CN102399523B - Nano-grade-silver-filled room-temperature-cured conductive adhesive - Google Patents
Nano-grade-silver-filled room-temperature-cured conductive adhesive Download PDFInfo
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Abstract
The invention provides a nano-grade-silver-filled room-temperature-cured conductive adhesive. A preparation method of the conductive adhesive comprises steps that: (a) silver nitrate or silver acetate powder is mixed with a polyvinyl pyrrolidone (PVP) dispersing agent; the mixture is added to an ethylene glycol solution, such that a solution reaction system containing silver ions is prepared; (b) sodium chloride is added to the solution reaction system containing silver ions; the mixture is well mixed by stirring, such that a reaction precursor is prepared; (c) the obtained reaction precursor is irradiated by using microwaves, such that a mixed solution containing silver nanowires is obtained; water or ethanol is added to the mixed solution, and the mixture is subject to high-speed centrifugation drying, such that silver nanowire powder is obtained; (d) the silver nanowire powder is added to epoxy resin, and the mixture is well mixed by stirring; a curing agent is added to the obtained mixed colloid, and the mixture is mixed, such that a finished product is obtained. The conductive adhesive provided by the invention has better properties than a conductive adhesive filled with pure sheet-shaped silver powder. The conductive adhesive provided by the invention is advantaged in high conductivity, high shear strength, high impact strength, and the like. The conductive adhesive provided by the invention can be widely applied in the field of electronic packaging requiring low-temperature conductive connections.
Description
Technical field
The present invention relates to electronic package material preparing technical field, refer in particular to a kind of nano-grade-silver-filled room-temperature-cured conductive adhesive.
Background technology
Along with electronic product is to the development of miniaturization, portability, and Pb/Sn scolder connects temperature high (230 ℃), and thermal stresses is large, and Pb has the shortcomings such as severe toxicity constantly to manifest, in the urgent need to connecting material and the method for development of new.Conductive resin because of its coating process simple, the advantage such as solidification value is low, started to substitute Pb/Sn scolder, and its demand grows with each passing day.
Conductive resin be a kind of solidify or dry after there is the sizing agent of certain conductivity, it take matrix resin and conductive filler material is conventionally that conducting particles is chief component composition, bonding effect by matrix resin combines conducting particles, form conductive path, realize by the conduction of sticky material and connecting. because the body material of conductive resin is resin and solidifying agent, its mixture is a kind of sizing agent, by the selection of matrix resin and solidifying agent type, can select suitable solidification value to carry out bonding, simultaneously, miniaturization due to electronic component, developing rapidly of the densification of microminiaturization and printed circuit board (PCB) and Highgrade integration, and conductive resin can be made slurry, realize very high linear resolution. and conductive resin technique is simple, easy handling, can enhance productivity, so conductive resin is to substitute slicker solder welding, realize the ideal chose that conduction connects.At present today of electronics industry high speed development, conductive resin has been widely used in each large industries such as LED encapsulation, IC encapsulation.
Conductive resin can be divided into self-vulcanizing, intermediate temperature setting (150 ℃ of <) and hot setting (150～300 ℃) three classes by solidification value.Intermediate temperature setting, hot setting conductive resin need Baking out in solidification process, yet, in real life, the material of some large-sizes, be subject to the restriction of workpiece size, cannot realize workpiece and toast in baking oven, or matrix material can not stand the restriction of the factors such as high bake, this is restricted conductive resin application in a lot of fields.The key of problem is to make heat-resisting electro-conductive adhesive to realize self-vulcanizing.So-called self-vulcanizing, be exactly by under room temperature for after liquid epoxy resin and curing agent component hybrid modulation, can be under room temperature condition certain hour inner gel, and be no more than the curing that solidifies and reach usable intensity in time of seven days completely.The electro-conductive adhesive of self-vulcanizing have in use save time, laborsaving, saving of labor, the saving energy, the series of advantages such as easy to use, not only can reduce electro-conductive adhesive cost, and can simplify the course of processing, be specially adapted to the bonding of the high temperature maintenance of large-size components and shrink-down material.Therefore, the heat-resisting electro-conductive adhesive of development ambient temperature curable just becomes one of important development direction of epoxy adhesive.
