CN106811170A - A kind of polymer-based in-situ nano silver electrically conductive binding material and preparation method - Google Patents
A kind of polymer-based in-situ nano silver electrically conductive binding material and preparation method Download PDFInfo
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- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
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Abstract
The present invention relates to a kind of polymer-based in-situ nano silver electrically conductive binding material and preparation method, a kind of electrically conductive binding material of the macromolecule matrix of in-situ preparation nano-Ag particles of invention includes macromolecule matrix resin, conducting metal particles and the silver nitrate and reducing agent for in-situ preparation Nano Silver.Percentage by weight of the conducting metal particles in electrically conductive binding material is 5 90%；The percentage by weight of silver nitrate and reducing agent in electrically conductive binding material is less than or equal to 10%.Its advantage is：Selected by silver nitrate and reducing material and its content, allow electrically conductive binding material in the starting stage in-situ preparation nano-Ag particles of elevated cure, Nano Silver has surface energy higher, can be melted before macromolecule matrix is fully cured, and be connected to form good conductive path with other metal packings infiltration, so that the conductance of the electrically conductive binding material after solidification lifts 2 ~ 10 times.
Description
Technical field
The present invention relates to polymer-based electrically conductive binding material field, more particularly to a kind of polymer-based in-situ nano silver is conductive
Adhesives and preparation method.
Background technology
Electrically conductive binding material is provided simultaneously with bonding and electric conductivity, application can meet electronics in less boundary of works area
Thin layer and precise treatment the requirement of industry, and room temperature or low-temperature setting, therefore electrically conductive binding material can be realized in electronics industry
Field has obtained quick development in recent years as the substitute of soldering process.Electrically conductive binding material is broadly divided into two classes：One class
It is slug type electrically conductive binding material；Another kind of is polymer-based electrically conductive binding material.Wherein slug type electrically conductive binding material be with
The inorganic conductive material such as conductive glass powder or conductive oxide for bonding at a temperature of higher than 500 DEG C sinter realize bonding with
It is conductive.Slug type electrically conductive binding material can only use dispensing, silk-screen printing or spraying etc. due to needing high temperature in implementation process
Method is implemented, and it is severely limited in the range of application of electronic technology.
Polymer-based electrically conductive binding material is mainly with high molecular polymer as matrix, adds various types of conduction
Metal powder realizes its electric conductivity for filler.Because the use environment of polymer-based electrically conductive binding material is different, it is also possible in matrix
The auxiliary agent such as middle addition catalyst, coupling agent and toughener make it possess as rapid curing, cold curing, low-temperature setting, low viscosity,
High viscosity simultaneously has the operational characteristiies such as adhesive strength higher simultaneously.Conventional conductive metal powder mainly has bronze, silver powder at present
With copper powder etc., wherein the polymer-based electrically conductive binding material with bronze as filler possess excellent combination property in itself because of bronze therefore
It neutralizes performance preferably, but bronze is expensive, high as conductive filler cost with bronze, is normally only used for space shuttle etc.
Particular component；Silver powder takes second place, but the silver powder same price is higher and can be produced " migration " under hot and humid environment, and its application is received
To certain limitation.Copper powder due to with the close electric conductivity of silver and price is low, commercially have certain applications, but its shortcoming
It is that copper powder is easily aoxidized under high temperature, makes its electric conductivity unstable, therefore market progressively occurs in that silver-coated copper powder for macromolecule
Base electrically conductive binding material.
The electrical conduction mechanism of polymer-based electrically conductive binding material is construed generically as seepage theory, tunnel-effect theory and field extremely
Transmitting is theoretical, i.e., conductive material forms being uniformly distributed spatially in macromolecule matrix, when conductive material content is more, filler grain
Contact with each other to form conductive channel between son, when conductive filler content is few, filler internal electron is made in thermal vibration or internal electric field
Electric current is formed with lower generation particle migration.Be but whether bronze, silver powder, silver-coated copper powder or copper powder as conductive material
When preparing polymer-based electrically conductive binding material, addition crosses conference causes that high expensive, viscosity are bigger than normal to be unfavorable for constructing and be bonded
A series of problems, such as intensity decreases, addition is too low, the adverse effect that resistivity can be caused excessive.Therefore one kind is developed low
The polymer-based electrically conductive binding material that high conductivity is capable of achieving under addition is significant.
