CN115073693A - Toughening resin-based conductive silver paste and preparation method thereof - Google Patents
Toughening resin-based conductive silver paste and preparation method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/4825—Polyethers containing two hydroxy groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
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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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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention relates to a preparation method of toughened resin-based conductive silver paste, which comprises the steps of substituting a polyurethane prepolymer with-NCO end capping for H on a secondary amine N at the 1-position on an imidazole (EMI) ring to synthesize an EMI end capping polyurethane prepolymer; uniformly mixing the EMI end-capped polyurethane prepolymer and epoxy resin according to a certain proportion to prepare toughened latent epoxy resin; mixing the toughened latent epoxy resin, the silver powder, the silane coupling agent and the catalyst by a three-roll machine until metal luster appears, and reacting the epoxy resin-based conductive silver paste at 90-130 ℃ for 2 hours to obtain toughened resin-based conductive silver paste; the toughened epoxy resin-based conductive silver paste has both mechanical property and high conductivity, and has application prospects in intelligent displays, 5G communication and chip research and development.
Description
Technical Field
The invention belongs to the technical field of conductive materials, relates to toughened resin-based conductive silver paste and a preparation method thereof, and particularly relates to epoxy resin-based conductive silver paste which is moderate in curing temperature, long in latency and capable of improving the toughness of a cured material of the material and a preparation method thereof.
Background
With the rapid development of the electronic industry in recent years, the demand of electronic products such as membrane switches, flexible printed circuit boards, electromagnetic shields, potentiometers, radio frequency identification systems, solar cells and the like is rapidly increased, and the development and application of conductive silver paste as a key functional material for preparing such electronic components are also widely concerned by people. The analysis shows that the market for conductive silver paste alone has a billion dollars of market size each year. In the rapid development process of the information industry, the slurry plays an important role as a key material. Along with the development of the intelligent Internet of things, the demand of brushing flexible circuits is more and more extensive, and new requirements are provided for silver paste.
The epoxy resin can be cured by amine, anhydride, polyamide, imidazole and other curing agents to form a three-dimensional network structure, and has the characteristics of high chemical corrosion resistance, heat resistance, easy processability, excellent mechanical property, good adhesive force, low curing shrinkage, easy viscosity control, light color after curing and the like. The conductive silver paste taking the epoxy resin as the matrix is taken as a thermosetting conductive polymer composite material, has both mechanical property and high conductivity, and is focused on intelligent displays, 5G communication and chip research and development. On one hand, the long-term application of the epoxy resin-based conductive silver paste is limited due to the poor storage performance of the epoxy resin-based conductive silver paste. On the other hand, the cured epoxy resin-based conductive silver paste product has poor toughness. In order to meet the requirements of the epoxy resin-based conductive silver paste on storage performance and toughness, the room-temperature storage performance and toughness of the epoxy cured material are improved by carrying out molecular design on the curing agent. Therefore, a toughened resin-based conductive silver paste is developed to improve the storage period and toughness of the silver paste at room temperature.
Disclosure of Invention
In view of the above, the invention provides a toughened resin-based conductive silver paste and a preparation method thereof, aiming at solving the problems that the storage performance of the existing epoxy resin-based conductive silver paste is poor, the toughness of the cured epoxy resin-based conductive silver paste product is poor, and the long-term application of the cured epoxy resin-based conductive silver paste product is limited.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of toughened resin-based conductive silver paste comprises the following steps:
s1, preparing an imidazole-terminated polyurethane prepolymer: dripping phosphoric acid, a catalyst and polyether polyol into solvent-diluted diisocyanate in batches under a dry protective atmosphere, and reacting for 1-2 h at 40-50 ℃; after the reaction is finished, dripping imidazole diluted by a solvent into the reaction liquid at the temperature of 60-70 ℃, and reacting for 2-3 h to prepare an imidazole-terminated polyurethane prepolymer;
s2, preparing toughened latent epoxy resin: uniformly mixing the imidazole-terminated polyurethane prepolymer obtained in the step S1 with epoxy resin according to the proportion of 5-12.5 wt%;
s3, toughening epoxy resin-based conductive silver paste: uniformly mixing the toughened latent epoxy resin, the silver powder, the silane coupling agent and the catalyst in the step S2 by a three-roll machine according to the proportion of 63-65: 3-3.5: 0.5-0.7 until metal luster appears, and reacting epoxy resin-based conductive silver paste at 90-130 ℃ for 2 hours to obtain toughened resin-based conductive silver paste; the blocked polyurethane prepolymer is deblocked in the heating process to generate imidazole and the polyurethane prepolymer, the imidazole is used as a curing agent to perform a crosslinking reaction with epoxy resin, a-NCO group in the polyurethane prepolymer reacts with-OH in the epoxy resin to graft a polyether flexible long chain into an epoxy curing system, the movement capacity of a chain segment is increased, the toughening effect is achieved, and the toughened epoxy resin-based conductive silver paste with good mechanical properties is prepared.
