CN113421693A - Conductive paste and preparation method and application thereof - Google Patents
Conductive paste and preparation method and application thereof Download PDFInfo
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- CN113421693A CN113421693A CN202110733311.9A CN202110733311A CN113421693A CN 113421693 A CN113421693 A CN 113421693A CN 202110733311 A CN202110733311 A CN 202110733311A CN 113421693 A CN113421693 A CN 113421693A
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
- B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
- B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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- 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
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Abstract
The invention provides conductive paste and a preparation method and application thereof, wherein the conductive paste comprises, by weight, 55-65 parts of flake silver powder, 24-28 parts of tin-bismuth-silver alloy coated spherical silver powder, 3-9 parts of an organic binder and 2-8 parts of an organic carrier. The conductive paste provided by the invention has good conductive effect and strong adhesive force.
Description
Technical Field
The invention belongs to the field of conductive materials, particularly relates to conductive paste and a preparation method and application thereof, and particularly relates to conductive paste with a good conductive effect and a preparation method and application thereof.
Background
With the rapid development of the electronic industry, the conductive paste is widely applied to the preparation of electronic devices and photoelectric devices as an electronic material. The low-temperature curing type conductive paste is a conductive paste which is cured at a lower temperature (100-200 ℃).
The low-temperature curing type conductive paste generally consists of a conductive phase, a bonding phase, an organic carrier and an auxiliary agent. The conductive phase is the main component of the conductive slurry and provides the conductivity of the conductive slurry; the binding phase ensures that the electrode and the matrix have good binding force; organic solvents and auxiliaries are used to adjust the paste to make it suitable for screen printing. Noble metal powders such as silver are used as a conductive phase because of their excellent conductivity. Although a conductive paste mainly composed of silver has been conventionally used, silver is an expensive rare metal and it is difficult to satisfy the requirement of low cost. Attempts have therefore been made to replace silver with lower cost materials such as aluminium, zinc, copper etc. but these materials are difficult to apply due to low oxidation stability and high electrical resistance after low temperature sintering. And secondly, the particle size of the silver powder for preparing the low-temperature conductive paste is micron-sized, so that a large number of gaps are formed among the silver particles in the silver powder, the effective contact among the silver particles is reduced, and a potential barrier is formed to increase the series resistance of the electrode.
CN104650653B discloses a nanometer conductive silver paste and a preparation method thereof, which is characterized by being prepared from the following components in parts by weight: 0.5-5 parts of nano silver; 10-30 parts of resin; 0.01-2 parts of a dispersant; 0.01-2 parts of surface auxiliary agent; 0.01-2 parts of anti-settling agent; 0.01-2 parts of a leveling agent; 0.1-2 parts of nano auxiliary agent; 0.5-2 parts of a thickening agent; 50-95 parts of an organic solvent; 0.01-10 parts of pigment; 0.01-5 parts of curing agent. The product prepared by the invention can be widely applied to electronic components such as integrated circuits, multi-chip components, membrane switches, keyboard circuits and the like aiming at the requirement of matching the low-temperature curing slurry with the printing of electronic circuits.
CN109585090B discloses a high-adhesion low-temperature curing conductive paste and a preparation method thereof, wherein the preparation method comprises the following steps: (1) ball-milling silver powder, graphite powder, nickel powder and glass powder to prepare a conductive phase; (2) preparing a conductive phase coated with gold; (3) modifying bisphenol F type epoxy resin, bismaleimide resin and alkyd resin by using a silane coupling agent and a titanate coupling agent; (4) and preparing the high-adhesion low-temperature curing conductive paste. The conductive paste prepared by the method has good adhesive force and conductivity, the resin is modified by the coupling agent to promote the improvement of the adhesive force of the conductive paste, and meanwhile, the conductive phase is coated by gold to reduce the resistance, so that the conductive paste has an important effect on the improvement of the conductivity.
The particle size of the silver powder for preparing the low-temperature conductive paste is micron-sized, so that the series resistance of the electrode is increased, and the use is not facilitated. Therefore, how to provide a conductive paste with strong conductive capability becomes a problem to be solved urgently.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide conductive paste and a preparation method and application thereof, and particularly provides conductive paste with good conductive effect and a preparation method and application thereof. The conductive paste provided by the invention has good conductive effect and strong adhesive force.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides conductive paste, which comprises, by weight, 55-65 parts of flake silver powder, 24-28 parts of tin-bismuth-silver alloy-coated spherical silver powder, 3-9 parts of an organic binder and 2-8 parts of an organic carrier.
