CN117275796A - Low-temperature silver paste prepared based on metal grid conductive film and preparation method thereof - Google Patents
Low-temperature silver paste prepared based on metal grid conductive film and preparation method thereof Download PDFInfo
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- CN117275796A CN117275796A CN202311094737.XA CN202311094737A CN117275796A CN 117275796 A CN117275796 A CN 117275796A CN 202311094737 A CN202311094737 A CN 202311094737A CN 117275796 A CN117275796 A CN 117275796A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 85
- 239000004332 silver Substances 0.000 title claims abstract description 85
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 52
- 239000011347 resin Substances 0.000 claims abstract description 52
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 43
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 43
- 229920002545 silicone oil Polymers 0.000 claims abstract description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000013034 phenoxy resin Substances 0.000 claims abstract description 20
- 229920006287 phenoxy resin Polymers 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000011159 matrix material Substances 0.000 claims description 14
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 230000003014 reinforcing effect Effects 0.000 claims description 9
- 239000002060 nanoflake Substances 0.000 claims description 7
- 229920002050 silicone resin Polymers 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- -1 amine salt Chemical class 0.000 claims description 4
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229920006150 hyperbranched polyester Polymers 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000010408 film Substances 0.000 claims 8
- 239000010409 thin film Substances 0.000 claims 2
- 238000004132 cross linking Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 229920005992 thermoplastic resin Polymers 0.000 abstract description 5
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 4
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 17
- 238000011049 filling Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 238000005452 bending Methods 0.000 description 9
- 239000003822 epoxy resin Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 2
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000005429 filling process Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- KUBDPQJOLOUJRM-UHFFFAOYSA-N 2-(chloromethyl)oxirane;4-[2-(4-hydroxyphenyl)propan-2-yl]phenol Chemical compound ClCC1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 KUBDPQJOLOUJRM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003897 fog Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Landscapes
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to low-temperature silver paste prepared based on a metal grid conductive film and a preparation method thereof, and belongs to the technical field of silver paste. The low-temperature silver paste comprises the following raw materials in parts by mass: 4-10 parts of phenoxy resin, 1-4 parts of reinforced resin, 8-30 parts of organic solvent, 0.5-3 parts of curing agent, 0.01-0.05 part of catalyst, 0.2-2 parts of coupling agent, 0.2-2 parts of dispersing agent and 60-85 parts of conductive powder; the reinforced resin is prepared from liquid vinyl MQ silicon resin, double-end vinyl silicone oil and methyl end-capped side chain hydrogen-containing silicone oil according to the weight ratio of 7.5-10:5-7.5:1, and mixing. The low-temperature silver paste uses the phenoxy resin as the main resin and uses the latent curing agent for crosslinking and curing, so that the low-temperature silver paste has excellent binding force, corrosion resistance and weather resistance of the thermosetting resin to a base material, and simultaneously has the flexibility of the thermoplastic resin. The phenoxy resin is used as the main resin to endow the low-temperature silver paste with good mechanical properties.
Description
Technical Field
The invention belongs to the technical field of silver paste, and particularly relates to low-temperature silver paste prepared based on a metal grid conductive film and a preparation method thereof.
Background
The transparent conductive film has excellent conductivity and high light transmittance in the visible light range, and is a core material for application fields such as touch display, transparent electrodes, electromagnetic shielding, photovoltaic devices and the like. At present, the most widely used transparent conductive film in the market is an ITO (indium tin oxide) conductive film. However, with the development of flexible electronic industry, the ITO conductive film has performance defects of intolerance to bending, poor flexibility, etc., and meanwhile, the deposition process of ITO needs to be performed under vacuum condition, so that the manufacturing cost is high, which limits the application of the ITO conductive film in novel flexible electronic devices.
A Metal Mesh (Metal Mesh) transparent conductive film is an alternative scheme with competitive and application potential for an ITO conductive film. The transparent conductive film with metal mesh generally uses PET (polyethylene terephthalate) film as a base material, and the transparent conductive film is exposed, developed and etched to obtain a latticed groove with specified width and depth, and conductive silver paste is filled in the groove in a doctor-blading mode, and the conductive mesh is formed by low-temperature solidification, so that the transparent conductive film has the performance advantages of low resistance, flex resistance, high light transmittance and the like. The conductive silver paste is one of core materials for preparing the metal grid transparent conductive film, and the conductivity, adhesive force, bending resistance and thin line filling property of the silver paste directly determine the actual performance of the transparent conductive film.
