CN112735629A - Low-temperature polymer conductive silver paste with low silver content and preparation method thereof - Google Patents

Low-temperature polymer conductive silver paste with low silver content and preparation method thereof Download PDF

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CN112735629A
CN112735629A CN202011387772.7A CN202011387772A CN112735629A CN 112735629 A CN112735629 A CN 112735629A CN 202011387772 A CN202011387772 A CN 202011387772A CN 112735629 A CN112735629 A CN 112735629A
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powder
silver
low
paste
silver paste
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CN112735629B (en
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游立
张奕
张杜娟
常意川
丁刚强
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Wuhan Institute of Marine Electric Propulsion China Shipbuilding Industry Corp No 712 Institute CSIC
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Wuhan Institute of Marine Electric Propulsion China Shipbuilding Industry Corp No 712 Institute CSIC
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    • H01—ELECTRIC ELEMENTS
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    • 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
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Abstract

The invention discloses low-temperature polymer conductive silver paste with low silver content, which comprises 37-43% of flake silver powder, 0-6% of flake nickel powder, 43% of hydroxyl modified ternary vinyl chloride-vinyl acetate resin carrier, 8% of carboxyl modified ternary vinyl chloride-vinyl acetate resin carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro-powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic ester (DBE), wherein a conductive phase is formed by matching and combining the flake silver powder and the flake nickel powder, the flake silver powder is one or more of four kinds of mixture, and the flake nickel powder is one or more of two kinds of mixture; the silver paste is prepared by mixing different types and contents of flaky silver powder, flaky nickel powder and ternary vinyl chloride-acetate copolymer resin, and performing optimized rolling with an auxiliary agent, an organic solvent and the like, can show the remarkable characteristics of small film sheet resistance, low silver content, short supply period, good printability and the like, has strong market competitiveness, and provides scientific basis for research and development of the low-temperature polymer conductive silver paste industry.

Description

Low-temperature polymer conductive silver paste with low silver content and preparation method thereof
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to low-temperature polymer conductive silver paste with low silver content and a preparation method thereof.
Background
The low-temperature polymer conductive silver paste is used as a key functional material in the field of electronic industrial information, and a conductive film layer prepared by a screen printing process is widely applied to aspects such as a film switch, a keyboard, a touch screen, a radio frequency identification tag and the like. Electronic components are developing towards miniaturization and function integration, so that the conductive silver paste has excellent conductivity, printability, water resistance, hardness and flexibility, needs to have lower production cost, and is particularly critical to research and screening of the types and proportions of conductive metal phases. The conductive metal phase is usually composed of Au, Ag, Cu, Ni and the like, the flake silver powder is most commonly used as the conductive metal phase at present, and in consideration of factors such as cost and the like, the base metal flake nickel powder is also commonly used as an auxiliary conductive metal phase to be matched with silver powder with high flake degree, and the morphology, size, particle size distribution and the like of the base metal flake nickel powder can influence the conductivity of the conductive film layer.
At present, the domestic silver paste manufacturers such as the companies of noble platinum industry, Shanghai treasure silver, Shanghai Jiujiu silver, Zhongkonaton, Beibeili and the like also have low-temperature polymer conductive silver paste products with higher quality, but the technical levels of reducing the silver content and ensuring excellent conductivity, weather resistance, stability and the like have a larger gap with foreign countries.
Disclosure of Invention
One of the purposes of the invention is to provide a low-temperature polymer conductive silver paste which is fine in appearance, excellent in printing property, water resistance, hardness, adhesive force, weather resistance and low in silver content, aiming at the defects of the prior art.
The technical scheme adopted by the invention for solving the technical problems is as follows: the low-temperature polymer conductive silver paste with the low silver content comprises a conductive phase formed by matching and combining 37-43% of superfine flaky silver powder and 0-6% of flaky nickel powder in percentage by mass, 43% of hydroxyl modified ternary vinyl chloride-acetate copolymer resin carrier, 8% of carboxyl modified ternary vinyl chloride-acetate copolymer resin carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro-powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic acid ester (DBE), wherein the superfine flaky silver powder is one or a mixture of SF-1# silver powder, SF-2# silver powder, SF-3# silver powder and SF-4# silver powder with four different flaky degrees, specific surface areas and tap densities, and D50 values of the SF-1# silver powder, the SF-2# silver powder, the SF-3# silver powder and the SF-4# silver powder are respectively 3.49 mu m, 4.16 μm, 2.97 μm and 1.46 μm, wherein the flaky nickel powder is one or a mixture of two of NF-1# nickel powder and NF-2# nickel powder with different flaking degrees, specific surface areas and tap densities, and the D50 values of the NF-1# nickel powder and the NF-2# nickel powder are respectively 8.28 μm and 5.84 μm.