The conductive paste is low-temperature curing conductive paste.
The number of the silver flakes may be 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, or 65, the number of the silver powder coated with the tin-bismuth-silver alloy may be 24, 25, 26, 27, or 28, the number of the organic binder may be 3, 4, 5, 6, 7, 8, or 9, and the number of the organic vehicle may be 2, 3, 4, 5, 6, 7, or 8, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range of values may be equally applicable.
The conductive paste has the advantages that the specific tin-bismuth-silver alloy is adopted to coat the spherical silver powder, so that the conductive effect and the adhesive force of the conductive paste are obviously improved.
Preferably, the conductive paste further comprises 0-4 parts by weight of additives, such as 0.5 part, 1 part, 1.5 parts, 2 parts, 2.5 parts, 3 parts, 3.5 parts or 4 parts, but not limited to the above-listed values, and other values within the above-mentioned range are also applicable, but 0 part is not included.
Preferably, the additive includes any one or a combination of at least two of a thixotropic agent, a leveling agent, an antifoaming agent, a surfactant, or a curing agent, such as a combination of a thixotropic agent and a leveling agent, a combination of a leveling agent and an antifoaming agent, or a combination of an antifoaming agent and a surfactant, and the like, but is not limited to the above-listed combinations, and other combinations not listed within the above-mentioned combination range are also applicable.
Preferably, in the tin-bismuth-silver alloy-coated spherical silver powder, the mass fraction of the tin-bismuth-silver alloy is 10-70%.
Preferably, the tin-bismuth-silver alloy coated spherical silver powder is powder, and the particle size of the powder is 0.07-1 μm.
Preferably, the particle size of the spherical silver powder in the tin-bismuth-silver alloy coated spherical silver powder is 0.05-0.8 μm.
Preferably, the tin-bismuth-silver alloy coated spherical silver powder is prepared by a preparation method comprising the following steps: and melting the tin-bismuth-silver alloy, mixing and stirring the melted tin-bismuth-silver alloy with the spherical silver powder, and performing spray granulation to obtain the tin-bismuth-silver alloy coated spherical silver powder.
Preferably, in the tin-bismuth-silver alloy, the mole percentage of tin is 50-86%, the mole percentage of bismuth is 12-47%, the mole percentage of silver is 0.1-3.2%, and the sum of the three is 100%.
Preferably, the tin-bismuth-silver alloy has a melting point of 180-.
Preferably, the mass ratio of the flake silver powder to the tin-bismuth-silver alloy coated spherical silver powder is 7:2-7: 4.
Preferably, the plate-like silver powder has a particle size of 5 to 8 μm.
Wherein the mass fraction of the tin-bismuth-silver alloy may be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, etc., the particle size of the powder may be 0.07 μm, 0.08 μm, 0.09 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, 0.8 μm, 0.9 μm, or 1 μm, etc., the particle size of the spherical silver powder may be 0.05 μm, 0.1 μm, 0.2 μm, 0.3 μm, 0.4 μm, 0.5 μm, 0.6 μm, 0.7 μm, or 0.8 μm, etc., the molar percentage of tin may be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, or 86%, etc., the molar percentage of bismuth may be 12%, 15%, 20%, 25%, 40%, 47%, or 0.8%, etc., the molar percentage of silver may be 50%, 55%, 25%, or 0.47%, etc., the molar percentage of the molar percentage may be 0.07%, or 0.6%, or 0.3%, etc., the percentage of the silver may be 0.6%, the percentage of the silver may be 0.5%, or the percentage of the silver may be 0.7%, or the percentage of the silver may be 0.5%, or the percentage of the silver may be 0.5%, or the percentage of the silver percentage of the silver of, 0.7%, 0.9%, 1.1%, 1.3%, 1.5%, 1.7%, 1.9%, 2.1%, 2.3%, 2.5%, 2.7%, 2.9%, 3.1%, 3.2%, etc., the melting point of the tin-bismuth-silver alloy may be 180 ℃, 185 ℃, 190 ℃, 195 ℃, or 200 ℃, etc., the mass ratio of the flake-like silver powder to the tin-bismuth-silver alloy-coated spherical silver powder may be 7:2, 7:2.5, 7:3, 7:3.5, or 7:4, etc., the particle size of the flake-like silver powder may be 5 μm, 6 μm, 7 μm, or 8 μm, etc., but is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned range are also applicable.
