CN116709667A - Silver paste hole filling process method for circuit board - Google Patents
Silver paste hole filling process method for circuit board Download PDFInfo
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- CN116709667A CN116709667A CN202310793341.8A CN202310793341A CN116709667A CN 116709667 A CN116709667 A CN 116709667A CN 202310793341 A CN202310793341 A CN 202310793341A CN 116709667 A CN116709667 A CN 116709667A
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- CN
- China
- Prior art keywords
- silver paste
- circuit board
- conductive
- conductive silver
- alginate
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 37
- 239000004332 silver Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000005429 filling process Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 51
- 239000004005 microsphere Substances 0.000 claims abstract description 48
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 7
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 claims description 44
- 229940072056 alginate Drugs 0.000 claims description 44
- 235000010443 alginic acid Nutrition 0.000 claims description 44
- 229920000615 alginic acid Polymers 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 32
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 30
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 26
- 229920000767 polyaniline Polymers 0.000 claims description 25
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 16
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 15
- 239000002562 thickening agent Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 13
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 13
- 239000004925 Acrylic resin Substances 0.000 claims description 12
- 229920000178 Acrylic resin Polymers 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 12
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 239000000648 calcium alginate Substances 0.000 claims description 7
- 235000010410 calcium alginate Nutrition 0.000 claims description 7
- 229960002681 calcium alginate Drugs 0.000 claims description 7
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 claims description 7
- 150000001412 amines Chemical group 0.000 claims description 6
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 5
- 239000001856 Ethyl cellulose Substances 0.000 claims description 4
- 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 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000020 Nitrocellulose Substances 0.000 claims description 4
- 229920002367 Polyisobutene Polymers 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 4
- 229920001249 ethyl cellulose Polymers 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229920001220 nitrocellulos Polymers 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims 7
- 241000276425 Xiphophorus maculatus Species 0.000 abstract 1
- 229920000128 polypyrrole Polymers 0.000 description 32
- 239000002923 metal particle Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000005299 abrasion Methods 0.000 description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- 150000004965 peroxy acids Chemical class 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229940043237 diethanolamine Drugs 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- -1 carbonium ions Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/40—Forming printed elements for providing electric connections to or between printed circuits
- H05K3/4038—Through-connections; Vertical interconnect access [VIA] connections
-
- 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
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
-
- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
-
- 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
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/124—Intrinsically conductive polymers
- H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Conductive Materials (AREA)
Abstract
The invention belongs to the technical field of conductive silver paste preparation, and particularly relates to a circuit board silver paste hole filling process method. The method comprises the following steps: firstly spraying a surfactant at an orifice of the circuit board, placing the circuit board in a horizontal state, then injecting conductive silver paste into the orifice, oscillating by a vibrator, placing the circuit board into a heating oven for drying, and finally sintering the dried circuit board; wherein the conductive silver paste comprises composite microspheres and platy nanometer copper powder. The product obtained by the invention has good conductivity.
Description
Technical Field
The invention belongs to the technical field of conductive silver paste preparation, and particularly relates to a circuit board silver paste hole filling process method.
Background
The silver paste for the circuit board is a conductive material for manufacturing the circuit board and is generally composed of nano silver particles, a solvent, an auxiliary agent, a stabilizer and the like. Its main use is to make conductive lines of circuit boards and to make electronic components and printed circuit boards. The main characteristics of silver paste are high conductivity, high adhesiveness and high stability, which makes it an extremely ideal conductive material.
Although the conductive silver paste for the circuit board has a plurality of advantages, the conductive silver paste still has the problem of poor conductive capability due to easy oxidation.
Disclosure of Invention
The invention aims to solve the technical problem of poor conductivity of the traditional conductive silver paste.
The invention aims to provide a circuit board silver paste hole filling process method.
