CN112735628A - Low-temperature polymer conductive silver paste and preparation method thereof - Google Patents
Low-temperature polymer conductive silver paste and preparation method thereof Download PDFInfo
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- CN112735628A CN112735628A CN202011387771.2A CN202011387771A CN112735628A CN 112735628 A CN112735628 A CN 112735628A CN 202011387771 A CN202011387771 A CN 202011387771A CN 112735628 A CN112735628 A CN 112735628A
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Abstract
The invention discloses low-temperature polymer conductive silver paste with high adhesive force and strong weather resistance, which comprises 39% of flake silver powder, 4% of flake nickel powder, 46-49% of hydroxyl modified ternary vinyl chloride-vinyl acetate resin carrier, 0-8% 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 3.5-8.5% of dibasic ester, wherein the flake silver powder is divided into two types, the hydroxyl modified ternary vinyl chloride-vinyl acetate resin carrier is prepared by fully dissolving one of three different organic resins in DBE, and the carboxyl modified ternary vinyl chloride-vinyl acetate resin carrier is prepared by fully dissolving one of the three different organic resins in DBE; the silver paste is prepared by mixing the flaky silver powder, the flaky nickel powder and the vinyl chloride-vinyl acetate copolymer, and optimally rolling the mixture with an auxiliary agent, an organic solvent and the like, has the remarkable characteristics of high adhesive force, strong weather resistance, small film sheet resistance, short supply period, good printability and the like, has strong market competitiveness, and provides scientific basis for the research and development of the low-temperature polymer conductive silver paste industry.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to low-temperature polymer conductive silver paste with high adhesive force and strong weather resistance 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, and needs to have more excellent adhesion and weather resistance.
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 have larger differences with foreign countries on the technical levels of mass production capacity, adhesive force, weather resistance, stability and the like.
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: a low-temperature polymer conductive silver paste comprises a conductive phase, 46-49% of hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer resin carrier, 0-8% of carboxyl modified ternary vinyl chloride-vinyl 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 3.5-8.5% of dibasic acid ester (DBE), wherein the conductive phase is formed by matching and combining 39% of flaky silver powder and 4% of flaky nickel powder in percentage by mass; the flake silver powder is one or a mixture of two of SF-1# silver powder and SF-2# silver powder with different flake degrees, specific surface areas and tap densities, and the D50 values of the SF-1# silver powder and the SF-2# silver powder 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 hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier is prepared by mixing one or more of No. 1 organic carriers, No. 2 organic carriers and No. 3 organic carriers with different molecular weights, wherein the No. 1 organic carrier is prepared by fully stirring and dispersing 12% of Dow VAGH-004 resin in 88% of DBE, the No. 2 organic carrier is prepared by fully stirring and dispersing 20% of Dow VAGH-003A resin in 80% of DBE, and the No. 3 organic carrier is prepared by fully stirring and dispersing 20% of Dow VAGH resin in 80% of DBE; the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin carrier is prepared by mixing one or more of No. 4 organic carriers, No. 5 organic carriers and No. 6 organic carriers with different molecular weights, wherein the No. 4 organic carrier is prepared by fully stirring and dispersing 20% of Pan-high chemical HVAMA resin in 80% of DBE, the No. 5 organic carrier is prepared by fully stirring and dispersing 20% of Dow VMCH resin in 80% of DBE, and the No. 6 organic carrier is prepared by fully stirring and dispersing 20% of Dow VMCC resin in 80% of DBE.
Further, the conductive phase is composed of 38% of SF-1# silver powder, 1% of SF-2# silver powder and 4% of NF-1# flaky nickel powder.
Further, the average molecular weight of the Dow VAGH-004 resin is about 85000, the K value is about 120, the average molecular weight of the Dow VAGH-003A resin is about 48000, the K value is about 59, the average molecular weight of the Dow VAGH resin is about 27000, the K value is about 46-48, the average molecular weight of the Pan-high chemical engineering HVAMA resin is about 34000, the K value is about 58, the average molecular weight of the Dow VMCH resin is about 27000, the K value is about 44-46, the average molecular weight of the Dow VMCC resin is about 19000, and the K value is about 39.