In the conductive resin of application, be mainly to adopt micro-silver powder and flake silver powder as filler at present, and the content of conductive filler material generally all to surpass and more than 75% just can have the sudden change of specific conductivity.And along with the increase of conductive filler material content, the viscosity of conductive resin can obviously increase, impact is used, simultaneously its mechanical property generally all can weaken, thus develop there is high electric conductivity simultaneously, suitable viscosity and the high-performance room-temperature Curing conductive adhesive with high shear strength and resistance to impact shock have wide market application foreground.
Patent ZL 200610154638.6 adopts filling nano silver wire and Nano silver grain mixing material to prepare conductive resin, really when reducing silver powder loading level, also improved the mechanical property of conductive resin, yet the silver nano material technology of preparing adopting has seriously restricted the scale operation of high-performance conducting resin.Simultaneously, another patent (publication number: CN 101310899A) disclose a method of utilizing microwave method to prepare on a large scale nano silver wire, but every liter of ethylene glycol can reduce the Ag nano wire of preparation also only only has 1.7～8.5g, can not meet the requirement of suitability for industrialized production far away.In addition, the conductive resin that above patent is developed all need to toast under more than 100 ℃ hot conditionss, cannot meet the demand of present low-temperature curing.
The present invention combines conductive resin under the low filling ratio condition of nano-silver thread and just has advantages of satisfactory electrical conductivity, a kind of nano-grade-silver-filled room-temperature-cured conductive adhesive is disclosed, overcome whole employing micro-silver powders and filled the shortcoming that viscosity is high, mechanical property weakens that high fill-ratio brings, overcome the deficiency that intermediate temperature setting and hot setting type conductive resin need to toast simultaneously.The present invention has adopted Microwave-assisted Reduction legal system for nano silver wire, has greatly shortened the preparation time of nano silver wire; The conductive resin that conductive filler material using the nano silver wire of preparation in self-vulcanizing conductive resin prepares, the conductive resin that flake silver powder than with pure is filled has more excellent performance, comprise the features such as high conductivity, high shear strength, high impact strength, can widespread use with need to realize the application of low-temperature conductive interconnection Electronic Packaging.
Summary of the invention
The object of the invention is to avoid the deficiencies in the prior art and a kind of room temperature curing type nanometer silver filled conductive glue is provided, overcome whole employing micro-silver powders and filled the shortcoming that viscosity is high, mechanical property weakens that high fill-ratios bring, realized the feature of the self-vulcanizing that hot setting type conductive resin cannot realize simultaneously.Object of the present invention realizes by following steps:
A), by Silver Nitrate or Silver monoacetate powder and polyvinylpyrrolidone (PVP) dispersant and join in ethylene glycol solution, prepare the solution reaction system of silver ion;
B) in the solution reaction system that contains silver ions to this, add sodium-chlor, stir, obtain reacting precursor;
C) adopt the method for microwave exposure, resulting reaction precursor irradiation under microwave is obtained to the mixing liquid containing nano silver wire, in this mixing liquid, add water or ethanol high speed centrifugation, obtain nano-silver thread throw out, after being dried, obtain nano silver wire powder;
D) prepared nano silver wire powder is added in epoxy resin and stirred, after mixing, to adding solidifying agent in this colloid mixture, mix again, just obtain nano-grade-silver-filled room-temperature-cured conductive adhesive.
Preferably, self-vulcanizing agent used is modified amine self-vulcanizing agent, and amine value is 92-392mgKOH/g.
Preferably, described steps d) also comprise, in colloid mixture, add silane coupling agent, oxidation inhibitor, protective agent and mix.
Preferably, the ratio of quality and the number of copies of nano silver wire powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent is: silver powder: 60-82; Epoxy resin: 10-20; Self-vulcanizing agent: 5-16; Silane coupling agent: 1-3; Antioxidant: 1-2; Antiaging agent: 1-2.
