CN115124951A - Nano conductive adhesive and preparation method thereof - Google Patents
Nano conductive adhesive and preparation method thereof Download PDFInfo
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- CN115124951A CN115124951A CN202210519722.2A CN202210519722A CN115124951A CN 115124951 A CN115124951 A CN 115124951A CN 202210519722 A CN202210519722 A CN 202210519722A CN 115124951 A CN115124951 A CN 115124951A
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- conductive adhesive
- nano conductive
- thermoplastic resin
- modified thermoplastic
- silver powder
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 44
- 239000000853 adhesive Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 18
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 4
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- CWPKTBMRVATCBL-UHFFFAOYSA-N 3-[1-[1-[(2-methylphenyl)methyl]piperidin-4-yl]piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound CC1=CC=CC=C1CN1CCC(N2CCC(CC2)N2C(NC3=CC=CC=C32)=O)CC1 CWPKTBMRVATCBL-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 2
- 229940072049 amyl acetate Drugs 0.000 claims description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002334 glycols Chemical class 0.000 claims description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003999 initiator Substances 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 238000004377 microelectronic Methods 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 2
- 239000000843 powder Substances 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 8
- 238000011160 research Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 239000002270 dispersing agent Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 239000004332 silver Substances 0.000 description 9
- 229910052709 silver Inorganic materials 0.000 description 9
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000004925 Acrylic resin Substances 0.000 description 6
- 229920000178 Acrylic resin Polymers 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 238000013459 approach Methods 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920005479 Lucite® Polymers 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001010 compromised effect Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/062—Copolymers with monomers not covered by C09J133/06
- C09J133/068—Copolymers with monomers not covered by C09J133/06 containing glycidyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
-
- 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
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Conductive Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a nano conductive adhesive and a preparation method thereof, wherein the preparation method comprises the following steps: 3-8 parts of sulfydryl modified thermoplastic resin, 20-50 parts of solvent, 40-70 parts of nano conductive silver powder and 0.2-2 parts of dispersing aid. In the research, the invention discovers that the mercapto-modified thermoplastic resin can react with the nano silver powder because of the mercapto structure, so that the silver powder can achieve a better sintering effect in the subsequent curing process.
Description
Technical Field
The invention relates to the field of conductive adhesives, in particular to a nano conductive adhesive and a preparation method thereof.
Background
The nano conductive adhesive attracts more and more attention in the field of microelectronic packaging because the nano conductive adhesive has special electrical and mechanical properties compared with the traditional conductive adhesive. The current research on nano conductive adhesive relates to the preparation of high-performance conductive adhesive by adopting nano particles, nano wires, carbon nano tubes and the like as conductive fillers.
The nano silver adhesive has the advantages of small granularity and good fluidity, and can form a fine, smooth and conductive film layer with good adhesive force on various substrate materials after being cured.
The nano conductive adhesive can reach 10 degrees above 170 degrees centigrade -6 Volume resistance on the order of ohm-cm, but conductivity is compromised at low temperature curing.
Patent CN 109652005 a discloses a conductive adhesive, which is prepared by mixing A, B silver powders with diethylene glycol and cyanate ester resin as organic mixed solvent, and adding a dispersant. The A, B two silver powders are prepared by high-energy ball milling silver powders with the purity of 99.95 percent into micro-nano silver powders, and then separating A silver particles with the diameter of 3-20 mu m and B silver particles with the diameter of less than 200 nm. However, it is very susceptible to cracking.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a nano conductive adhesive composition and a preparation method thereof.
In view of this, the technical solution provided by the present invention is as follows:
the nanometer conductive adhesive comprises the following components in parts by weight:
3-8 parts of mercapto-modified thermoplastic resin
20 to 50 parts of solvent
40-70 parts of nano conductive silver powder
0.2-2 parts of a dispersing aid.
The mercapto-modified thermoplastic resin has a molecular weight of 3 to 20 ten thousand and is soluble in a solvent.
The mercapto group-modified thermoplastic resin is a modified thermoplastic resin that contains a mercapto group and is soluble in a solvent.
The solvent comprises one or a mixture of more of aromatic hydrocarbon, aliphatic hydrocarbon, ester cyclic hydrocarbon, ester, glycol derivative, alcohol and ketone.
Further, the solvent is at least one of toluene, xylene, pentane, hexane, octane, cyclohexane, absolute ethyl alcohol, ethyl acetate, butyl acetate, amyl acetate, isopropanol, n-butanol, ethylene glycol ethyl ether acetate, propylene glycol methyl ether, and diethylene glycol butyl ether acetate.
The nano conductive silver powder comprises nano conductive silver powder with the D50 particle size within 5nm-1 micron.