Furthermore, the hydroxyl modified ternary vinyl chloride-acetate copolymer resin carrier is prepared by dissolving 42-46% of Dow VAGH-004 resin, 0-7% of Dow VAGH-003A resin and 0-7% of Dow VAGH resin in DBE.
Furthermore, the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin carrier is prepared by dissolving 0-8% of Pan-high chemical HVAMA resin, 0-8% of Dow VMCH resin and 0-8% of Dow VMCC resin in DBE.
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 comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing No. 1 organic carrier, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and dibasic acid ester (DBE) in a container by using a high-speed dispersion machine, uniformly dispersing, pouring flake silver powder and flake nickel powder NF-1, 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, eliminating 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.
Furthermore, the No. 2 organic carrier or the No. 3 organic carrier or the mixture of the two is also added in the step one.
Furthermore, the mixture of one or more of No. 4 organic carrier, No. 5 organic carrier and No. 6 organic carrier is also added in the first step.
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 (ethanol solution of organic silicon resin prepolymer) 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 the flaky silver powder and the flaky nickel powder with different types and contents of vinyl chloride-vinyl acetate copolymer, and optimally rolling the mixture with the auxiliary agent, the organic solvent and the like according to a certain ratio has the remarkable characteristics of high adhesive force, strong weather resistance, 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 micrograph of the nickel flake of the present invention;
FIG. 4 is a scanning electron microscope comparison of front and cross sections of a cured conductive film layer of a paste according to the present invention;
fig. 5 is a diagram of a low-temperature polymer conductive silver paste product of the 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 performance indexes of the flake silver powder SF-1#, SF-2# and flake nickel powder NF-1# of the invention are shown in the following table.
Example 1
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-2#, 4% of flake nickel powder NF-1#, 46% of organic carrier 1#, 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 8.5% of dibasic ester (DBE).
D50 values of the flaky silver powder SF-1# and SF-2# are respectively 3.49 microns and 1.46 microns, the D50 value of the flaky nickel powder NF-1# is 8.28 microns, and the organic carrier 1# is 12% Dow VAGH-004 resin which is fully stirred and dispersed in 88% DBE.
The preparation method of the conductive silver paste comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing an organic carrier No. 1, organic bentonite, polyethylene micro powder wax, YL-2 glass resin, 9100 gloss oil and DBE in a container by using a high-speed disperser, uniformly dispersing, pouring flaky silver powder SF-1 No. and SF-2 No. and flaky nickel powder NF-1 No. 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: 38% of flake silver powder SF-1#, 1% of SF-2#, 4% of flake nickel powder NF-1#, 42% of organic carrier 1#, 7% of organic carrier 2#, 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 5.5% of dibasic ester (DBE).
D50 values of the flaky silver powder SF-1# and the flaky silver powder SF-2# are respectively 3.49 microns and 1.46 microns, the D50 value of the flaky nickel powder NF-1# is 8.28 microns, the organic carrier 1# is 12% Dow VAGH-004 resin, and is fully stirred and dispersed in 88% DBE, and the organic carrier 2# is 20% Dow VAGH-003 resin, and 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 an organic carrier No. 1, an organic carrier No. 2, 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, then pouring flaky silver powder SF-1, SF-2 and flaky nickel powder NF-1, 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: 38% of flake silver powder SF-1#, 1% of SF-2#, 4% of flake nickel powder NF-1#, 42% of organic carrier 1#, 7% of organic carrier 3#, 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 5.5% of dibasic ester (DBE).
D50 values of the flaky silver powder SF-1# and the flaky silver powder SF-2# are respectively 3.49 microns and 1.46 microns, the D50 value of the flaky nickel powder NF-1# is 8.28 microns, the organic carrier 1# is 12% of Dow VAGH-004 resin, and is fully stirred and dispersed in 88% of DBE, and the organic carrier 3# is 20% of Dow VAGH resin, and is fully stirred and dispersed 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 an organic carrier No. 1, an organic carrier No. 3, 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, then pouring flaky silver powder SF-1, SF-2 and flaky nickel powder NF-1, 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: 38% of flake silver powder SF-1#, 1% of SF-2#, 4% of flake nickel powder NF-1#, 42% of organic carrier 1#, 7% of organic carrier 4#, 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 5.5% of dibasic ester (DBE).
