CN115124951B - Nanometer conductive adhesive and preparation method thereof - Google Patents
Nanometer conductive adhesive and preparation method thereof Download PDFInfo
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- CN115124951B CN115124951B CN202210519722.2A CN202210519722A CN115124951B CN 115124951 B CN115124951 B CN 115124951B CN 202210519722 A CN202210519722 A CN 202210519722A CN 115124951 B CN115124951 B CN 115124951B
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- 230000001070 adhesive effect Effects 0.000 title claims abstract description 35
- 239000000853 adhesive Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 29
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-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
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 238000002156 mixing Methods 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
- 238000007599 discharging Methods 0.000 claims description 5
- 239000000203 mixture Substances 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
- 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
- 238000004321 preservation Methods 0.000 claims description 4
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 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
- 230000002378 acidificating effect Effects 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
- 239000006185 dispersion Substances 0.000 claims description 2
- 150000002148 esters Chemical class 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
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 12
- 239000000843 powder Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 18
- 239000002270 dispersing agent Substances 0.000 description 17
- 239000002253 acid Substances 0.000 description 12
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 239000004332 silver Substances 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004925 Acrylic resin Substances 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000002313 adhesive film Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 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
- 238000013459 approach Methods 0.000 description 2
- 238000013035 low temperature curing Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920005479 Lucite® Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 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
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding 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
- 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
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003573 thiols Chemical class 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
Abstract
The invention discloses a nanometer conductive adhesive and a preparation method thereof, comprising the following steps: 3 to 8 parts of sulfhydryl modified thermoplastic resin, 20 to 50 parts of solvent, 40 to 70 parts of nano conductive silver powder and 0.2 to 2 parts of dispersing auxiliary agent. According to the invention, the thiol-modified thermoplastic resin has a thiol structure, so that the thiol-modified thermoplastic resin can react with the nano silver powder, and a better sintering effect of the silver powder is achieved in a subsequent curing process.
Description
Technical Field
The invention relates to the field of conductive adhesive, in particular to nano conductive adhesive and a preparation method thereof.
Background
The nanometer conductive adhesive is attracting attention in the microelectronic packaging field, because the nanometer conductive adhesive has special electric property and mechanical property compared with the traditional conductive adhesive. The current research of nanometer conductive adhesive relates to the preparation of high-performance conductive adhesive by adopting nanometer particles, nanometer wires, carbon nanometer tubes and the like as conductive fillers.
The nano silver colloid has the advantages of small granularity and good fluidity, and can form a fine and smooth conductive film layer with good adhesive force on various substrate materials after solidification.
The nanometer conductive adhesive can reach 10 at 170 ℃ or above -6 Volume resistance on the order of ohm.cm, but conductivity is compromised when cured at low temperatures.
Patent CN 109652005A discloses a conductive adhesive, which is prepared by using diethylene glycol and cyanate ester resin as organic mixed solvents, doping A, B two silver powder types, and adding a dispersing agent to mix. The A, B silver powder is prepared by grinding silver powder with purity of 99.95% into micro-nano silver powder by high-energy ball, and separating out A silver particles with diameter of 3-20 μm and B silver particles with diameter below 200 nm. However, it is extremely prone to cracking.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a nanometer conductive adhesive composition and a preparation method thereof.
In view of this, the technical scheme provided by the invention is as follows:
the nano conductive adhesive comprises the following components in parts by weight:
3-8 parts of sulfhydryl modified thermoplastic resin
20-50 parts of solvent
40-70 parts of nano conductive silver powder
0.2-2 parts of dispersing auxiliary.
The molecular weight of the sulfhydryl modified thermoplastic resin is 3 ten thousand to 20 ten thousand, and the sulfhydryl modified thermoplastic resin is soluble in solvent.
The mercapto-modified thermoplastic resin is a modified thermoplastic resin containing mercapto groups and being soluble in a solvent.
The solvent comprises one or a mixture of more of aromatic hydrocarbon, aliphatic hydrocarbon, ester cyclic hydrocarbon, esters, glycol derivatives, alcohols and ketones.
Further, 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 diethyl ether acetate, propylene glycol methyl ether, diethylene glycol butyl ether acetate.
The nanometer conductive silver powder comprises nanometer conductive silver powder with the D50 particle diameter within 5nm-1 micron.
Preferably, the particle size of the nano conductive silver powder is 10-500 nanometers.
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 butyl ether acetate and propylene glycol methyl ether acetate, uniformly stirring, heating to reflux reaction, and keeping the temperature at 130-150 ℃ to obtain a reaction solution A;
s2, uniformly mixing methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, glycidyl methacrylate and a TBPB initiator to obtain a reaction solution 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, continuing dripping, 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 mercapto-modified thermoplastic resin.
According to the invention, the effect of silver powder sintering can be achieved only by the specific content of the mercapto-modified thermoplastic resin, and although the modified thermoplastic resin enables the silver powder to be bonded, excessive coating can be caused if the resin content is excessive, so that the catalytic sintering of the acid dispersant on the silver powder is difficult to achieve in the post-curing process; the content of the nano silver powder is also required to be controlled because the silver powder is too high in content and is easily cracked although it can be sintered, resulting in a decrease in conductivity.
