CN113292956A - Reworkable epoxy conductive adhesive composition, preparation method thereof and reworking method - Google Patents
Reworkable epoxy conductive adhesive composition, preparation method thereof and reworking method Download PDFInfo
- Publication number
- CN113292956A CN113292956A CN202110665806.2A CN202110665806A CN113292956A CN 113292956 A CN113292956 A CN 113292956A CN 202110665806 A CN202110665806 A CN 202110665806A CN 113292956 A CN113292956 A CN 113292956A
- Authority
- CN
- China
- Prior art keywords
- conductive adhesive
- epoxy
- epoxy resin
- parts
- silver powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004593 Epoxy Substances 0.000 title claims abstract description 125
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 124
- 239000000853 adhesive Substances 0.000 title claims abstract description 122
- 239000000203 mixture Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 12
- 239000003822 epoxy resin Substances 0.000 claims abstract description 91
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 91
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000013008 thixotropic agent Substances 0.000 claims abstract description 19
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 16
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000002270 dispersing agent Substances 0.000 claims abstract description 16
- 238000009736 wetting Methods 0.000 claims abstract description 15
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 claims abstract 5
- 238000002156 mixing Methods 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 9
- LTVUCOSIZFEASK-MPXCPUAZSA-N (3ar,4s,7r,7as)-3a-methyl-3a,4,7,7a-tetrahydro-4,7-methano-2-benzofuran-1,3-dione Chemical compound C([C@H]1C=C2)[C@H]2[C@H]2[C@]1(C)C(=O)OC2=O LTVUCOSIZFEASK-MPXCPUAZSA-N 0.000 claims description 8
- AOBIOSPNXBMOAT-UHFFFAOYSA-N 2-[2-(oxiran-2-ylmethoxy)ethoxymethyl]oxirane Chemical compound C1OC1COCCOCC1CO1 AOBIOSPNXBMOAT-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- QNYBOILAKBSWFG-UHFFFAOYSA-N 2-(phenylmethoxymethyl)oxirane Chemical compound C1OC1COCC1=CC=CC=C1 QNYBOILAKBSWFG-UHFFFAOYSA-N 0.000 claims description 5
- UIDDPPKZYZTEGS-UHFFFAOYSA-N 3-(2-ethyl-4-methylimidazol-1-yl)propanenitrile Chemical compound CCC1=NC(C)=CN1CCC#N UIDDPPKZYZTEGS-UHFFFAOYSA-N 0.000 claims description 5
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 5
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 4
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 4
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 3
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- HHRACYLRBOUBKM-UHFFFAOYSA-N 2-[(4-tert-butylphenoxy)methyl]oxirane Chemical compound C1=CC(C(C)(C)C)=CC=C1OCC1OC1 HHRACYLRBOUBKM-UHFFFAOYSA-N 0.000 claims description 3
- WTYYGFLRBWMFRY-UHFFFAOYSA-N 2-[6-(oxiran-2-ylmethoxy)hexoxymethyl]oxirane Chemical compound C1OC1COCCCCCCOCC1CO1 WTYYGFLRBWMFRY-UHFFFAOYSA-N 0.000 claims description 3
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 3
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 claims description 3
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 3
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- LMMDJMWIHPEQSJ-UHFFFAOYSA-N bis[(3-methyl-7-oxabicyclo[4.1.0]heptan-4-yl)methyl] hexanedioate Chemical compound C1C2OC2CC(C)C1COC(=O)CCCCC(=O)OCC1CC2OC2CC1C LMMDJMWIHPEQSJ-UHFFFAOYSA-N 0.000 claims description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 3
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 3
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 3
- JAYXSROKFZAHRQ-UHFFFAOYSA-N n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC=CC=1)CC1CO1 JAYXSROKFZAHRQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004843 novolac epoxy resin Substances 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- MAYDTZUGOTYIBH-UHFFFAOYSA-N CC(CC1OC1C1)C1C1(CCCCC1)C(O)=O Chemical compound CC(CC1OC1C1)C1C1(CCCCC1)C(O)=O MAYDTZUGOTYIBH-UHFFFAOYSA-N 0.000 claims 1
- 238000004377 microelectronic Methods 0.000 abstract description 4
- 239000005022 packaging material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 39
- 150000001241 acetals Chemical group 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 238000002791 soaking Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000004806 packaging method and process Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 229910021485 fumed silica Inorganic materials 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 230000000593 degrading effect Effects 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000440 bentonite Substances 0.000 description 3
- 229910000278 bentonite Inorganic materials 0.000 description 3
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 3
- 239000004359 castor oil Substances 0.000 description 3
- 235000019438 castor oil Nutrition 0.000 description 3
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 3
- 238000004021 metal welding Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 3, 4-epoxycyclohexylmethyl Chemical group 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 229910000978 Pb alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- VRAIHTAYLFXSJJ-UHFFFAOYSA-N alumane Chemical compound [AlH3].[AlH3] VRAIHTAYLFXSJJ-UHFFFAOYSA-N 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000003466 welding 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
- C08G59/24—Di-epoxy compounds carbocyclic
-
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Conductive Materials (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a reworkable epoxy conductive adhesive composition, a preparation method and a reworking method thereof, and relates to the technical field of microelectronic packaging materials. The reworkable epoxy conductive adhesive composition provided by the invention comprises the following preparation raw materials in parts by weight: 7-15 parts of epoxy resin, 0-4 parts of epoxy diluent, 5-10 parts of anhydride curing agent, 0.1-0.4 part of accelerator, 0.1-0.4 part of coupling agent, 0.1-0.3 part of wetting dispersant, 0.1-0.3 part of thixotropic agent, 0.1-0.3 part of defoaming agent and 75-85 parts of conductive silver powder; the epoxy resin comprises an acetal structure-containing epoxy resin, and the mass of the acetal structure-containing epoxy resin accounts for 70-100% of the total mass of the epoxy resin. After being cured, the reworkable epoxy conductive adhesive composition provided by the invention can be degraded in an organic solution of acid, so that the reworking treatment of the conductive adhesive is realized.