Chinese patent notification number is CN103275590A, and publication date is to provide in the patent of invention of on 05 11st, 2016
A kind of preparation method of submicron/micrometersilver silver composite system epoxy resin conductive adhesive, prepares sub-micron/micron silver compound first
System, then by dissolvings such as epoxy resin, curing agent, auxiliary agent, sub-micron/micron silver compound systems in a solvent, by reactant
Material resolidification after ball milling, is obtained submicron/micrometersilver silver composite system epoxy resin conductive adhesive.The method needs to enter micron silver
Row ball milling prepares the compound silver powder of sub-micron/micron, and production method is complicated, and particle diameter only reaches submicron order, it is impossible to very
The electrical conductivity of good raising conducting resinl.Chinese patent notification number CN101781541B, publication date is on December 05th, 2012
Provided in patent of invention the invention discloses a kind of in-situ preparation method of nano silver/epoxy conductive adhesive, it is in situ first to prepare
Nano Silver：By epoxy resin, curing agent, accelerator dissolving in a solvent, reducing agent is added, presoma is added after stirring, reacted
Vacuum distillation afterwards removes solvent, is further continued for reaction, obtains the Nano Silver/ring during Nano Silver is uniformly dispersed in epoxy resin-base
Oxygen tree fat complexes.In the nano silver/epoxy resin complexes of above-mentioned preparation, add silver strip, stirring, prepare Nano Silver/
Epoxy conducting.The method will first prepare nano silver/epoxy resin complexes, need decompression to steam using solvent not environmentally, after reaction
Evaporate except solvent, technical process is cumbersome.Therefore, one kind is found more effectively to be prepared with low sizing with reliable solution
It is still the target of the continuous pursuit of industry than, the polymer-based electrically conductive binding material of high conductivity, high-weatherability, high adhesiveness.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of polymer-based in-situ nano silver conductive adhesive
Material and preparation method.Polymer-based in-situ nano silver electrically conductive binding material of the invention is based on polymer base material, metal powder, nitre
The multiple combinations such as sour silver, reducing agent, crosslinking agent, catalyst, plasticizer, initiator, tackifier with low sizing ratio, high electric
The property led, high adhesiveness polyblend.
A kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles that the present invention is provided, including following technology
Scheme：
A kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles, including macromolecule matrix resin, polymeric main
Body resin includes Argent grain, silver-colored copper-clad particle or copper particle, and for the silver nitrate and reducing agent of in-situ preparation Nano Silver.
The percentage by weight of Argent grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 5-90%；Silver nitrate and reducing agent exist
Percentage by weight in electrically conductive binding material is less than or equal to 10%.
Wherein, the percentage by weight of Argent grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 50-85%；Nitre
Sour silver and percentage by weight of the reducing agent in electrically conductive binding material are 0.1-5%.
Wherein, the percentage by weight of Argent grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 65-80%；Nitre
Sour silver and percentage by weight of the reducing agent in electrically conductive binding material are 0.5-3%
Wherein, Argent grain, silver-colored copper-clad particle or copper particle are spherical, sheet or fibrous Argent grain, silver-colored copper-clad particle or copper
Particle, its a diameter of 0.1 ~ 100um.
Wherein, reducing agent includes the one kind or several in triethanolamine, hydrazine, phosphorous acid, glycerine, aldehyde compound, glucose
Kind.
Wherein, macromolecule matrix material includes organosilicon, epoxy resin, acrylic resin, polyurethane resin or phenolic aldehyde
In resin any one or appoint it is several, the electrically conductive binding material also include catalyst, coupling agent, tackifier, crosslinking agent, initiation
Agent and plasticizer.
Wherein, crosslinking agent is the polyfunctional compound containing unsaturated double-bond；The initiator is at relatively high temperatures can
The rapid compound for decomposing and discharging free radical；The tackifier be relative molecular mass 200~2000, softening point is 5
Oligomer or aerosil between~150 DEG C；The plasticizer is phthalate.