The above object of the present invention is achieved by the following technical scheme:
the invention provides a circuit board silver paste hole filling process method, which comprises the following steps: firstly spraying a surfactant at an orifice of the circuit board, placing the circuit board in a horizontal state, then injecting conductive silver paste into the orifice, oscillating by a vibrator, placing the circuit board into a heating oven for drying, and finally sintering the dried circuit board;
the preparation method of the conductive silver paste comprises the following steps:
(1) At room temperature of 25 ℃, adding pyrrole monomers into silver nitrate solution, stirring, then adding polyvinylpyrrolidone and manganese dioxide, continuously stirring, standing, and centrifuging to obtain composite microspheres;
(2) Adding the composite microsphere into N, N-dimethylformamide, stirring and mixing, adding polyethylene glycol, continuously stirring, adding sheet nanometer copper powder and sodium dodecyl benzene sulfonate, and finally adding acrylic resin to obtain the conductive silver paste.
According to the technical scheme, the pyrrole monomer and the silver nitrate are mixed and under the action of polyvinylpyrrolidone, so that the silver/polypyrrole conductive composite microsphere is formed, on one hand, the conductive polypyrrole coated metal particles are adopted to prolong the stability of the metal silver particles in the air, the conductivity of the metal silver particles is kept, on the other hand, abrasion easily occurs between the metal particles in the material mixing and stirring process, the contact area of the metal particles is reduced due to pits generated by abrasion on the surfaces of the metal particles, so that the conductivity is reduced, and the conductive composite microsphere has certain flexibility due to the fact that the surface of the conductive composite microsphere is coated with a polypyrrole layer, so that abrasion of flaky copper powder and the conductive composite microsphere can be effectively prevented, and further the conductivity is weakened.
Further, the conductive silver paste comprises the following raw materials in parts by weight:
100-120 parts of composite microspheres, 40-60 parts of flaky nanometer copper powder, 10-13 parts of acrylic resin, 0.2-0.4 part of sodium dodecyl benzene sulfonate and 2-3 parts of polyethylene glycol.
Further, the surfactant is selected from amine surfactants, and the amine surfactants are selected from any one of diethanolamine and N-methyldiethanolamine.
Further, the conductive silver paste also comprises polyaniline accounting for 0.3 to 0.6 percent of the mass of the flaky nanometer copper powder.
According to the technical scheme, polyaniline is added, so that the polyaniline has reducibility, silver powder can be prevented from being oxidized, and the conductive capability of conductive silver paste is weakened, and oxidized polyaniline also has conductive capability, so that the conductive capability of the conductive silver paste can be further improved.
Further, the sintering conditions include: the sintering temperature is 200-300 ℃; the sintering time is 20-30min.
Further, the conductive silver paste also comprises molybdenum disulfide powder accounting for 0.1-0.3% of the mass of the flaky nanometer copper powder.
Further, the pH of the conductive silver paste is 6.0-6.5.
According to the technical scheme, the pH of the conductive silver paste is controlled to be weak acid, so that on one hand, polypyrrole can be prevented from aging under a peracid environment to weaken conductive capacity, and on the other hand, hydroxide in an alkaline solution can be prevented from being deprotonated with carbonium ions in the polypyrrole under a peracid environment to prevent the formation of a polypyrrole film.
Further, the conductive silver paste further comprises a thickener; the thickener is selected from any one of ethyl cellulose, nitrocellulose and polyisobutylene.
Further, the conductive silver paste also comprises alginate accounting for 0.2 to 0.3 percent of the mass of the flaky nanometer copper powder.
Further, the alginate is selected from one of calcium alginate and manganese alginate.
According to the technical scheme, the alginate is added into the weakly acidic conductive silver paste, COO-of the alginate is converted into COOH in an acidic environment, negative electricity is prevented from deprotonating carbocations of polypyrrole, and meanwhile, hydrogen bonds are formed between hydrogen on amino groups in the polypyrrole and oxygen of hydroxyl groups on an alginate main chain because the alginate has the functions of a reducing agent and a stabilizing agent, so that the composite conductive microspheres are loaded on an alginate molecular chain, and the alginate can better protect the composite conductive microspheres.