By above technical scheme, the beneficial effect that the present invention has is:
1) this nano-grade-silver-filled room-temperature-cured conductive adhesive can solidify under the envrionment conditions of <50 ℃, has excellent electroconductibility simultaneously.
2) in prepared conductive resin, silver-colored loading level reduces, and in the time of cost reduction, mechanical property improves.
Accompanying drawing explanation
The stereoscan photograph of the nano silver wire of Fig. 1 embodiment 1 preparation;
The stereoscan photograph of the nano silver wire of Fig. 2 embodiment 2 preparations;
The stereoscan photograph of the nano silver wire of Fig. 3 embodiment 3 preparations;
The XRD of the nano silver wire of Fig. 4 embodiment 3 preparations characterizes;
Fig. 5
the conductive adhesive performance comparison sheet 1 of embodiment 1～embodiment 6;
the conductive adhesive performance comparison sheet 2 of Fig. 6 embodiment 7～embodiment 13.
Embodiment
The invention discloses a kind of nano-grade-silver-filled room-temperature-cured conductive adhesive, belong to electronic package material preparing technical field.The present invention combines conductive resin under the low filling ratio condition of nano-silver thread and just has advantages of satisfactory electrical conductivity, a kind of nano-grade-silver-filled room-temperature-cured conductive adhesive is disclosed, overcome whole employing micro-silver powders and filled the shortcoming that viscosity is high, mechanical property weakens that high fill-ratio brings, overcome the deficiency that intermediate temperature setting and hot setting type conductive resin need to toast simultaneously.The present invention has adopted Microwave-assisted Reduction legal system for nano silver wire, has greatly shortened the preparation time of nano silver wire; The conductive resin that conductive filler material using the nano silver wire of preparation in self-vulcanizing conductive resin prepares, the conductive resin that flake silver powder than with pure is filled has more excellent performance, comprise the features such as high conductivity, high shear strength, high impact strength, can widespread use with need to realize the application of low-temperature conductive interconnection Electronic Packaging.
In the present invention, the mass ratio of Silver Nitrate or Silver monoacetate powder and polyvinylpyrrolidone (PVP) dispersion agent is: 1:3 to 1:1, the ratio of the quality of Silver Nitrate or Silver monoacetate powder and polyvinylpyrrolidone (PVP) dispersant powder quality and ethylene glycol is 1:25 ~ 1:100.
To add the ratio of Silver Nitrate quality in the quality of sodium-chlor and solution be 1:1000～1:100.
In described step c), microwave exposure power used is 320W～480W, and irradiation time is 6～20 minutes.
Step c) gained silver nanoparticle powder is nano silver wire, and the wire diameter of gained nano silver wire material is between 92nm～280nm, and length-to-diameter ratio surpasses 20.
Steps d) oxirane value of epoxy resin used is 0.4-0.8.
Steps d) solidifying agent used is modified amine curing agent, and amine value is 92-392mgKOH/g.
In step d), the ratio of quality and the number of copies of the formula of silver nanoparticle powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent is: silver powder: 60-82; Epoxy resin: 10-20; Solidifying agent: 5-16; Silane coupling agent: 1-3; Antioxidant: 1-2; Antiaging agent: 1-2.
The conductive resin of prior art, is often difficult to obtain preferably solidification effect in 24 hours.The present invention has adopted existing solidifying agent as a comparison simultaneously: comprise that acid anhydrides, Dyhard RU 100, hydrazides and modified amine curing agent are as aliphatic polyamine, alicyclic polyamine etc.
Found through experiments, modified amine curing agent solidification effect is best, itself and dihydroxyphenyl propane based epoxy resin or bisphenol f type epoxy resin can be realized cured article conduction and have good mechanical property simultaneously in 24 hours, and at room temperature solidify 24 hours after fixing things as acid anhydrides, Dyhard RU 100 etc., there are some in gel state, although there are some to solidify, can not conduct electricity.