Further, the specific step of step S1 is:
s11, sequentially dripping polyether polyol and a catalyst into a tetrahydrofuran-diluted diisocyanate solution under the protection of dry nitrogen; reacting for 1-2 h at 45-50 ℃, wherein the mechanical stirring reaction is carried out for 0.5-1 h, and a blocked isocyanate prepolymer is obtained;
s12, under the protection atmosphere of dry nitrogen, the molar ratio n (imidazole): and n (diisocyanate) is 1-1.2: 1, adding tetrahydrofuran diluted sealing agent imidazole and supplementing a catalyst, controlling the temperature at 60-70 ℃, and reacting for 2-3 hours to obtain the imidazole-terminated polyurethane prepolymer.
Further, the diisocyanate is one or a mixture of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate.
Further, the polyether polyol is one or a mixture of polypropylene glycol and polyethylene glycol with different molecular weights.
Furthermore, the imidazole is one or a mixture of 2-methylimidazole, 2-ethylimidazole, 4-nitroimidazole, 2-methyl-5-nitroimidazole, 2-phenyl-imidazole, 2-isopropylimidazole and 2-ethyl-4-methylimidazole.
Further, the solvent is any one of tetrahydrofuran, N-dimethylformamide, dichloromethane, toluene or acetone.
Further, the solvent, the diisocyanate and the polyether polyol are dried, and any one of drying, namely drying by using a 4A molecular sieve, adding anhydrous magnesium sulfate and anhydrous calcium chloride, drying and vacuum dehydrating is adopted for drying.
Further, the molar ratio of the diisocyanate, the polyether polyol and the imidazole is 1:1: 1-1.2.
Further, the catalyst was dibutyltin dilaurate.
Further, the silver powder is one of silver particles, silver nanosheets and silver nanowires.
The toughened resin-based conductive silver paste is prepared based on the preparation method of the toughened resin-based conductive silver paste.
The invention has the beneficial effects that:
1. the preparation method of the toughened resin-based conductive silver paste disclosed by the invention has higher curing activity and better room-temperature storage stability. The toughened epoxy resin-based conductive silver paste overcomes the contradiction between the storage period and the curing activity of the traditional conductive silver paste, greatly improves the storage period of the conductive silver paste at room temperature, can regulate and control the curing temperature between 90 ℃ and 130 ℃, obviously improves the mechanical property of a cured product, and is suitable for the fields of intelligent displays, 5G communication, chip research and development and the like.
2. In the preparation method of the toughened resin-based conductive silver paste disclosed by the invention, the compatibility of the urethane modified imidazole and the epoxy resin is better, and the obtained conductive silver paste has more stable performance and good operability and manufacturability. Good storage performance and high curing activity. H on N at the 1 position of the imidazole ring is replaced, and the reactivity is lost at room temperature. Meanwhile, the electron-withdrawing effect of-CONH-in the polyurethane prepolymer and the steric effect of a long alkyl chain in the polyether polyol can reduce the ring-opening capability of the 3-N to the epoxy resin. the-NCO group in the polyurethane prepolymer generated by deblocking the EMI end-capped polyurethane prepolymer reacts with-OH in the epoxy resin to graft the polyether flexible long chain into an epoxy curing system, so that the movement capability of the chain segment is increased, and the toughening effect is achieved. The raw materials are all marketized products, the synthesis process is simple, and the mass production is easy to realize.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims thereof.