The beneficial effects are that: (1) According to the technical scheme, pyrrole monomers and silver nitrate are mixed and under the action of polyvinylpyrrolidone, silver/polypyrrole conductive composite microspheres are formed, on one hand, conductive polypyrrole coated metal particles are adopted to prolong the stability of the metal silver particles in air and keep the conductivity of the metal silver particles, on the other hand, abrasion easily occurs between the metal particles in the material mixing and stirring process, pits generated on the surfaces of the metal particles due to abrasion can reduce the contact area of the metal particles, so that the conductivity is reduced, and the conductive composite microspheres have certain flexibility due to the fact that the surfaces of the conductive composite microspheres are coated with a layer of polypyrrole layer, so that abrasion of flaky copper powder and the conductive composite microspheres can be effectively prevented, and further the conductivity is weakened.
(2) According to the technical scheme, polyaniline is added, so that the polyaniline has reducibility, silver powder can be prevented from being oxidized, and the conductive capability of conductive silver paste is weakened, and oxidized polyaniline also has conductive capability, so that the conductive capability of the conductive silver paste can be further improved.
(3) According to the technical scheme, the pH of the conductive silver paste is controlled to be weak acid, so that on one hand, polypyrrole can be prevented from aging under a peracid environment to weaken conductive capacity, and on the other hand, hydroxide in an alkaline solution can be prevented from playing a deprotonation role with carbocation in the polypyrrole to prevent the formation of a polypyrrole film.
(4) According to the technical scheme, alginate is added into weakly acidic conductive silver paste, COO-of the alginate is converted into COOH in an acidic environment, negative electricity is prevented from deprotonating carbocation of polypyrrole, and meanwhile, hydrogen bonds are formed between hydrogen on amino in the polypyrrole and oxygen of hydroxyl on an alginate main chain because the alginate has the functions of a reducing agent and a stabilizing agent, so that the composite conductive microsphere is loaded on an alginate molecular chain, and the alginate can better protect the composite conductive microsphere.
Detailed Description
The present invention is further illustrated below with reference to specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
The invention provides a circuit board silver paste hole filling process method, which comprises the following steps: firstly spraying a surfactant at an orifice of the circuit board, placing the circuit board in a horizontal state, then injecting conductive silver paste into the orifice, oscillating by a vibrator, placing the circuit board into a heating oven for drying, and finally sintering the dried circuit board;
the preparation method of the conductive silver paste comprises the following steps:
(1) At room temperature of 25 ℃, adding pyrrole monomers into silver nitrate solution, stirring, then adding polyvinylpyrrolidone and manganese dioxide, continuously stirring, standing, and centrifuging to obtain composite microspheres;
(2) Adding the composite microsphere into N, N-dimethylformamide, stirring and mixing, adding polyethylene glycol, continuously stirring, adding sheet nanometer copper powder and sodium dodecyl benzene sulfonate, and finally adding acrylic resin to obtain the conductive silver paste.
According to the technical scheme, the pyrrole monomer and the silver nitrate are mixed and under the action of polyvinylpyrrolidone, so that the silver/polypyrrole conductive composite microsphere is formed, on one hand, the conductive polypyrrole coated metal particles are adopted to prolong the stability of the metal silver particles in the air, the conductivity of the metal silver particles is kept, on the other hand, abrasion easily occurs between the metal particles in the material mixing and stirring process, the contact area of the metal particles is reduced due to pits generated by abrasion on the surfaces of the metal particles, so that the conductivity is reduced, and the conductive composite microsphere has certain flexibility due to the fact that the surface of the conductive composite microsphere is coated with a polypyrrole layer, so that abrasion of flaky copper powder and the conductive composite microsphere can be effectively prevented, and further the conductivity is weakened.
Further, the conductive silver paste comprises the following raw materials in parts by weight:
100-120 parts of composite microspheres, 40-60 parts of flaky nanometer copper powder, 10-13 parts of acrylic resin, 0.2-0.4 part of sodium dodecyl benzene sulfonate and 2-3 parts of polyethylene glycol.
Further, the surfactant is selected from amine surfactants, and the amine surfactants are selected from any one of diethanolamine and N-methyldiethanolamine.
Further, the conductive silver paste also comprises polyaniline accounting for 0.3 to 0.6 percent of the mass of the flaky nanometer copper powder.
According to the technical scheme, polyaniline is added, so that the polyaniline has reducibility, silver powder can be prevented from being oxidized, and the conductive capability of conductive silver paste is weakened, and oxidized polyaniline also has conductive capability, so that the conductive capability of the conductive silver paste can be further improved.