D50 values of the flaky silver powder SF-1# and the flaky silver powder SF-2# are respectively 3.49 microns and 1.46 microns, the D50 value of the flaky nickel powder NF-1# is 8.28 microns, the organic carrier 1# is 12% Dow VAGH-004 resin, and is fully stirred and dispersed in 88% DBE, and the organic carrier 4# is 20% Pan high chemical engineering HVAMA resin, and is fully stirred and dispersed in 80%.
The preparation method of the conductive silver paste comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing an organic carrier No. 1, an organic carrier No. 4, 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, then pouring flaky silver powder SF-1, SF-2 and flaky nickel powder NF-1, 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: 38% of flake silver powder SF-1#, 1% of SF-2#, 4% of flake nickel powder NF-1#, 43% of organic carrier 1#, 8% of organic carrier 4#, 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).
D50 values of the flaky silver powder SF-1# and the flaky silver powder SF-2# are respectively 3.49 microns and 1.46 microns, the D50 value of the flaky nickel powder NF-1# is 8.28 microns, the organic carrier 1# is 12% Dow VAGH-004 resin, and is fully stirred and dispersed in 88% DBE, and the organic carrier 4# is 20% Pan high chemical engineering HVAMA resin, and is fully stirred and dispersed in 80%.
The preparation method of the conductive silver paste comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing an organic carrier No. 1, an organic carrier No. 4, 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, then pouring flaky silver powder SF-1, SF-2 and flaky nickel powder NF-1, 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-2#, 4% of flake nickel powder NF-1#, 43% of organic carrier 1#, 8% of organic carrier 5#, 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).
D50 values of the flaky silver powder SF-1# and SF-2# are respectively 3.49 microns and 1.46 microns, the D50 value of the flaky nickel powder NF-1# is 8.28 microns, the organic carrier 1# is 12% of Dow VAGH-004 resin, and is fully stirred and dispersed in 88% of DBE, and the organic carrier 5# is 20% of Dow VMCH resin, and is fully stirred and dispersed in 80%.
The preparation method of the conductive silver paste comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing an organic carrier No. 1, an organic carrier No. 5, 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, then pouring flaky silver powder SF-1, SF-2 and flaky nickel powder NF-1, 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: 38% of flake silver powder SF-1#, 1% of SF-2#, 4% of flake nickel powder NF-1#, 43% of organic carrier 1#, 8% of organic carrier 6#, 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).
D50 values of the flaky silver powder SF-1# and SF-2# are respectively 3.49 microns and 1.46 microns, the D50 value of the flaky nickel powder NF-1# is 8.28 microns, the organic carrier 1# is 12% of Dow VAGH-004 resin, and is fully stirred and dispersed in 88% of DBE, and the organic carrier 6# is 20% of Dow VMCC resin, and is fully stirred and dispersed in 80%.
The preparation method of the conductive silver paste comprises the following steps:
step one, premixing slurry: firstly, fully dissolving and mixing an organic carrier No. 1, an organic carrier No. 6, 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, then pouring flaky silver powder SF-1, SF-2 and flaky nickel powder NF-1, 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 results of the slurry performance tests of examples 1-7 are shown in the following table:
as shown in fig. 1 to 5, the preparation method of the present invention is significantly different from the prior art, meanwhile, the hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier is mainly prepared by mixing a plurality of hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer carriers (an organic carrier No. 1, an organic carrier No. 2 and an organic carrier No. 3) with different molecular weights and a plurality of carboxyl modified ternary vinyl chloride-vinyl acetate copolymer carriers (an organic carrier No. 4, an organic carrier No. 5 and an organic carrier No. 6) with different molecular weights according to a certain mass ratio, wherein the molecular weight of an organic polymer binding phase VAGH-004 is large, the prepared carrier has high viscosity, and the prepared carrier is used as a matrix framework of a conductive film layer to ensure that the silver powder has good suspension dispersibility and greatly reduce the silver, the molecular chain is too long, and the silver powder is not sufficiently wrapped and bonded, so that the hydroxyl-modified or carboxyl-modified ternary vinyl chloride-vinyl acetate copolymer with lower molecular weight is selected as an auxiliary organic carrier to improve the adhesive force and weather resistance of the slurry. The ternary vinyl chloride-acetate copolymer resin with large molecular weight is found to have insufficient coating on the flaky silver powder, the flaky nickel powder and the auxiliary agent, so that the ternary vinyl chloride-acetate copolymer resin has good printing performance and conductivity, but has insufficient bonding performance and coating on the silver powder, thereby influencing the adhesive force and weather resistance of the product.