In a second aspect, the present invention also provides a method for preparing the aforementioned nano conductive adhesive composition, which includes the following steps:
mixing the sulfhydryl modified thermoplastic resin with a solvent, mechanically stirring until the sulfhydryl modified thermoplastic resin is completely dissolved, then adding a dispersing auxiliary agent, uniformly stirring, adding nano conductive silver powder, discharging after high-speed dispersion, and preparing the nano conductive adhesive. Wherein the material is discharged after being dispersed to the large particles (the large particles with the particle size of more than 5 um) without agglomeration at high speed.
The conductive adhesive prepared by the invention can be cured for 1h at 130C, and can obtain the conductive adhesive with the curing time of less than 9 x 10 -6 The ohm.cm volume resistance, under which conditions the silver powder sintered together as seen by SEM images; the principle is that when the nano silver particles are at high temperature, the acid auxiliary agent corrodes the surfaces of the nano silver particles, so that the silver particles are close to each other to form sintering, and higher conductivity is obtained.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the silver powder is bonded by adding the thermoplastic resin, and the silver powder is more regularly arranged by the reaction of the resin and the silver powder, so that the subsequent sintering of the silver powder is more promoted on the molecular level;
2. the invention discovers that not all thermoplastic resins have excellent effects in the research, and the inventor discovers that the mercapto-modified thermoplastic resin has a mercapto structure, so that the mercapto-modified thermoplastic resin can react with nano silver powder, and the silver powder can achieve better sintering effect in the subsequent curing process. Some of the commonly used thermoplastic resins available in the art, such as some acrylic monomers polymerized without modification (Paraloideb 44, A11, lucite's Elvacite 2016, etc.), do not achieve this synergistic effect;
3. the purpose of adding the acid dispersing agent in the invention is to enable the nano silver powder to be sintered better at low temperature. The invention further carries out comparative researches on the acid dispersing agent, the polymer dispersing agent, the amine dispersing agent and the like, and discovers that the acid dispersing agent can enable silver powder to be more close in the curing process due to the acid washing property, so that the effect of low-temperature sintering is realized. However, polymeric dispersants and amine dispersants do not achieve the sintering effect at all;
4. according to the invention, the modified thermoplastic resin, the nano silver powder and the acid dispersing agent are mutually synergistic, and sintering of the silver powder can be realized under the simultaneous action of the three components;
5. the invention provides low-temperature curing type high-conductivity nano conductive adhesive, thereby improving conductivity;
6. the nano conductive adhesive provided by the invention has excellent adhesive property, and meanwhile, the product has better ageing resistance.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
Preparation example
Preparation of modified mercapto acrylic resin:
and (3) a component A:
diethylene glycol butyl ether acetate 300 parts
Propylene glycol methyl ether acetate 100 parts
And the component B comprises the following components:
stirring and heating the component A in the formula amount until reflux reaction, and keeping the temperature at about 140 ℃;
uniformly stirring the component B in the formula amount, then dripping the component B into the system in the step 1 for 4 times, wherein the dripping time is 15-20min each time, the dripping is continued after the heat preservation is carried out for 40min after the component B is dripped for the first three times, and the heat preservation is carried out for 60min after the last dripping; and cooling the system to 80 ℃, adding 100 parts of ethanedithiol, reacting for 2 hours, cooling and discharging to prepare 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 stirred and mixed with the solvent, then the acid auxiliary agent is added, the nano silver powder is added after stirring uniformly, 2000R is dispersed at high speed until no large agglomerated particles (the large agglomerated particles refer to particles with the particle size larger than 5 um) are discharged for testing.
Conductivity test: scraping the prepared conductive adhesive film to prepare an adhesive film with the size of 3mm and 100mm and the thickness of 0.05mm, then placing the adhesive film in a baking oven with the temperature of 130 ℃ for 1h, taking out and cooling the adhesive film to normal temperature, testing the resistance by using a four-probe method, and calculating the volume resistance.
For comparison, the amounts of the resin and the solvent of the original mixed solution in the table are calculated amounts respectively.
Table 1 Components (in parts by weight) of the nanometer conductive adhesive of examples 1 to 4
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 gums prepared in examples 1 to 4
As can be seen from the results of 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 < -6 > ohm.
Comparative example 1
Comparative example 1 differs from example 1 in that: the addition amount of the acid dispersant BYK-111 was 0.5 part.
Comparative example 2
Comparative example 1 differs from example 3 in that: the nano silver powder was replaced with micron silver powder (D50:2 microns).
Comparative example 3
Comparative example 1 differs from example 3 in that: 60 parts of the nano silver powder was replaced with 20 parts of nano silver powder and 40 parts of micron silver powder (D50: 2 microns).