Description
Technical Field
The invention relates to the technical field of microelectronic packaging materials, in particular to a reworkable epoxy conductive adhesive composition, a preparation method and a reworking method thereof.
Background
In recent years, electronic products are gradually miniaturized, thinned, high-performance, multifunctional and green, and the packaging density, integration level and safety of packaging materials of printed circuit boards are increasingly required. In the field of microelectronic packaging, metal welding is widely used for packaging connection, but the metal welding is easy to generate a continuous welding phenomenon when high-density packaging is carried out, and the requirements of fine pitch and multi-lead interconnection are difficult to meet. In addition, the conventional Sn — Pb alloy solder has been gradually banned from being used in daily electronic products by developed countries such as europe, america, and the day because it has adverse effects on human health and natural environment.
The conductive adhesive connection is considered as an ideal lead-free connection technology for replacing the traditional metal welding, and has the advantages of environmental friendliness, simple process, low curing temperature, good reliability, high packaging line resolution and the like. At present, the conductive adhesive is widely applied to bonding and packaging of electronic devices and components such as LEDs, integrated circuit chips, solar cells, printed circuit board components, liquid crystal display screens, digital tubes, quartz resonators, ceramic capacitors and the like. The conductive adhesive consists of polymer matrix resin, a curing agent, a conductive filler and a functional auxiliary agent. Among various types of conductive adhesives, the silver powder filled epoxy resin conductive adhesive is one of the most widely used products, mainly because the epoxy resin has excellent adhesive property, processing property and chemical corrosion resistance, and the conductive silver filler has the characteristics of low resistivity, high thermal conductivity and difficult oxidation in air.
However, the conventional epoxy resin has a highly crosslinked three-dimensional network structure after being cured, and has the characteristics of insolubility and infusibility, and once the conductive adhesive is applied and cured, the reworking treatment of connected electronic components is difficult, which is not beneficial to the maintenance of integrated circuits and the replacement and recovery of expensive semiconductor components.
Therefore, the development of the conductive adhesive with the reworkable function has important practical application value and economic benefit and is worthy of research.
Disclosure of Invention
The reworkable epoxy conductive adhesive composition provided by the invention can be degraded in an organic solution of acid after being cured, so that the reworking treatment of the conductive adhesive is realized.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a reworkable epoxy conductive adhesive composition which comprises the following preparation raw materials in parts by weight: 7-15 parts of epoxy resin, 0-4 parts of epoxy diluent, 5-10 parts of anhydride curing agent, 0.1-0.4 part of accelerator, 0.1-0.4 part of coupling agent, 0.1-0.3 part of wetting dispersant, 0.1-0.3 part of thixotropic agent, 0.1-0.3 part of defoaming agent and 75-85 parts of conductive silver powder;
the epoxy resin comprises an acetal structure-containing epoxy resin, and the mass of the acetal structure-containing epoxy resin accounts for 70-100% of the total mass of the epoxy resin.
Preferably, the acetal structure-containing epoxy resin includes:
one or more of them.
Preferably, the epoxy resin further includes one or more of electronic grade bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac epoxy resin, hydrogenated bisphenol a type epoxy resin, polyfunctional glycidyl amine type epoxy resin, biphenyl type glycidyl ether epoxy resin, naphthol epoxy resin, 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, 3, 4-epoxy-6-methylcyclohexylcarboxylic acid-3 ',4' -epoxy-6 ' -methylcyclohexylmethyl ester, and bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate.
Preferably, the epoxy diluent comprises one or more of benzyl glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, cardanol glycidyl ether, 4-tert-butylphenyl glycidyl ether, vinylcyclohexene dioxide and diglycidyl aniline.
Preferably, the anhydride curing agent includes one or more of methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, methyl nadic anhydride, and hydrogenated methyl nadic anhydride.
Preferably, the promoter comprises one or more of metallic zinc acetylacetonate, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, imidazole adduct, and tertiary amine adduct.
Preferably, the conductive silver powder includes a flake silver powder, a sphere-like silver powder, and a nano silver powder;
the average flake diameter of the flake silver powder is 1-20 mu m; the average grain diameter of the sphere-like silver powder is 0.2-3 mu m; the average particle size of the nano silver powder is 20-100 nm.