Therefore, it is the modified amine curing agent of 92-392mgKOH/g that the present invention adopts amine value, below by specific embodiment, sets forth:
Embodiment 1:
1:1 mixes 10g Silver Nitrate to add in the beaker that fills 500g ethylene glycol with 10g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 100mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 20min.After reaction, add water in solution, adopt after the centrifugal 20min of 2000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.Sem test sample is that sample is sticked in aluminium base sample table, and Fig. 1 has provided according to embodiment 1 and obtained nano silver wire SEM photo, and this nano wire wire diameter is 100nm left and right, and length-to-diameter ratio surpasses 100; By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 75, epoxy resin E44:11, amine value is the room temperature modified amine curing agent of 392mgKOH/g: 10, silane coupling agent: 2, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 1.
It is 13 that the employing acid anhydride type curing agent conductive resin of take at room temperature needs set time, the shearing resistance of 10-48 hour, nano silver wire content is 85 percent to compare, the conductive resin that the present embodiment obtains only needs 5 hours, just can reach common conductive resin and at least need 10 hours above solidification effects, greatly shorten set time, and shearing resistance reaches 15.12, the content of nano silver wire only needs 75 percent, and silver conductive adhesive more in the past has probably been saved 10 cost.
Embodiment 2:
1:3 mixes 20g Silver monoacetate to add in the beaker that fills 400g ethylene glycol with 60g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 60mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 400W, 18min.After reaction, add water in solution, adopt after the centrifugal 10min of 3000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.Sem test sample is that sample is sticked in aluminium base sample table, and Fig. 2 has provided the nano silver wire SEM photo obtaining according to embodiment 2; The wire diameter of this nano wire is 280nm, and length-to-diameter ratio surpasses 20, by prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, is
Nano silver wire powder: 78, epoxy resin E51:12, amine value is the room temperature modified amine curing agent of 260mgKOH/g: 6, silane coupling agent: 1, antioxidant: 1, protective agent: after 2 weighings are good, nano-silver thread powder added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 1.
To adopt acid anhydride type curing agent conductive resin at room temperature to need set time, the shearing resistance of 10-48 hour to be less than 13MPa, nano silver wire content is 85 percent to compare, the conductive resin that the present embodiment obtains only needs 5 hours, just can reach common conductive resin and at least need 10 hours above solidification effects, greatly shorten set time, and shearing resistance reaches 15.54, the content of nano silver wire only needs 78 percent, and silver conductive adhesive more in the past has probably been saved 7 percent cost.
Embodiment 3:
1:1 mixes 15g Silver Nitrate to add in the beaker that fills 500g ethylene glycol with 30g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 100mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 480W, 16min.After reaction, add water in solution, adopt after the centrifugal 20min of 2000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.Sem test sample is that sample is sticked in aluminium base sample table, and Fig. 3 has provided the nano silver wire SEM photo obtaining according to embodiment 3, and the wire diameter of this nano wire is 92nm, and length-to-diameter ratio surpasses 50; Figure tetra-is the XRD photo of nano silver wire material.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano silver wire powder: 72, epoxy resin E51:14, amine value is the room temperature modified amine curing agent of 92mgKOH/g: 8, silane coupling agent: 2, antioxidant: 2, protective agent: after 2 weighings are good, nano-silver thread powder added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 1.
It is 13 that the employing acid anhydride type curing agent conductive resin of take at room temperature needs set time, the shearing resistance of 10-48 hour, nano silver wire content is 85 percent to compare, the conductive resin that the present embodiment obtains only needs 3 hours, just can reach common conductive resin and at least need 10 hours above solidification effects, greatly shorten set time, and shearing resistance reaches 16.51, the content of nano silver wire only needs 72 percent, and silver conductive adhesive more in the past has probably been saved 1 13 cost.
