CN115651586B - Anti-migration epoxy conductive silver adhesive and preparation method thereof - Google Patents
Anti-migration epoxy conductive silver adhesive and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention provides an anti-migration epoxy conductive silver adhesive, which comprises the following raw materials: the structural formula of the epoxy conductive silver adhesive prepared by the invention is shown in the following formula I, the epoxy conductive silver adhesive has good conductivity, and the specific resistance of the conductive silver adhesive added with the epoxy chloropropane modified hydroxyl betaine is kept stable and has good reliability through 1000h double-eight-five wet heat aging experiments; it has also been found that tackifier KH-580 has a synergistic effect on epichlorohydrin modified hydroxy betaine to further improve the resistance to migration of humid heat aged silver. The epoxy conductive silver adhesive has good excellent conductivity and damp-heat stability after being cured, and is suitable for packaging optical communication electronic components with higher requirements on conductivity and damp-heat reliability.
Description
Technical Field
The invention belongs to the technical field of conductive silver adhesive, and particularly relates to an anti-migration epoxy conductive silver adhesive and a preparation method thereof.
Background
Along with the development of technology, microelectronic products are gradually transformed into multifunctional, high-performance, portable, low-cost, environment-friendly and the like, and the defects of the wide tin-lead solder used in the traditional electronic packaging industry are gradually exposed: the wire resolution is low, the tin-lead solder paste is seriously bridged, the welding temperature is too high, the device is damaged, and the method is not friendly to the environment.
The epoxy conductive silver adhesive is also called as "polymer solder", is an environment-friendly tin-lead welding substitute product, and can be used for connecting various conductive materials after being solidified or dried, so that a conductive path is formed by the newly connected parts. The epoxy conductive silver adhesive mainly comprises epoxy or modified epoxy main resin, metallic silver, a curing agent, a curing accelerator, an auxiliary agent and the like, wherein the cured epoxy resin is a three-dimensional cross-linked structure with compact and closed structure, no active groups and free ions exist any more, and low molecular substances are not emitted in the curing process, so that the epoxy conductive silver adhesive has the advantages of high bonding strength, acid and alkali resistance, small curing shrinkage rate and the like, and is widely applied to the technical field of electronic packaging at present, such as a HJT conductive silver adhesive composition disclosed in patent CN202111128927.X, a preparation method thereof and a HJT solar cell, and the composition comprises: silver powder, epoxy resin, a flexible compound, a curing agent, a diluent and an auxiliary agent; the flexible compound includes one or more of a flexible block copolymer, a flexible graft copolymer, and a flexible polymer blend. Comprises the following components in percentage by weight: 80 to 95 weight percent of silver powder, 1 to 10 weight percent of epoxy resin, 1 to 10 weight percent of flexible compound, 1 to 5 weight percent of curing agent, 1 to 5 weight percent of diluent and 0.01 to 0.5 weight percent of auxiliary agent. The patent CN201610083990.9 discloses a conductive silver adhesive and a preparation method thereof, wherein the conductive silver adhesive comprises the following components in percentage by weight: 10-20% of epoxy resin, 65-75% of metal silver powder, 1-10% of curing agent, 0.1-0.5% of curing accelerator, 10-20% of diluent and 0.1-1% of auxiliary agent. The technology is that the conductive silver adhesive prepared by taking epoxy resin as a base material and silver powder as a filler, and a circuit connected by taking the conductive silver adhesive as a polymer solder has the advantages of high bonding strength, high linear resolution, small curing shrinkage, no bridging and the like, but the compatibility of Ag and the base material resin is poor, migration phenomenon is generated under the damp-heat condition, the conductivity is reduced, the reliability is influenced, the service life is further shortened, and the conductive silver adhesive is not suitable for optical communication electronic devices with a large amount of electromagnetic radiation converted into heat energy.
Therefore, how to reduce silver migration of the epoxy conductive silver adhesive under the condition of damp and hot, and to improve the service life are important work points for expanding the application of the epoxy conductive silver adhesive in the field of optical communication at present.