At present, the conductive silver paste for preparing the metal grid transparent conductive film is low-temperature silver paste, and is generally composed of high polymer resin, silver powder, an organic solvent and an auxiliary agent, and is baked and cured at the temperature below 200 ℃ to form a conductive circuit. Conventional low temperature silver pastes on the market generally use micron-sized silver powder as conductive filler and have poor filling properties when facing metal mesh grooves of 3 μm and below. As the polymer resin as the binder phase, a thermoplastic resin typified by polyester and polyurethane or a thermosetting resin typified by epoxy resin is generally used as the low-temperature silver paste. The polyester and polyurethane resin has good flexibility, but has poor tolerance to constant temperature and humidity, salt fog and acid and alkali, and meanwhile, has the risk of poor adhesive force during long-term use, so that the whole metal grid transparent conductive film fails. The epoxy resin has good binding force to the base material and excellent long-term stability and weather resistance, but is hard and brittle after being cured, is not bending-resistant, and cannot meet the flexible requirement of the transparent conductive film of the metal grid.
In conclusion, the development of the low-temperature silver paste with good comprehensive performances of conductivity, adhesive force, flexibility, weather resistance and the like, which is suitable for ultra-fine linewidth filling and low-temperature curing processes, is suitable for the transparent conductive film of the metal grid, and has very important significance.
Disclosure of Invention
In order to solve the technical problems, the invention provides the low-temperature silver paste prepared based on the metal grid conductive film and the preparation method thereof, wherein the low-temperature silver paste can be baked and cured at 120 ℃, has good conductivity, adhesive force, bending resistance and weather resistance, and is suitable for a metal grid 3 mu m superfine line width slot filling process.
The invention provides low-temperature silver paste prepared based on a metal grid conductive film, which comprises the following raw materials in parts by mass: 4-10 parts of phenoxy resin, 1-4 parts of reinforced resin, 8-30 parts of organic solvent, 0.5-3 parts of curing agent, 0.01-0.05 part of catalyst, 0.2-2 parts of coupling agent, 0.2-2 parts of dispersing agent and 60-85 parts of conductive powder;
the reinforced resin is prepared from liquid vinyl MQ silicon resin, double-end vinyl silicone oil and methyl end-capped side chain hydrogen-containing silicone oil according to the weight ratio of 7.5-10:5-7.5:1, and mixing.
In one embodiment of the present invention, the phenoxy resin has a weight average molecular weight Mw of 45000-65000 and an epoxy equivalent of 7000g/eq-9500g/eq, and a high molecular weight, high epoxy equivalent phenoxy resin is used as a host resin. The phenoxy resin is a special type of epoxy resin having a high degree of polymerization, and the higher the degree of polymerization, the higher the molecular weight and the epoxy equivalent. At high polymerization degree, the phenoxy resin has flexibility of thermoplastic resin and also has reactive epoxy groups, and is crosslinked and cured by a curing agent, so that the phenoxy resin has hardness, cohesive force and weather resistance of the epoxy resin. The conventional epoxy resin has low weight average molecular weight and epoxy equivalent, is used as a main resin, is hard and brittle after silver paste is cured, has insufficient flexibility, and does not have the excellent comprehensive performance of phenoxy resin.
Further, the phenoxy resin is selected from one or more of mitsubishi JER1256, mitsubishi JER4250, mitsubishi JER4275, united states carbon-linked PKHH, and united states carbon-linked PKHJ.
In one embodiment of the invention, the liquid vinyl MQ silicone resin has a vinyl content of 0.8wt% to 1.6wt% and a viscosity of 3000cP to 10000cP; the vinyl content of the double-end vinyl silicone oil is 0.10-0.35 wt% and the viscosity is 900-12000 cP; the hydrogen content in the methyl end-capped side chain hydrogen-containing silicone oil is 0.25-0.60 wt% and the viscosity is 30-110 cP. The reinforced resin consists of liquid vinyl MQ silicon resin with moderate vinyl content, double-end vinyl silicone oil and methyl end-capped side chain hydrogen silicone oil with moderate hydrogen content. Wherein, the side chain hydrogen atoms of the vinyl and the hydrogen-containing silicone oil are reactive groups. Under the proper vinyl content and hydrogen content, the reinforced resin can effectively enhance the flexibility and weather resistance of the low-temperature silver paste after being crosslinked and cured. If the vinyl content and the hydrogen content are too high, the silver paste is hard and brittle after being solidified; if the content is too low, the crosslinking density of the reinforced resin is difficult to ensure, and the mechanical strength after curing is low, so that the reinforced resin cannot play a role in reinforcement.