When the spherical silver powder coated with the tin-bismuth-silver alloy prepared by the specific preparation method is solidified, the external tin-bismuth-silver alloy is melted and filled into the gap of the silver powder, so that the interface between the electrode and the base material is better filled, the contact surface is increased, and the conductivity is improved; the silver powder surface is coated by the tin-bismuth-silver alloy, so that the silver migration of the device in the use process is slowed down; the silver powder is coated in a melting mode, so that the silver powder and the tin-bismuth-silver alloy can be fully mixed on a microscopic layer; the content of silver is reduced, and the cost is saved; the tin-bismuth-silver alloy is adopted, so that the weldability of the conductive paste is improved; the melting point of the tin-bismuth-silver alloy is controlled by adopting a specific component ratio and the synergistic effect of the three metals, so that the tin-bismuth-silver alloy can be applied to low-temperature solidification and meets the use requirement; meanwhile, the proportion of the specific silver powder can reduce gaps existing in the lapping process of the silver powder, so that a conductive path between the powder bodies is enlarged.
Preferably, the organic binder comprises any one of or a combination of at least two of phenolic resin, epoxy resin, acrylic resin, silicone resin, vinyl acetate resin, polyester resin, vinyl resin, polyurethane resin, alkyd resin, aldehyde ketone, polyketone resin, nitrocellulose resin or ethylcellulose.
Preferably, the organic vehicle includes any one of terpineol, turpentine, propylene glycol phenyl ether, dibutyl phthalate, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, dibasic ester, N-methylpyrrolidone, dimethylformamide, alcohol ester 12, ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, or ethylene glycol butyl ether acetate, or a combination of at least two thereof.
The organic binder may be a combination of a phenol resin and an epoxy resin, a combination of an acrylic resin and a silicone resin, a combination of a polyester resin and a polyurethane resin, or the like, and the organic vehicle may be a combination of terpineol and turpentine, a combination of propylene glycol phenyl ether and dibutyl phthalate, a combination of alcohol ester 12 and diethylene glycol ethyl ether acetate, or the like, but is not limited to the above-mentioned combinations, and other combinations not listed within the above-mentioned combinations are also applicable.
In a second aspect, the present invention provides a method for preparing the conductive paste as described above, comprising the steps of: and mixing and heating the organic binder and the organic carrier, and then mixing and grinding the organic binder, the flaky silver powder and the spherical silver powder coated with the tin-bismuth-silver alloy to obtain the conductive paste.
Preferably, the mixing with the flake silver powder and the tin-bismuth-silver alloy-coated spherical silver powder further includes mixing with an additive.
Preferably, the grinding is carried out until the fineness of the mixture is 3 to 13 μm, for example 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm or 13 μm, but is not limited to the above-listed values, and other values not listed in the above-mentioned range of values are equally applicable.
In a third aspect, the present invention also provides the use of the conductive paste as described above for the manufacture of electronic and optoelectronic devices.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a conductive paste, which is characterized in that a specific tin-bismuth-silver alloy is adopted to coat spherical silver powder, so that the conductive effect of the conductive paste is obviously improved; when the spherical silver powder coated with the tin-bismuth-silver alloy prepared by the specific preparation method is solidified, the external tin-bismuth-silver alloy is melted and filled into the gap of the silver powder, so that the interface between the electrode and the base material is better filled, the contact surface is increased, and the conductivity is improved; the silver powder surface is coated by the tin-bismuth-silver alloy, so that the silver migration of the device in the use process is slowed down; the silver powder is coated in a melting mode, so that the silver powder and the tin-bismuth-silver alloy can be fully mixed on a microscopic layer; the content of silver is reduced, and the cost is saved; the tin-bismuth-silver alloy is adopted, so that the weldability of the conductive paste is improved; the melting point of the tin-bismuth-silver alloy is controlled by adopting a specific component ratio and the synergistic effect of the three metals, so that the tin-bismuth-silver alloy can be applied to low-temperature solidification and meets the use requirement; meanwhile, the proportion of the specific silver powder can reduce gaps existing in the lapping process of the silver powder, so that a conductive path between the powder bodies is enlarged.