Disclosure of Invention
In order to solve the technical problems, the invention provides an anti-migration epoxy conductive silver adhesive and a preparation method thereof, wherein the base material resin is bisphenol epoxy resin, epichlorohydrin modified hydroxy betaine and a single-functionality active diluent are used as active diluents, the epichlorohydrin modified hydroxy betaine is a compound with epoxy groups and carboxylic acid betaine functional groups, which is prepared by using raw materials of epichlorohydrin, dihydroxybetaine and alkali through two-step reaction, when the conductive silver adhesive is subjected to reaction and solidification, a three-dimensional cross-linked structure taking the base material resin as a main body is formed, the epichlorohydrin modified hydroxy betaine can form a framework of the cross-linked structure, and on the other hand, the carboxylic acid betaine functional groups on the epoxy propane modified hydroxy betaine can adsorb silver, so that migration is reduced, the conductivity of silver is not influenced, and the service life of the conductive silver adhesive is greatly prolonged.
In order to achieve the above purpose, the following specific technical scheme is adopted:
an anti-migration epoxy conductive silver adhesive, which comprises the following raw materials: bisphenol type epoxy resin, epichlorohydrin modified hydroxy betaine, monofunctional reactive diluent, curing agent, curing accelerator and silver powder.
The structural formula of the epichlorohydrin modified hydroxy betaine is shown as the following formula I:
wherein m is an integer of 12-14, 16-18, and n is an integer of 25-29, 33-37.
Further, the epoxy conductive silver adhesive comprises the following raw materials in parts by weight: 15-20 parts of bisphenol epoxy resin, 5-10 parts of epichlorohydrin modified hydroxy betaine, 1-5 parts of monofunctional reactive diluent, 1-5 parts of latent curing agent, 1-5 parts of curing accelerator and 70-80 parts of silver powder.
The epoxy chloropropane modified hydroxy betaine is generated by the reaction of dihydroxybetaine and epoxy chloropropane according to the mol ratio of 1:2.8-3.2.
The dihydroxybetaine is one or more selected from dodecyl dihydroxyethyl betaine, tridecyl dihydroxyethyl betaine, tetradecyl dihydroxyethyl betaine, hexadecyl dihydroxyethyl betaine, heptadecyl dihydroxyethyl betaine and octadecyl dihydroxyethyl betaine.
Preferably, the dihydroxybetaine is selected from one or a combination of two or more of dodecyl dihydroxyethyl betaine and octadecyl dihydroxyethyl betaine.
The epichlorohydrin modified hydroxy betaine is prepared by a method comprising the following steps:
1) Under inert atmosphere, heating dihydroxybetaine and keeping the temperature, adding a catalyst, uniformly stirring, then dropwise adding epichlorohydrin, keeping the temperature after the dropwise adding, reacting, and naturally cooling to room temperature after the reaction is finished;
2) And (3) dissolving the product obtained in the step (1) in an organic solvent, heating and keeping the temperature, dropwise adding an alkali-containing solution, then carrying out reaction, naturally cooling to room temperature after the reaction is finished, standing for layering, removing a water layer, washing an oil layer by deionized water until the separated water layer is neutral, and carrying out reduced pressure distillation to obtain the epichlorohydrin modified hydroxy betaine.
The temperature rise in the step 1) is up to 85-100 ℃, and the catalyst is selected from SnCl 4 、BF 3 The catalyst is one of diethyl ether complex, and the dosage of the catalyst is 0.1-0.5wt% of the total weight of dihydroxybetaine and epichlorohydrin; the epichlorohydrin is dripped for 1-3h, and the reaction time is 1-3h.
The organic solvent in the step 2) is selected from one or a combination of two or more of ethanol, diethyl ether, isopropyl ether, chloroform and carbon tetrachloride; raising the temperature to 50-60 ℃; the concentration of the alkali-containing solution is 10-20wt%, the solvent used in the alkali-containing solution is ethanol after the dripping within 0.5-2h, the type of the alkali is not particularly limited, the alkali is selected from one or a combination of two or more of sodium hydroxide and potassium hydroxide commonly used in the field, and the molar ratio of the alkali to the dihydroxybetaine is 2.22-2.40:1.