Wherein, crosslinking agent is cumyl peroxide or 2,5- dimethyl -2,5 di-t-butyl hexane peroxides；It is described to draw
Hair agent is dibenzoyl peroxide, TBHP or peroxidized t-butyl perbenzoate；The tackifier are rosin, terpene
Class or silane coupler；The phthalate be diisononyl phthalate, diisooctyl phthalate or
Person's dioctyl phthalate.
Wherein, catalyst is chloroplatinic acid, metal rhodium complex, metal platinum complex, metal ruthenium complex.
Wherein, macromolecule matrix resin is processed by chemical modification or physical modification.
A kind of preparation method of the polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles that the present invention is provided, to
Addition percentage by weight is that Argent grain, silver-colored copper-clad particle or copper particle, the percentage by weight of 5-90% are in macromolecule matrix resin
The silver nitrate and reducing agent of 0.1-5%, and other auxiliary agents mixing and stirring under 0-30 C obtain polymer-based conductive adhesive
Material.
Wherein, other auxiliary agents include crosslinking agent, the initiator of 1%-10%, the tackifier of 1%-10%, the 1%-10% of 1%-10%
Plasticizer, the catalyst agent of 1%-10% and the coupling agent of 1%-10%.
Implementation of the invention includes following technique effect：
Low sizing ratio, high conductivity, the polymer-based in-situ nano silver electrically conductive binding material of high adhesiveness that the present invention is provided,
Polymer-based electrically conductive binding material is modified using silver nitrate and reducing agent.Nitric acid in polymer-based electrically conductive binding material
In-situ preparation nano-Ag particles when silver and the electrically conductive adhesives of reducing agent solidify the initial temperature rise period.Silver point is
960.3 DEG C ~ 960.7 DEG C, and nanometer silver point is then 100 DEG C, therefore generated in-situ Nano Silver can be in conductive polymer
The hot stage of material warms solidification is melted and infiltrates metal conductive powder, and metallic conduction is set in again after solidification completes cooling
The conductive network of three-dimensional is formed between powder so as to realize the high conductivity and high adhesiveness under low sizing ratio.Leading after solidification
The conductance of electric adhesives does not carry out the modified electrically conductive binding material of in-situ nano silver and lifts 2 ~ 10 times.
The resistivity of electrically conductive binding material can be regulated and controled by the content of silver nitrate and reducing agent, applicant warp
Cross substantial amounts of experiment to select the content of silver nitrate and reducing agent so that electrically conductive binding material inside has efficiently three-dimensional
Conductive network passage, traditional simple of resistivity ratio that electrically conductive binding material can be greatly reduced is to fill out using conductive metal powder
The electrically conductive binding material of material has obvious advantage, therefore can meet the requirement of low-resistivity in electronics industry, high adhesiveness.
Additionally, the underlying plating layer of most of electrically conductive binding materials coating in the market is all metallic tin, silver nitrate plus
Entering can stablize contact resistance of the conducting resinl on tin face as sacrificial anode, greatly improve the contact stabilization of electrically conductive binding material
Property.
Brief description of the drawings
Fig. 1 is traditional polymer-based electrically conductive binding material internal structure schematic diagram
Fig. 2 is the polymer-based in-situ nano silver electrically conductive binding material internal structure schematic diagram of the embodiment of the present invention（Bridging
" sea-island " structure）.
Specific embodiment
The present invention is described in detail below in conjunction with embodiment and accompanying drawing, it should be pointed out that described reality
Apply example and be intended merely to facilitate the understanding of the present invention, and do not play any restriction effect to it.
A kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles that the present embodiment is provided, including macromolecule
Matrix resin, macromolecule matrix resin includes Argent grain, silver-colored copper-clad particle or copper particle, and for in-situ preparation Nano Silver
Silver nitrate and reducing agent.The percentage by weight of Argent grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 5-
90%；The percentage by weight of silver nitrate and reducing agent in electrically conductive binding material is less than or equal to 10%.It is specific that silver may be selected
The percentage by weight of grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 50-85%；Silver nitrate and reducing agent are being led
Percentage by weight in electric adhesives is 0.1-5%.Further optimization Argent grain, silver-colored copper-clad particle or copper particle are viscous in conduction
It is 65-80% to connect the percentage by weight in material；The percentage by weight of silver nitrate and reducing agent in electrically conductive binding material is 0.5-
3%.By the restriction to above-mentioned material component and content so that metallic conductive fillers and generated in-situ Nano Silver can be in height
Efficient three dimentional heat conduction network channel is formed in molecular bulk resin curing process（As shown in Figure 2）, effectively reduce conductive adhesive
The resistivity of material.By the regulation to silver nitrate and reducing agent, the passage specific surface area of three-dimensional wire guide network can be effectively controlled
And channel density, it is expected to the conductance of electrically conductive binding material is lifted 2 ~ 10 times.The electrically conductive binding material that the present embodiment is obtained
Resistivity is 8.0 × 10-4Ω.cm~6.0×10-5Between Ω .cm.Electrically conductive binding material can be prepared by blending technology, be prepared
Method is simple, and resulting electrically conductive binding material has the good characteristics such as low packing ratio, high connductivity, high durable, high-adhesive-strength.
In the present embodiment, metal packing used can be Argent grain, silver-colored copper-clad particle or copper particle, preferably silver-colored copper-clad
Grain, or the mixture of several metallic particles, its pattern can be spherical, sheet or threadiness, preferably sheet, metal
Filler a diameter of 0.1 arrives 100um microns, preferably 1 ~ 10 micron.
Reducing agent is one or more in triethanolamine, hydrazine, phosphorous acid, glycerine, aldehyde compound, glucose.Reduction
Agent can occur reduction reaction with silver nitrate under certain condition, be argent by silver ion reduction in silver nitrate.
During macromolecule matrix resin is organosilicon, epoxy resin, acrylic resin, polyurethane resin or phenolic resin
Any one or appoint it is several, the electrically conductive binding material also include catalyst, coupling agent, tackifier, crosslinking agent and plasticizer.It is used
Crosslinking agent is the polyfunctional compound containing unsaturated double-bond, such as divinylbenzene or triallyl isocyanurate etc., its
Distinguishing feature is to carry out free radicals copolymerization reaction under free radical initiation.Tackifier used can be dramatically increased between matrix
Bonding force, including natural and artificial synthesized relative molecular mass is in 200~2000, the oligomerization between 5~150 DEG C of softening point
Thing.Than it is more typical such as, rosin, terpene and silane coupler etc..Plasticizer used can significantly attenuate the work between macromolecule
Firmly, the mobility of polymer molecular chain is increased, the crystallinity of polymer molecular chain is reduced, be increased the plasticity of polymer.
Compare typically phthalate, such as diisononyl phthalate, diisooctyl phthalate, O-phthalic
Dioctyl phthalate etc..
The molecular bulk resin high such as organosilicon, epoxy resin, acrylic resin, polyurethane resin or phenolic resin, silver
Particle, the silver-colored conductive metal powder such as copper-clad particle or copper particle, silver nitrate, reducing agent, crosslinking agent, initiator, tackifier and plasticising
The mixtures such as agent are uniformly mixed to get at 0 ~ 30 DEG C low packing ratio, high connductivity, high durable, high-adhesive-strength through planet stirring
Electrically conductive binding material.
Compared with prior art, the present invention can form preferably solid conductive network using in-situ nano silver technology, make powder
It is three-dimensional vertical that the conductive particle of shape forms " sea-island of bridging " in conductive material solidification process by the melting and infiltration of Nano Silver
Body structure (as shown in Figure 2) and be no longer scattered, isolated " sea-island " structure (as shown in Figure 1), such special construction makes
The electrical conductivity of electrically conductive binding material is significantly lifted.
It is following the preparation method of above-mentioned polymer-based in-situ nano silver electrically conductive binding material is carried out with multiple embodiments
Description.
