caused when stress,
And then capacitance short-circuit is caused to fail.Therefore in order to improve this respect deficiency, low temperature curing type silver terminal electrode paste is usually selected, is somebody's turn to do
The electrode layer that slurry is formed is equivalent to one layer of elastic layer, therefore can more effectively absorb external carbuncle, protection electricity due to there is resin
Container so that capacitor under manufacturing process and external environment influence (as vibrate and temperature change etc.) caused by pcb board it is curved
It is not damaged still in the case of song deformation.To largely avoid the situation of short circuit so that starched using the type
In the environment of this capacitor of material is more suitable for military industry field, automobile, power circuit etc. to reliability requirement higher.
But there is also some shortcomings for the type slurry, when：The epoxy resin that existing slurry is generally selected uses temperature
Degree is no more than 200 DEG C, but in the high temperature welding process such as wave-soldering, Reflow Soldering, in order to reach solder fusion temperature, welding temperature
Usually all at 230 DEG C or more, therefore sub-fraction resin can be thermally decomposed in the welding process, so as to cause product electrode layer it
Between generate delamination phenomenon, cause product failure, and more crisp after curable epoxide, toughness is poor；Second is that：Existing curing type tree
Fat slurry usually all adds curing agent, and resin coexists for a long time with curing agent can cause the rotten of resin, so as to cause use
Electrode service life made by existing gel-type resin slurry is shorter, is usually no more than 6 months.
Invention content
Place in view of the above-mentioned deficiencies in the prior art, the present invention provide a kind of low-temperature setting thermoplastic polyimide
The silver-colored terminal electrode pastes of MLCC, the silver-colored terminal electrode pastes of low-temperature setting thermoplastic polyimide MLCC include conducting particles and gather
Amide acid resin, wherein the conducting particles and the polyamic acid resin uniformly mix, and in the silver-colored terminal electrode paste,
The mass fraction of the conducting particles is between 60%~85%.
Optionally, the conducting particles is the combination of one or both of spherical particle and platy particle.
Optionally, the mass ratio of the spherical particle in the conducting particles and platy particle is 0~5:1.
Optionally, the particle size range of the spherical particle is between 0.5um~5um, the granularity of platy particle 0.5um~
Between 10um.
Correspondingly, the present invention also provides a kind of low-temperature setting thermoplastic polyimide MLCC preparations of silver-colored terminal electrode paste
Method, the preparation method include：
Conducting particles is added in organic solvent and coupling agent is added in the organic solvent, then through ultrasonic disperse
After be obtained by filtration pretreated conducting particles, the addition of the coupling agent be the conducting particles quality 0.5%~
5%；
Polyamic acid resin is obtained by the polymerization of diamines and dianhydride, the viscosity of the polyamic acid resin exists
10000mPa.s between~40000mPa.s；
The pretreated conducting particles is added in the polyamic acid resin, then stirring makes in a kettle
The pretreated conducting particles is dispersed in the polyamic acid resin, obtains the pretreated conducting particles
With the mixture of the polyamic acid resin；
The mixture is poured into vacuum defoamation kettle, sloughs the bubble in the mixture；
The mixture for completing deaeration is passed through into grinder roll compacting, obtains fineness in 10um slurries below；
The slurry is stored by the laggard luggage tank of filter-cloth filtering.
Optionally, the step of polymerization by diamines and dianhydride obtains polyamic acid resin include：
In temperature it is 60 DEG C by dianhydride and diamines, vacuum degree is that 4 hours are placed in the vacuum drying oven of 0.01MPa,
Processing is dried；
By diamines of the solvent dissolving after dry, the dianhydride after drying is added into the solvent after diamines is completely dissolved
5 hours of reaction obtain polyamic acid resin solution；The mass fraction of polyamic acid resin is 3%~18% in the solution
Between；
Plasticizer is added into the solution, obtains polyamic acid of the viscosity between 10000mPa.s~40000mPa.s
Resin；The addition of the plasticizer is the 5%~30% of the polyamic acid resin quality.
Optionally, the mesh of the filter cloth in described the step of storing the slurry by the laggard luggage tank of filter-cloth filtering
Number is 500 mesh.
Optionally, the stirring in a kettle is so that the pretreated conducting particles is dispersed in the polyamides
It is 4~6 hours a length of when stirring in the step in amino acid resin.