The epoxy value of the bisphenol type epoxy resin is 0.4-0.6, and the bisphenol type epoxy resin is one or the combination of two of bisphenol A type epoxy resin and bisphenol F type epoxy resin.
The monofunctional reactive diluent is selected from one or a combination of two or more of butyl glycidyl ether, phenyl glycidyl ether, 2-ethylhexyl glycidyl ether, cresol glycidyl ether, p-tert-butylphenyl glycidyl ether and o-toluene glycidyl ether.
The latent curing agent comprises one or a combination of two or more of dicyandiamide, dicyandiamide derivatives, imidazole compounds and organic acid hydrazides.
The curing accelerator is selected from one or more of imidazole compounds, organic guanidine compounds, organic urea curing accelerators, boron trifluoride amine compounds and tertiary amine compounds, and specifically comprises one or more of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, N, N ' -dimethyl diphenyl urea, N, N ' -diethyl diphenyl urea, N-p-chlorophenyl-N, N ' -dimethyl urea, 3-phenyl-1, 1-dimethyl urea, tetramethyl guanidine, boron trifluoride monoethylamine and benzyl dimethylamine.
Preferred curing accelerators are imidazoles, including specifically but not limited to one or a combination of two or more of 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole.
The silver powder is a compound of micron silver powder and nanometer silver powder, the weight ratio of the micron silver powder to the nanometer silver powder is 1-5:3, the micron silver powder is flaky or spherical silver powder, and the average diameter or particle size of the micron silver powder is 1-5 mu m; the nanometer silver powder is spherical silver powder, and the average particle size of the nanometer silver powder is 0.1-0.5 mu m.
The anti-migration epoxy conductive silver adhesive also comprises 0.1-3 parts of an auxiliary agent, wherein the auxiliary agent comprises one or a combination of two or more of a thixotropic agent, a leveling agent, a tackifier and a defoaming agent.
The thixotropic agent is selected from one or a combination of two or more of fumed silica, hydrogenated castor oil and polyamide wax.
The leveling agent type is selected from one or two types of organosilicon leveling agent and acrylate leveling agent.
The tackifier is one or more selected from KH-550, A-151, KH-570, KH-560 and KH-580. Preferably, the tackifier is KH-580.
The type of the defoaming agent is selected from one or a combination of two or more of organic siloxane, polyether, polyethylene glycol, ethylene-acrylic acid copolymer, polyglycerol fatty acid ester, polydimethylsiloxane and polyether modified organic silicon.
The invention also provides a preparation method of the anti-migration epoxy conductive silver adhesive, which comprises the following steps:
s1, uniformly mixing bisphenol epoxy resin, epichlorohydrin modified hydroxy betaine, a curing agent and a curing accelerator, and adding the mixture into a grinder for grinding;
s2, adding the grinding product obtained in the step S1 to a stirrer, controlling the temperature and stirring uniformly, adding the monofunctional reactive diluent, continuing controlling the temperature and stirring uniformly, and optionally adding an auxiliary agent and controlling the temperature and stirring uniformly;
s3, adding silver powder into the mixture obtained in the step S2, uniformly stirring at a controlled temperature, and then stirring in vacuum at a controlled temperature for defoaming to obtain the anti-migration epoxy conductive silver adhesive.
The grinding machine in the step S1 is a three-roller grinding machine, the main shaft gap is 10-15 mu m, the main shaft gap is 20-40 mu m, and the grinding is carried out for 2-4 times.
The stirring speed in the step S2 is 80-120r/min, the stirring time is 10-40min, and the temperature is controlled at 15-25 ℃.