In addition, the invention adopts two different types of flake silver powder SF-1#, SF-2# and flake nickel powder NF-1# to prepare the low-temperature polymer conductive silver paste, the scanning electron microscope pictures of the two types of flake silver powder and flake nickel powder of the invention refer to fig. 1-3, the scanning electron microscope pictures of the front and the section refer to fig. 4 after the slurry conductive film is cured, certain gaps or 'slippage' exist between the flakes mainly through surface contact or line contact, a small amount of flake powder or ball powder with low flaking degree is added in the actual production, the point or surface contact is carried out between the flake silver powders, the 'slippage' between the flakes is reduced, the compaction degree of the conductive silver powder is effectively improved, the contact resistance is effectively reduced, the conductive network is more compact, the conductivity is more excellent, and the low-temperature polymer conductive silver paste product is shown in fig. 5.
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 1-3 is fine and smooth in appearance, good in printability and excellent in conductivity and hardness, but has the characteristics of poor adhesion and poor weather resistance, and the coating and bonding of silver powder are still insufficient due to the fact that the molecular weight of VAGH-003A added in the embodiment 2 is large; the silver powder is fully wrapped by adding the VAGH with a low molecular weight in the example 3, but the VAGH belongs to hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer, and the adhesive property of the VAGH to the silver powder is not enough, so that the adhesive force and the weather resistance are only slightly improved.
The low-temperature polymer conductive silver paste prepared in the embodiments 4 to 5 is fine and smooth in appearance and good in printability, the conductive performance of the embodiment 4 is slightly superior to that of the embodiment 5, but a small amount of silver layer is peeled off, the adhesive force and the weather resistance are inferior to those of the embodiment 5, the silver powder is fully wrapped and the adhesive property is more obvious mainly due to the fact that the resin content is increased, and therefore the carboxyl modified ternary vinyl chloride-acetate resin has the effect of improving the adhesive force and the weather resistance of the paste.
The low-temperature polymer conductive silver paste prepared in the embodiments 6 to 7 has the characteristics of fine and smooth appearance, good printability, good hardness, high adhesive force, strong weather resistance and the like, the embodiment 6 shows that the conductivity is obviously superior to that of the embodiments 5 and 4, the embodiments 4 to 6 have no silver layer shedding phenomenon, and the products have the characteristics of good high temperature and high humidity resistance, mainly because the HVAMA belongs to the ultrahigh molecular weight carboxyl modified ternary vinyl chloride-acetate resin, the molecular chain of the HVAMA has larger degree of wrapping the silver powder, and the overlong molecular chain of the resin obstructs the layer-by-layer stacking of the silver powder, the conductivity is inferior to that of the embodiment 6, although the adhesion to the silver powder is strong, a small amount of silver powder shedding still exists in an adhesion test, and the weather resistance is generally strong at; the VMCH belongs to a 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; and VMCC belongs to a medium molecular weight carboxyl modified ternary vinyl chloride-vinyl acetate copolymer, the molecular chain of the VMCC is short, the silver powder is wrapped excessively fully, and meanwhile, the VMCC has strong adhesion to the silver powder, so that the conductivity is deteriorated, and the adhesive force and the weather resistance are obviously improved.