Optionally, the dianhydride is pyromellitic acid anhydride, connection pyromellitic anhydride dianhydride, the double adjacent dicarboxylic acid anhydrides of 4,4 oxygen, inclined benzene
One kind in three anhydride chlorides；The diamines is bis- amido phenylates of 4,4-, 4,4- diaminodiphenylmethane, p-phenylenediamine, 2,2 '-
One kind in bis- (4- amino-benzene oxygens) benzene of dimethyl -4,4 '-benzidine, 1,4-, 1,3 bis- (4- amino-benzene oxygens) benzene；
The plasticizer is repefral.
Optionally, the organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide and N- crassitudes
One kind in ketone；The coupling agent is titanate coupling agent or silane coupling agent.
It is sub- that low-temperature setting thermoplasticity polyamides is made in the present invention by directly mixing conducting particles and polyamic acid resin
The silver-colored terminal electrode pastes of amine MLCC, preparation method are easy.And the electrode made by silver-colored terminal electrode paste through the invention is not only
Mechanical performance is excellent, and heat resisting temperature is up to 250 DEG C~400 DEG C, therefore can be widely applied in a wider scope, this
Outside, due to being free of curing agent in the slurry obtained by the present invention, but imidization is utilized to realize solidification, therefore passes through this hair
The electrode life made by slurry in bright is longer.
Description of the drawings
Fig. 1 be MLCC chips coating the present invention in silver-colored terminal electrode paste after plating be finished product schematic diagram.
Reference sign：
1：MLCC chips, 2：Metal electrode bottom, 3：Electroconductive resin electrode layer,
4：Nickel metal plate metal layer, 5：Tin or tin-lead electroplated metal layer.
Specific implementation mode
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
The every other embodiment that member is obtained without making creative work, shall fall within the protection scope of the present invention.
First embodiment
By pyromellitic acid anhydride monomer and 4, it is 60 DEG C that bis- amido phenylate monomers of 4-, which are put into temperature, and vacuum degree is
In the vacuum drying oven of 0.01MPa, and processing is dried in 4 hours of placement；Then in solvent N,N-dimethylformamide
(DMF) the equal of formula ratio is added after 4,4-, bis- amido phenylates are completely dissolved in 4,4-, the bis- amido phenylates of dissolving formula ratio in
Pyromellitic dianhydride is simultaneously reacted 5 hours, is controlled the mass fraction of polyamic acid resin in solution 18%, is obtained presenting reddish brown
Then plasticizer is added in color or flaxen polyamic acid resin solution in the polyamic acid resin solution, control polyamides
For the viscosity of amino acid resin between 40000 ± 1000mPa.s, the addition of plasticizer is the 20% of polyamic acid resin quality.
Silver powder is added in solvent n,N-Dimethylformamide (DMF), and the titanate esters that quality of cathode silver 0.5% is added are even
Join agent, pretreated silver powder is obtained after ultrasonic disperse and filtering；Then pretreated silver powder is added to completely reacted
Polyamic acid resin solution in, agitated reaction kettle high-speed stirred 4~6 hours.It is subsequently poured into vacuum defoamation kettle, sloughs polyamides
Bubble in amino acid resin；Slurry after deaeration is poured into progress roll compacting in three-roll grinder and obtains the slurry that fineness is met the requirements
Afterwards, slurry is filtered by 500 mesh filter clothes and filtered slurry is received into bottle storage.
Carrying out the process of roll compacting to the slurry after deaeration above by three-roll grinder can make the silver powder in slurry exist
It is sufficiently mixed in slurry and opens the grinding of the silver powder of reunion.Wherein mass fraction of the silver powder in gained slurry is 60%, used
Silver powder is mixed by spherical particle and platy particle, and the mass ratio of spheroidal particle and platy particle is in above-mentioned silver powder
1:5, the particle size range of spherical particle is between 0.5um~5um, and the granularity of platy particle is between 0.5um~10um.
Above-mentioned silver powder can also use wicker copper powder, silver coated aluminum powder body, silver-colored packet carbon fiber powder, silver-colored packet glass microballoon powder
Or other coat of metal powders replace, and in coat of metal powder used contained metal mass fraction should 10%~
Between 70%.