The speed of the step S3 is 80-120r/min, the stirring time is 60-120min, and the temperature is controlled to be 15-25 ℃; the vacuum stirring speed is 80-120r/min, the stirring time is 10-200min, and the temperature is 15-25 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the base material resin is bisphenol epoxy resin, epichlorohydrin modified hydroxy betaine and a monofunctional reactive diluent are used as reactive diluents, the epichlorohydrin modified hydroxy betaine is a compound with epoxy groups and carboxylic acid betaine functional groups, which is prepared by using raw materials of epichlorohydrin and dihydroxybetaine and is prepared through two-step reaction, when the conductive silver colloid system is reacted and solidified, a three-dimensional cross-linked structure taking the base material resin as a main body is formed, the epichlorohydrin modified hydroxy betaine can form a framework of the cross-linked structure on one hand, and the carboxylic acid betaine functional groups on the epoxy propane modified hydroxy betaine can adsorb silver on the other hand, so that migration is reduced, the conductivity of silver is not influenced, and the service life of the conductive silver colloid can be greatly prolonged.
The epoxy conductive silver adhesive has good excellent conductivity and damp-heat stability after being cured, and is suitable for packaging optical communication electronic components with higher requirements on conductivity and damp-heat reliability.
The preparation method is simple, easy to operate, low in energy consumption and low in cost.
Drawings
FIG. 1 is a photograph of application example 1 after curing at 30 Xmagnification under an Austenite micro AO-HK830-0750 high magnification electron microscope;
FIG. 2 is a photograph of comparative application example 1 after curing at 30 Xmagnification under an Austenite micro AO-HK830-0750 high magnification electron microscope.
The invention will now be further described with reference to the accompanying drawings and examples:
Detailed Description
The invention is further illustrated below in connection with specific examples, but is not limited to the disclosure. Unless otherwise specified, "parts" are parts by weight in the examples of the present invention. All reagents used are those commercially available in the art.
E51 is available from Yue Yangshi Baling petrochemical company, hunan province.
Octadecyl dihydroxyethyl betaine is available from Shandong Pingming remote chemical technology Co.
Dodecyl dihydroxyethyl betaine was purchased from the company markami sciences.
Stearyl (dihydroxyethyl) methyl ammonium chloride was purchased from Hubei Jiang Mintai Hua chemical Co., ltd.
Preparation of epichlorohydrin modified hydroxy betaine
Preparation example 1
1) Under nitrogen atmosphere, 0.1mol of octadecyl dihydroxyethyl betaine is heated to 90 ℃ and kept at constant temperature, and 0.35g of SnCl is added 4 Dropwise adding 0.32mol of epichlorohydrin after uniformly stirring, keeping the temperature for reaction for 1h after 2h of dropwise adding, and naturally cooling to room temperature after the reaction is finished;
2) Dissolving the product obtained in the step 1) in 90mL of a mixed organic solvent consisting of ethanol and carbon tetrachloride according to the volume ratio of 1:2.6, heating to 60 ℃, keeping the temperature, dropwise adding 64g of 20wt% sodium hydroxide ethanol solution for 1.5h, reacting, naturally cooling to room temperature after the reaction is finished, standing for 2h for layering, removing a water layer, washing an oil layer with deionized water for 4 times, wherein the separated water layer is neutral, and distilling under reduced pressure to remove water, ethanol and carbon tetrachloride.
The reaction formula is as follows:
preparation example 2
The remainder was the same as in preparation example 1, except that dodecyl dihydroxyethyl betaine was used instead of octadecyl dihydroxyethyl betaine.
Preparation example 3
The remainder was the same as in preparation example 1 except that epichlorohydrin was used in an amount of 0.28mol.
Preparation example 4
The remainder was the same as in preparation example 1 except that the amount of 20% by weight of sodium hydroxide was 59.2g.
Comparative preparation example 1
The remainder was the same as in preparation example 1, except that stearyl (dihydroxyethyl) methyl ammonium chloride was used instead of stearyl dihydroxyethyl betaine.