In one embodiment of the invention, the organic solvent is selected from the group consisting of ester organic solvents and/or ketone organic solvents; the boiling point of the organic solvent is 150-220 ℃.
Further, the ester organic solvent is selected from one or more of ethylene glycol butyl ether acetate, diethylene glycol diethyl ether acetate, dimethyl succinate, dimethyl glutarate, dimethyl adipate and DBE;
further, the ketone organic solvent is selected from one or more of cyclohexanone, diisobutylketone and isophorone.
In one embodiment of the invention, the curing agent is a latent curing agent; the deblocking temperature of the latent curing agent is 80-120 ℃.
Further, the latent curing agent is selected from one or more of blocked isocyanate, modified imidazole curing agent, and modified amine curing agent.
Preferably, the blocked isocyanate curing agent is selected from one or more of DesmodurBL3370, ACRAFIX FAB, trixene BI 7963, trixene BI 7982, trixene BI 7986, durate MF-K60X, durate SBN-70D and UN 7038.
Preferably, the modified imidazole curative is selected from one or more of 2E4MZ-CN, EH-3293S, EH-5011S, AJICURE PN-23J, AJICURE PN-31J, AJICURE PN-40 and AJICURE PN-40J.
Preferably, the modified amine curative is selected from one or more of EH-3842, EH-4357S, EH-4360S, EH-5031S, EH-5001P, AJICURE MY-24, and AJICURE MY-25.
In one embodiment of the invention, the catalyst is selected from platinum catalysts; the platinum content of the platinum catalyst is 800ppm to 2000ppm.
In one embodiment of the present invention, the coupling agent is selected from one or more of a silane coupling agent, a fluorosilane coupling agent, and a titanate coupling agent.
Further, the silane coupling agent is selected from one or more of KH-151, KH-171, KH-560, KH-570 and KH-792.
Further, the fluorosilane coupling agent is one or more of Dynasylanf8261, KH-1731, and KH-1732.
Further, the titanate coupling agent is one or more of KR-TTS, KR-238T, KR-9S and KR-12.
In one embodiment of the present invention, the dispersant is selected from one or more of amine salt type dispersants, block copolymer type dispersants, acrylate type dispersants, and hyperbranched polyester type dispersants.
Further, the amine salt type dispersant is selected from one or more of DISPERBYK-180, DISPERBYK-181 and DISPERBYK-187.
Further, the block copolymer type dispersant is selected from one or more of DISPERBYK-190, DISPERBYK-2008, TEGO Dispers 670, and TEGO Dispers 690.
Further, the acrylate type dispersing agent is selected from DISPERBYK-191 and/or DISPERBYK-2009.
Further, the hyperbranched polyester dispersant is selected from one or more of DIPERBYK-2152, silok-7145 and Silok-7631.
In one embodiment of the invention, the conductive powder is prepared by mixing nano flake silver powder and nano spherical silver powder according to a mass ratio of 1: 1.5-3.5.
In one embodiment of the invention, the particle diameter of the nano flake silver powder is 250nm-500nm, and the tap density is 2.0g/cm 3 -3.5g/cm 3 The grain diameter of the nano spherical silver powder is 100nm-300nm, and the tap density is 4.5g/cm 3 -6.0g/cm 3 . The nanometer spherical silver powder with the grain diameter below 300nm and the high tap density is used as the main silver powder. If the particle size of the silver powder is too large, it is difficult to ensure the filling property in a fine line width of 3. Mu.m. Meanwhile, the high tap density silver powder has lower adsorptivity to the organic carrier, reduces the trend of rising viscosity of silver paste after silver powder is added, ensures fluidity of the silver paste, and is beneficial to filling of fine line grooves.