Further, the sintering conditions include: the sintering temperature is 200-300 ℃; the sintering time is 20-30min.
Further, the conductive silver paste also comprises molybdenum disulfide powder accounting for 0.1-0.3% of the mass of the flaky nanometer copper powder.
Further, the pH of the conductive silver paste is 6.0-6.5.
According to the technical scheme, the pH of the conductive silver paste is controlled to be weak acid, so that on one hand, polypyrrole can be prevented from aging under a peracid environment to weaken conductive capacity, and on the other hand, hydroxide in an alkaline solution can be prevented from being deprotonated with carbonium ions in the polypyrrole under a peracid environment to prevent the formation of a polypyrrole film.
Further, the conductive silver paste further comprises a thickener; the thickener is selected from any one of ethyl cellulose, nitrocellulose and polyisobutylene.
Further, the conductive silver paste also comprises alginate accounting for 0.2 to 0.3 percent of the mass of the flaky nanometer copper powder.
Further, the alginate is selected from one of calcium alginate and manganese alginate.
According to the technical scheme, the alginate is added into the weakly acidic conductive silver paste, COO-of the alginate is converted into COOH in an acidic environment, negative electricity is prevented from deprotonating carbocations of polypyrrole, and meanwhile, hydrogen bonds are formed between hydrogen on amino groups in the polypyrrole and oxygen of hydroxyl groups on an alginate main chain because the alginate has the functions of a reducing agent and a stabilizing agent, so that the composite conductive microspheres are loaded on an alginate molecular chain, and the alginate can better protect the composite conductive microspheres.
The beneficial effects are that: (1) According to the technical scheme, pyrrole monomers and silver nitrate are mixed and under the action of polyvinylpyrrolidone, silver/polypyrrole conductive composite microspheres are formed, on one hand, conductive polypyrrole coated metal particles are adopted to prolong the stability of the metal silver particles in air and keep the conductivity of the metal silver particles, on the other hand, abrasion easily occurs between the metal particles in the material mixing and stirring process, pits generated on the surfaces of the metal particles due to abrasion can reduce the contact area of the metal particles, so that the conductivity is reduced, and the conductive composite microspheres have certain flexibility due to the fact that the surfaces of the conductive composite microspheres are coated with a layer of polypyrrole layer, so that abrasion of flaky copper powder and the conductive composite microspheres can be effectively prevented, and further the conductivity is weakened.
(2) According to the technical scheme, polyaniline is added, so that the polyaniline has reducibility, silver powder can be prevented from being oxidized, and the conductive capability of conductive silver paste is weakened, and oxidized polyaniline also has conductive capability, so that the conductive capability of the conductive silver paste can be further improved.
(3) According to the technical scheme, the pH of the conductive silver paste is controlled to be weak acid, so that on one hand, polypyrrole can be prevented from aging under a peracid environment to weaken conductive capacity, and on the other hand, hydroxide in an alkaline solution can be prevented from playing a deprotonation role with carbocation in the polypyrrole to prevent the formation of a polypyrrole film.
(4) According to the technical scheme, alginate is added into weakly acidic conductive silver paste, COO-of the alginate is converted into COOH in an acidic environment, negative electricity is prevented from deprotonating carbocation of polypyrrole, and meanwhile, hydrogen bonds are formed between hydrogen on amino in the polypyrrole and oxygen of hydroxyl on an alginate main chain because the alginate has the functions of a reducing agent and a stabilizing agent, so that the composite conductive microsphere is loaded on an alginate molecular chain, and the alginate can better protect the composite conductive microsphere.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1: preparation of composite microspheres:
sequentially weighing the following components in parts by weight:
60 parts of pyrrole monomer, 40 parts of silver nitrate solution with mass fraction of 30%, 20 parts of polyvinylpyrrolidone and 5 parts of manganese dioxide;
at room temperature of 25 ℃, adding pyrrole monomers into silver nitrate solution, stirring for 1h at a rotating speed of 600r/min by using a stirrer, adding polyvinylpyrrolidone and manganese dioxide, continuously stirring for 3h, standing, centrifuging, washing with deionized water for 5 times, and finally drying in a vacuum drying oven at 60 ℃ for 48h to obtain composite microspheres;
preparing conductive silver paste:
sequentially weighing the following components in parts by weight:
110 parts of composite microspheres, 50 parts of flaky nanometer copper powder, 12 parts of acrylic resin, 0.3 part of sodium dodecyl benzene sulfonate, 2.5 parts of polyethylene glycol and 2 parts of thickener.