Preparation of epoxy conductive silver adhesive
Example 1
S1, uniformly mixing 20 parts of E51, 10 parts of epoxy chloropropane modified hydroxy betaine prepared in preparation example 1, 5 parts of dicyandiamide and 3 parts of 2-methylimidazole, adding the mixture into a three-roller grinder, wherein the main shaft gap is 10 mu m, and the main shaft gap is 20 mu m, and grinding for 2 times;
s2, adding the grinding product obtained in the step S1 to a stirrer, controlling the temperature to be 25 ℃, stirring for 30min at the stirring speed of 80r/min, adding 5 parts of butyl glycidyl ether, continuously stirring at the stirring speed of 80r/min, stirring for 10min, adding 0.5 part of tackifier KH-580, stirring at the stirring speed of 80r/min, and stirring for 10min at the stirring speed of 25 ℃;
s3, adding 50 parts of micron silver powder with the average diameter of 5 mu m and 30 parts of nanometer silver powder with the average particle diameter of 0.3 mu m into the mixture obtained in the step S2, stirring at the temperature of 25 ℃, controlling the stirring speed to be 80r/min, stirring for 90min, stirring at the temperature of 25 ℃ under the vacuum degree of 0.1MPa, controlling the stirring speed to be 80r/min, stirring for 30min, and defoaming to obtain the anti-migration epoxy conductive silver adhesive.
Examples 2 to 4
The remainder was the same as in example 1 except that epichlorohydrin-modified hydroxy betaine was prepared in preparation examples 2 to 4.
Example 5
The remainder was the same as in example 1 except that the epichlorohydrin-modified hydroxy betaine prepared in preparation example 1 was used in an amount of 5 parts.
Example 6
The remainder was the same as in example 1 except that the amount of tackifier KH-580 was 0.3 part.
Example 7
The remainder is the same as in example 1, except that KH-550 is used instead of the tackifier KH-580 in step S2.
Comparative example 1
The remainder was the same as in example 1, except that epichlorohydrin-modified hydroxy betaine was prepared in comparative preparation example 1.
Application example 1
And (3) dispensing the conductive silver paste prepared in the embodiment 1 on a gold-plated substrate by using a Shinewa SEC-DP300 dispenser, wherein the glue line is 0.25mm high and 0.33mm wide, and then curing at 150 ℃ for 60 min. The photograph of the glass magnified 30 times under a high-power electron microscope is shown in FIG. 1, and it can be seen that silver is less precipitated.
Application examples 2 to 7
Otherwise, the same as in application example 1 was conducted except that the conductive silver paste used was prepared in examples 2 to 7.
Comparative application example 1
Otherwise, the same as in application example 1 was conducted except that the conductive silver paste used was prepared in comparative example 1. The photograph of the glass magnified 30 times under the high-power electron microscope is shown in FIG. 2, and it can be seen that silver is significantly more precipitated than in application example 1.
The epoxy conductive adhesives prepared in the above application examples 1 to 7 and comparative application example 1 were subjected to the following performance tests:
conductive properties: the volume resistivity test of the conductive silver paste was performed with reference to the standard test method of volume resistivity of the standard ASTM D2739-1997 (2010) conductive paste.
Wet heat resistance: the solution was left at 85℃for 1000 hours in an atmosphere of 85% RH, and the volume resistivity retention of the conductive silver paste was measured.
TABLE 1
| Project | Volume resistivity is multiplied by 10 < -4 > omega cm | Volume resistivity after humid heat aging is multiplied by 10 < -4 > omega cm |
| Application example 1 | 1.01 | 1.01 |
| Application example 2 | 1.05 | 1.05 |
| Application example 3 | 1.04 | 1.04 |
| Application example 4 | 1.07 | 1.07 |
| Application example 5 | 1.12 | 1.52 |
| Application example 6 | 1.01 | 1.10 |
| Application example 7 | 1.23 | 1.86 |
| Comparative application example 1 | 2.97 | 4.55 |
As can be seen from Table 1, the epoxy conductive silver adhesive prepared by the invention has good conductivity, and the conductive silver adhesive volume resistivity of the epoxy chloropropane modified hydroxy betaine added can be kept stable through a 1000h double-eight-five wet heat aging experiment, so that the epoxy conductive silver adhesive has good reliability; from application examples 1, 6 and 7 and comparative application example 1, it can be seen that the tackifier KH-580 has the effect of improving the migration resistance of the humid heat aging silver further by synergistically modifying the hydroxy betaine with epichlorohydrin.