Preferably, the particle size of the nano conductive silver powder is 10-500 nm.
The dispersing aid is preferably an acidic dispersing aid. Such as BYK111, BYK130, BYK192, etc.;
the preparation method of the sulfhydryl modified thermoplastic resin comprises the following steps:
s1, mixing diethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate, uniformly stirring, heating to reflux reaction, and keeping the temperature at 130-150 ℃ to obtain a reaction liquid A;
s2, uniformly mixing methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, glycidyl methacrylate and a TBPB initiator to obtain a reaction liquid B;
s3, slowly dripping the reaction liquid A into the reaction liquid B for 4 times, wherein the dripping time is 15-20min each time, keeping the temperature for 40min after the reaction liquid is dripped for the first three times, keeping the temperature for 60min after the last dripping, cooling the system to 80 ℃, adding ethanedithiol, reacting for 2h, cooling and discharging to obtain the sulfhydryl modified thermoplastic resin.
The invention further discovers in research that the silver powder sintering effect can be achieved only by the mercapto-modified thermoplastic resin with specific content, although the modified thermoplastic resin can bond the silver powder, if the resin amount is too much, the silver powder can be excessively coated, so that the catalytic sintering of the silver powder by the acidic dispersant is difficult to achieve in the post-curing process; the content of the silver nanoparticles is also controlled because the silver powder is too high to be sintered, but is easily cracked, resulting in a decrease in conductivity.
In a second aspect, the present invention also provides a method for preparing the nano conductive adhesive composition, which comprises the following steps:
and (2) mixing the mercapto-modified thermoplastic resin with a solvent, mechanically stirring until the mercapto-modified thermoplastic resin is completely dissolved, then adding a dispersing aid, uniformly stirring, adding the nano conductive silver powder, dispersing at a high speed, and discharging to prepare the nano conductive adhesive. Wherein the materials are discharged and tested after being dispersed to non-agglomerated large particles (large particles with the particle size of more than 5 um) at high speed.
The curing time of the conductive adhesive prepared by the invention at 130 ℃ reaches 1h, namely less than 9 x 10 can be obtained -6 Cm, under which the silver powder can be seen to sinter together by SEM images; the principle is that the acid additive corrodes the surface of the nano silver particles at high temperature, so that the silver particles approach to each other to form sintering, and high conductivity is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the thermoplastic resin is added to bond the silver powder, so that the silver powder is more regularly arranged due to the reaction of the resin and the silver powder, and the subsequent sintering of the silver powder is promoted on a molecular level;
2. the inventor discovers in the research that not all thermoplastic resins have excellent effects, and the inventor discovers in the research that the mercapto-modified thermoplastic resin can react with the nano silver powder because the mercapto-modified thermoplastic resin has a mercapto structure, so that the silver powder can achieve better sintering effect in the subsequent curing process. Some conventional thermoplastic resins, such as unmodified acrylic resins (paraloid db44 of dow, a11, Elvacite 2016 of Lucite, etc.) obtained by polymerizing acrylic monomers, do not achieve such synergistic effects;
3. the purpose of adding the acidic dispersing agent in the invention is to enable the nano silver powder to be sintered at a low temperature better. Compared with the acid dispersant, the polymer dispersant, the amine dispersant and the like, the invention discovers that the acid dispersant can enable the silver powder to be more easily close in the curing process due to the acid washing property, thereby realizing the effect of low-temperature sintering. However, the polymer type dispersant and the amine type dispersant cannot achieve the sintering effect at all;
4. the modified thermoplastic resin, the nano silver powder and the acidic dispersant in the invention are synergistic, and the silver powder can be sintered only by the simultaneous action of the modified thermoplastic resin, the nano silver powder and the acidic dispersant;
5. the invention provides the low-temperature curing type high-conductivity nano conductive adhesive, so that the conductivity is improved;
6. the nano conductive adhesive provided by the invention has excellent adhesive property, and simultaneously, the product has better aging resistance.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Preparation example
Preparation of modified mercapto acrylic resin:
the component A comprises:
diethylene glycol monobutyl ether acetate 300 parts
Propylene glycol methyl ether acetate 100 parts
And the component B comprises:
stirring and heating the component A according to the formula amount until reflux reaction is carried out, and keeping the temperature at about 140 ℃;
uniformly stirring the component B with the formula amount, and then dropwise adding the component B into the system in the step 1 for 4 times, wherein the dropwise adding time is 15-20min each time, after dropwise adding the component B for the first three times, keeping the temperature for 40min, then continuously dropwise adding the component B, and keeping the temperature for 60min after dropwise adding for the last time; and cooling the system to 80 ℃, adding 100 parts of ethanedithiol, reacting for 2 hours, cooling and discharging, and preparing the modified mercapto acrylic resin.