Further, the hydroxyl modified ternary vinyl chloride-acetate copolymer resin carrier is prepared by fully stirring 12% of Tao-modified VAGH-004 resin and dispersing the resin in 88% of DBE, wherein the average molecular weight of the resin is about 85000, and the K value of the resin is about 120. The organic polymer resin VAGH-004 has large molecular weight, and the prepared carrier has high viscosity and can play a role in ensuring good suspension dispersibility of silver powder and greatly reducing the content of silver when being used as a matrix skeleton of a conductive film layer.
Further, the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin carrier is a Dow VMCH prepared by fully stirring and dispersing 20% of Dow VMCH resin in 80% of DBE, the average molecular weight is about 27000, and the K value is about 44-46. VMCH belongs to medium-high molecular weight carboxyl modified ternary vinyl chloride-vinyl acetate copolymer, the molecular chain size of the VMCH is moderate, the silver powder is fully wrapped, the length of the molecular chain is moderate, the conductive layer stacking cannot be hindered, and the VMCH has the characteristics of excellent conductivity, high adhesive force and strong weather resistance.
The second purpose of the invention is to provide a preparation method of the low-temperature polymer conductive silver paste. The technical scheme adopted by the invention for solving the technical problems is as follows:
a preparation method of low-temperature polymer conductive silver paste with low silver content comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing a hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier, a carboxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and dibasic acid ester in a container by using a high-speed dispersion machine, uniformly dispersing, and then pouring flaky silver powder into the container to be fully and uniformly stirred;
step two, uniformly mixing and finely rolling: fully mixing, rolling and fine grinding by a three-roller grinder to obtain conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m;
removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
A preparation method of low-temperature polymer conductive silver paste with low silver content comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing a hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier, a carboxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and dibasic acid ester in a container by using a high-speed dispersion machine, uniformly dispersing, and then pouring flaky silver powder and flaky nickel powder into the container and fully and uniformly stirring;
step two, uniformly mixing and finely rolling: fully mixing, rolling and fine grinding by a three-roller grinder to obtain conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m;
removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
Further, the flake silver powder in the first step is one or a mixture of SF-1# silver powder, SF-2# silver powder, SF-3# silver powder and SF-4# silver powder.
Further, the flaky nickel powder in the step one is NF-1# nickel powder or NF-2# nickel powder or the mixture of the two.
The invention has the following effects:
the hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier adopted by the invention has high viscosity and is used as a matrix skeleton of a conductive film layer, so that the silver powder can be suspended and dispersed well and the silver content can be greatly reduced; the molecular chain of the adopted carboxyl modified ternary vinyl chloride-acetate resin carrier is moderate in size, so that the silver powder is fully wrapped, the conductive layer stacking cannot be hindered due to the moderate length of the molecular chain, and the conductive coating has the characteristics of excellent conductivity, high adhesive force and strong weather resistance; the organic bentonite adopted as a rheological additive has good thickening property, thixotropy, suspension stability, lubricity, water resistance, chemical stability and the like; the adopted polyethylene micro powder wax has good dispersion effect in the slurry, good leveling property and high temperature resistance, and improves the hardness, wear resistance, scratch resistance and the like of the conductive film layer; the YL-2 glass resin has low-temperature curing property and is used as a surface protective film of the conductive film layer, and the cured film is hard and transparent, has good insulating property, and has the characteristics of wear resistance, aging resistance, radiation resistance, low-temperature embrittlement resistance, water resistance, no toxicity, strong light transmittance and the like; the 9100 gloss oil has good printing reproducibility, improves the adhesive force of the slurry on a polyester film (PET), and has the advantages of good weather resistance, soft light sensation, good scratch resistance and the like.