The epoxy conductive silver adhesive has good excellent conductivity and damp-heat stability after being cured, and is suitable for packaging optical communication electronic components with higher requirements on conductivity and damp-heat reliability.
The preparation method is simple, easy to operate, low in energy consumption and low in cost.
The foregoing detailed description is directed to one of the possible embodiments of the present invention, which is not intended to limit the scope of the invention, but is to be accorded the full scope of all such equivalents and modifications so as not to depart from the scope of the invention.
Claims (8)
1. The anti-migration epoxy conductive silver adhesive is characterized by comprising the following raw materials: 15-20 parts of bisphenol epoxy resin, 5-10 parts of epichlorohydrin modified hydroxy betaine, 1-5 parts of monofunctional reactive diluent, 1-5 parts of curing agent, 1-5 parts of curing accelerator, 70-80 parts of silver powder and 0.1-3 parts of auxiliary agent, wherein the auxiliary agent comprises tackifier which is KH-580; optionally, the auxiliary agent further comprises one or a combination of two or more of a thixotropic agent, a leveling agent and an antifoaming agent; the structural formula of the epichlorohydrin modified hydroxy betaine is shown as the following formula I:
a formula I;
wherein m is an integer of 12-14, 16-18, and n is an integer of 25-29, 33-37.
2. The migration-resistant epoxy conductive silver adhesive of claim 1, wherein the epichlorohydrin modified hydroxy betaine is generated by reacting dihydroxybetaine with epichlorohydrin according to a molar ratio of 1:2.8-3.2.
3. The migration-resistant epoxy conductive silver adhesive of claim 2, wherein the dihydroxybetaine is selected from one or a combination of two or more of dodecyl dihydroxyethyl betaine, tridecyl dihydroxyethyl betaine, tetradecyl dihydroxyethyl betaine, hexadecyl dihydroxyethyl betaine, heptadecyl dihydroxyethyl betaine, and octadecyl dihydroxyethyl betaine.
4. The migration-resistant epoxy conductive silver adhesive of claim 1, wherein the epichlorohydrin modified hydroxy betaine is prepared by a method comprising the steps of:
1) Under inert atmosphere, heating dihydroxybetaine and keeping the temperature, adding a catalyst, uniformly stirring, then dropwise adding epichlorohydrin, keeping the temperature after the dropwise adding, reacting, and naturally cooling to room temperature after the reaction is finished;
2) And (3) dissolving the product obtained in the step (1) in an organic solvent, heating and keeping the temperature, dropwise adding an alkali-containing solution, then carrying out reaction, naturally cooling to room temperature after the reaction is finished, standing for layering, removing a water layer, washing an oil layer by deionized water until the separated water layer is neutral, and carrying out reduced pressure distillation to obtain the epichlorohydrin modified hydroxy betaine.
5. The migration-resistant epoxy conductive silver paste of claim 4, wherein in step 1) said temperature is raised to 85-100deg.C, and said catalyst is selected from the group consisting of SnCl 4 、BF 3 The catalyst is one of diethyl ether complex, and the dosage of the catalyst is 0.1-0.5wt% of the total weight of dihydroxybetaine and epichlorohydrin; the epoxy chloropropane is dripped for 1-3 hours, and the reaction time is 1-3 hours;
the organic solvent in the step 2) is selected from one or a combination of two or more of ethanol, diethyl ether, isopropyl ether, chloroform and carbon tetrachloride; raising the temperature to 50-60 ℃; the concentration of the alkali-containing solution is 10-20wt%, the alkali-containing solution is ethanol after dripping for 0.5-2h, and the molar ratio of the alkali to the dihydroxybetaine is 2.22-2.40:1.