Examples 1 to 4
According to the table 1, the modified mercapto resin solution prepared in the preparation example is firstly stirred and mixed with the solvent, then the acid auxiliary agent is added, the nano silver powder is added after the stirring is uniform, 2000R is dispersed at a high speed to form non-agglomerated large particles (the agglomerated large particles refer to particles with the particle size of more than 5 um), and then the discharge test is carried out.
And (3) conductivity test: and scraping the prepared conductive adhesive into a film with the size of 3mm x 100mm and the thickness of 0.05mm, then placing the film in a 130C oven, preserving the heat for 1h, taking out the film, cooling the film to the normal temperature, testing the resistance by using a four-probe method, and calculating the volume resistance.
For the sake of comparison, the amounts of the resin and the solvent of the original mixed solution in the table are calculated respectively.
TABLE 1 Components of the Nano-conductive adhesive of examples 1-4 (by weight)
The conductivity of the nano conductive adhesive obtained in examples 1 to 4 was measured, and the results are shown in table 2:
TABLE 2 Properties of the Nano-conductive pastes prepared in examples 1 to 4
As can be seen from the results in Table 2, the volume resistance of the nano conductive adhesive prepared by the methods of examples 1 to 4 can reach the level of 10-6ohm.
Comparative example 1
Comparative example 1 differs from example 1 in that: the amount of the acidic dispersant BYK-111 added was 0.5 part.
Comparative example 2
Comparative example 1 differs from example 3 in that: the nano silver powder was replaced with a micro silver powder (D50: 2 micron).
Comparative example 3
Comparative example 1 differs from example 3 in that: the 60 parts of silver powder was replaced with 20 parts of silver powder and 40 parts of silver powder (D50: 2 μm).
Comparative example 4
Comparative example 1 differs from example 4 in that: the acidic dispersant BYK-111 is replaced by a polymer dispersant BYK-180.
Comparative example 5
Comparative example 5 differs from example 2 in that: the modified mercaptoacrylic resin was replaced with a linear acrylic resin (Paraloid B44).
TABLE 3 Components of Nano conductive adhesive for comparative examples 1 to 5
The conductivity of the nano conductive adhesive obtained in comparative examples 1 to 5 was tested, and the results are shown in table 4:
TABLE 4 Properties of the nano conductive adhesives prepared in comparative examples 1 to 5
From the results of table 4 it can be seen that:
the conductivity of the nano conductive adhesive prepared by the method of comparative example 1 (compared with that of example 1) cannot reach 10 - 6 Ohm.cm; because the amount of the acidic dispersing agent is insufficient, the silver powder cannot approach each other to form sintering during high-temperature curing, and therefore higher conductivity cannot be achieved;
with the nano conductive paste prepared in comparative examples 2-3 (compared with example 3), the conductivity could not reach 10 - 6 Ohm.cm; because micron-sized silver powder is adopted, the particle size is large, and the particle shape is irregular, so that the sintering of the silver powder is hindered;
in comparison with example 4 using comparative example 4, the conductivity became poor after the acidic dispersant was replaced with the polymeric dispersant because the polymeric dispersant had a limited effect on the surface of the silver powder and could not promote sintering;
by using comparative example 5, compared with example 2, the conductivity of the mercapto group-modified acrylic resin was changed to a conventional mercapto group-free acrylic resin and could not reach 10 -6 Ohm. cm, because the mercapto resin has a synergistic effect on the approach of the silver particles, if the reactivity is removed, the approach of the silver particles cannot be achieved, and the sintering effect is achieved;
the invention provides a method for greatly improving the conductivity under low-temperature curing aiming at a nano conductive silver adhesive system, and can greatly reduce the curing cost aiming at the application of the nano conductive adhesive. Meanwhile, the material cost can be saved by reducing the glue consumption.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. The nanometer conductive adhesive is characterized by comprising the following components in parts by weight:
3 to 8 parts of a mercapto group-modified thermoplastic resin,
20-50 parts of a solvent, and a solvent,
40 to 70 parts of nano conductive silver powder,
0.2-2 parts of a dispersing aid.
2. The nano conductive adhesive according to claim 1, wherein the mercapto-modified thermoplastic resin has a molecular weight of 3 to 20 ten thousand and is soluble in the solvent.
3. The nano conductive adhesive according to claim 1, wherein the thiol-modified thermoplastic resin is a modified thermoplastic resin containing thiol groups and being soluble in a solvent.
4. The nano conductive adhesive according to claim 1, wherein the solvent comprises one or more of aromatic hydrocarbon, aliphatic hydrocarbon, ester cyclic hydrocarbon, ester, glycol derivative, alcohol and ketone.