The second object of the invention is to provide a method for preparing low-temperature silver paste based on the metal grid conductive film, which comprises the following steps:
s1, mixing phenoxy resin and an organic solvent, and stirring at 60-90 ℃ for 6-12 hours to obtain an organic carrier;
s2, adding reinforcing resin, a curing agent, a catalyst, a coupling agent and a dispersing agent into the organic carrier in the S1, and stirring at 800-1500 rpm for 2-5 min to obtain a silver paste matrix;
s3, adding conductive powder into the silver paste matrix in the step S2, stirring for 3-7 min at 1200-2000 rpm, grinding and vacuum defoaming to obtain the low-temperature silver paste.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The low-temperature silver paste disclosed by the invention uses the phenoxy resin with high flexibility and active epoxy groups as the main resin through selection and allocation of the components, and has the characteristics of crosslinking reaction in the curing process, and the active groups have higher polarity so as to easily interact with the polar groups of the silver powder surface treating agent, so that the interface combination effect of the silver powder and the resin is improved, and the defect that the nano silver powder is not easy to disperse is greatly overcome; meanwhile, auxiliaries such as a coupling agent, a dispersing agent and the like are added, so that the dispersing effect of the nano silver powder in the silver paste matrix is further promoted, and unstable factors caused by agglomeration of the nano silver powder are prevented, and the low-temperature silver paste disclosed by the invention still keeps uniform and stable resistance after the 3-mu m superfine line width is filled into the groove; the organic solvent used in the invention is used for adjusting the viscosity and fluidity of the silver paste, has proper boiling point and volatilization rate, has low volatility in the groove filling process at room temperature, ensures that the silver paste is kept in a flowing filling state, is quickly dried at the curing temperature, and provides more volatilization channels by taking the nano spherical silver powder as a main silver powder as a solvent, so that the silver paste is cured more thoroughly. Under the synergistic effect of the components, the low-temperature silver paste disclosed by the invention overcomes the defect that the conventional low-temperature silver paste in the market cannot be suitable for filling grooves in fine wires, is suitable for a low-temperature baking and curing process, and has excellent filling property, compactness and conductivity.
(2) The low-temperature silver paste uses the phenoxy resin as the main resin and uses the latent curing agent for crosslinking and curing, so that the low-temperature silver paste has excellent binding force, corrosion resistance and weather resistance of the thermosetting resin to a base material, and simultaneously has the flexibility of the thermoplastic resin. The phenoxy resin is used as the main resin to endow the low-temperature silver paste with good mechanical properties.
(3) The low-temperature silver paste disclosed by the invention uses the organic silicon system resin as the reinforcing resin, and the organic silicon system resin has excellent flexibility and stretchability, and can be used for reinforcing the flexibility of the low-temperature silver paste after filling the ultra-fine line width grooves of the metal grid. Meanwhile, the organic silicon system resin has the characteristics of high and low temperature resistance, water resistance, salt fog resistance and the like, and the weather resistance of the low-temperature silver paste is further enhanced.
Detailed Description
The present invention will be further described with reference to specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the present invention and practice it.
Example 1
The invention discloses a low-temperature silver paste prepared based on a metal grid conductive film and a preparation method thereof, and the preparation method specifically comprises the following steps:
s1, preparation of a reinforced resin mixture: 12g of liquid vinyl MQ silicone resin (vinyl content 1.2wt%, viscosity 6000 cP), 6.75g of double-end vinyl silicone oil (vinyl content 0.16wt%, viscosity 5200 cP) and 1.25g of methyl-terminated side chain hydrogen silicone oil (hydrogen content 0.35wt%, viscosity 80 cP) are weighed and uniformly mixed in a planetary centrifugal mixer at a rotational speed of 800rpm for 2min to prepare a reinforced resin mixture;
s2, preparing an organic carrier: 60g JER1256 resin (with weight average molecular weight Mw of 51000 and epoxy equivalent of 7800 g/eq), 60g ethylene glycol butyl ether acetate and 60g DBE are weighed, mixed and stirred at 80 ℃ for 8 hours until the mixture is completely dissolved, a 400-mesh filter screen is used for removing impurities, and the mixture is cooled to room temperature for standby, so that an organic carrier is prepared;
s3, preparing a silver paste matrix: uniformly mixing 15g of a blocked isocyanate curing agent DesmodurBL3370 (deblocking temperature 100 ℃), 0.2g of a platinum catalyst (platinum content 1000 ppm), 10g of a silane coupling agent KH-560 and 10g of a dispersing agent DISPERBYK-180 with an organic carrier prepared by S2 and a reinforced resin mixture prepared by S1 in a planetary centrifugal mixer, and obtaining a silver paste matrix at 1000rpm for 3 min;
s4, preparing low-temperature silver paste: 254.9g of nano flake silver powder (average particle diameter 300nm, tap density 3.0 g/cm) 3 ) With 509.9g of nano spherical silver powder (average particle diameter 200nm, tap density 5.1g/cm 3 ) Adding the silver paste into the silver paste matrix prepared in the step S3, uniformly mixing in a planetary centrifugal mixer at a rotating speed of 1500rpm for 5min, grinding by using a three-roll machine until the fineness is less than 2 mu m, and performing vacuum defoaming to form low-temperature silver paste.