Preferably, the weight ratio of the flake silver powder, the sphere-like silver powder and the nano silver powder is 60-90: 5-25: 2-10.
The invention provides a preparation method of the reworkable epoxy conductive adhesive composition, which comprises the following steps:
mixing other preparation raw materials except the conductive silver powder to obtain a liquid mixture;
and mixing the liquid mixture with the conductive silver powder, and defoaming to obtain the reworkable epoxy conductive adhesive composition.
The invention provides a reworking method of a cured epoxy conductive adhesive, which comprises the following steps: dipping the cured epoxy conductive adhesive in an organic solution of acid for degradation; the cured epoxy conductive adhesive is obtained by curing the reworkable epoxy conductive adhesive composition or the reworkable epoxy conductive adhesive composition prepared by the preparation method in the technical scheme.
The invention provides a reworkable epoxy conductive adhesive composition which comprises the following preparation raw materials in parts by weight: 7-15 parts of epoxy resin, 0-4 parts of epoxy diluent, 5-10 parts of anhydride curing agent, 0.1-0.4 part of accelerator, 0.1-0.4 part of coupling agent, 0.1-0.3 part of wetting dispersant, 0.1-0.3 part of thixotropic agent, 0.1-0.3 part of defoaming agent and 75-85 parts of conductive silver powder; the epoxy resin comprises an acetal structure-containing epoxy resin, and the mass of the acetal structure-containing epoxy resin accounts for 70-100% of the total mass of the epoxy resin. The invention adopts the acetal bond-containing epoxy resin component, introduces acetal dynamic chemical bonds into the epoxy conductive adhesive after curing, and the acetal bonds can be degraded in an organic solution of acid, thereby endowing the epoxy conductive adhesive with a reworkable function. Through the cooperation of the components, the mechanical property, the heat resistance, the bonding property and the conductivity of the reworkable epoxy conductive adhesive composition can be improved, and the reworkable epoxy conductive adhesive composition has a good application prospect in the field of microelectronic packaging.
Detailed Description
The invention provides a reworkable epoxy conductive adhesive composition which comprises the following preparation raw materials in parts by weight: 7-15 parts of epoxy resin, 0-4 parts of epoxy diluent, 5-10 parts of anhydride curing agent, 0.1-0.4 part of accelerator, 0.1-0.4 part of coupling agent, 0.1-0.3 part of wetting dispersant, 0.1-0.3 part of thixotropic agent, 0.1-0.3 part of defoaming agent and 75-85 parts of conductive silver powder;
the epoxy resin comprises an acetal structure-containing epoxy resin, and the mass of the acetal structure-containing epoxy resin accounts for 70-100% of the total mass of the epoxy resin.
In the present invention, all the starting materials for the preparation are commercially available products known to those skilled in the art unless otherwise specified.
The reworkable epoxy conductive adhesive composition comprises 7-15 parts by mass of epoxy resin, and preferably 9.5-12 parts by mass. In the invention, the epoxy resin comprises an acetal structure-containing epoxy resin, and the mass of the acetal structure-containing epoxy resin accounts for 70-100% of the total mass of the epoxy resin, preferably 80-87%.
In the present invention, the acetal structure-containing epoxy resin preferably includes:
one or more of them.
In the present invention, the epoxy resin preferably further includes one or more of electronic grade bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac epoxy resin, hydrogenated bisphenol a type epoxy resin, polyfunctional glycidyl amine type epoxy resin, biphenyl type glycidyl ether epoxy resin, naphthol epoxy resin, 3, 4-epoxycyclohexylmethyl 3',4' -epoxycyclohexyl carboxylate, 3, 4-epoxy-6-methylcyclohexylcyclohexanecarboxylate-3 ',4' -epoxy-6 ' -methylcyclohexylmethyl ester and bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate. The invention adopts the epoxy resin as an auxiliary epoxy resin component, and can adjust the mechanical, thermal and adhesive properties of the conductive adhesive.
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 0-4 parts of epoxy diluent, preferably 2-4 parts. In the present invention, the epoxy diluent preferably includes one or more of benzyl glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, cardanol glycidyl ether, 4-tert-butylphenyl glycidyl ether, vinylcyclohexene dioxide, and diglycidyl aniline. In the invention, compared with other diluents, the epoxy diluent has smaller influence on the heat resistance, rigidity and bonding performance of the conductive adhesive.
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 5-10 parts of an anhydride curing agent, preferably 5.6-9.7 parts, and more preferably 7.8-8.8 parts. In the present invention, the acid anhydride curing agent preferably includes one or more of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic anhydride. Compared with the conventional curing agent, the anhydride curing agent adopted by the invention has low viscosity and good manufacturability; the physiological toxicity is low, and the irritation to the human body is small; the curing shrinkage is small, and the heat resistance of the cured product is good.