The low-temperature polymer conductive silver paste prepared by mixing different types and contents of flaky silver powder, flaky nickel powder and ternary vinyl chloride-acetate copolymer resin and optimally rolling the mixture with an auxiliary agent, an organic solvent and the like according to a certain proportion has the remarkable characteristics of low silver content, small film square resistance, short supply period, good printability and the like.
Drawings
FIG. 1 is a scanning electron microscope image of SF-1# silver flake according to the present invention;
FIG. 2 is a scanning electron microscope image of the SF-2# silver flake according to the present invention;
FIG. 3 is a scanning electron microscope image of the SF-3# silver flake according to the present invention;
FIG. 4 is a scanning electron microscope image of the SF-4# silver flake powder of the present invention;
FIG. 5 is a scanning electron microscope image of two different types of flaky nickel powders according to the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the specific embodiments.
The organic polymer resin is used as a matrix skeleton of the conductive film layer, so that the conductive silver powder is stably suspended and bonded in the matrix skeleton, the conductive film layer and the base material are adhered, and the wrapping degree of the conductive silver powder and the shrinkage capacity of a molecular chain in the curing process directly influence the adhesive force and the conductive performance of the conductive film layer.
The organic solvent should be selected as little toxic as possible, should have good dissolving capacity for film-forming substances, and should be noted with solvent volatility, too high volatilization speed may result in poor leveling property of the film layer, too low volatilization speed may result in too long curing time, which has influence on both printability and curing process of the paste.
The organic assistant is mainly used for improving the printing effect, the curing process, the dispersibility and the like of the slurry, and the addition of common assistants such as a leveling agent, a thixotropic agent, an adhesion promoter and the like can bring certain adverse factors to the conductivity of the slurry, so that the addition proportion is strictly controlled.
The D50 values of the flaky silver powder SF-1#, SF-2#, SF-3# and SF-4# are respectively 3.49 mu m, 4.16 mu m, 2.97 mu m and 1.46 mu m, and the D50 values of the flaky nickel powder NF-1# and NF-2# are respectively 8.28 mu m and 5.84 mu m. The performance indexes of the flaky silver powder SF-1#, SF-2#, SF-3#, SF-4# and the flaky nickel powder NF-1#, NF-2# of the invention are shown in the following table.
Figure DEST_PATH_IMAGE001
Example 1
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: sheet silver powder SF-1#43%, VAGH-004 organic carrier 43%, VMCH organic carrier 8%, organic bentonite 0.8%, polyethylene micro powder wax 0.5%, YL-2 glass resin 0.5%, 9100 gloss oil 0.7%, dibasic ester (DBE) 3.5%.
The D50 value of the flake silver powder SF-1# is 3.49 mu m, the VAGH-004 organic carrier is prepared by fully stirring and dispersing 12% of Dow VAGH-004 resin in 88% of DBE, and the VMCH organic carrier is prepared by fully stirring and dispersing 20% of Dow VMCH resin in 80% of DBE.
The preparation method of the conductive silver paste comprises the following steps.
Step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flake silver powder SF-1# into the container, and fully and uniformly stirring and dispersing.
Step two, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding by using a three-roll grinder to obtain the conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m.
Removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
The organic bentonite is a montmorillonite/organic ammonium compound, is usually used as a rheological additive, is mainly made to swell and disperse in a medium-high polar solvent system to form gel by utilizing a lamellar structure of the montmorillonite, and has good thickening property, thixotropy, suspension stability, lubricity, water resistance, chemical stability and the like.
The polyethylene micro-powder wax has good dispersion effect in slurry, good leveling property, high temperature resistance, poor compatibility with resin, high hardness, high toughness and easy dispersibility, floats to the surface of the film layer in the film forming process to form a uniformly distributed protective layer, and improves the hardness, wear resistance, scratch resistance and the like of the conductive film layer.
YL-2 glass resin (ethanol solution of organic silicon resin prepolymer) has low-temperature curing property, is commonly used as a surface protective film of a conductive film layer, and the cured film is hard and transparent, has good insulating property, and has the characteristics of wear resistance, aging resistance, radiation resistance, low-temperature embrittlement resistance, water resistance, no toxicity, strong light transmittance and the like.