6. The migration resistant epoxy conductive silver adhesive of claim 1, wherein the bisphenol type epoxy resin has an epoxy value of 0.4 to 0.6 and is selected from one or a combination of two of bisphenol type a epoxy resin and bisphenol type F epoxy resin; the curing agent comprises one or a combination of two or more of dicyandiamide, dicyandiamide derivatives, imidazole compounds and organic acid hydrazides.
7. The anti-migration epoxy conductive silver adhesive of claim 1, wherein the silver powder is a compound of micron silver powder and nanometer silver powder, the weight ratio of the micron silver powder to the nanometer silver powder is 1-5:3, the micron silver powder is flake or spherical silver powder, and the average diameter or particle size of the micron silver powder is 1-5 μm; the nanometer silver powder is spherical silver powder, and the average particle size of the nanometer silver powder is 0.1-0.5 mu m.
8. The method for preparing the migration-resistant epoxy conductive silver adhesive according to any one of claims 1 to 7, comprising the steps of:
s1, uniformly mixing bisphenol epoxy resin, epichlorohydrin modified hydroxy betaine, a curing agent and a curing accelerator, and adding the mixture into a grinder for grinding;
s2, adding the grinding product obtained in the step S1 to a stirrer, controlling the temperature and stirring uniformly, adding the monofunctional reactive diluent, continuing controlling the temperature and stirring uniformly, and optionally adding an auxiliary agent and controlling the temperature and stirring uniformly;
s3, adding silver powder into the mixture obtained in the step S2, uniformly stirring at a controlled temperature, and then stirring in vacuum at a controlled temperature for defoaming to obtain the anti-migration epoxy conductive silver adhesive.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56115782A (en) * | 1980-02-20 | 1981-09-11 | Kao Corp | Preparation of gycidyl ether |
| JP2007045931A (en) * | 2005-08-10 | 2007-02-22 | Fujikura Ltd | Epoxy adhesive, coverlay, prepreg, metal-clad laminate and printed circuit board |
| CN103306134A (en) * | 2013-07-02 | 2013-09-18 | 席敏皓 | Surface treating agent capable of modifying protein fibers and preparation method and usage thereof |
| CN110504046A (en) * | 2019-08-28 | 2019-11-26 | 湖南诺尔得材料科技有限公司 | A kind of conductive silver paste and the preparation method and application thereof |
| CN114446511A (en) * | 2022-01-14 | 2022-05-06 | 乾宇电子材料（深圳）有限公司 | Radium-shine conductive silver thick liquid of using |
| CN114874722A (en) * | 2022-06-29 | 2022-08-09 | 东莞市德聚胶接技术有限公司 | Moisture-heat-resistant epoxy conductive adhesive, preparation method and application thereof |
| CN115232589A (en) * | 2022-08-05 | 2022-10-25 | 东莞市德聚胶接技术有限公司 | High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof |
-
2022
- 2022-10-28 CN CN202211337428.6A patent/CN115651586B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56115782A (en) * | 1980-02-20 | 1981-09-11 | Kao Corp | Preparation of gycidyl ether |
| JP2007045931A (en) * | 2005-08-10 | 2007-02-22 | Fujikura Ltd | Epoxy adhesive, coverlay, prepreg, metal-clad laminate and printed circuit board |
| CN103306134A (en) * | 2013-07-02 | 2013-09-18 | 席敏皓 | Surface treating agent capable of modifying protein fibers and preparation method and usage thereof |
| CN110504046A (en) * | 2019-08-28 | 2019-11-26 | 湖南诺尔得材料科技有限公司 | A kind of conductive silver paste and the preparation method and application thereof |
| CN114446511A (en) * | 2022-01-14 | 2022-05-06 | 乾宇电子材料（深圳）有限公司 | Radium-shine conductive silver thick liquid of using |
| CN114874722A (en) * | 2022-06-29 | 2022-08-09 | 东莞市德聚胶接技术有限公司 | Moisture-heat-resistant epoxy conductive adhesive, preparation method and application thereof |
| CN115232589A (en) * | 2022-08-05 | 2022-10-25 | 东莞市德聚胶接技术有限公司 | High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof |
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