Embodiment 4
1:1.5 mixes 1.0g Silver Nitrate to add in the beaker that fills 50g ethylene glycol with 1.5g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 100mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 6min.After reaction, add water in solution, adopt after the centrifugal 5min of 6000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 66, epoxy resin E51:20, amine value is the room temperature modified amine curing agent of 287mgKOH/g: 10, silane coupling agent: 2, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 1.
It is 13 that the employing acid anhydride type curing agent conductive resin of take at room temperature needs set time, the shearing resistance of 10-48 hour, nano silver wire content is 85 percent to compare, the conductive resin that the present embodiment obtains only needs 5 hours, just can reach common conductive resin and at least need 10 hours above solidification effects, greatly shorten set time, and shearing resistance reaches 18.32, the content of nano silver wire only needs 66 percent, and silver conductive adhesive more in the past has probably been saved nearly cost of 20 percent.
Embodiment 5
1:2 mixes 1g Silver Nitrate to add in the beaker that fills 200g ethylene glycol with 1g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 50mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 10min.After reaction, add water in solution, adopt after the centrifugal 12min of 3500rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 75, epoxy resin E-44: 14, amine value is the room temperature modified amine curing agent of 327mgKOH/g: 7, silane coupling agent: 2, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 1.
It is 13 that the employing acid anhydride type curing agent conductive resin of take at room temperature needs set time, the shearing resistance of 10-48 hour, nano silver wire content is 85 percent to compare, the conductive resin that the present embodiment obtains only needs 3 hours, just can reach common conductive resin and at least need 10 hours above solidification effects, greatly shorten set time, and shearing resistance reaches 13.86, the content of nano silver wire only needs 75 percent, and silver conductive adhesive more in the past has probably been saved 10 cost.
Embodiment 6
1:2.5 mixes 10g Silver monoacetate to add in the beaker that fills 500g ethylene glycol with 25g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 10mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 400W, 20min.After reaction, add water in solution, adopt after the centrifugal 10min of 4000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 75, epoxy resin E-44: 13, amine value is the room temperature modified amine curing agent of 231mgKOH/g: 7, silane coupling agent: 3, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 1.
It is 13 that the employing acid anhydride type curing agent conductive resin of take at room temperature needs set time, the shearing resistance of 10-48 hour, silver content is that content is 85 percent to compare, the conductive resin that the present embodiment obtains only needs 4 hours, just can reach common conductive resin and at least need 10 hours above solidification effects, greatly shorten set time, and shearing resistance reaches 14.2, the content of nano silver wire only needs 75 percent, and silver conductive adhesive more in the past has probably been saved 10 cost.
Embodiment 7
1:2 mixes 17g Silver Nitrate to add in the beaker that fills 550g ethylene glycol with 34g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 60mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 20min.After reaction, add water in solution, adopt after the centrifugal 20min of 2000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be nano-silver thread powder: 82, epoxy resin E-44: 10, amine value is the room temperature modified amine curing agent of 212mgKOH/g: 5, silane coupling agent: 1, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stirred, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.This conductive resin at room temperature solidifies and tests its electricity and mechanical property after 5 hours, and performance index are in Table 2.
Embodiment 8
1:1 mixes 10g Silver Nitrate to add in the beaker that fills 500g ethylene glycol with 10g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 100mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 20min.After reaction, add water in solution, adopt after the centrifugal 20min of 2000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 75, epoxy resin E-44: 11, amine value is the room temperature modified amine curing agent of 300mgKOH/g: 10, silane coupling agent: 2, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 2.
Embodiment 9:
1:1 mixes 10g Silver monoacetate to add in the beaker that fills 500g ethylene glycol with 10g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 100mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 20min.After reaction, add water in solution, adopt after the centrifugal 20min of 2000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 70, epoxy resin E51:15, amine value is the room temperature modified amine curing agent of 245mgKOH/g: 10, silane coupling agent: 2, antioxidant: 1, protective agent: after 2 weighings are good, nano-silver thread powder added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 2.