Decomposition temperature by the slurry obtained by aforesaid way is 350 DEG C.It is being formed using painting terminal when use
The both ends of the MLCC chips 1 of metal electrode bottom 2 are coated through slurry made from aforesaid way, then will coat the product of slurry
Dried according to specific drying curve, when drying temperature from 80 DEG C to 150 DEG C gradient increased temperature further to remove slurry
In solvent, to form polyamic acid resin dry film；It finally enters baking oven and handles 1h at a temperature of 160 DEG C, then at 200 DEG C
At a temperature of handle 4h, to complete imidization to form electroconductive resin electrode layer 3 at the both ends of MLCC chips 1, subsequently again
Carry out generating the link of nickel metal plate metal layer 4 and tin or tin-lead electroplated metal layer 5, final finished product such as Fig. 1 institutes successively
Show.
Second embodiment
Pyromellitic anhydride dianhydride monomer and 4 will be joined, it is 60 DEG C that 4- diaminodiphenylmethane monomers, which are put into temperature, and vacuum degree is
In the vacuum drying oven of 0.01MPa, and processing is dried in 4 hours of placement；Then in solvent DMAC N,N' dimethyl acetamide
(DMAc) 4, the 4- diaminodiphenylmethane of dissolving formula ratio is added after 4,4- diaminodiphenylmethane is completely dissolved in
The connection pyromellitic anhydride dianhydride of formula ratio simultaneously reacts 5 hours, controls the mass fraction of polyamic acid resin in solution 15%, obtains
To bronzing or flaxen polyamic acid resin solution is presented, plasticising is then added in the polyamic acid resin solution
Agent controls the viscosity of polyamic acid resin between 35000 ± 1000mPa.s.The addition of above-mentioned plasticizer is polyamic acid
The 30% of resin quality.
Silver powder is added in solvent n,N-dimethylacetamide (DMAc), and the silane coupled of quality of cathode silver 1% is added
Agent obtains pretreated silver powder after ultrasonic disperse and filtering；Then pretreated silver powder is added to completely reacted
In polyamic acid resin solution, agitated reaction kettle high-speed stirred 4~6 hours.It is subsequently poured into vacuum defoamation kettle, sloughs polyamide
Bubble in acid resin；Slurry after deaeration is poured into progress roll compacting in three-roll grinder and obtains the slurry that fineness is met the requirements
Afterwards, slurry is filtered by 500 mesh filter clothes and filtered slurry is received into bottle storage.
Carrying out the process of roll compacting to the slurry after deaeration above by three-roll grinder can make the silver powder in slurry exist
It is sufficiently mixed in slurry and opens the grinding of the silver powder of reunion.Wherein mass fraction of the silver powder in gained slurry is 65%, used
Silver powder is mixed by spherical particle and platy particle, and the ratio of spheroidal particle and platy particle is 1 in above-mentioned silver powder:1,
The particle size range of spherical particle is between 0.5um~5um, and the granularity of platy particle is between 0.5um~10um.
Decomposition temperature by the slurry obtained by aforesaid way is 320 DEG C.It is being formed using painting terminal when use
The both ends of the MLCC chips 1 of metal electrode bottom 2 are coated through slurry made from aforesaid way, then will coat the product of slurry
Dried according to specific drying curve, when drying temperature from 80 DEG C to 150 DEG C gradient increased temperature further to remove slurry
In solvent, to form polyamic acid resin dry film；It finally enters baking oven and handles 1h at a temperature of 160 DEG C, then at 200 DEG C
At a temperature of handle 4h, to complete imidization to form electroconductive resin electrode layer 3 at the both ends of MLCC chips 1, subsequently again
Carry out generating the link of nickel metal plate metal layer 4 and tin or tin-lead electroplated metal layer 5 successively.Final finished product such as Fig. 1 institutes
Show.
3rd embodiment
It is 60 DEG C that the double adjacent dicarboxylic acid anhydride monomers of 4,4 oxygen and p-phenylenediamine monomer, which are put into temperature, and vacuum degree is 0.01MPa's
In vacuum drying oven and processing is dried in 4 hours of placement；Then dissolving is matched in solvent N-methyl pyrilidone (NMP)
The 4 of formula ratio are added after p-phenylenediamine is completely dissolved in the p-phenylenediamine just measured, and the double adjacent dicarboxylic acid anhydrides of 4 oxygen simultaneously react 5
Hour, the mass fraction of polyamic acid resin in solution is controlled 12%, obtains that bronzing or flaxen polyamide is presented
Plasticizer is added in the polyamic acid resin solution in acid resin solution, control the viscosity of polyamic acid resin 30000 ±
Between 1000mPa.s, the addition of plasticizer is the 25% of polyamic acid resin quality.