Drawings
For a better understanding of the objects, aspects and advantages of the present invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a mechanism diagram of the preparation method of the toughened resin-based conductive silver paste of the present invention;
FIG. 2 is a graph of experimental data on viscosity of toughened epoxy resins prepared in examples 1-3 and comparative example;
FIG. 3 is a graph illustrating the viscosity effect of toughened epoxy resins prepared in example 3 and comparative examples;
FIG. 4 is a DSC chart of the toughened epoxy resin prepared in example 1 measured at different temperature rising rates;
FIG. 5 is a DSC chart of the toughened epoxy resin prepared in example 2 measured at different temperature rising rates;
FIG. 6 is a DSC chart of different temperature rise rate tests of the toughened epoxy resin prepared in example 3;
FIG. 7 is a DSC chart of the toughened epoxy resin prepared by the comparative example obtained by different temperature rising speed tests;
FIG. 8 is a graph showing the initial temperature changes of the toughened epoxy resins prepared in examples 1 to 3 and comparative example at different heating rates;
FIG. 9 is a graph showing the peak temperature changes of the toughened epoxy resins prepared in examples 1 to 3 and comparative example at different heating rates;
FIG. 10 is a graph comparing the mechanical properties of toughened epoxy resins prepared in examples 1-3 and comparative examples;
FIG. 11 is a coating and curing diagram of toughened epoxy resin-based conductive silver paste prepared in examples 1 to 3 and a comparative example;
fig. 12 is an adhesion diagram of a toughened epoxy based conductive silver paste prepared in example 1 and comparative example.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Wherein the showings are for the purpose of illustrating the invention only and not for the purpose of limiting the same, and in which there is shown by way of illustration only and not in the drawings in which there is no intention to limit the invention thereto; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if there is an orientation or positional relationship indicated by terms such as "upper", "lower", "left", "right", "front", "rear", etc., based on the orientation or positional relationship shown in the drawings, it is only for convenience of description and simplification of description, but it is not an indication or suggestion that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes, and are not to be construed as limiting the present invention, and the specific meaning of the terms may be understood by those skilled in the art according to specific situations.
Example 1
Preparation of PPG-400/EMI toughening resin base conductive silver paste
The preparation method of the PPG-400/EMI toughening resin-based conductive silver paste comprises the following steps:
s1, adding 100ml of 0.5mol/L toluene diisocyanate solution and a proper amount of phosphoric acid into a three-neck flask with a mechanical stirrer, a thermometer, a condenser and a nitrogen inlet, sequentially dropwise adding 0.25mol of polypropylene glycol-400 and dibutyltin dilaurate into the toluene diisocyanate solution diluted by a tetrahydrofuran solvent under the dry nitrogen protection atmosphere, and after dropwise adding, mechanically stirring and reacting at 45-50 ℃ for 1h to obtain a blocked isocyanate-based prepolymer; dripping 0.55mol of sealing agent 2-ethyl-4-methylimidazole (2,4-EMI imidazole) diluted by tetrahydrofuran solvent at the temperature of 60 ℃ in the protective atmosphere of dry nitrogen, and reacting for 2 hours at the temperature to obtain a 2,4-EMI imidazole end-capped polyurethane prepolymer; wherein the tetrahydrofuran solvent is tetrahydrofuran which is dehydrated by a 4A molecular sieve.
S2, mixing the 2,4-EMI imidazole end-capping polyurethane prepolymer prepared in the step S1 with epoxy resin according to the mass ratio of 10: 100 is placed in epoxy resin for mechanical stirring for 15min and is subjected to ultrasonic treatment for 1h, and then the epoxy resin is placed in a drying oven at the temperature of 60 ℃ for multiple times of vacuum pumping and bubble removal to obtain a uniform toughened latent epoxy resin matrix for latency test, curing behavior test, cured product mechanical property test and Dynamic Mechanical Analysis (DMA) test;
and S3, uniformly mixing the toughened latent epoxy resin prepared in the step S2, silver nanowires, a silane coupling agent and a catalyst in a ratio of 63:3:0.5 by using a three-roll machine until metal luster appears, and thus obtaining the PPG-400/EMI toughened resin-based conductive silver paste.