Embodiment 10:
1:1 mixes 18g Silver Nitrate to add in the beaker that fills 500g ethylene glycol with 18g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 20mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 400W, 15min.After reaction, add water in solution, adopt after the centrifugal 20min of 3000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 72, epoxy resin E-44: 16, amine value is the room temperature modified amine curing agent of 392mgKOH/g: 8, silane coupling agent: 2, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 2.
Embodiment 11:
1:1 mixes 10g Silver Nitrate to add in the beaker that fills 500g ethylene glycol with 10g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 10mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 20min.After reaction, add water in solution, adopt after the centrifugal 20min of 6000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 68, epoxy resin E51:18, amine value is the room temperature modified amine curing agent of 392mgKOH/g: 9, silane coupling agent: 2, antioxidant: 1, protective agent: 2., after weighing well, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 2.
Embodiment 12:
1:3 mixes 5g Silver Nitrate to add in the beaker that fills 200g ethylene glycol with 15g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 10mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 10min.After reaction, add water in solution, adopt after the centrifugal 20min of 4000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 79, epoxy resin E44:12, amine value is the room temperature modified amine curing agent of 392mgKOH/g: 6, silane coupling agent: 1, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 2.
Embodiment 13:
1:2 mixes 15g Silver Nitrate to add in the beaker that fills 500g ethylene glycol with 30g PVP in mass ratio, and ultrasonic agitation obtains homogeneous transparent solution; Prepare the solution reaction system of silver ion; In the solution reaction system that contains silver ions to this, add 60mg sodium-chlor, stir, obtain reacting precursor; To prepare suspension liquid and put into microwave oven, reaction conditions is: 320W, 20min.After reaction, add water in solution, adopt after the centrifugal 20min of 2000rpm rotating speed, be precipitated thing, and then with deionized water, dehydrated alcohol or acetone cleaning three to four times, through Air drying, obtain Solid Silver nano wire powder.By prepared silver powder and epoxy resin, solidifying agent, silane coupling agent, oxidation inhibitor, protective agent, according to parts by weight, be
Nano-silver thread powder: 60, epoxy resin E51:20, amine value is the room temperature modified amine curing agent of 292mgKOH/g: 16, silane coupling agent: 2, antioxidant: 1, protective agent: after 1 weighing is good, nano-silver thread powder is added in epoxy resin and stir, to adding solidifying agent, silane coupling agent, oxidation inhibitor, protective agent in colloid mixture, mix again, just obtain self-vulcanizing conductive silver glue.Its electricity of test and mechanical property after this conductive resin at room temperature solidifies, performance index are in Table 2.
For reaching illustration purpose; with preferred embodiments narration as above, so it is not in order to limit the present invention for this patent, and any affiliated technical field without departing from the spirit and scope of the present invention; when doing a little change and polishing, so protection scope of the present invention is when being limited with claims.
Claims (4)
1. a nano-grade-silver-filled room-temperature-cured conductive adhesive, is characterized in that described conductive resin making processes comprises the following steps:
A), by Silver Nitrate or Silver monoacetate powder and polyvinylpyrrolidone (PVP) dispersant and join in ethylene glycol solution, prepare the solution reaction system of silver ion;
B) in the solution reaction system that contains silver ions to this, add sodium-chlor, stir, obtain reacting precursor;
C) adopt the method for microwave exposure, resulting reaction precursor irradiation under microwave is obtained to the mixing liquid containing nano silver wire, in this mixing liquid, add water or ethanol, centrifugal after stirring, collection obtains nano silver wire, after being dried, obtains nano silver wire powder;
D) prepared nano silver wire powder is added in epoxy resin and is stirred, after mixing, in this colloid mixture, add room temperature solidifying agent and mix again, just obtain nano-grade-silver-filled room-temperature-cured conductive adhesive,
The oxirane value of epoxy resin used is 0.4-0.8;
Self-vulcanizing agent used is modified amine self-vulcanizing agent, and amine value is 92-392mgKOH/g;
Described steps d) also comprise, in colloid mixture, add silane coupling agent, oxidation inhibitor, protective agent and mix;
The ratio of quality and the number of copies of nano silver wire powder and epoxy resin, self-vulcanizing agent, silane coupling agent, oxidation inhibitor, protective agent is: nano silver wire powder: 60-82; Epoxy resin: 10-20; Self-vulcanizing agent: 5-16; Silane coupling agent: 1-3; Oxidation inhibitor: 1-2; Protective agent: 1-2.