Example 2
The invention discloses a low-temperature silver paste prepared based on a metal grid conductive film and a preparation method thereof, and the preparation method specifically comprises the following steps:
s1, preparation of a reinforced resin mixture: 10.64g of liquid vinyl MQ silicone resin (vinyl content 1.4wt%, viscosity 8000 cP), 8.19g of double-ended vinyl silicone oil (vinyl content 0.23wt%, viscosity 2000 cP) and 1.17g of methyl-terminated side chain hydrogen-containing silicone oil (hydrogen content 0.55wt%, viscosity 50 cP) were weighed and uniformly mixed in a planetary centrifugal mixer at a rotational speed of 800rpm for 2 minutes to prepare a reinforced resin mixture;
s2, preparing an organic carrier: 70g JER4250 resin (weight average molecular weight Mw is 59000, epoxy equivalent is 8200 g/eq), 50g cyclohexanone and 100g isophorone are weighed, mixed and stirred at 80 ℃ for 8 hours until complete dissolution, a 400-mesh filter screen is used for removing impurities, and the mixture is cooled to room temperature for standby, so that an organic carrier is prepared;
s3, preparing a silver paste matrix: uniformly mixing 13g of modified imidazole curing agent EH-3293S (deblocking temperature 110 ℃), 0.2g of platinum catalyst (platinum content 1000 ppm), 12g of titanate coupling agent KR-TTS and 14g of dispersing agent TEGO Dispers 670, and a reinforced resin mixture prepared by an organic carrier prepared by S2 and S1 in a planetary centrifugal mixer at a rotating speed of 1000rpm for 3min to prepare a silver paste matrix;
s4, preparing low-temperature silver paste: 205.9g of nano flake silver powder (average particle diameter 400nm, tap density 2.6 g/cm) 3 ) And 514.9g of nano spherical silver powder (average particle diameter 150nm, tap density 5.5g/cm 3 ) Adding the silver paste into the silver paste matrix prepared in the step S3, uniformly mixing in a planetary centrifugal mixer at a rotating speed of 1500rpm for 5min, grinding by using a three-roll machine until the fineness is less than 2 mu m, and performing vacuum defoaming to form low-temperature silver paste.