Example 2
Preparation of PPG-1000/EMI toughened resin-based conductive silver paste
The preparation method of the PPG-1000/EMI toughening resin-based conductive silver paste comprises the following steps:
s1, adding 100ml of 0.5mol/L toluene diisocyanate solution and a proper amount of phosphoric acid into a three-neck flask provided with a mechanical stirrer, a thermometer, a condenser and a nitrogen inlet, sequentially dropwise adding 0.25mol of polypropylene glycol-1000 and dibutyltin dilaurate into the toluene diisocyanate solution diluted by a tetrahydrofuran solvent under the dry nitrogen protection atmosphere, and after dropwise adding, mechanically stirring and reacting at 45-50 ℃ for 1h to obtain an end-capped isocyanate prepolymer; dripping 0.55mol of sealing agent 2-ethyl-4-methylimidazole (2,4-EMI imidazole) diluted by tetrahydrofuran solvent at the temperature of 60 ℃ in the protective atmosphere of dry nitrogen, and reacting for 2 hours at the temperature to obtain a 2,4-EMI imidazole end-capped polyurethane prepolymer; wherein the tetrahydrofuran solvent is tetrahydrofuran which is dehydrated by a 4A molecular sieve.
S2, mixing the 2,4-EMI imidazole end-capping polyurethane prepolymer prepared in the step S1 with epoxy resin according to the mass ratio of 10: 100 is placed in epoxy resin for mechanical stirring for 15min and is subjected to ultrasonic treatment for 1h, and then the epoxy resin is placed in a drying oven at the temperature of 60 ℃ for multiple times of vacuum pumping and bubble removal to obtain a uniform toughened latent epoxy resin matrix for latency test, curing behavior test, cured product mechanical property test and Dynamic Mechanical Analysis (DMA) test;
s3, uniformly mixing the toughened latent epoxy resin prepared in the step S2 with silver nanowires, a silane coupling agent and a catalyst in a ratio of 63:3:0.5 through a three-roll machine until metal luster appears, and obtaining the PPG-1000/EMI toughened resin-based conductive silver paste.
Example 3
Preparation of PPG-2000/EMI toughened resin-based conductive silver paste
The preparation method of the PPG-2000/EMI toughening resin-based conductive silver paste comprises the following steps:
s1, adding 100ml of 0.5mol/L toluene diisocyanate solution and a proper amount of phosphoric acid into a three-neck flask provided with a mechanical stirrer, a thermometer, a condenser and a nitrogen inlet, sequentially dropwise adding 0.25mol of polypropylene glycol-2000 and dibutyltin dilaurate into the toluene diisocyanate solution diluted by a tetrahydrofuran solvent under the dry nitrogen protection atmosphere, and after dropwise adding, mechanically stirring and reacting at 45-50 ℃ for 1h to obtain an end-capped isocyanate prepolymer; dripping 0.55mol of sealing agent 2-ethyl-4-methylimidazole (2,4-EMI imidazole) diluted by tetrahydrofuran solvent at the temperature of 60 ℃ in the protective atmosphere of dry nitrogen, and reacting for 2 hours at the temperature to obtain 2,4-EMI imidazole end-capped polyurethane prepolymer; wherein the tetrahydrofuran solvent is tetrahydrofuran which is dehydrated by a 4A molecular sieve.