Comparative example 4
Comparative example 1 differs from example 4 in that: the acid 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 composition of nano-conductive adhesives of comparative examples 1-5
The conductivity of the nano conductive adhesive obtained in comparative examples 1 to 5 was measured, and the results are shown in table 4:
TABLE 4 Properties of the nano conductive pastes prepared in comparative examples 1 to 5
As can be seen from the results in table 4:
the nano conductive adhesive prepared by the method of comparative example 1 (compared with example 1) has conductivity not reaching 10 - 6 Ohm.cm; because the acid dispersant dose is insufficient, silver powder cannot be mutually close to form sintering during high-temperature curing, so that higher conductivity cannot be achieved;
the nano-conductive adhesive prepared by comparative examples 2-3 (compared with example 3) did not have conductivity of 10 - 6 Ohm.cm; the sintering of the silver powder is blocked because the micron-sized silver powder is adopted, the particle size is large, and the particle shape is irregular;
in the comparison of comparative example 4 and example 4, after the acid dispersant was changed to the polymer type dispersant, the conductivity was deteriorated because the polymer type dispersant had a limited effect on the surface of silver powder and could not promote sintering;
using comparative example 5, the conductivity was not 10 as compared with example 2 by changing the mercapto-modified acrylic resin to a general mercapto-free acrylic resin -6 Ohm.cm, because the thiol resin has a synergistic effect on the approach of silver particles, if this reactivity is removed, then the approach of silver particles is not achieved, and the sintering effect is achieved;
the invention provides a method for greatly improving conductivity under low-temperature curing aiming at a nano conductive silver colloid system, and can greatly reduce curing cost aiming at application of nano conductive adhesive. And meanwhile, the material cost can be saved by reducing the glue consumption.
The foregoing describes specific embodiments of the present invention. It is to be understood that the invention is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the invention. The embodiments of the present application and features in the embodiments may be combined with each other arbitrarily without conflict.
Claims (5)
1. The nano conductive adhesive is characterized by comprising the following components in parts by weight:
3 to 8 parts of sulfhydryl modified thermoplastic resin,
20 to 50 parts of solvent, and the solvent is mixed with the solvent,
40-70 parts of nano conductive silver powder,
0.2-2 parts of dispersing auxiliary;
the particle size of the nano conductive silver powder is 10-500 nanometers;
the mercapto-modified thermoplastic resin is a modified thermoplastic resin which contains mercapto groups and is soluble in a solvent;
the molecular weight of the sulfhydryl modified thermoplastic resin is 3-20 ten thousand, and the sulfhydryl modified thermoplastic resin is soluble in the solvent;
the dispersing aid is an acidic dispersing aid;
the preparation method of the sulfhydryl modified thermoplastic resin comprises the following steps:
s1, mixing diethylene glycol butyl ether acetate and propylene glycol methyl ether acetate, uniformly stirring, heating to reflux reaction, and keeping the temperature at 130-150 ℃ to obtain a reaction solution A;
s2, uniformly mixing methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate, glycidyl methacrylate and a TBPB initiator to obtain a reaction solution 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 heat preservation for 40-60min after the reaction liquid is dripped for the first three times, and after heat preservation for 60-80min after the last dripping, cooling the system to 80-90 ℃, adding ethanedithiol, reacting for 2-2.5 h, cooling and discharging to obtain the mercapto-modified thermoplastic resin.
2. The nano conductive adhesive according to claim 1, wherein the solvent comprises one or a mixture of several of aromatic hydrocarbon, aliphatic hydrocarbon, ester cyclic hydrocarbon, ester, glycol derivative, alcohol and ketone.
3. The nano conductive adhesive according to claim 2, wherein the solvent is at least one of toluene, xylene, pentane, hexane, octane, cyclohexane, absolute ethanol, ethyl acetate, butyl acetate, amyl acetate, isopropyl alcohol, n-butanol, ethylene glycol ethyl ether acetate, propylene glycol methyl ether, diethylene glycol butyl ether acetate.
4. A method for preparing the nano conductive adhesive as claimed in any one of claims 1 to 3, comprising the steps of:
mixing the sulfhydryl modified thermoplastic resin with a solvent, mechanically stirring until the sulfhydryl modified thermoplastic resin is completely dissolved, then adding a dispersing auxiliary agent, uniformly stirring, adding nano conductive silver powder, discharging after high-speed dispersion, and preparing the nano conductive adhesive.
5. Use of the nano-conductive paste of any one of claims 1-3 or the nano-conductive paste prepared by the preparation method of claim 4 in the field of microelectronic packaging.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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Citations (4)
| 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 |
| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105579533B (en) * | 2013-08-16 | 2020-04-14 | 汉高知识产权控股有限责任公司 | Submicron silver particle ink compositions, methods and uses |
| CN110272686B (en) * | 2019-05-22 | 2021-10-26 | 北京蓝海黑石科技有限公司 | Low-halogen fast-curing conductive adhesive composition and preparation method thereof |
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Patent Citations (4)
| 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 |
| 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 |
| 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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