Silver powder is added in solvent N-methyl pyrilidone (NMP), and the titanate esters coupling of quality of cathode silver 2% is added
Agent obtains pretreated silver powder after ultrasonic disperse and filtering；Then pretreated silver powder is added to completely reacted
In polyamic acid resin solution, agitated reaction kettle high-speed stirred 4~6 hours.It is subsequently poured into vacuum defoamation kettle, sloughs polyamide
Bubble in acid resin；Slurry after deaeration is poured into progress roll compacting in three-roll grinder and obtains the slurry that fineness is met the requirements
Afterwards, slurry is filtered by 500 mesh filter clothes and filtered slurry is received into bottle storage.
Carrying out the process of roll compacting to the slurry after deaeration above by three-roll grinder can make the silver powder in slurry exist
It is sufficiently mixed in slurry and opens the grinding of the silver powder of reunion.Wherein mass fraction of the silver powder in gained slurry is 70%, used
Silver powder is mixed by spherical particle and platy particle, and the ratio of spheroidal particle and platy particle is 5 in above-mentioned silver powder:1,
The particle size range of spherical particle is between 0.5um~5um, and the granularity of platy particle is between 0.5um~10um.
Decomposition temperature by the slurry obtained by aforesaid way is 340 DEG C.It is being formed using painting terminal when use
The both ends of the MLCC chips 1 of metal electrode bottom 2 are coated through slurry made from aforesaid way, then will coat the product of slurry
Dried according to specific drying curve, when drying temperature from 80 DEG C to 150 DEG C gradient increased temperature further to remove slurry
In solvent, to form polyamic acid resin dry film；It finally enters baking oven and handles 1h at a temperature of 160 DEG C, then at 200 DEG C
At a temperature of handle 4h, to complete imidization to form electroconductive resin electrode layer 3 at the both ends of MLCC chips 1, subsequently again
Carry out generating the link of nickel metal plate metal layer 4 and tin or tin-lead electroplated metal layer 5, final finished product such as Fig. 1 institutes successively
Show.
Fourth embodiment
By Trimellitic Anhydride Chloride monomer and 2,2 ' dimethyl -4, it is 60 DEG C that 4 ' benzidine monomers, which are put into temperature, very
Reciprocal of duty cycle be 0.01MPa vacuum drying oven in, and place 4 hours processing is dried；Then in solvent N, N- dimethyl
2,2 ' dimethyl -4 of dissolving formula ratio in formamide (DMF), 4 ' benzidines, until 2,2 ' dimethyl -4,4 ' diamino
After biphenyl is completely dissolved, the Trimellitic Anhydride Chloride of formula ratio is added and reacts 5 hours, controls polyamic acid resin in solution
Mass fraction 9%, obtain that bronzing or flaxen polyamic acid resin solution is presented, it is molten in the polyamic acid resin
Plasticizer is added in liquid, controls the viscosity of polyamic acid resin between 25000 ± 1000mPa.s, the addition of plasticizer is
The 10% of polyamic acid resin quality.
Silver powder is added in solvent n,N-Dimethylformamide (DMF), and the silane coupled of quality of cathode silver 3% is added
Agent obtains pretreated silver powder after ultrasonic disperse and filtering；Then pretreated silver powder is added to completely reacted
In polyamic acid resin solution, agitated reaction kettle high-speed stirred 4~6 hours.It is subsequently poured into vacuum defoamation kettle, sloughs polyamide
Bubble in acid resin；Slurry after deaeration is poured into progress roll compacting in three-roll grinder and obtains the slurry that fineness is met the requirements
Afterwards, slurry is filtered by 500 mesh filter clothes and filtered slurry is received into bottle storage.
Carrying out the process of roll compacting to the slurry after deaeration above by three-roll grinder can make the silver powder in slurry exist
It is sufficiently mixed in slurry and opens the grinding of the silver powder of reunion.Wherein mass fraction of the silver powder in gained slurry is 75%, used
Silver powder is mixed by spherical particle and platy particle, and the ratio of spheroidal particle and platy particle is 1 in above-mentioned silver powder:3,
The particle size range of spherical particle is between 0.5um~5um, and the granularity of platy particle is between 0.5um~10um.