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 0.1-0.4 part of accelerator, preferably 0.2-0.3 part. In the present invention, the accelerator preferably includes one or more of metallic zinc acetylacetonate, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, an imidazole adduct, and a tertiary amine adduct. In the present invention, the imidazole adduct preferably includes one or more of ajinomotol PN-23, ajinomotol PN-31, ajinomotol PN-40 and ajinomotol PN-50. In the present invention, the tertiary amine adduct preferably includes one or more of ajinomotol MY-24, ajinomotol MY-25, ajinomotol MY-H, and ajinomotol MY-HK-1. In the invention, the accelerator can promote the curing of the conductive adhesive and improve the curing reaction rate.
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 0.1-0.4 part of coupling agent, preferably 0.2-0.3 part. In the present invention, the coupling agent preferably includes one or more of A-187 (manufacturer: Meiji), A-1871 (manufacturer: Meiji), SCA-HE87M (manufacturer: Nanjing Needt new), SCA-E86M (manufacturer: Nanjing Needt new), and SCA-E86E (manufacturer: Nanjing Needt new). In the invention, the coupling agent can improve the bonding property of the conductive adhesive.
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 0.1-0.3 part of wetting dispersant, preferably 0.2 part. In the invention, the wetting dispersant preferably comprises one or more of VATIX 2017 (the manufacturer is Shanghai Junjiang technology), VATIX 2018 (the manufacturer is Shanghai Junjiang technology), BYK-W969 (the manufacturer is Germany bike), BYK-W980 (the manufacturer is Germany bike) and BYK996 (the manufacturer is Germany bike). In the present invention, the lubricating dispersant can improve the dispersion quality of the conductive silver powder.
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 0.1-0.3 part of thixotropic agent, preferably 0.2 part of thixotropic agent. In the present invention, the thixotropic agent preferably includes one or more of fumed silica, polyamide-modified hydrogenated castor oil, organic bentonite, and polyamide wax. In the present invention, the thixotropic agent can improve the thixotropy of the conductive paste, and has a higher viscosity at low shear and a lower viscosity at high shear.
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 0.1-0.3 part of defoaming agent, and preferably 0.2 part. In the invention, the defoaming agent preferably comprises one or more of VATIX 830 (the manufacturer is Shanghai Junjiang technology), VATIX 866 (the manufacturer is Shanghai Junjiang technology), VATIX 820W (the manufacturer is Shanghai Junjiang technology), BYK-A530 (the manufacturer is Germany bike) and BYK-320 (the manufacturer is Germany bike).
Based on the weight parts of the epoxy resin, the reworkable epoxy conductive adhesive composition provided by the invention comprises 75-85 parts of conductive silver powder, more preferably 77-81 parts, and even more preferably 78-80 parts. In the present invention, the conductive silver powder preferably includes a flake silver powder, a sphere-like silver powder, and a nano silver powder; the average plate diameter of the flaky silver powder is preferably 1-20 μm, more preferably 1-15 μm, even more preferably 1-10 μm, and particularly preferably 5.6 μm, 2.4 μm, 3.5 μm or 8.2 μm; the average particle size of the spherical-like silver powder is preferably 0.2-3 μm, more preferably 0.2-1 μm, and particularly preferably 0.3 μm, 0.5 μm, 0.7 μm or 0.9 μm; the average particle size of the nano silver powder is preferably 20-100 nm, and more preferably 50-80 nm. In the invention, the weight ratio of the flake silver powder, the sphere-like silver powder and the nano silver powder is preferably 60-90: 5-25: 2-10, more preferably 65-85: 8-20: 3-8, and further preferably 66-68: 9-14: 4-5.
The conductive silver powder combined by the flake silver powder, the sphere-like silver powder and the nano silver powder can enable the silver powder to be stacked more tightly, wherein the small-scale silver powder plays a role in filling gaps, so that a conductive path is formed better; and the melting point of the nano silver powder is lower, the nano silver powder can be sintered at a lower temperature, the contact resistance among the silver powders is reduced, and the improvement of the conductivity of the conductive adhesive is facilitated.
The invention provides a preparation method of the reworkable epoxy conductive adhesive composition, which comprises the following steps:
mixing other preparation raw materials except the conductive silver powder to obtain a liquid mixture;
and mixing the liquid mixture with the conductive silver powder, and defoaming to obtain the reworkable epoxy conductive adhesive composition.
According to the invention, other preparation raw materials except the conductive silver powder are mixed to obtain a liquid mixture. In the present invention, the mixing is preferably performed in a revolution and rotation disperser; the mixing time is preferably 2-8 min, and more preferably 3-5 min.
After the liquid mixture is obtained, the reworkable epoxy conductive adhesive composition is obtained by mixing the liquid mixture with the conductive silver powder and defoaming. In the present invention, the mixing is preferably performed in a revolution and rotation disperser; the mixing time is preferably 2-8 min, and more preferably 3-5 min.
In the invention, the mixture is preferably dispersed by a three-roller machine after being mixed in a revolution and rotation disperser. In the invention, the dispersing time of the three-roller machine is preferably 0.5-1.5 h, and more preferably 0.8-1 h. The invention is favorable for further improving the dispersing effect of the conductive silver powder by three-roller dispersing.
In the present invention, the defoaming is preferably performed under vacuum conditions; the time for defoaming is preferably 30-60 min.