Detailed Description
To further illustrate the technical means and effects of the present invention, the following further describes the technical solution of the present invention with reference to the preferred embodiments of the present invention, but the present invention is not limited to the scope of the embodiments.
In the comparative examples below, the defoamer was obtained from Kyong chemical Co., Ltd, Shanghai, model Airex 931;
the surfactant is toluene, and is purchased from chemical corporation of Shingan;
thixotropic agent is purchased from Hamming Silite, and is THIXATROL;
the leveling agent is purchased from Pico chemistry and is of a model number BYK-310;
the curing agent was purchased from Nippon monosodium glutamate Fine Chemicals, model number PN-40.
Preparation example 1
The preparation example provides a tin-bismuth-silver alloy coated spherical silver powder (the total mass of all preparation raw materials is 100 wt%), and the preparation method comprises the following steps:
30 wt% of tin-bismuth-silver alloy (69 mol% of tin, 28 mol% of bismuth and 3 mol% of silver) is taken to be melted, and 70w of silver is addedt% spherical silver powder (granularity is 0.05-0.8 μm), stirring, pressurizing the melting reaction kettle by nitrogen, pressing the materials to a spray granulation tower, granulating by adopting an airflow type spray granulation mode, and performing spray granulation, wherein the technological parameters of the spray granulation are as follows: the inlet temperature is 200 ℃, the feeding rate is 10mL/min, and the flow rate of the spraying gas is 28m3And h, carrying out spray granulation to obtain the tin-bismuth-silver alloy coated spherical silver powder.
Preparation example 2
The preparation example provides a tin-bismuth-silver alloy coated spherical silver powder (the total mass of all preparation raw materials is 100 wt%), and the preparation method comprises the following steps:
taking 10 wt% of tin-bismuth-silver alloy (the mol percent of tin is 86%, the mol percent of bismuth is 13%, and the mol percent of silver is 1%) to melt, then adding 90 wt% of spherical silver powder (the granularity is 0.05-0.8 mu m), stirring, pressurizing a melting reaction kettle by using nitrogen, pressing the mixture to a spray granulation tower, granulating by adopting an airflow type spray granulation mode, and carrying out spray granulation according to the process parameters: the inlet temperature is 200 ℃, the feeding rate is 10mL/min, and the flow rate of the spraying gas is 28m3And h, carrying out spray granulation to obtain the tin-bismuth-silver alloy coated spherical silver powder.
Preparation example 3
The preparation example provides a tin-bismuth-silver alloy coated spherical silver powder (the total mass of all preparation raw materials is 100 wt%), and the preparation method comprises the following steps:
taking 70 wt% of tin-bismuth-silver alloy (the mol percent of tin is 50%, the mol percent of bismuth is 47%, and the mol percent of silver is 3%) to melt, then adding 30 wt% of spherical silver powder (the granularity is between 0.05 and 0.8 mu m), stirring, pressurizing a melting reaction kettle by using nitrogen, pressing the material to a spray granulation tower, granulating by adopting an airflow type spray granulation mode, and carrying out spray granulation process parameters: the inlet temperature is 200 ℃, the feeding rate is 10mL/min, and the flow rate of the spraying gas is 28m3And h, carrying out spray granulation to obtain the tin-bismuth-silver alloy coated spherical silver powder.
Comparative preparation example 1
This comparative preparation example provides a tin-bismuth-silver alloy-coated spherical silver powder, and the preparation method is the same as preparation example 1 except that the alloy does not contain tin, and the reduced portion is proportionally distributed to bismuth and silver.
Comparative preparation example 2
This comparative preparation example provides a tin-bismuth-silver alloy-coated spherical silver powder, and the preparation method is the same as preparation example 1 except that the alloy does not contain bismuth, and the reduced portion is proportionally distributed to tin and silver.