Decomposition temperature by the slurry obtained by aforesaid way is 380 DEG C.It is being formed using painting terminal when use
The both ends of the MLCC chips 1 of metal electrode bottom 2 are coated through slurry made from aforesaid way, then will coat the product of slurry
Dried according to specific drying curve, when drying temperature from 80 DEG C to 150 DEG C gradient increased temperature further to remove slurry
In solvent, to form polyamic acid resin dry film；It finally enters baking oven and handles 1h at a temperature of 160 DEG C, then at 200 DEG C
At a temperature of handle 4h, to complete imidization to form electroconductive resin electrode layer 3 at the both ends of MLCC chips 1, subsequently again
Carry out generating the link of nickel metal plate metal layer 4 and tin or tin-lead electroplated metal layer 5, final finished product such as Fig. 1 institutes successively
Show.
5th embodiment
It is 60 DEG C that bis- (4- amino-benzene oxygens) benzene monomers of pyromellitic acid anhydride monomer and Isosorbide-5-Nitrae-, which are put into temperature, vacuum degree
For in the vacuum drying oven of 0.01MPa and place 4 hours processing is dried；Then in solvent DMAC N,N' dimethyl acetamide
(DMAc) bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae-of dissolving formula ratio in, until bis- (4- amino-benzene oxygens) benzene of Isosorbide-5-Nitrae-are completely dissolved
Afterwards, the pyromellitic acid anhydride of formula ratio is added and reacts 5 hours, the mass fraction for controlling polyamic acid resin in solution exists
6%, it obtains that bronzing or flaxen polyamic acid resin solution is presented, plasticising is added in the polyamic acid resin solution
Agent controls the viscosity of polyamic acid resin between 20000 ± 1000mPa.s, and the addition of plasticizer is polyamic acid resin
The 5% of quality.
Silver powder is added in solvent n,N-dimethylacetamide (DMAc), and the titanate esters that quality of cathode silver 5% is added are even
Join agent, pretreated silver powder is obtained after ultrasonic disperse and filtering；Then pretreated silver powder is added to completely reacted
Polyamic acid resin solution in, agitated reaction kettle high-speed stirred 4~6 hours.It is subsequently poured into vacuum defoamation kettle, sloughs polyamides
Bubble in amino acid resin；Slurry after deaeration is poured into progress roll compacting in three-roll grinder and obtains the slurry that fineness is met the requirements
Afterwards, slurry is filtered by 500 mesh filter clothes and filtered slurry is received into bottle storage.
Carrying out the process of roll compacting to the slurry after deaeration above by three-roll grinder can make the silver powder in slurry exist
It is sufficiently mixed in slurry and opens the grinding of the silver powder of reunion.Wherein mass fraction of the silver powder in gained slurry is 80%, used
Silver powder is mainly platy particle, and in the granularity of the platy particle of composition silver powder between 0.5um~10um.
Decomposition temperature by the slurry obtained by aforesaid way is 400 DEG C.It is being formed using painting terminal when use
The both ends of the MLCC chips 1 of metal electrode bottom 2 are coated through slurry made from aforesaid way, then will coat the product of slurry
Dried according to specific drying curve, when drying temperature from 80 DEG C to 150 DEG C gradient increased temperature further to remove slurry
In solvent, to form polyamic acid resin dry film；It finally enters baking oven and handles 1h at a temperature of 160 DEG C, then at 200 DEG C
At a temperature of handle 4h, to complete imidization to form electroconductive resin electrode layer 3 at the both ends of MLCC chips 1, subsequently again
Carry out generating the link of nickel metal plate metal layer 4 and tin or tin-lead electroplated metal layer 5, final finished product such as Fig. 1 institutes successively
Show.