S2, mixing the 2,4-EMI imidazole end-capping polyurethane prepolymer prepared in the step S1 with epoxy resin according to the mass ratio of 10: 100 is placed in epoxy resin for mechanical stirring for 15min and is subjected to ultrasonic treatment for 1h, and then the epoxy resin is placed in a drying oven at the temperature of 60 ℃ for multiple times of vacuum pumping and bubble removal to obtain a uniform toughened latent epoxy resin matrix for latency test, curing behavior test, cured product mechanical property test and Dynamic Mechanical Analysis (DMA) test;
s3, uniformly mixing the toughened latent epoxy resin prepared in the step S2 with silver nanowires, a silane coupling agent and a catalyst in a ratio of 63:3:0.5 through a three-roll machine until metal luster appears, and obtaining the PPG-1000/EMI toughened resin-based conductive silver paste.
Comparative example
Preparation of 2,4-EMI conductive silver paste
The preparation method of the 2,4-EMI conductive silver paste comprises the following steps:
s1, mixing 2,4-EMI imidazole and epoxy resin according to the mass ratio of 10: 100 is placed in epoxy resin for mechanical stirring for 15min, ultrasonic treatment is carried out for 1h, the epoxy resin is placed in a drying oven at 60 ℃ for multiple times, vacuum pumping is carried out to remove bubbles, and the uniform toughened epoxy resin matrix is obtained to be subjected to latency test, curing behavior test, cured product mechanical property test and Dynamic Mechanical Analysis (DMA) test;
s3, uniformly mixing the toughened epoxy resin prepared in the step S2, the silver nanowires, the silane coupling agent and the catalyst according to the proportion of 63:3:0.5 by using a three-roll machine until metal luster appears, and obtaining the 2,4-EMI conductive silver paste.
Latency test
The toughened latent epoxy resin matrix prepared in the step S2 in the embodiments 1 to 3 is placed at 25 ℃ to observe the change of the system viscosity, the latent period is examined, the latent period test is carried out, the test result is shown in the figures 2 to 3, and compared with the comparative example, the latent period of the embodiments 1 to 3 is greatly improved, and is increased from 2 days to 82 days.
Curing behavior test results
The toughened latent epoxy resin matrix prepared in step S2 of examples 1 to 4 was tested for initial temperature, peak temperature, and end temperature using a DSC thermal analysis tester, with a test temperature range of 25 to 300 ℃, a temperature rise rate of 5 ℃/min, 10 ℃/min, 15 ℃/min, 20 ℃/min, and a DSC curve obtained by testing in a nitrogen atmosphere, as shown in fig. 4 to 7. The initial temperature, the peak temperature and the termination temperature of the polyurethane modified imidazole cured epoxy resin are all improved, and the test results are shown in figures 8-9. This shows that polyurethane modified imidazole and epoxy resin have good latency and high activity at room temperature, and the curing temperature can be controlled between 90 ℃ and 130 ℃.
Mechanical property test of cured product
The mechanical property test method of the condensate comprises the following steps: the one-component system obtained in example 5 was poured into a polytetrafluoroethylene mold and cured at 110 ℃ for 2 h. The cured mechanical properties were measured at room temperature using a universal tester and an impact tester, each sample was tested in parallel 5 times, and the tensile strength, elastic modulus, elongation at break and impact strength of the epoxy resin were all improved by averaging the results, as shown in fig. 10. The impact strength of the modified imidazole/E-51 single-component system cured material is measured by an impact tester, the sample is tested according to GB/T1043-93, the result is shown in figure 10, compared with the comparative example, the elongation at break of the examples 1-3 is increased by 5 times, and the impact strength is up to 10.02kJ/m 2 Increased to 16.11kJ/m 2 Thus showing that the toughening latent curing agent achieves the toughening effect.
Dynamic Mechanical Analysis (DMA) testing
The thermo-mechanical properties of the pure epoxy resin and the cured product of the modified imidazole/E-51 single-component system are tested by a dynamic thermo-mechanical analyzer. The test conditions are three-point bending mode, the heating rate is 3 ℃/min, the frequency is 1Hz, the heating interval is 0-300 ℃, and the result is shown in figure 10.