2. according to a kind of nano-grade-silver-filled room-temperature-cured conductive adhesive claimed in claim 1, it is characterized in that described step a) comprises, after the Silver Nitrate of 100 weight parts or Silver monoacetate powder are mixed with the polyvinylpyrrolidone of 100～300 weight parts, the mixed powder obtaining is added in ethylene glycol, and the ratio of the quality of mixed powder quality and ethylene glycol is 1:100 ~ 1:5.
3. according to a kind of nano-grade-silver-filled room-temperature-cured conductive adhesive claimed in claim 1, it is characterized in that described step b) in, adding the ratio of Silver Nitrate in the quality of sodium-chlor and solution or Silver monoacetate powder quality is 1:1000～1:100.
4. according to a kind of nano-grade-silver-filled room-temperature-cured conductive adhesive claimed in claim 1, it is characterized in that described step c) wire diameter of gained nano silver wire material is between 92nm～350nm, and length-to-diameter ratio surpasses 20.
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| TWI500048B (en) * | 2013-12-30 | 2015-09-11 | Ind Tech Res Inst | Transparent conductive film composite and transparent conductive film |
| CN105419444A (en) * | 2015-12-23 | 2016-03-23 | 苏州创科微电子材料有限公司 | Nano silver wire electric-conductive glue and electroplating method |
| TWI595073B (en) * | 2016-01-28 | 2017-08-11 | 光洋應用材料科技股份有限公司 | Conductive Silver Adhesive And Conductive Silver Layer |
| CN105957967A (en) * | 2016-06-14 | 2016-09-21 | 国家纳米科学中心 | Preparation method of large-area flexible transparent conductive substrate |
| CN108822782A (en) * | 2018-05-02 | 2018-11-16 | 苏州耐思特塑胶有限公司 | A kind of conductive adhesive of good mechanical performance |
| CN108913071A (en) * | 2018-05-02 | 2018-11-30 | 苏州耐思特塑胶有限公司 | A kind of conductive adhesive of anti-aging stability |
| CN109581767A (en) * | 2019-01-16 | 2019-04-05 | 深圳市华星光电半导体显示技术有限公司 | Display module and display device |
| CN110791136A (en) * | 2019-09-25 | 2020-02-14 | 深圳市华科创智技术有限公司 | Silver nanowire coating solution and transparent conductive film |
| CN114181586B (en) * | 2021-11-26 | 2022-07-22 | 洛阳双瑞防腐工程技术有限公司 | Water-based epoxy static-conducting oil-resistant anticorrosive paint and preparation method thereof |
| CN114806476B (en) * | 2022-06-01 | 2023-09-01 | 山东大福粘合剂股份有限公司 | Epoxy resin conductive adhesive containing composite conductive filler and preparation method thereof |
| CN116573899B (en) * | 2023-07-11 | 2023-10-20 | 佛山市亿达胶粘制品有限公司 | Modified terpene resin water-based adhesive and preparation method and application thereof |
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| CN101942287A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Low-temperature electricity conducting glue and preparation method thereof |
| CN102029400A (en) * | 2010-11-25 | 2011-04-27 | 浙江科创新材料科技有限公司 | Method for preparing silver nanometer wire with controllable wire diameter by cation control microwave method |
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| CN101942287A (en) * | 2010-09-27 | 2011-01-12 | 彩虹集团公司 | Low-temperature electricity conducting glue and preparation method thereof |
| CN102029400A (en) * | 2010-11-25 | 2011-04-27 | 浙江科创新材料科技有限公司 | Method for preparing silver nanometer wire with controllable wire diameter by cation control microwave method |
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