Sixth embodiment
By Trimellitic Anhydride Chloride monomer and 1, it is 60 DEG C that 3 bis- (4- amino-benzene oxygens) benzene monomers, which are put into temperature, vacuum degree
For in the vacuum drying oven of 0.01MPa, and places 4 hours and processing is dried；Then in solvent N-methyl pyrilidone
(NMP) 1,3 bis- (4- amino-benzene oxygens) benzene of dissolving formula ratio in, after 1,3 bis- (4- amino-benzene oxygens) benzene are completely dissolved,
The Trimellitic Anhydride Chloride of formula ratio is added and reacts 5 hours, the mass fraction for controlling polyamic acid resin in solution exists
3%, it obtains that bronzing or flaxen polyamic acid resin solution is presented, plasticising is added in the polyamic acid resin solution
Agent controls the viscosity of polyamic acid resin between 10000 ± 1000mPa.s, and the addition of plasticizer is polyamic acid resin
The 15% of quality.
Silver powder is added in solvent N-methyl pyrilidone (NMP), and the silane coupling agent of quality of cathode silver 5% is added,
Pretreated silver powder is obtained after ultrasonic disperse and filtering；Then pretreated silver powder is added to completely reacted polyamides
In amino acid resin solution, agitated reaction kettle high-speed stirred 4~6 hours.It is subsequently poured into vacuum defoamation kettle, sloughs polyamic acid tree
Bubble in fat；Slurry after deaeration is poured into three-roll grinder and after roll compacting obtains the slurry that fineness is met the requirements, lead to
500 mesh filter clothes are crossed to be filtered slurry and filtered slurry is received bottle storage.
Carrying out the process of roll compacting to the slurry after deaeration above by three-roll grinder can make the silver powder in slurry exist
It is sufficiently mixed in slurry and opens the grinding of the silver powder of reunion.Wherein mass fraction of the silver powder in gained slurry is 85%, used
Silver powder is mixed by spherical particle and platy particle, and the mass ratio of spherical particle and platy particle is 3 in above-mentioned silver powder:
1, the particle size range of spherical particle is between 0.5um~5um, and the granularity of platy particle is between 0.5um~10um.
Decomposition temperature by the slurry obtained by aforesaid way is 350 DEG C.It is being formed using painting terminal when use
The both ends of the MLCC chips 1 of metal electrode bottom 2 are coated through slurry made from aforesaid way, then will coat the product of slurry
Dried according to specific drying curve, when drying temperature from 80 DEG C to 150 DEG C gradient increased temperature further to remove slurry
In solvent, to form polyamic acid resin dry film；It finally enters baking oven and handles 1h at a temperature of 160 DEG C, then at 200 DEG C
At a temperature of handle 4h, to complete imidization to form electroconductive resin electrode layer 3 at the both ends of MLCC chips 1, subsequently again
Carry out generating the link of nickel metal plate metal layer 4 and tin or tin-lead electroplated metal layer 5, final finished product such as Fig. 1 institutes successively
Show.
It is sub- that low-temperature setting thermoplasticity polyamides is made in the present invention by directly mixing conducting particles and polyamic acid resin
The silver-colored terminal electrode pastes of amine MLCC, preparation method are easy.And the electrode made by silver-colored terminal electrode paste through the invention is not only
Mechanical performance is excellent, and heat resisting temperature is up to 250 DEG C~400 DEG C, therefore can be widely applied in a wider scope, this
Outside, due to being free of curing agent in the slurry obtained by the present invention, but imidization is utilized to realize solidification, therefore passes through this hair
The electrode life made by slurry in bright is longer.
It should be noted that herein, the terms "include", "comprise" or its any other variant are intended to non-row
His property includes, so that process, method, article or terminal device including a series of elements are not only wanted including those
Element, but also include other elements that are not explicitly listed, or further include for this process, method, article or terminal
The intrinsic element of equipment.In the absence of more restrictions, the element limited by sentence "including a ...", is not arranged
Except there is also other identical elements in process, method, article or the terminal device including the element.
It these are only the preferred embodiment of the present invention, be not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.Any modification made by all within the spirits and principles of the present invention,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of silver-colored terminal electrode pastes of low-temperature setting thermoplastic polyimide MLCC, which is characterized in that the silver termination electrode slurry
Material includes conducting particles and polyamic acid resin, wherein the conducting particles and the polyamic acid resin uniformly mix, and
The mass fraction of conducting particles is between 60%~85% described in the silver terminal electrode paste.
2. the silver-colored terminal electrode pastes of low-temperature setting thermoplastic polyimide MLCC as described in claim 1, which is characterized in that institute
State the combination that conducting particles is one or both of spherical particle and platy particle.