The 9100PL series PET printing ink (9100 gloss oil for short) has the advantages of good printing reproducibility, improved adhesive force of the sizing agent on a polyester film (PET), good weather resistance, soft matte effect, good scratch resistance and the like.
Example 2
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: 43% of flake silver powder SF-2#, 43% of VAGH-004 organic carrier, 8% of VMCH organic carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic ester (DBE).
The D50 value of the flake silver powder SF-2# is 4.16 mu m, the VAGH-004 organic carrier is prepared by fully stirring and dispersing 12% of Dow VAGH-004 resin in 88% of DBE, and the VMCH organic carrier is prepared by fully stirring and dispersing 20% of Dow VMCH resin in 80% of DBE.
The preparation method of the conductive silver paste comprises the following steps.
Step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flake silver powder SF-2# into the container, and fully and uniformly stirring and dispersing.
Step two, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding by using a three-roll grinder to obtain the conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m.
Removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
Example 3
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: 43% of flake silver powder SF-3#, 43% of VAGH-004 organic carrier, 8% of VMCH organic carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic ester (DBE).
The D50 value of the flake silver powder SF-3# is 2.97 mu m, the VAGH-004 organic carrier is prepared by fully stirring and dispersing 12% of Dow VAGH-004 resin in 88% of DBE, and the VMCH organic carrier is prepared by fully stirring and dispersing 20% of Dow VMCH resin in 80% of DBE.
The preparation method of the conductive silver paste comprises the following steps.
Step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flake silver powder SF-3# into the container, and fully and uniformly stirring and dispersing.
Step two, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding by using a three-roll grinder to obtain the conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m.
Removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
Example 4
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: 42 percent of flake silver powder SF-1#, 1 percent of SF-4#, 43 percent of VAGH-004 organic carrier, 8 percent of VMCH organic carrier, 0.8 percent of organic bentonite, 0.5 percent of polyethylene micro powder wax, 0.5 percent of YL-2 glass resin, 0.7 percent of 9100 gloss oil and 3.5 percent of dibasic ester (DBE).
The D50 values of the flake silver powders SF-1# and SF-4# are respectively 3.49 μm and 1.46 μm, the VAGH-004 organic carrier is prepared by fully stirring and dispersing 12% of Dow VAGH-004 resin in 88% of DBE, and the VMCH organic carrier is prepared by fully stirring and dispersing 20% of Dow VMCH resin in 80% of DBE.
The preparation method of the conductive silver paste comprises the following steps.
Step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flake silver powder SF-1# and SF-4# into the container, and fully and uniformly stirring and dispersing.
Step two, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding by using a three-roll grinder to obtain the conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m.
Removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
Example 5
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: 40% of flake silver powder SF-1#, 1% of SF-4#, 2% of flake nickel powder NF-1#, 43% of VAGH-004 organic carrier, 8% of VMCH organic carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro-powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic ester (DBE).
The D50 values of the flaky silver powder SF-1# and SF-4# are respectively 3.49 mu m and 1.46 mu m, the D50 value of the flaky nickel powder NF-1# is 8.28 mu m, the VAGH-004 organic carrier is 12% Dow VAGH-004 resin which is fully stirred and dispersed in 88% DBE, and the VMCH organic carrier is 20% Dow VMCH resin which is fully stirred and dispersed in 80% DBE.
The preparation method of the conductive silver paste comprises the following steps.
Step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flaky silver powder SF-1# and SF-4# and flaky nickel powder NF-1# into the container, and fully and uniformly stirring and dispersing.
Step two, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding by using a three-roll grinder to obtain the conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m.
Removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
Example 6
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: 38% of flake silver powder SF-1#, 1% of SF-4#, 4% of flake nickel powder NF-1#4%, 43% of VAGH-004 organic carrier, 8% of VMCH organic carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic ester (DBE).
The D50 values of the flaky silver powder SF-1# and SF-4# are respectively 3.49 mu m and 1.46 mu m, the D50 value of the flaky nickel powder NF-1# is 8.28 mu m, the VAGH-004 organic carrier is 12% Dow VAGH-004 resin which is fully stirred and dispersed in 88% DBE, and the VMCH organic carrier is 20% Dow VMCH resin which is fully stirred and dispersed in 80% DBE.
The preparation method of the conductive silver paste comprises the following steps.