The toughened resin-based conductive silver paste prepared in the above examples 1 to 4 was coated on a PET film and a PC board, and cured at 110 ℃ for 2 hours, and the cured product was shown in fig. 11. And testing the sheet resistance of the toughened epoxy conductive silver paste cured film by using a four-probe sheet resistance tester. The adhesion of the conductive silver paste was tested by the scribing test according to ISO 2409 standard. The sample was cut out with a knife edge to form intersecting grid lines, and the grid was attached with a 3M tape and peeled off, and the adhesion of the sample was evaluated by the peeling of the grid as shown in fig. 12. The abrasion resistance of the RCA paper tape is tested by using an abrasion resistant machine. The results are shown in Table 1.
TABLE 1
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (8)
1. The preparation method of the toughened resin-based conductive silver paste is characterized by comprising the following steps:
s1, preparing an imidazole-terminated polyurethane prepolymer: dripping phosphoric acid, a catalyst and polyether polyol into solvent-diluted diisocyanate in batches under a dry protective atmosphere, and reacting for 1-2 h at 40-50 ℃; after the reaction is finished, dripping imidazole diluted by a solvent into the reaction liquid at the temperature of 60-70 ℃, and reacting for 2-3 h to prepare an imidazole-terminated polyurethane prepolymer;
s2, preparing toughened latent epoxy resin: uniformly mixing the imidazole-terminated polyurethane prepolymer obtained in the step S1 with epoxy resin according to the proportion of 5-12.5 wt%;
s3, toughening epoxy resin-based conductive silver paste: uniformly mixing the toughened latent epoxy resin, the silver powder, the silane coupling agent and the catalyst in the step S2 by a three-roll machine according to the proportion of 63-65: 3-3.5: 0.5-0.7 until metal luster appears, and reacting epoxy resin-based conductive silver paste at 90-130 ℃ for 2 hours to obtain toughened resin-based conductive silver paste; the blocked polyurethane prepolymer is deblocked in the heating process to generate imidazole and the polyurethane prepolymer, the imidazole is used as a curing agent to perform a crosslinking reaction with epoxy resin, a-NCO group in the polyurethane prepolymer reacts with-OH in the epoxy resin to graft a polyether flexible long chain into an epoxy curing system, the movement capacity of a chain segment is increased, the toughening effect is achieved, and the toughened epoxy resin-based conductive silver paste with good mechanical properties is prepared.
2. The preparation method of the toughened resin-based conductive silver paste according to claim 1, wherein the step S1 comprises the following steps:
s11, sequentially dripping polyether polyol and a catalyst into a tetrahydrofuran-diluted diisocyanate solution under the protection of dry nitrogen; reacting for 1-2 h at 45-50 ℃ to obtain a blocked isocyanate-based prepolymer;
s12, under the protection atmosphere of dry nitrogen, the molar ratio n (imidazole): and (3) adding a sealing agent imidazole diluted by slightly excessive tetrahydrofuran into n (diisocyanate) of 1-1.2: 1, supplementing a catalyst, controlling the temperature at 60-70 ℃, and reacting for 2-3 hours to obtain the imidazole-terminated polyurethane prepolymer.
3. The method for preparing the toughened resin-based conductive silver paste according to claim 1, wherein the diisocyanate is one or more of toluene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate.
4. The method for preparing the toughening resin-based conductive silver paste of claim 1, wherein the polyether polyol is one or a mixture of polypropylene glycol and polyethylene glycol with different molecular weights.
5. The method for preparing the toughening resin-based conductive silver paste of claim 1, wherein the imidazole is one or a mixture of 2-methylimidazole, 2-ethylimidazole, 4-nitroimidazole, 2-methyl-5-nitroimidazole, 2-phenyl-imidazole, 2-isopropylimidazole and 2-ethyl-4-methylimidazole.
6. The preparation method of the toughening resin-based conductive silver paste of claim 2, wherein the molar ratio of the diisocyanate, the polyether polyol and the imidazole is 1:1: 1-1.2.
7. The method for preparing the toughening resin-based conductive silver paste of claim 1, wherein the silver powder is one of silver particles, silver nanosheets and silver nanowires.
8. The toughened resin-based conductive silver paste prepared by the preparation method of the toughened resin-based conductive silver paste according to any one of claims 1 to 7.
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