According to the invention, the adhesive force and weather resistance of the low-temperature polymer conductive silver paste are closely related to the type, molecular weight and content of organic resin, the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin is fully wrapped and bonded on the silver powder, nickel powder, resin particles and organic auxiliary agent powder in the paste, the conductive performance of the paste is not benefited by excessively large or excessively small molecular weight, the VMCH with moderate molecular weight and the VAGH-004 with ultrahigh molecular weight are matched for use, and the low-temperature polymer conductive silver paste with high adhesive force, strong weather resistance and small film sheet 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 (8)
1. A low-temperature polymer conductive silver paste is characterized in that: the conductive coating is composed of 39 mass percent of flake silver powder, 4 mass percent of flake nickel powder, 46-49 mass percent of hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier, 0-8 mass percent of carboxyl modified ternary vinyl chloride-vinyl acetate copolymer carrier, 0.8 mass percent of organic bentonite, 0.5 mass percent of polyethylene micro-powder wax, 0.5 mass percent of YL-2 glass resin, 0.7 mass percent of 9100 gloss oil and 3.5-8.5 mass percent of dibasic acid ester, wherein the flake silver powder and the flake nickel powder are matched and combined to form a conductive phase; the flake silver powder is one or a mixture of two of SF-1# silver powder and SF-2# silver powder with different flake degrees, specific surface areas and tap densities, and the D50 values of the SF-1# silver powder and the SF-2# silver powder are respectively 3.49 mu m and 1.46 mu m; the D50 value of the flaky nickel powder is 8.28 mu m; the hydroxyl modified ternary vinyl chloride-vinyl acetate copolymer resin carrier is prepared by mixing one or more of No. 1 organic carriers, No. 2 organic carriers and No. 3 organic carriers with different molecular weights, wherein the No. 1 organic carrier is prepared by fully stirring and dispersing 12% of Dow VAGH-004 resin in 88% of DBE, and the No. 2 organic carrier and the No. 3 organic carrier are prepared by fully stirring and dispersing 20% of Dow VAGH-003 resin and 80% of Dow VAGH resin in 80% of DBE respectively; the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin carrier is prepared by mixing one or more of No. 4 organic carriers, No. 5 organic carriers and No. 6 organic carriers with different molecular weights, wherein the No. 4 organic carriers, the No. 5 organic carriers and the No. 6 organic carriers are respectively 20% of Pan high chemical engineering HVAMA, Dow VMCH and Dow VMCC resin and fully stirred and dispersed in 80% of DBE.
2. The low-temperature polymer conductive silver paste according to claim 1, wherein the conductive phase comprises 38% of SF-1# silver powder, 1% of SF-2# silver powder and 4% of flake nickel powder.
3. The low-temperature polymer conductive silver paste as claimed in claim 1, wherein the dow VAGH-004 average molecular weight is 85000, the K value is 120, the dow VAGH-003A average molecular weight is 48000, the K value is 59, the dow VAGH average molecular weight is 27000, the K value is 46-48, the pan-high chemical HVAMA average molecular weight is 34000, the K value is 58, the dow VMCH average molecular weight is 27000, the K value is 44-46, the dow VMCC average molecular weight is 19000, and the K value is 39.
4. The low-temperature polymer conductive silver paste as claimed in claim 1, wherein the hydroxyl-modified ternary vinyl chloride-acetate copolymer resin carrier is prepared by dissolving 42-46% of Dow VAGH-004 resin, 0-7% of Dow VAGH-003A resin and 0-7% of Dow VAGH resin in DBE.
5. The low-temperature polymer conductive silver paste as claimed in claim 1, wherein the carboxyl modified ternary vinyl chloride-vinyl acetate copolymer resin carrier is prepared by dissolving 0-8% of Pan-high chemical HVAMA resin, 0-8% of Dow VMCH resin and 0-8% of Dow VMCC resin in DBE.
6. 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 No. 1 organic 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 flake nickel 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.
7. The method for preparing low-temperature polymer conductive silver paste according to claim 6, wherein No. 2 organic vehicle or No. 3 organic vehicle or a mixture of the two is further added in the first step.
8. The method for preparing low-temperature polymer conductive silver paste according to claim 6, wherein a mixture of one or more of organic vehicle # 4, organic vehicle # 5 and organic vehicle # 6 is further added in the first step.
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