Adding the composite microsphere into N, N-dimethylformamide, stirring and mixing for 80min at a rotation speed of 700r/min by using a stirrer, adding polyethylene glycol and polyaniline, continuously stirring for 40min, adding sheet nanometer copper powder, molybdenum disulfide powder, alginate and sodium dodecyl benzene sulfonate, stirring and mixing for 60min at a rotation speed of 800r/min by using the stirrer, and finally adding acrylic resin and a thickener, and regulating the pH value to 6.3 by using citric acid to obtain conductive silver paste;
wherein the mass of the polyaniline is 0.5% of the mass of the flaky nanometer copper powder; the mass of the molybdenum disulfide is 0.2% of the mass of the flaky nanometer copper powder; the thickener is selected from ethyl cellulose; the mass of the alginate is 0.25% of that of the flaky nanometer copper powder; the alginate is selected from calcium alginate;
the hole filling process of the silver paste of the circuit board comprises the following steps:
firstly spraying a surfactant at an orifice of the circuit board, placing the circuit board in a horizontal state, then injecting the prepared conductive silver paste into the orifice, oscillating for 3min under the condition of 40Hz through a vibrator, placing the circuit board into a heating oven for drying under the condition of 70 ℃, and finally sintering the dried circuit board for 25min under the condition of 250 ℃; the surfactant is selected from diethanolamine, and the mass of the surfactant is 1% of the mass of the conductive silver paste.
Example 2: preparation of composite microspheres:
sequentially weighing the following components in parts by weight:
60 parts of pyrrole monomer, 40 parts of silver nitrate solution with mass fraction of 30%, 20 parts of polyvinylpyrrolidone and 5 parts of manganese dioxide;
at room temperature of 25 ℃, adding pyrrole monomers into silver nitrate solution, stirring for 1h at a rotating speed of 600r/min by using a stirrer, adding polyvinylpyrrolidone and manganese dioxide, continuously stirring for 3h, standing, centrifuging, washing with deionized water for 5 times, and finally drying in a vacuum drying oven at 60 ℃ for 48h to obtain composite microspheres;
preparing conductive silver paste:
sequentially weighing the following components in parts by weight:
100 parts of composite microspheres, 40 parts of flaky nanometer copper powder, 10 parts of acrylic resin, 0.2 part of sodium dodecyl benzene sulfonate, 2 parts of polyethylene glycol and 1 part of thickener.
Adding the composite microsphere into N, N-dimethylformamide, stirring and mixing for 80min at a rotation speed of 700r/min by using a stirrer, adding polyethylene glycol and polyaniline, continuously stirring for 40min, adding sheet nanometer copper powder, molybdenum disulfide powder, alginate and sodium dodecyl benzene sulfonate, stirring and mixing for 60min at a rotation speed of 800r/min by using the stirrer, and finally adding acrylic resin and a thickener, and regulating the pH value to 6.0 by using citric acid to obtain conductive silver paste;
wherein the mass of the polyaniline is 0.3% of the mass of the flaky nanometer copper powder; the mass of the molybdenum disulfide is 0.1% of that of the flaky nanometer copper powder; the thickener is selected from nitrocellulose; the mass of the alginate is 0.2% of that of the flaky nanometer copper powder; the alginate is selected from calcium alginate;
the hole filling process of the silver paste of the circuit board comprises the following steps:
firstly spraying a surfactant at an orifice of the circuit board, placing the circuit board in a horizontal state, then injecting the prepared conductive silver paste into the orifice, oscillating for 3min under the condition of 40Hz through a vibrator, placing the circuit board into a heating oven for drying under the condition of 70 ℃, and finally sintering the dried circuit board for 20min under the condition of 200 ℃; the surfactant is selected from N-methyl diethanol amine, and the mass of the surfactant is 1% of the mass of the conductive silver paste.