Comparative preparation example 3
This comparative preparation example provides a tin-bismuth-silver alloy coated spherical silver powder, and the preparation method is the same as preparation example 1 except that the alloy does not contain silver, and the reduced portion is proportionally distributed to bismuth and tin.
Comparative preparation example 4
The comparative preparation example provides a tin-bismuth-silver alloy-silver powder mixture (taking the total mass of all preparation raw materials as 100 wt%), and the preparation method comprises the following steps:
and (3) mixing and crushing 30 wt% of tin-bismuth-silver alloy (the mole percentage of tin is 69%, the mole percentage of bismuth is 28% and the mole percentage of silver is 3%) and 70 wt% of spherical silver powder (the particle size is between 0.05 and 0.8 mu m) to obtain the tin-bismuth-silver alloy-silver powder mixture.
Example 1
This example provides a conductive paste (based on 100 wt% of the total mass of the raw materials), which is prepared by the following steps:
(1) adding 6 wt% of epoxy resin into a mixture of 5 wt% of N-methyl pyrrolidone and turpentine (the mass ratio of the N-methyl pyrrolidone to the turpentine is 1:1), heating and stirring for 6 hours at the temperature of 75 ℃, and cooling to obtain a mixture A;
(2) and (2) mixing 25.8 wt% of the tin-bismuth-silver alloy coated spherical silver powder provided by the preparation example 1, 60.2 wt% of flake silver powder, 0.4 wt% of defoaming agent, 0.6 wt% of surfactant, 0.6 wt% of thixotropic agent, 0.7 wt% of leveling agent, 0.7 wt% of curing agent and the mixture A obtained in the step (1), and repeatedly rolling the mixture A on a three-roll grinder until the fineness is 7 microns to obtain the conductive paste.
Example 2
This example provides a conductive paste (based on 100 wt% of the total mass of the raw materials), which is prepared by the following steps:
(1) adding 3 wt% of epoxy resin into a mixture of 2 wt% of dimethylformamide and turpentine (the mass ratio of the two is 1:1), heating and stirring for 6 hours at the temperature of 75 ℃, and cooling to obtain a mixture A;
(2) and (2) mixing 27.6 wt% of the tin-bismuth-silver alloy coated spherical silver powder provided by the preparation example 2, 64.4 wt% of flaky silver powder, 0.4 wt% of defoaming agent, 0.6 wt% of surfactant, 0.6 wt% of thixotropic agent, 0.7 wt% of leveling agent, 0.7 wt% of curing agent and the mixture A obtained in the step (1), and repeatedly rolling the mixture A on a three-roll grinder until the fineness is 13 mu m to obtain the conductive paste.
Example 3
This example provides a conductive paste (based on 100 wt% of the total mass of the raw materials), which is prepared by the following steps:
(1) adding 9 wt% of epoxy resin into a mixture of 8 wt% of N-methyl pyrrolidone and dimethylformamide (the mass ratio of the two is 1:1), heating and stirring for 6 hours at the temperature of 75 ℃, and cooling to obtain a mixture A;
(2) and (2) mixing 24 wt% of the tin-bismuth-silver alloy coated spherical silver powder, 56 wt% of the flaky silver powder, 0.4 wt% of a defoaming agent, 0.6 wt% of a surfactant, 0.6 wt% of a thixotropic agent, 0.7 wt% of a leveling agent, 0.7 wt% of a curing agent and the mixture A obtained in the step (1), and repeatedly rolling the mixture A on a three-roll grinder until the fineness of the mixture A is 3 micrometers to obtain the conductive paste.
Comparative example 1
The comparative example provides a conductive paste (based on 100 wt% of the total mass of the raw materials), which is prepared by the following steps:
(1) adding 1 wt% of epoxy resin into a mixture of 1 wt% of N-methyl pyrrolidone and turpentine (the mass ratio of the N-methyl pyrrolidone to the turpentine is 1:1), heating and stirring for 6 hours at the temperature of 75 ℃, and cooling to obtain a mixture A;
(2) and (2) mixing 75 wt% of the tin-bismuth-silver alloy coated spherical silver powder, 20 wt% of flaky silver powder, 0.4 wt% of defoaming agent, 0.6 wt% of surfactant, 0.6 wt% of thixotropic agent, 0.7 wt% of leveling agent, 0.7 wt% of curing agent and the mixture A obtained in the step (1), and repeatedly rolling the mixture A on a three-roll grinder until the fineness is 7 microns to obtain the conductive paste.