Step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flaky silver powder SF-1# and SF-4# and flaky nickel powder NF-1# into the container, and fully and uniformly stirring and dispersing.
Step two, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding by using a three-roll grinder to obtain the conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m.
Removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
Example 7
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: 36% of flake silver powder SF-1#, 1% of SF-4#, 6% of flake nickel powder NF-1#, 43% of VAGH-004 organic carrier, 8% of VMCH organic carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro-powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic ester (DBE).
The D50 values of the flaky silver powder SF-1# and SF-4# are respectively 3.49 mu m and 1.46 mu m, the D50 value of the flaky nickel powder NF-1# is 8.28 mu m, the VAGH-004 organic carrier is 12% Dow VAGH-004 resin which is fully stirred and dispersed in 88% DBE, and the VMCH organic carrier is 20% Dow VMCH resin which is fully stirred and dispersed in 80% DBE.
The preparation method of the conductive silver paste comprises the following steps.
Step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flaky silver powder SF-1# and SF-4# and flaky nickel powder NF-1# into the container, and fully and uniformly stirring and dispersing.
Step two, uniformly mixing and finely rolling: and fully mixing, rolling and finely grinding by using a three-roll grinder to obtain the conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m.
Removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
Example 8
The conductive silver paste of the embodiment comprises the following substances in percentage by mass: 38% of flake silver powder SF-1#, 1% of SF-4#, 4% of flake nickel powder NF-2#4%, 43% of VAGH-004 organic carrier, 8% of VMCH organic carrier, 0.8% of organic bentonite, 0.5% of polyethylene micro powder wax, 0.5% of YL-2 glass resin, 0.7% of 9100 gloss oil and 3.5% of dibasic ester (DBE).
The D50 values of the flaky silver powder SF-1# and SF-4# are respectively 3.49 mu m and 1.46 mu m, the D50 value of the flaky nickel powder NF-2# is 5.84 mu m, the VAGH-004 organic carrier is 12% Dow VAGH-004 resin which is fully stirred and dispersed in 88% DBE, and the VMCH organic carrier is 20% Dow VMCH resin which is fully stirred and dispersed in 80% DBE.
The preparation method of the conductive silver paste comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing VAGH-004 and VMCH organic carriers, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flaky silver powder SF-1# and SF-4# and flaky nickel powder NF-2# into the container, and fully and uniformly stirring and dispersing;
step two, uniformly mixing and finely rolling: fully mixing, rolling and fine grinding by a three-roller grinder to obtain conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 mu m;
removing impurities, defoaming and packaging: and D, filtering and vacuumizing the conductive silver paste obtained in the step two by using a paste impurity removal system, removing residues and air bubbles in the silver paste, cleaning a container of the paste, covering the container with a cover, and labeling to obtain the low-temperature polymer conductive silver paste.
The performance test results of the slurries of examples 1-8 are shown in the following table:
Figure DEST_PATH_IMAGE002
the preparation method has obvious difference with the preparation method in the prior art, and simultaneously, one or more of four different flaky silver powders (SF-1 #, SF-2#, SF-3#, SF-4 #) and two different flaky nickel powders (NF-1 #, NF-2 #) are mainly mixed according to a certain mass ratio, the organic polymer resin VAGH-004 has large molecular weight, the prepared carrier has large viscosity, and the prepared carrier is used as a matrix skeleton of a conductive film layer to play a role in ensuring good suspension dispersibility of the silver powders and greatly reducing silver content; VMCH belongs to medium-high molecular weight carboxyl modified ternary vinyl chloride-vinyl acetate copolymer, the molecular chain size of the VMCH is moderate, the silver powder is fully wrapped, the length of the molecular chain is moderate, the conductive layer stacking cannot be hindered, and the VMCH has the characteristics of excellent conductivity, high adhesive force and strong weather resistance.