Example 3: preparation of composite microspheres:
sequentially weighing the following components in parts by weight:
60 parts of pyrrole monomer, 40 parts of silver nitrate solution with mass fraction of 30%, 20 parts of polyvinylpyrrolidone and 5 parts of manganese dioxide;
at room temperature of 25 ℃, adding pyrrole monomers into silver nitrate solution, stirring for 1h at a rotating speed of 600r/min by using a stirrer, adding polyvinylpyrrolidone and manganese dioxide, continuously stirring for 3h, standing, centrifuging, washing with deionized water for 5 times, and finally drying in a vacuum drying oven at 60 ℃ for 48h to obtain composite microspheres;
preparing conductive silver paste:
sequentially weighing the following components in parts by weight:
120 parts of composite microspheres, 60 parts of flaky nano copper powder, 13 parts of acrylic resin, 0.4 part of sodium dodecyl benzene sulfonate, 3 parts of polyethylene glycol and 3 parts of thickener.
Adding the composite microsphere into N, N-dimethylformamide, stirring and mixing for 80min at a rotation speed of 700r/min by using a stirrer, adding polyethylene glycol and polyaniline, continuously stirring for 40min, adding sheet nanometer copper powder, molybdenum disulfide powder, alginate and sodium dodecyl benzene sulfonate, stirring and mixing for 60min at a rotation speed of 800r/min by using the stirrer, and finally adding acrylic resin and a thickener, and regulating the pH value to 6.5 by using citric acid to obtain conductive silver paste;
wherein the mass of the polyaniline is 0.6% of the mass of the flaky nanometer copper powder; the mass of the molybdenum disulfide is 0.3% of the mass of the flaky nanometer copper powder; the thickener is selected from polyisobutylene; the mass of the alginate is 0.3% of that of the flaky nanometer copper powder; the alginate is selected from calcium alginate;
the hole filling process of the silver paste of the circuit board comprises the following steps:
firstly spraying a surfactant at an orifice of the circuit board, placing the circuit board in a horizontal state, then injecting the prepared conductive silver paste into the orifice, oscillating for 3min under the condition of 40Hz through a vibrator, placing the circuit board into a heating oven for drying under the condition of 70 ℃, and finally sintering the dried circuit board for 30min under the condition of 300 ℃; the surfactant is selected from N-methyl diethanol amine, and the mass of the surfactant is 1% of the mass of the conductive silver paste.
Example 4:
this embodiment differs from embodiment 1 in that: polyaniline was not added, and the rest of the conditions were unchanged.
Example 5:
this embodiment differs from embodiment 1 in that: molybdenum disulfide powder was not added, and the remaining conditions were unchanged.
Example 6:
this embodiment differs from embodiment 1 in that: no alginate was added and the rest of the conditions were unchanged.
Example 7:
this embodiment differs from embodiment 1 in that: the manganese alginate is used for replacing calcium alginate, and the rest conditions are unchanged.
Example 8:
this embodiment differs from embodiment 1 in that: the pH of the conductive silver paste is not adjusted by citric acid, and the rest conditions are unchanged.
Comparative example 1:
this comparative example differs from example 1 in that: the spherical silver powder is used for replacing the composite microsphere, and the rest conditions are unchanged.
Comparative example 2:
this comparative example differs from example 1 in that: the flaky nanometer copper powder is not added, and the rest conditions are unchanged.
Comparative example 3:
this comparative example differs from example 1 in that: manganese dioxide was not added, and the remaining conditions were unchanged.
Comparative example 4:
this comparative example differs from example 1 in that:
preparing polyaniline/silver composite material:
the silver nitrate solid and the aniline monomer were fully complexed by stirring with a stirrer at 600r/min for 2h, then the beaker was placed in an ice-water bath, the reactants were continuously stirred while ammonium persulfate was slowly added, and when all the reactants became a dark blue solid powder, they were transposed to react fully at 4 ℃ for 24h. Washing with ice water for 5 times to obtain polyaniline/silver composite material;
wherein the ratio of the silver nitrate solid to the aniline monomer substance is 1:50; the mass ratio of ammonium persulfate to aniline monomer is 1:1;
replacing the composite microsphere with polyaniline/silver composite material; the remaining conditions were unchanged.