In the invention, the reworkable epoxy conductive adhesive composition is in a liquid state, and is cured when in use, so that the cured reworkable epoxy conductive adhesive is obtained. In the present invention, the curing temperature is preferably 180 ℃, and the curing time is preferably 2 hours.
The invention also provides a reworking method of the cured epoxy conductive adhesive, which comprises the following steps: dipping the cured epoxy conductive adhesive in an organic solution of acid for degradation; the cured epoxy conductive adhesive is obtained by curing the reworkable epoxy conductive adhesive composition or the reworkable epoxy conductive adhesive composition prepared by the preparation method in the technical scheme.
In the present invention, the organic solution of the acid is preferably prepared from an aqueous acid solution and an organic solvent. In the present invention, the acid aqueous solution preferably includes one or more of an aqueous hydrochloric acid solution, an aqueous sulfuric acid solution, an aqueous phosphoric acid solution, an aqueous benzenesulfonic acid solution and an aqueous p-toluenesulfonic acid solution; the concentration of the acid aqueous solution is preferably 0.1 to 2mol/L, and more preferably 0.1 to 1 mol/L. In the present invention, the organic solvent preferably includes one or more of ethanol, acetone, tetrahydrofuran, N-dimethylformamide, and N-methylpyrrolidone. In the present invention, the volume ratio of the acid aqueous solution to the organic solvent is preferably 1:8 to 10, and more preferably 1: 9.
The invention has no special requirement on the dosage of the organic solution of the acid, and can ensure that the cured epoxy conductive adhesive is completely soaked in the organic solution of the acid. In the invention, the impregnation is preferably carried out under a standing condition, and the impregnation temperature is preferably 25-60 ℃, and more preferably 25-40 ℃; the dipping time is preferably 0.1-0.5 h, and more preferably 0.2-0.3 h.
In the dipping process, the epoxy resin component is degraded, other components are small molecular additives or silver powder and are easy to remove, and the reworkable epoxy conductive adhesive composition can be completely removed by adopting the method provided by the invention.
In the invention, after the cured epoxy conductive adhesive is degraded, fragments of epoxy resin micromolecules or oligomers are generated, and the fragments can be recycled as organic fuel.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Weighing and putting epoxy resin EP-110.0 parts, curing agent methyl hexahydrophthalic anhydride 7.8 parts, accelerant zinc acetylacetonate 0.3 parts, coupling agent SCA-HE87M (the manufacturer is Nanjing Neidede new material) 0.3 parts, wetting dispersant BYK-W980 (the manufacturer is Germany Bike) 0.2 parts, thixotropic agent fumed silica 0.2 parts and defoaming agent VATIX 830 (the manufacturer is Shanghai Junjiang science) 0.2 parts into a revolution autorotation disperser, mixing and stirring for 2min to obtain a liquid mixture;
65.0 parts of flake silver powder with the average flake diameter of 5.6 microns, 14.0 parts of spheroidal silver powder with the average particle diameter of 0.9 microns and 2.0 parts of nano silver powder with the average particle diameter of 50nm are added into the obtained liquid mixture, the mixture is put into a revolution and rotation disperser again and dispersed for 2min, then the mixture is dispersed for 1h by a three-roller machine, and the obtained mixture is defoamed for 30min under the vacuum condition to obtain the reworkable epoxy conductive adhesive composition.
And curing the reworkable epoxy conductive adhesive composition for 2h at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 1mol/L hydrochloric acid solution and acetone according to the volume ratio of 1:9 to obtain organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, standing for 0.3h at room temperature, completely degrading the epoxy resin component, and performing rework treatment.
The properties of the reworkable epoxy conductive adhesive composition prepared in this example are shown in table 1.
Example 2
Weighing EP-47.0 parts of epoxy resin, 1.5 parts of epoxy resin bisphenol F epoxy resin, 5.6 parts of curing agent methyl tetrahydrophthalic anhydride, 230.4 parts of promoter monosodium PN-4, 0.2 part of coupling agent A-187 (manufacturer: Mei chart), 0.2 part of wetting dispersant VATIX 2017 (manufacturer: Shanghai Junjiang science), 0.3 part of thixotropic agent organic bentonite and 0.3 part of defoaming agent BYK-A530 (manufacturer: Germany bike), putting into a revolution and rotation dispersing instrument, mixing and stirring for 5min to obtain a liquid mixture;
68 parts of flake silver powder with the average flake diameter of 8.2 microns, 13 parts of spheroidal silver powder with the average particle diameter of 0.7 microns and 4 parts of nano silver powder with the average particle diameter of 80nm are added into the obtained liquid mixture, the mixture is put into a revolution and rotation disperser again to be dispersed for 5min, and then the mixture is dispersed for 1.5h through a three-roller machine, and the obtained mixture is defoamed for 60min under the vacuum condition to obtain the reworkable epoxy conductive adhesive composition.
And curing the reworkable epoxy conductive adhesive composition for 2h at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 1mol/L sulfuric acid solution and ethanol according to the volume ratio of 1:9 to obtain an organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, standing for 0.2h at room temperature, completely degrading the epoxy resin component, and performing rework treatment.
The properties of the reworkable epoxy conductive adhesive composition prepared in this example are shown in table 1.