In addition, referring to fig. 1-4 of the scanning electron microscope images of the flake silver powder, certain gaps or 'slippage' exist between flakes mainly through surface contact or line contact, a small amount of flake powder or spherical powder with low flaking degree is added in actual production, point or surface contact is carried out between the flake silver powder, the 'slippage' between the flakes is reduced, the compactness degree of the conductive silver powder is effectively improved, the contact resistance is effectively reduced, the conductive network is more compact, and the conductive performance is more excellent. Although the nickel powder has lower conductivity than silver powder, a small amount of flaky nickel powder is often added in the actual production, a compact conductive network is formed by lapping a special three-dimensional chain bead-shaped ultrafine particle network structure of the flaky nickel powder and the flaky silver powder, and meanwhile, the flaky nickel powder has higher tap density and is beneficial to improving the film thickness of a conductive film layer, so that the aim of reducing the silver content can be fulfilled while the conductive performance is ensured.
The low-temperature polymer conductive silver paste prepared in the embodiments 1 to 3 is fine and smooth in appearance, the silver content is 43%, the sheet resistance value of the paste prepared by using the flaky silver powder SF-2# in the embodiment 2 is highest, and the paste is poor in conductivity mainly due to the fact that the sheet diameter D50 is the largest, the sheet forming degree is the largest, but the bulk density is high, and the overlapping compactness degree of the sheet powder is not as good as that of the sheet powder with low bulk density; the paste prepared from the flake silver powder SF-3# in example 3 has the lowest apparent density and the lowest paste sheet resistance value theoretically, but actually has the square resistance value almost the same as that of example 2, and the actual sheet resistance value is higher mainly because the flake diameter D50 is the smallest and the lap joint compactness of the conductive network between the flakes is not enough; the paste prepared from the plate-like silver powder SF-1# in example 1 had the smallest square resistance value, and exhibited excellent conductive properties mainly due to the relatively densest degree of overlap between the plate powders, although the bulk density and the plate diameter D50 were both between SF-2# and SF-3 #. It can be seen from example 4 that appropriate addition of SF-4# with low flaking degree is beneficial to reducing the square resistance value, and meanwhile, the surface dispersant of the silver powder may be related to the influence of shrinkage tension between molecular chains of the resin, the apparent density of the silver powder is moderate, the shrinkage of the molecular chains of the resin during curing is more beneficial to layer-by-layer stacking of flake powder, and the excessive density is not beneficial to the shrinkage of the silver powder through the molecular chains, so that a compact conductive film layer is obtained.
Example 5 contains 2% of flaky nickel powder NF-1# relative to example 4, and has larger square resistance but still has excellent conductive performance; the increase in the sheet resistance of example 6 relative to example 4, which contained 4% NF-1#, was not significant; with the continuous increase of the content of NF-1#, the embodiment 7 contains 6% of NF-1#, compared with the embodiment 4, the conductive film layer has poor parallelism of resistance values and poor stability of conductive performance, mainly because the sheet-shaped nickel powder and the sheet-shaped silver powder have different resistivities, are dispersed in the slurry by grinding or high-speed stirring, are mutually overlapped, and form a compact conductive film layer in the curing process by the shrinkage tension of a resin molecular chain, when the content of the nickel powder is relatively low, the contact resistance is small, with the continuous increase of the content of the sheet-shaped nickel powder, the content of the sheet-shaped silver powder is relatively reduced, the overlapping compactness of the conductive film layer is relatively weakened, the dispersion uniformity of the sheet-shaped nickel powder and the sheet-shaped silver powder in the slurry is poor, the stability of the conductive film layer is poor, and the cost is increased by increasing the content of the nickel powder, thereby ensuring the conductive performance of the, the addition amount of the flaky nickel powder NF-1# is less than or equal to 4 percent.
For example 6 and example 8, the flaking degree of the flake nickel powder NF-2# added in example 8 is not as good as NF-1#, but the square resistance value is basically equivalent to that of example 6, mainly because the content of the flake nickel powder added in the slurry is not high, and although the flaking degree of NF-2# is not high, the special three-dimensional chain bead-shaped ultrafine particle network structure of the flake nickel powder is more favorable for being lapped with the flake silver powder SF-1# to form a compact conductive network, so that the defect of poor flaking degree is overcome.
According to the invention, the conductivity of the low-temperature polymer conductive silver paste is closely related to the types and contents of the flaky silver powder and the flaky nickel powder, the flaky silver powder with high flaking degree and low flaking degree is matched for use, the square resistance value can be effectively reduced, meanwhile, the flaky nickel powder with the content less than or equal to 4% is added into the system, the influence on the conductivity of the paste is small, the silver content and the production cost can be effectively reduced, and the low-temperature polymer conductive silver paste with low silver content and small film layer square resistance value can be prepared.