Embodiment 1
The preparation method of the polymer-based in-situ nano silver electrically conductive binding material of the present embodiment is to organic under conditions of stirring
63% is added in silicones（wt%）The micron flakes silver powder of diameter 1 ~ 3 do pre-dispersed.Pre-dispersed good resin containing silver powder is placed
1.5% is sequentially added in planetary stirrer（wt%）Silver nitrate, 1%（wt%）Triethanolamine, 0.8%（wt%）Aminopropyl three
Ethoxysilane and 1.5%（wt%）Aerosil.It is passed through cooling water, it is ensured that dispersion 2 is small at temperature of charge is less than 25 DEG C
When after add 0.5%（wt%）Chloroplatinic acid redisperse 1 hour, low pressure deaeration obtains organosilicon in-situ nano silver conductive adhesive material
Material, concrete property is as follows：
Viscosity：31,500mPa.s
Adhesive strength：8MPa（Bonding base material is aluminium）
Curing rate：10 minutes（120℃）
Specific insulation：1.5×10-4Ω.cm
It is hot and humid（85 DEG C, 85%RH, 500 hours）Aging rear specific insulation：1.8×10-4Ω.cm
The specific insulation of organosilicon in-situ nano silver electrically conductive binding material prepared in the present embodiment is organic far below conventional
Silicon electrically conductive binding material, and performance is highly stable after tropical deterioration.
Embodiment 2
The preparation method of the polymer-based in-situ nano silver electrically conductive binding material of the present embodiment is to epoxy under conditions of stirring
70% is added in resin（wt%）6 ~ 15 microns of spherical silver-coated copper powders of diameter（Silver content 20%）Do pre-dispersed.Will be pre-dispersed good
Argentiferous bag powder resin sequentially adds 1% in being positioned over planetary stirrer（wt%）Silver nitrate, 0.8%（wt%）Hydrazine and 0.8%
（wt%）Aminopropyl triethoxysilane.It is passed through cooling water, it is ensured that temperature of charge adds 2% after disperseing 3 hours at being less than 25 DEG C
（wt%）Maleic anhydride redisperse 2 hours, low pressure deaeration obtains epoxy resin in situ nano-silver conductive adhesives, specifically
Characteristic is as follows：
Viscosity：45,000mPa.s
Adhesive strength：14MPa（Bonding base material is aluminium）
Curing rate：8 minutes（140℃）
Specific insulation：2.6×10-4Ω.cm
The specific insulation of organosilicon in-situ nano silver electrically conductive binding material prepared in the present embodiment is far below Conventional epoxy
Resin conductive adhesives.
Embodiment 3
The preparation method of the polymer-based in-situ nano silver electrically conductive binding material of the present embodiment is to organic under conditions of stirring
75% is added in silicones（wt%）The micron flakes silver-coated copper powder of diameter 6 ~ 15（Silver content 20%）Do pre-dispersed.Will be pre-dispersed good
Resin containing silver powder be positioned over planetary stirrer in sequentially add 2%（wt%）Silver nitrate, 1%（wt%）Glycerine, 0.8%（wt%）
Aminopropyl triethoxysilane and 1.5%（wt%）Aerosil.It is passed through cooling water, it is ensured that temperature of charge is less than 25 DEG C
Lower dispersion adds 0.5% after 2 hours（wt%）Metal rhodium complex redisperse 1 hour, low pressure deaeration obtains organosilicon original position and receives
The silver-colored electrically conductive binding material of rice, concrete property is as follows：
Viscosity：50,500mPa.s
Adhesive strength：6MPa（Bonding base material is aluminium）
Curing rate：3 minutes（130℃）
Specific insulation：7.8×10-5Ω.cm
It is hot and humid（85 DEG C, 85%RH, 500 hours）Aging rear specific insulation：0.9×10-5Ω.cm
The specific insulation of organosilicon in-situ nano silver electrically conductive binding material prepared in the present embodiment is organic far below conventional
Silicon electrically conductive binding material, and performance is highly stable after tropical deterioration.