3. the silver-colored terminal electrode pastes of low-temperature setting thermoplastic polyimide MLCC as claimed in claim 2, which is characterized in that institute
The mass ratio for stating the spherical particle and platy particle in conducting particles is 0~5:1.
4. the silver-colored terminal electrode pastes of low-temperature setting thermoplastic polyimide MLCC as claimed in claim 2, which is characterized in that institute
The particle size range of spherical particle is stated between 0.5um~5um, the granularity of platy particle is between 0.5um~10um.
5. a kind of silver-colored terminal electrode pastes of low-temperature setting thermoplastic polyimide MLCC as described in any one of claim 1-4
Preparation method, which is characterized in that the preparation method includes：
Conducting particles is added in organic solvent and coupling agent is added in the organic solvent, then the mistake after ultrasonic disperse
Filter obtains pretreated conducting particles, and the addition of the coupling agent is the 0.5%~5% of the conducting particles quality；
Obtain polyamic acid resin by the polymerization of diamines and dianhydride, the viscosity of the polyamic acid resin 10000mPa.s~
Between 40000mPa.s；
The pretreated conducting particles is added in the polyamic acid resin, is then stirred in a kettle so that described
Pretreated conducting particles is dispersed in the polyamic acid resin, obtains the pretreated conducting particles and institute
State the mixture of polyamic acid resin；
The mixture is poured into vacuum defoamation kettle, sloughs the bubble in the mixture；
The mixture for completing deaeration is passed through into grinder roll compacting, obtains fineness in 10um slurries below；
The slurry is stored by the laggard luggage tank of filter-cloth filtering.
6. the low-temperature setting thermoplastic polyimide MLCC as claimed in claim 5 preparation methods of silver-colored terminal electrode paste,
It is characterized in that, the step of polymerization by diamines and dianhydride obtains polyamic acid resin includes：
In temperature it is 60 DEG C by dianhydride and diamines, vacuum degree is that 4 hours are placed in the vacuum drying oven of 0.01MPa, is carried out
It is dried；
By diamines of the solvent dissolving after dry, two anhydride reactants after drying are added into the solvent after diamines is completely dissolved
5 hours obtain polyamic acid resin solution；In the solution mass fraction of polyamic acid resin 3%~18% it
Between；
Plasticizer is added into the solution, obtains polyamic acid tree of the viscosity between 10000mPa.s~40000mPa.s
Fat；The addition of the plasticizer is the 5%~30% of the polyamic acid resin quality.
7. the low-temperature setting thermoplastic polyimide MLCC as claimed in claim 5 preparation methods of silver-colored terminal electrode paste,
It is characterized in that, the mesh number of the filter cloth in described the step of storing the slurry by the laggard luggage tank of filter-cloth filtering is
500 mesh.
8. the low-temperature setting thermoplastic polyimide MLCC as claimed in claim 5 preparation methods of silver-colored terminal electrode paste,
It is characterized in that, the stirring in a kettle is so that the pretreated conducting particles is dispersed in the polyamic acid tree
It is 4~6 hours a length of when stirring in the step in fat.
9. the low-temperature setting thermoplastic polyimide MLCC as claimed in claim 6 preparation methods of silver-colored terminal electrode paste,
It is characterized in that, the dianhydride is pyromellitic acid anhydride, connection pyromellitic anhydride dianhydride, the double adjacent dicarboxylic acid anhydrides of 4,4 oxygen, trimellitic anhydride
One kind in acyl chlorides；The diamines is bis- amido phenylates of 4,4-, 4,4- diaminodiphenylmethane, p-phenylenediamine, 2,2 '-diformazans
One kind in bis- (4- amino-benzene oxygens) benzene of base -4,4 '-benzidine, 1,4-, 1,3 bis- (4- amino-benzene oxygens) benzene；It is described
Plasticizer is repefral.
10. the low-temperature setting thermoplastic polyimide MLCC as claimed in claim 5 preparation methods of silver-colored terminal electrode paste,
It is characterized in that, the organic solvent is in n,N-Dimethylformamide, n,N-dimethylacetamide and N-Methyl pyrrolidone
It is a kind of；The coupling agent is titanate coupling agent or silane coupling agent.
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| CN113192664A (en) * | 2021-06-17 | 2021-07-30 | 航天特种材料及工艺技术研究所 | High-temperature-resistant resin-based conductive silver paste and preparation method thereof |
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