Example 3
Weighing EP-57.0 parts of epoxy resin, 3.0 parts of epoxy resin electronic grade bisphenol A epoxy resin, 4.0 parts of epoxy diluent 1, 4-butanediol diglycidyl ether, 9.7 parts of curing agent methyl nadic anhydride, 0.3 parts of accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole, 0.2 parts of coupling agent SCA-HE87M (the manufacturer is Nanjing Needwood), 0.2 parts of wetting dispersant BYK-W969 (the manufacturer is Germany Big), 0.3 parts of thixotropic agent polyamide modified hydrogenated castor oil and 0.3 parts of defoaming agent VATIX 866 (the manufacturer is Shanghai Junjiang river science and technology), putting the epoxy resin EP-57.0 parts, the curing agent methyl nadic anhydride, the accelerator 1-cyanoethyl-2-ethyl-4-methylimidazole, the thixotropic agent polyamide modified hydrogenated castor oil and the defoaming agent VATIX 866 (the manufacturer is Shanghai Junjiang river science and technology) into a self-rotation dispersing instrument, and mixing and stirring for 5min to obtain a liquid mixture;
60 parts of flaky silver powder with the average flake diameter of 3.5 microns, 13 parts of spheroidal silver powder with the average particle diameter of 0.5 microns and 4 parts of nano silver powder with the average particle diameter of 100nm are added into the obtained liquid mixture, the mixture is put into a revolution and rotation disperser again to be dispersed for 5min, and then the mixture is dispersed for 0.5h by a three-roller machine, and the obtained mixture is defoamed for 30min under the vacuum condition to obtain the reworkable epoxy conductive adhesive composition.
And curing the reworkable epoxy conductive adhesive composition for 2h at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 1mol/L phosphoric acid solution and tetrahydrofuran according to the volume ratio of 1:9 to obtain organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, heating for 0.2h at 40 ℃, completely degrading the epoxy resin component, and performing rework treatment.
The properties of the reworkable epoxy conductive adhesive composition prepared in this example are shown in table 1.
Example 4
Weighing EP-78.0 parts of epoxy resin, 2.0 parts of 3, 4-epoxy cyclohexyl formic acid-3 ',4' -epoxy cyclohexyl methyl ester of epoxy resin, 2.0 parts of benzyl glycidyl ether of epoxy diluent, 8.4 parts of curing agent methyl hexahydrophthalic anhydride, 0.2 parts of promoter gourmet PN-500.4 parts, 0.2 parts of coupling agent SCA-E86M (the manufacturer is Nanjing Needuncut material), 0.2 parts of wetting dispersant VATIX 2018 (the manufacturer is Shanghai Junjiang science and technology), 0.3 parts of thixotropic agent fumed silica and 0.3 parts of defoaming agent BYK-A530 (the manufacturer is German Bike) by weight, putting the epoxy resin, the 3, 4' -epoxy cyclohexyl methyl ester, the curing agent methyl hexahydrophthalic anhydride, and the thixotropic agent into a revolution autorotation dispersion instrument, mixing and stirring for 4min to obtain a liquid mixture;
66 parts of flaky silver powder with the average flake diameter of 2.4 microns, 9 parts of spheroidal silver powder with the average particle diameter of 0.3 microns and 5 parts of nano silver powder with the average particle diameter of 50nm are added into the obtained liquid mixture, the mixture is put into a revolution and rotation disperser again to be dispersed for 4min, and then the mixture is dispersed for 1.2h by a three-roller machine, and the obtained mixture is defoamed for 30min under the vacuum condition to obtain the reworkable epoxy conductive adhesive composition.
And curing the reworkable epoxy conductive adhesive composition for 2h at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 1mol/L p-toluenesulfonic acid solution and N, N-dimethylformamide according to the volume ratio of 1:9 to obtain an organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, heating for 0.1h at the temperature of 60 ℃, completely degrading the epoxy resin component, and performing rework treatment.
The properties of the reworkable epoxy conductive adhesive composition prepared in this example are shown in table 1.
Example 5
Weighing epoxy resin EP-1010.0 parts, epoxy diluent neopentyl glycol diglycidyl ether 2.0 parts, curing agent methyl hexahydrophthalic anhydride 8.8 parts, accelerator 2-ethyl-4 methylimidazole 0.2 parts, coupling agent SCA-E86M (the manufacturer is: Nanjing Neede new materials) 0.3 parts, wetting dispersant VATIX 2018 (the manufacturer is: Shanghai Junjiang science) 0.2 parts, thixotropic agent fumed silica 0.3 parts, defoaming agent BYK-A530 (the manufacturer is: Germany Bike) 0.2 parts by weight based on the weight parts, putting the materials into a revolution autorotation dispersion instrument, and mixing and stirring for 3min to obtain a liquid mixture;
66 parts of flaky silver powder with the average flake diameter of 5.6 microns, 8 parts of spheroidal silver powder with the average particle diameter of 0.5 microns and 4 parts of nano silver powder with the average particle diameter of 100nm are added into the obtained liquid mixture, the mixture is put into a revolution and rotation disperser again to be dispersed for 3min, and then the mixture is dispersed for 0.8h by a three-roller machine, and the obtained mixture is defoamed for 30min under the vacuum condition to obtain the reworkable epoxy conductive adhesive composition.