It is to be understood that the above-described embodiments are only a few, and not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (7)

1. A low-temperature polymer conductive silver paste with low silver content is characterized in that: the conductive phase consists of 37-43% by mass of superfine flaky silver powder, 0-6% by mass of flaky nickel powder, 43% by mass of hydroxyl modified ternary vinyl chloride-vinyl acetate resin carrier, 8% by mass of carboxyl modified ternary vinyl chloride-vinyl acetate resin carrier, 0.8% by mass of organic bentonite, 0.5% by mass of polyethylene micro-powder wax, 0.5% by mass of YL-2 glass resin, 0.7% by mass of 9100 gloss oil and 3.5% by mass of dibasic acid ester, the superfine flaky silver powder and the flaky nickel powder are combined into a conductive phase, the superfine flaky silver powder is one or a mixture of SF-1# silver powder, SF-2# silver powder, SF-3# silver powder and SF-4# silver powder with different flaky degrees, specific surface areas and tap densities, the D50 values of the SF-1# silver powder, the SF-2# silver powder, the SF-3# silver powder and the SF-4# silver powder are respectively 3.49 mu m, 4.16 μm, 2.97 μm and 1.46 μm, wherein the flaky nickel powder is one or a mixture of two of NF-1# nickel powder and NF-2# nickel powder with different flaking degrees, specific surface areas and tap densities, and the D50 values of the NF-1# nickel powder and the NF-2# nickel powder are respectively 8.28 μm and 5.84 μm.
2. The low-temperature polymer conductive silver paste with low silver content according to claim 1, wherein the hydroxyl modified ternary vinyl chloride-acetate copolymer carrier is prepared by fully stirring 12% of Dow VAGH-004 resin and dispersing the resin in 88% of DBE, and has an average molecular weight of 85000 and a K value of 120.
3. The low-temperature polymer conductive silver paste with low silver content according to claim 1, wherein the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier is prepared by fully stirring 20% of Dow VMCH resin and dispersing the resin in 80% of DBE, and has an average molecular weight of 27000 and a K value of 44-46.
4. The preparation method of the low-temperature polymer conductive silver paste as claimed in claim 1, wherein the preparation method comprises the following steps:
firstly, fully dissolving and mixing a hydroxyl modified ternary vinyl chloride-vinyl acetate resin carrier, a carboxyl modified ternary vinyl chloride-vinyl acetate resin carrier, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and dibasic acid ester in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flake silver powder, and fully and uniformly stirring;
step two, fully mixing and finely grinding the mixture by a three-roller grinder to obtain conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 microns;
and step three, filtering and vacuumizing the obtained conductive silver paste, and eliminating residues and bubbles in the silver paste to obtain the low-temperature polymer conductive silver paste.
5. The method for preparing the low-temperature polymer conductive silver paste with low silver content according to claim 1, is characterized by comprising the following steps:
firstly, fully dissolving and mixing a hydroxyl modified ternary vinyl chloride-vinyl acetate resin carrier, a carboxyl modified ternary vinyl chloride-vinyl acetate resin carrier, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and dibasic acid ester in a container by using a high-speed dispersion machine, uniformly dispersing, and then pouring flake silver powder and flake nickel powder into the container and fully and uniformly stirring;
step two, fully mixing and finely grinding the mixture by a three-roller grinder to obtain conductive silver paste, wherein the fineness of the paste measured by a scraper blade fineness meter is less than 10 microns;
and step three, filtering and vacuumizing the obtained conductive silver paste, and eliminating residues and bubbles in the silver paste to obtain the low-temperature polymer conductive silver paste.
6. The method for preparing low-temperature polymer conductive silver paste with low silver content according to claim 4 or 5, wherein the silver flakes in the first step are one or more of SF-1# silver powder, SF-2# silver powder, SF-3# silver powder and SF-4# silver powder.
7. The method for preparing low-temperature polymer conductive silver paste with low silver content according to claim 5, wherein the flaky nickel powder in the step one is NF-1# nickel powder or NF-2# nickel powder or a mixture of the NF-1# nickel powder and the NF-2# nickel powder.
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