Embodiment 4
The preparation method of the polymer-based in-situ nano silver electrically conductive binding material of the present embodiment is to polyhydroxy under conditions of stirring
68% is added in base polyether resin（wt%）The copper powder of diameter 30 ~ 50 do pre-dispersed.Pre-dispersed good resin containing copper powder is positioned over
1.3% is sequentially added in planetary stirrer（wt%）Silver nitrate, 0.8%（wt%）The third three aldehyde.It is passed through cooling water, it is ensured that material temperature
Degree adds 4% after disperseing 2 hours at being less than 25 DEG C（wt%）Toluene-2,4-diisocyanate, 4- diisocyanate trimers redisperse 10 minutes is low
Pressure-off bubble obtains polyurethane in-situ nano silver electrically conductive binding material, and concrete property is as follows：
Viscosity：8,000mPa.s
Adhesive strength：9MPa（Bonding base material is aluminium）
Curing rate：2 minutes（150℃）
Specific insulation：5.8×10-4Ω.cm
The specific insulation of organosilicon in-situ nano silver electrically conductive binding material prepared in the present embodiment is organic far below conventional
Silicon electrically conductive binding material, and performance is highly stable after tropical deterioration
Embodiment 5
The preparation method of the polymer-based in-situ nano silver electrically conductive binding material of the present embodiment is to organic under conditions of stirring
25% is added in silicones（wt%）The micron flakes silver-coated copper powder of diameter 6 ~ 15（Silver content 20%）With 45%（wt%）Diameter 1 ~ 3 is micro-
Rice flake silver powder does pre-dispersed.Pre-dispersed good resin containing silver powder is positioned in planetary stirrer and sequentially adds 2%（wt%）'s
Silver nitrate, 1%（wt%）Phosphorous acid and 1.2%（wt%）Methacryloxypropyl trimethoxy silane.It is passed through cooling water,
Dispersion adds 0.5% after 2 hours at ensuring temperature of charge less than 25 DEG C（wt%）Metal platinum complex redisperse 1 hour, low pressure
Deaeration obtains organosilicon in-situ nano silver electrically conductive binding material, and concrete property is as follows：
Viscosity：60,000mPa.s
Adhesive strength：5MPa（Bonding base material is aluminium）
Curing rate：2 minutes（130℃）
Specific insulation：6.6×10-5Ω.cm
The specific insulation of organosilicon in-situ nano silver electrically conductive binding material prepared in the present embodiment is organic far below conventional
Silicon electrically conductive binding material, and performance is highly stable after tropical deterioration
Embodiment 6
The preparation method of the polymer-based in-situ nano silver electrically conductive binding material of the present embodiment is to epoxy under conditions of stirring
10% is added in resin（wt%）Polyurethane resin and 68%（wt%）40 ~ 60 microns of spherical copper powders of diameter do pre-dispersed.Will be pre-
Scattered resin containing powder sequentially adds 1.2% in being positioned over planetary stirrer（wt%）Silver nitrate and 0.5%（wt%）Grape
Sugar.It is passed through cooling water, it is ensured that temperature of charge adds 2% after disperseing 5 hours at being less than 25 DEG C（wt%）Maleic anhydride redisperse 2
Hour, low pressure deaeration obtains epoxy resin in situ nano-silver conductive adhesives, and concrete property is as follows：
Viscosity：60,000mPa.s
Adhesive strength：11MPa（Bonding base material is aluminium）
Curing rate：15 minutes（140℃）
Specific insulation：8.8×10-4Ω.cm
The specific insulation of organosilicon in-situ nano silver electrically conductive binding material prepared in the present embodiment is organic far below conventional
Silicon electrically conductive binding material, and performance is highly stable after tropical deterioration
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than to present invention protection model
The limitation enclosed, although being explained to the present invention with reference to preferred embodiment, one of ordinary skill in the art should manage
Solution, technical scheme can be modified or equivalent, without deviating from technical solution of the present invention essence and
Scope.
Claims (12)
1. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles, including macromolecule matrix resin, its feature
It is：The macromolecule matrix resin includes Argent grain, silver-colored copper-clad particle or copper particle, and for in-situ preparation Nano Silver
Silver nitrate and reducing agent, the percentage by weight of Argent grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 5-
90%；The percentage by weight of silver nitrate and reducing agent in electrically conductive binding material is less than or equal to 10%.
2. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 1, its feature
It is：The percentage by weight of Argent grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 50-85%；Silver nitrate and also
Percentage by weight of the former agent in electrically conductive binding material is 0.1-5%.
3. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 2, its feature
It is：The percentage by weight of Argent grain, silver-colored copper-clad particle or copper particle in electrically conductive binding material is 65-80%；Silver nitrate and also
Percentage by weight of the former agent in electrically conductive binding material is 0.5-3%.
4. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 3, its feature
It is：The Argent grain, silver-colored copper-clad particle or copper particle are spherical, sheet or fibrous Argent grain, silver-colored copper-clad particle or copper
Particle, its a diameter of 0.1 ~ 100um.
5. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 1, its feature
It is：The reducing agent includes one or more in triethanolamine, hydrazine, phosphorous acid, glycerine, aldehyde compound, glucose.
6. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 1, its feature
It is：The macromolecule matrix material includes organosilicon, epoxy resin, acrylic resin, polyurethane resin or phenolic resin
In any one or appoint it is several, the electrically conductive binding material also include catalyst, coupling agent, tackifier, crosslinking agent, initiator and
Plasticizer.
7. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 6, its feature
It is：The crosslinking agent is the polyfunctional compound containing unsaturated double-bond；The initiator is at relatively high temperatures can be rapid
Decompose and discharge the compound of free radical；The tackifier be relative molecular mass 200~2000, softening point is 5~150
Oligomer or aerosil between DEG C；The plasticizer is phthalate.
8. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 7, its feature
It is：The crosslinking agent is cumyl peroxide, maleic anhydride, the di-t-butyl hexane peroxide of 2,5- dimethyl -2,5；
The initiator is dibenzoyl peroxide, TBHP or peroxidized t-butyl perbenzoate；The tackifier are pines
Fragrant class, terpene or silane coupler；The phthalate is different diisononyl phthalate, phthalic acid two
Last of the ten Heavenly stems ester or dioctyl phthalate.
9. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 7, its feature
It is：The catalyst is chloroplatinic acid, metal rhodium complex, metal platinum complex, metal ruthenium complex, alkaline-earth metal catalysis
Agent.
10. a kind of polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 1, its feature
It is：The macromolecule matrix resin is processed by chemical modification or physical modification.
A kind of 11. preparation methods of the polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles, it is characterised in that：Xiang Gao
Addition percentage by weight is that Argent grain, silver-colored copper-clad particle or copper particle, the percentage by weight of 5-90% are in molecular bulk resin
The silver nitrate and reducing agent of 0.1-5%, and other auxiliary agents mixing and stirring under 0-30 C obtain polymer-based conductive adhesive
Material.
A kind of 12. preparations of the polymer-based electrically conductive binding material of in-situ preparation nano-Ag particles according to claim 11
Method, it is characterised in that：The auxiliary agent includes crosslinking agent, the initiator of 1%-10%, the tackifier of 1%-10%, the 1%- of 1%-10%
The catalyst agent of 10% plasticizer, 1%-10% and the coupling agent of 1%-10%.
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| CN107987747A (en) * | 2017-12-22 | 2018-05-04 | 有研粉末新材料（北京）有限公司 | A kind of preparation method of nanometer of silver-coated copper powder collaboration flake silver powder conducting resinl |
| CN110358367A (en) * | 2019-05-31 | 2019-10-22 | 南开大学 | A kind of elastic conductor material being used as stretchable microelectronic circuit electrically conductive ink and its synthetic method |
| CN111180318A (en) * | 2020-01-06 | 2020-05-19 | 贵州振华风光半导体有限公司 | Method for improving bonding quality in integrated circuit by using in-situ bonding technology |
| CN114437509A (en) * | 2020-10-30 | 2022-05-06 | 臻鼎科技股份有限公司 | Conductive resin composition, conductive layer using same and circuit board |
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| US4904414A (en) * | 1986-09-25 | 1990-02-27 | Siemens Aktiengesellschaft | Electrically conductive adhesive for a broad range of temperatures |
| CN102863924A (en) * | 2012-08-25 | 2013-01-09 | 华南理工大学 | Preparation method of silver-plated copper powder/epoxy resin conductive adhesive |
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| CN110358367A (en) * | 2019-05-31 | 2019-10-22 | 南开大学 | A kind of elastic conductor material being used as stretchable microelectronic circuit electrically conductive ink and its synthetic method |
| CN111180318A (en) * | 2020-01-06 | 2020-05-19 | 贵州振华风光半导体有限公司 | Method for improving bonding quality in integrated circuit by using in-situ bonding technology |
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Application publication date: 20170609 |