Example 3
The invention discloses a low-temperature silver paste prepared based on a metal grid conductive film and a preparation method thereof, and the preparation method specifically comprises the following steps:
s1, preparation of a reinforced resin mixture: 14.04g of liquid vinyl MQ silicone resin (vinyl content 1.0wt%, viscosity 4000 cP), 9.40g of double-ended vinyl silicone oil (vinyl content 0.32wt%, viscosity 1000 cP) and 1.56g of methyl-terminated side chain hydrogen-containing silicone oil (hydrogen content 0.55wt%, viscosity 50 cP)) were weighed and uniformly mixed in a planetary centrifugal mixer at a rotational speed of 800rpm for 2 minutes to prepare a reinforced resin mixture;
s2, preparing an organic carrier: weighing 55g JER4275 resin (weight average molecular weight Mw of 60000 and epoxy equivalent of 8800 g/eq), 70g dimethyl adipate and 30g diisobutyl ketone, mixing and stirring at 80 ℃ for 10h until the mixture is completely dissolved, removing impurities by using a 400-mesh filter screen, and cooling to room temperature for standby to prepare an organic carrier;
s3, preparing a silver paste matrix: uniformly mixing 11g of modified amine curing agent EH-5001P (deblocking temperature 100 ℃), 0.2g of platinum catalyst (platinum content 1000 ppm), 10g of fluorosilane coupling agent Dynasylan F8261 and 15g of dispersing agent Silok-7631 with an organic carrier prepared by S2 and a reinforced resin mixture prepared by S1 in a planetary centrifugal mixer, and obtaining a silver paste matrix at a rotating speed of 1000rpm for 3 min;
s4, preparing low-temperature silver paste: 195.9g of nano flake silver powder (average particle diameter 300nm, tap density 3.0 g/cm) 3 ) With 587.9g of nano spherical silver powder (average particle diameter 150nm, tap density 5.5g/cm 3 ) Adding the silver paste into the silver paste matrix prepared in the step S3, uniformly mixing in a planetary centrifugal mixer at the speed of 1800rpm for 5min, grinding by using a three-roll mill until the fineness is less than 2 mu m, and performing vacuum defoaming to form low-temperature silver paste.
Comparative example 1
Substantially the same as in example 1, except that the total addition amount of the reinforcing resin mixture was changed from 20g to 5g.
Comparative example 2
Basically, the same as in example 1, the difference is that the addition amounts of the nano plate-like silver powder and the nano spherical silver powder are 382.4g, i.e., the total weight of the two is unchanged, and the weight ratio is 1:1.
comparative example 3
Substantially the same as in example 1, except that the phenoxy resin JER1256 was replaced with a conventional epoxy resin E51.
Comparative example 4
Substantially the same as in example 1, except that the reinforcing resin mixture was replaced with a liquid vinyl MQ silicone resin (vinyl content 2.0wt%, viscosity 12000 cP), a double-ended vinyl silicone oil (vinyl content 0.47wt%, viscosity 440 cP) and a methyl-terminated side chain hydrogen-containing silicone oil (hydrogen content 0.80wt%, viscosity 20 cP), the amounts added were unchanged.
Comparative example 5
Substantially the same as in example 1, except that the reinforcing resin mixture was replaced with a liquid vinyl MQ silicone resin (vinyl content 0.6wt%, viscosity 2200 cP), a double-ended vinyl silicone oil (vinyl content 0.08wt%, viscosity 60000 cP) and a methyl-terminated side chain hydrogen-containing silicone oil (hydrogen content 0.15wt%, viscosity 120 cP), the amounts added were unchanged.
Test example 1
The low temperature silver pastes prepared in examples 1 to 3 and comparative examples 1 to 5 were sampled, respectively, blade-coated on a planar PET film and a PET film containing grooves with a line width of 3 μm, baked and cured at 120℃for 20 minutes, and tested for various properties.
(1) Sheet resistance: testing the planar PET film material by using a four-probe tester;
(2) Adhesion force: performing a hundred-grid test on the planar PET film;
(3) Filling property: observing the filling effect of the 3 mu m line width groove by using a Scanning Electron Microscope (SEM);
(4) Constant temperature and humidity test: treating the silver paste for 720 hours at 85 ℃ under 85% RH by using a constant temperature and humidity test box, and testing the resistance change of the 3 mu m linewidth filling silver paste before and after the constant temperature and humidity treatment;
(5) Salt spray test: treating for 96 hours under the salt spray condition of 5% NaCl at 35 ℃ by using a salt spray test box, and testing the resistance change of the 3 mu m linewidth filling silver paste before and after salt spray treatment;
(5) Bending resistance: the positive and negative bending were performed 100 times under the condition of a bending diameter of 5mm, and the resistance change of the 3 μm linewidth filled silver paste before and after bending was tested.