And curing the reworkable epoxy conductive adhesive composition for 2h at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 0.5mol/L sulfuric acid solution and N-methyl pyrrolidone according to the volume ratio of 1:9 to obtain an organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, heating for 0.1h at 40 ℃, completely degrading the epoxy resin component, and performing rework treatment.
The properties of the reworkable epoxy conductive adhesive composition prepared in this example are shown in table 1.
Comparative example 1
Weighing 8.0 parts of bisphenol A epoxy resin, 2.0 parts of epoxy diluent 1.4-butanediol diglycidyl ether, 11.7 parts of curing agent methyl hexahydrophthalic anhydride, 0.3 part of accelerant zinc acetylacetonate, 0.3 part of coupling agent SCA-HE87M (the manufacturer is Nanjing Needunculus newwood), 0.2 part of wetting dispersant BYK-W980 (the manufacturer is Germany Bike), 0.2 part of thixotropic agent fumed silica and 0.2 part of defoaming agent VATIX 830 (the manufacturer is Shanghai Junjiang science and technology), putting the materials into a revolution dispersion instrument, and mixing and stirring for 2min to obtain a liquid mixture;
65.0 parts of flake silver powder with the average flake diameter of 5.6 microns, 14.0 parts of spheroidal silver powder with the average particle diameter of 0.9 microns and 2.0 parts of nano silver powder with the average particle diameter of 50nm are added into the obtained liquid mixture, the mixture is put into a revolution and rotation disperser again and dispersed for 2min, and then the mixture is dispersed for 1.2h by a three-roller machine, and the obtained mixture is defoamed for 30min under the vacuum condition to obtain the epoxy conductive adhesive.
And curing the epoxy conductive adhesive for 2 hours at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 1mol/L hydrochloric acid solution and acetone according to the volume ratio of 1:9 to obtain organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, standing for 48 hours at room temperature, wherein the epoxy resin component in the epoxy conductive adhesive is not degraded.
The properties of the epoxy conductive adhesive prepared in this comparative example are shown in table 1.
Comparative example 2
Weighing 7.5 parts of bisphenol F epoxy resin, 6.3 parts of curing agent methyl tetrahydrophthalic anhydride, 0.2 part of promoter monosodium PN-23 (monosodium glutamate), 0.3 part of coupling agent A-187 (manufacturer: Mei chart), 0.3 part of wetting dispersant VATIX 2017 (manufacturer: Shanghai Junjiang science), 0.2 part of thixotropic agent organic bentonite and 0.2 part of defoaming agent BYK-A530 (manufacturer: Germany Bike) by weight parts, putting the materials into a revolution autorotation disperser, mixing and stirring for 5min to obtain a liquid mixture;
and adding 68 parts of flaky silver powder with the average flake diameter of 8.2 microns, 13 parts of spheroidal silver powder with the average particle diameter of 0.7 microns and 4 parts of nano silver powder with the average particle diameter of 80nm into the obtained liquid mixture, putting the mixture into a revolution and rotation disperser again, dispersing for 5min, then dispersing for 1.5h by a three-roller machine, and defoaming the obtained mixture for 60min under a vacuum condition to obtain the epoxy conductive adhesive.
And curing the epoxy conductive adhesive for 2 hours at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 1mol/L sulfuric acid solution and ethanol according to the volume ratio of 1:9 to obtain an organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, standing for 48 hours at room temperature, wherein the epoxy resin component in the epoxy conductive adhesive is not degraded.
The properties of the epoxy conductive adhesive prepared in this comparative example are shown in table 1.
Comparative example 3
Weighing 8 parts of 3, 4-epoxy group cyclohexyl formic acid-3 ',4' -epoxy group cyclohexyl methyl ester, 2.0 parts of epoxy diluent benzyl glycidyl ether, 8.6 parts of curing agent methyl hexahydrophthalic anhydride, 0.3 part of accelerating agent gourmet PN-500.4 parts, 0.2 part of coupling agent SCA-E86M (the manufacturer is Nanjing Needuncus de new material), 0.2 part of wetting dispersant VATIX 2018 (the manufacturer is Shanghai Junjiang science) 0.3 part of thixotropic agent fumed silica and 0.3 part of defoaming agent BYK-A530 (the manufacturer is German Bike) by taking the parts by weight as reference, putting the components into a revolution autorotation disperser, mixing and stirring for 4min to obtain a liquid mixture;
66 parts of flaky silver powder with the average flake diameter of 2.4 microns, 9 parts of spheroidal silver powder with the average particle diameter of 0.3 microns and 5 parts of nano silver powder with the average particle diameter of 50nm are added into the obtained liquid mixture, the mixture is put into a revolution and rotation disperser again to be dispersed for 4min, and then the mixture is dispersed for 0.5h by a three-roller machine, and the obtained mixture is defoamed for 30min under the vacuum condition to obtain the epoxy conductive adhesive.
And curing the epoxy conductive adhesive for 2 hours at 180 ℃ to obtain the cured epoxy conductive adhesive.