5. The nano conductive adhesive as claimed in claim 4, wherein the solvent is at least one of toluene, xylene, pentane, hexane, octane, cyclohexane, absolute ethyl alcohol, ethyl acetate, butyl acetate, amyl acetate, isopropyl alcohol, n-butanol, ethylene glycol ethyl ether acetate, propylene glycol methyl ether, diethylene glycol butyl ether acetate.
6. The nano conductive adhesive according to claim 1, wherein the nano conductive silver powder comprises silver powder with a D50 particle size of 10nm-1 um.
7. The nano conductive adhesive according to claim 1, wherein the dispersion aid is an acidic dispersion aid.
8. The nano conductive adhesive according to claim 1, wherein the preparation method of the thiol-modified thermoplastic resin comprises the following steps:
s1, mixing diethylene glycol monobutyl ether acetate and propylene glycol monomethyl ether acetate, uniformly stirring, heating to reflux reaction, and keeping the temperature at 130-150 ℃ to obtain a reaction liquid A;
s2, uniformly mixing methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, glycidyl methacrylate and a TBPB initiator to obtain a reaction liquid B;
s3, slowly dripping the reaction liquid A into the reaction liquid B for 4 times, wherein the dripping time is 15-20min each time, continuously dripping after keeping the temperature for 40-60min after dripping the reaction liquid for the first three times, keeping the temperature for 60-80min after dripping for the last time, cooling the system to 80-90 ℃, adding ethanedithiol, reacting for 2h-2.5, cooling and discharging to obtain the mercapto-modified thermoplastic resin.
9. A method for preparing the nano conductive adhesive according to any one of claims 1 to 8, comprising the following steps:
and (2) mixing the mercapto-modified thermoplastic resin with a solvent, mechanically stirring until the mercapto-modified thermoplastic resin is completely dissolved, then adding a dispersing aid, uniformly stirring, adding the nano conductive silver powder, dispersing at a high speed, and discharging to prepare the nano conductive adhesive.
10. The application of the nano conductive adhesive prepared by the nano conductive adhesive of any one of claims 1 to 8 or the preparation method of claim 9 in the field of microelectronic packaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311714A (en) * | 2011-08-24 | 2012-01-11 | 浙江科创新材料科技有限公司 | High thermal and electric conducting adhesive filled with nanometer silver and preparation method thereof |
| CN104449455A (en) * | 2014-12-29 | 2015-03-25 | 中科院广州化学有限公司 | Medium temperature curing high-performance conductive silver adhesive, preparation method thereof and application |
| US20160160067A1 (en) * | 2013-08-16 | 2016-06-09 | Henkel IP & Holding GmbH | Submicron silver particle ink compositions, process and applications |
| CN110232984A (en) * | 2018-03-05 | 2019-09-13 | 宁波柔印电子科技有限责任公司 | A kind of printing conductive silver paste and preparation method thereof |
| US20210147732A1 (en) * | 2019-05-22 | 2021-05-20 | Blue Ocean & Black Stone Technology Co., Ltd. (Beijing) | Composition, Low Halogen and Fast Curing Conductive Adhesive and Its Preparation Method |
| CN114276766A (en) * | 2022-01-17 | 2022-04-05 | 深圳市郎搏万先进材料有限公司 | Nano-silver sintered conductive adhesive for microelectronic packaging and preparation method thereof |
-
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- 2022-05-13 CN CN202210519722.2A patent/CN115124951B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311714A (en) * | 2011-08-24 | 2012-01-11 | 浙江科创新材料科技有限公司 | High thermal and electric conducting adhesive filled with nanometer silver and preparation method thereof |
| US20160160067A1 (en) * | 2013-08-16 | 2016-06-09 | Henkel IP & Holding GmbH | Submicron silver particle ink compositions, process and applications |
| CN104449455A (en) * | 2014-12-29 | 2015-03-25 | 中科院广州化学有限公司 | Medium temperature curing high-performance conductive silver adhesive, preparation method thereof and application |
| CN110232984A (en) * | 2018-03-05 | 2019-09-13 | 宁波柔印电子科技有限责任公司 | A kind of printing conductive silver paste and preparation method thereof |
| US20210147732A1 (en) * | 2019-05-22 | 2021-05-20 | Blue Ocean & Black Stone Technology Co., Ltd. (Beijing) | Composition, Low Halogen and Fast Curing Conductive Adhesive and Its Preparation Method |
| CN114276766A (en) * | 2022-01-17 | 2022-04-05 | 深圳市郎搏万先进材料有限公司 | Nano-silver sintered conductive adhesive for microelectronic packaging and preparation method thereof |
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| CN115124951B (en) | 2024-03-12 |
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