Comparative example 2
The comparative example provides a conductive paste (based on 100 wt% of the total mass of the raw materials), which is prepared by the following steps:
(1) adding 14 wt% of epoxy resin into a mixture of 13 wt% of ethylene glycol monoethyl ether acetate and turpentine (the mass ratio of the two is 1:1), heating and stirring for 6 hours at the temperature of 75 ℃, and cooling to obtain a mixture A;
(2) and (2) mixing 35 wt% of the tin-bismuth-silver alloy coated spherical silver powder provided in preparation example 1, 35 wt% of flaky silver powder, 0.4 wt% of defoaming agent, 0.6 wt% of surfactant, 0.6 wt% of thixotropic agent, 0.7 wt% of leveling agent, 0.7 wt% of curing agent and the mixture A obtained in step (1), and repeatedly rolling the mixture A on a three-roll grinder until the fineness of the mixture A is 7 micrometers to obtain the conductive paste.
Comparative examples 3 to 5
Comparative examples 3 to 5 respectively provide an electroconductive paste, which was the same as in example 1 except that the tin-bismuth-silver-alloy-coated spherical silver powder obtained in preparation example 1 was replaced with the tin-bismuth-silver-alloy-coated spherical silver powder provided in comparative preparation examples 1 to 3, respectively.
Comparative example 6
This comparative example provides a conductive paste, which was identical to example 1 except that the tin-bismuth-silver alloy-coated spherical silver powder obtained in preparation example 1 was replaced with the tin-bismuth-silver alloy-silver powder mixture provided in comparative preparation example 4.
Comparative example 7
This comparative example provides a conductive paste prepared in the same manner as in example 1 except that the conductive paste does not contain the tin-bismuth-silver alloy coated spherical silver powder and a reduced portion is distributed to the plate-like silver powder.
Comparative example 8
This comparative example provides a conductive paste prepared in the same manner as in example 1 except that the paste does not contain the flake silver powder and a reduced portion is assigned to the tin-bismuth-silver alloy-coated spherical silver powder.
Comparative example 9
A commercially available conductive paste.
And (3) performance testing:
respectively printing the conductive paste provided by the examples 1-3 and the comparative examples 1-9 to a substrate by a screen printing mode, and heating and curing at 200 ℃ for 15 minutes to form a required conductive circuit sample; and the sheet resistance test and the adhesion test are respectively carried out on the adhesive tape.
And (3) testing the sheet resistance: testing the square cured pattern by using a four-probe tester, and recording the sheet resistance;
and (3) testing the adhesive force: the 3M810 tape was adhered to the cured hundred grid test pattern, the tape was laminated using a 2.5KG weight, after 1 minute the weight was removed and one end of the tape was pulled off vertically and the area ratio of the pattern that did not fall off was recorded.
The results are as follows:
the results show that the product provided by the invention has lower sheet resistance, better conductivity and higher adhesive force; comparing the example 1 with the comparative examples 3-5 and 7-8, it can be found that the invention remarkably improves the conductivity of the product by compounding the tin, bismuth and silver and compounding the flaky silver powder and the tin-bismuth-silver alloy coated spherical silver powder; comparing example 1 with comparative example 6, it can be seen that, by coating the spherical silver powder with the tin-bismuth-silver alloy in a melting manner, the tin-bismuth-silver alloy can be better filled into the gaps between the spherical silver powder and the flake silver powder during curing, so that the interface between the electrode and the base material can be better filled, the contact surface can be increased, and the conductivity can be improved, compared with the case of simply mixing the tin-bismuth-silver alloy powder with the silver powder.
The applicant states that the conductive paste and the preparation method and application thereof are illustrated by the above embodiments, but the invention is not limited to the above embodiments, i.e. the invention is not limited to the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
Claims (10)
1. The conductive paste is characterized by comprising, by weight, 55-65 parts of flake silver powder, 24-28 parts of tin-bismuth-silver alloy coated spherical silver powder, 3-9 parts of an organic binder and 2-8 parts of an organic carrier.