The test results are shown in table 1:
TABLE 1
As can be seen from Table 1, the low-temperature silver paste prepared by the invention uses the phenoxy resin with high molecular weight and high epoxy equivalent as the main resin, so that the low flexibility caused by using the conventional epoxy resin as the main resin is avoided, and the low-temperature silver paste has the excellent adhesive force and weather resistance of the thermosetting resin and the flexibility of the thermoplastic resin; the composition of liquid vinyl MQ silicon resin with moderate vinyl content, double-end vinyl silicone oil and methyl end-capped side chain hydrogen silicone oil with moderate hydrogen content is taken as reinforcing resin, so that the organosilicon system reinforcing resin has proper crosslinking density, and the bending resistance and weather resistance of low-temperature silver paste are further enhanced; the low-temperature silver paste overcomes the performance limitation of the conventional low-temperature silver paste and is suitable for the application of the high-flexibility metal grid transparent conductive film by the cooperation of the nano silver powder and the combination of various auxiliary agents and solvents, so that the excellent ultra-fine linewidth filling property, thorough curing and good conductivity are achieved.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. The low-temperature silver paste prepared based on the metal grid conductive film is characterized by comprising the following raw material components in parts by mass: 4-10 parts of phenoxy resin, 1-4 parts of reinforced resin, 8-30 parts of organic solvent, 0.5-3 parts of curing agent, 0.01-0.05 part of catalyst, 0.2-2 parts of coupling agent, 0.2-2 parts of dispersing agent and 60-85 parts of conductive powder;
the reinforced resin is prepared from liquid vinyl MQ silicon resin, double-end vinyl silicone oil and methyl end-capped side chain hydrogen-containing silicone oil according to the weight ratio of 7.5-10:5-7.5:1, and mixing.
2. The low-temperature silver paste prepared based on the metal mesh conductive film according to claim 1, wherein the weight average molecular weight Mw of the phenoxy resin is 45000-65000 and the epoxy equivalent is 7000g/eq-9500g/eq.
3. The low temperature silver paste prepared based on the metal mesh conductive film according to claim 1, wherein the vinyl content in the liquid vinyl MQ silicone resin is 0.8wt% to 1.6wt% and the viscosity is 3000cP to 10000cP; the vinyl content of the double-end vinyl silicone oil is 0.10-0.35 wt% and the viscosity is 900-12000 cP; the hydrogen content in the methyl end-capped side chain hydrogen-containing silicone oil is 0.25-0.60 wt% and the viscosity is 30-110 cP.
4. The low-temperature silver paste prepared based on the metal mesh conductive thin film according to claim 1, wherein the organic solvent is selected from an ester organic solvent and/or a ketone organic solvent; the boiling point of the organic solvent is 150-220 ℃.
5. The low-temperature silver paste prepared based on the metal mesh conductive film according to claim 1, wherein the curing agent is a latent curing agent; the deblocking temperature of the latent curing agent is 80-120 ℃.
6. The low temperature silver paste prepared based on the metal mesh conductive thin film according to claim 1, wherein the catalyst is selected from platinum catalysts; the platinum content of the platinum catalyst is 800ppm to 2000ppm.
7. The low-temperature silver paste prepared based on the metal mesh conductive film according to claim 1, wherein the coupling agent is selected from one or more of a silane coupling agent, a fluorosilane coupling agent and a titanate coupling agent.
8. The low-temperature silver paste prepared based on the metal mesh conductive film according to claim 1, wherein the dispersing agent is selected from one or more of an amine salt type dispersing agent, a block copolymer type dispersing agent, an acrylate type dispersing agent and a hyperbranched polyester type dispersing agent.
9. The low-temperature silver paste prepared based on the metal mesh conductive film according to claim 1, wherein the conductive powder is prepared by mixing nano flake silver powder and nano spherical silver powder according to a mass ratio of 1: 1.5-3.5; the particle diameter of the nano flake silver powder is 250nm-500nm, and the tap density is 2.0g/cm 3 -3.5g/cm 3 The grain diameter of the nano spherical silver powder is 100nm-300nm, and the tap density is 4.5g/cm 3 -6.0g/cm 3 。
10. A method for preparing low-temperature silver paste based on a metal mesh conductive film according to any one of claims 1 to 9:
s1, mixing phenoxy resin and an organic solvent, and stirring at 60-90 ℃ for 6-12 hours to obtain an organic carrier;
s2, adding reinforcing resin, a curing agent, a catalyst, a coupling agent and a dispersing agent into the organic carrier in the S1, and stirring at 800-1500 rpm for 2-5 min to obtain a silver paste matrix;
s3, adding conductive powder into the silver paste matrix in the step S2, stirring for 3-7 min at 1200-2000 rpm, grinding and vacuum defoaming to obtain the low-temperature silver paste.
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