The products obtained in examples 1 to 8 and comparative examples 1 to 4 were subjected to performance tests, and specific test methods and test results are as follows:
testing the resistivity of the circuit board by using an RTS-4 four-probe instrument;
the specific test results are shown in table 1;
table 1: product performance test results
| Resistivity/Ω·cm | |
| Example 1 | 0.08 |
| Example 2 | 0.09 |
| Example 3 | 0.08 |
| Example 4 | 0.23 |
| Example 5 | 0.12 |
| Example 6 | 0.17 |
| Example 7 | 0.13 |
| Example 8 | 0.20 |
| Comparative example 1 | 0.37 |
| Comparative example 2 | 0.31 |
| Comparative example 3 | 0.27 |
| Comparative example 4 | 0.16 |
As can be seen from the test results in Table 1, the product obtained by the invention has good conductivity.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. The circuit board silver paste hole filling process method is characterized by comprising the following steps of: firstly spraying a surfactant at an orifice of the circuit board, placing the circuit board in a horizontal state, then injecting conductive silver paste into the orifice, oscillating by a vibrator, placing the circuit board into a heating oven for drying, and finally sintering the dried circuit board;
the preparation method of the conductive silver paste comprises the following steps:
(1) At room temperature of 25 ℃, adding pyrrole monomers into silver nitrate solution, stirring, then adding polyvinylpyrrolidone and manganese dioxide, continuously stirring, standing, and centrifuging to obtain composite microspheres;
(2) Adding the composite microsphere into N, N-dimethylformamide, stirring and mixing, adding polyethylene glycol, continuously stirring, adding sheet nanometer copper powder and sodium dodecyl benzene sulfonate, and finally adding acrylic resin to obtain the conductive silver paste.
2. The circuit board silver paste hole filling process method according to claim 1, wherein the conductive silver paste comprises the following raw materials in parts by weight:
100-120 parts of composite microspheres, 40-60 parts of flaky nanometer copper powder, 10-13 parts of acrylic resin, 0.2-0.4 part of sodium dodecyl benzene sulfonate and 2-3 parts of polyethylene glycol.
3. The method for hole-filling silver paste of circuit board according to claim 1, wherein the surfactant is selected from amine surfactants, and the amine surfactants are selected from any one of diethanolamine and N-methyldiethanolamine.
4. The method for filling holes in silver paste of circuit board according to claim 1, wherein the conductive silver paste further comprises polyaniline accounting for 0.3-0.6% of the mass of the flaky nanometer copper powder.
5. The method for filling holes in silver paste on a circuit board according to claim 1, wherein the sintering conditions comprise: the sintering temperature is 200-300 ℃; the sintering time is 20-30min.
6. The circuit board silver paste hole filling process method according to claim 1, wherein the conductive silver paste further comprises molybdenum disulfide powder accounting for 0.1-0.3% of the mass of the flaky nanometer copper powder.
7. The method for filling holes in silver paste of circuit board according to claim 1, wherein the pH of the conductive silver paste is 6.0-6.5.
8. The method for filling holes in a silver paste of a circuit board according to claim 1, wherein the conductive silver paste further comprises a thickener; the thickener is selected from any one of ethyl cellulose, nitrocellulose and polyisobutylene.
9. The method for filling holes in silver paste of circuit board according to claim 1, wherein the conductive silver paste further comprises alginate accounting for 0.2-0.3% of the mass of the flaky nanometer copper powder.
10. The method for filling holes in silver paste on circuit board according to claim 9, wherein the alginate is one selected from the group consisting of calcium alginate and manganese alginate.
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| CN115274180A (en) * | 2022-08-30 | 2022-11-01 | 上海宝银电子材料有限公司 | Conductive silver paste for solid fuel cell and preparation method thereof |
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| KR20140040587A (en) * | 2012-09-26 | 2014-04-03 | 김상호 | Conductive powder and menufacturing method of thereof |
| US20140158948A1 (en) * | 2012-12-11 | 2014-06-12 | National Tsing Hua University | Method for fabricating a conductive paste |
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