2. The conductive paste according to claim 1, further comprising 0 to 4 parts by weight of an additive, excluding 0 part;
preferably, the additive comprises any one of or a combination of at least two of a thixotropic agent, a leveling agent, an antifoaming agent, a surfactant or a curing agent.
3. The conductive paste as claimed in claim 1 or 2, wherein the tin-bismuth-silver alloy is coated with the spherical silver powder in an amount of 10 to 70% by mass.
4. The electroconductive paste according to any one of claims 1 to 3, wherein the tin-bismuth-silver alloy-coated spherical silver powder is a powder having a particle size of 0.07 to 1 μm;
preferably, the particle size of the spherical silver powder in the tin-bismuth-silver alloy coated spherical silver powder is 0.05-0.8 μm.
5. The electroconductive paste according to any one of claims 1 to 4, wherein the tin-bismuth-silver alloy-coated spherical silver powder is prepared by a preparation method comprising the steps of: melting the tin-bismuth-silver alloy, mixing and stirring the melted tin-bismuth-silver alloy with spherical silver powder, and performing spray granulation to obtain the tin-bismuth-silver alloy coated spherical silver powder;
preferably, in the tin-bismuth-silver alloy, the mole percentage of tin is 50-86%, the mole percentage of bismuth is 12-47%, the mole percentage of silver is 0.1-3.2%, and the sum of the three is 100%;
preferably, the tin-bismuth-silver alloy has a melting point of 180-200 ℃;
preferably, the mass ratio of the flake silver powder to the tin-bismuth-silver alloy coated spherical silver powder is 7:2-7: 4;
preferably, the plate-like silver powder has a particle size of 5 to 8 μm.
6. The electroconductive paste according to any one of claims 1-5, wherein the organic binder comprises any one of or a combination of at least two of phenolic resin, epoxy resin, acrylic resin, silicone resin, vinyl chloride-vinyl acetate resin, polyester resin, vinyl resin, polyurethane resin, alkyd resin, aldehyde ketone, polyketone resin, nitrocellulose resin, or ethylcellulose.
7. The electroconductive paste according to any one of claims 1 to 6, wherein the organic vehicle comprises any one of terpineol, turpentine, propylene glycol phenyl ether, dibutyl phthalate, ethylene glycol ethyl ether, diethylene glycol monomethyl ether, a dibasic ester, N-methylpyrrolidone, dimethylformamide, alcohol ester 12, ethylene glycol ethyl ether acetate, diethylene glycol ethyl ether acetate, or ethylene glycol butyl ether acetate, or a combination of at least two thereof.
8. A method for preparing the electroconductive paste according to any one of claims 1 to 7, comprising the steps of: and mixing and heating the organic binder and the organic carrier, and then mixing and grinding the organic binder, the flaky silver powder and the spherical silver powder coated with the tin-bismuth-silver alloy to obtain the conductive paste.
9. The method for preparing an electroconductive paste according to claim 8, wherein the mixing with the flake silver powder and the tin-bismuth-silver alloy-coated spherical silver powder further comprises mixing with an additive;
preferably, the grinding is carried out until the fineness of the mixture is 3-13 μm.
10. Use of the conductive paste according to any one of claims 1-7 for the preparation of electronic and optoelectronic devices.
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| CN202110733311.9A CN113421693A (en) | 2021-06-30 | 2021-06-30 | Conductive paste and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114005573A (en) * | 2021-11-11 | 2022-02-01 | 中国有色桂林矿产地质研究院有限公司 | Preparation method of novel high-temperature electronic paste |
| CN115954129A (en) * | 2022-12-02 | 2023-04-11 | 上海苏煜新能源有限公司 | Conductive paste and preparation method thereof |
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2021
- 2021-06-30 CN CN202110733311.9A patent/CN113421693A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114005573A (en) * | 2021-11-11 | 2022-02-01 | 中国有色桂林矿产地质研究院有限公司 | Preparation method of novel high-temperature electronic paste |
| CN114005573B (en) * | 2021-11-11 | 2023-08-11 | 中国有色桂林矿产地质研究院有限公司 | Preparation method of high-temperature electronic paste |
| CN115954129A (en) * | 2022-12-02 | 2023-04-11 | 上海苏煜新能源有限公司 | Conductive paste and preparation method thereof |
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