Mixing 1mol/L p-toluenesulfonic acid solution and N, N-dimethylformamide according to the volume ratio of 1:9 to obtain an organic acid solution;
and (3) soaking the cured epoxy conductive adhesive in the organic solution of the acid, and heating for 6 hours at the temperature of 60 ℃, wherein the epoxy resin component in the epoxy conductive adhesive is not degraded.
The properties of the epoxy conductive adhesive prepared in this comparative example are shown in table 1.
TABLE 1 results of performance test of epoxy conductive adhesives of examples and comparative examples
In Table 1, the viscosity of the epoxy conductive adhesive prepared in the above examples and comparative examples was measured at room temperature using a rotational viscometer in accordance with GB/T22314-; volume resistivity the cured epoxy conductive adhesives prepared in the above examples and comparative examples were tested for volume resistivity according to ASTM D257-2007 test standard using a four-probe method; shear strength the cured epoxy conductive adhesives prepared in the above examples and comparative examples were tested for aluminum-aluminum lap shear strength using a universal mechanical testing machine in accordance with ASTM D1002 test standards.
As can be seen from the results in Table 1, the reworkable epoxy conductive adhesive composition provided by the invention can be subjected to degradation rework treatment, and the higher the degradation treatment temperature is, the faster the degradation rate is. And the conventional epoxy conductive adhesive in the comparative example can not be chemically degraded and is difficult to carry out reworking treatment. The reworkable epoxy conductive adhesive composition provided by the invention has better conductive performance and bonding performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The reworkable epoxy conductive adhesive composition is characterized by comprising the following preparation raw materials in parts by weight: 7-15 parts of epoxy resin, 0-4 parts of epoxy diluent, 5-10 parts of anhydride curing agent, 0.1-0.4 part of accelerator, 0.1-0.4 part of coupling agent, 0.1-0.3 part of wetting dispersant, 0.1-0.3 part of thixotropic agent, 0.1-0.3 part of defoaming agent and 75-85 parts of conductive silver powder;
the epoxy resin comprises an acetal structure-containing epoxy resin, and the mass of the acetal structure-containing epoxy resin accounts for 70-100% of the total mass of the epoxy resin.
2. The reworkable epoxy conductive adhesive composition according to claim 1, wherein the acetal structure-containing epoxy resin comprises:
one or more of them.
3. The reworkable epoxy conductive adhesive composition according to claim 1 or 2, wherein the epoxy resin further comprises one or more of an electronic grade bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a novolac epoxy resin, a hydrogenated bisphenol a type epoxy resin, a polyfunctional glycidyl amine type epoxy resin, a biphenyl type glycidyl ether epoxy resin, a naphthol epoxy resin, 3, 4-epoxycyclohexylcarboxylic acid-3 ',4' -epoxycyclohexylmethyl ester, 3, 4-epoxy-6-methylcyclohexylcyclohexanecarboxylic acid-3 ',4' -epoxy-6 ' -methylcyclohexylmethyl ester and bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate.
4. The reworkable epoxy conductive adhesive composition of claim 1, wherein the epoxy diluent comprises one or more of benzyl glycidyl ether, butyl glycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, cardanol glycidyl ether, 4-tert-butylphenyl glycidyl ether, vinylcyclohexene dioxide and diglycidyl aniline.
5. The reworkable epoxy conductive adhesive composition of claim 1, wherein the anhydride curing agent comprises one or more of methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride and hydrogenated methylnadic anhydride.
6. The reworkable epoxy conductive adhesive composition of claim 1, wherein the accelerator comprises one or more of metallic zinc acetylacetonate, iron acetylacetonate, nickel acetylacetonate, cobalt acetylacetonate, 2-ethyl-4 methylimidazole, 1-cyanoethyl-2-ethyl-4 methylimidazole, an imidazole adduct and a tertiary amine adduct.
7. The reworkable epoxy conductive adhesive composition according to claim 1, wherein the conductive silver powder comprises a plate-like silver powder, a sphere-like silver powder and a nano silver powder;
the average flake diameter of the flake silver powder is 1-20 mu m; the average grain diameter of the sphere-like silver powder is 0.2-3 mu m; the average particle size of the nano silver powder is 20-100 nm.
8. The reworkable epoxy conductive adhesive composition according to claim 7, wherein the weight ratio of the flake silver powder, the sphere-like silver powder and the nano silver powder is 60-90: 5-25: 2-10.
9. The method for preparing the reworkable epoxy conductive adhesive composition according to any one of claims 1 to 8, comprising the steps of:
mixing other preparation raw materials except the conductive silver powder to obtain a liquid mixture;
and mixing the liquid mixture with the conductive silver powder, and defoaming to obtain the reworkable epoxy conductive adhesive composition.
10. A reworking method of a cured epoxy conductive adhesive comprises the following steps: dipping the cured epoxy conductive adhesive in an organic solution of acid for degradation; the cured epoxy conductive adhesive is obtained by curing the reworkable epoxy conductive adhesive composition according to any one of claims 1 to 8 or the reworkable epoxy conductive adhesive composition prepared by the preparation method according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110665806.2A CN113292956A (en) | 2021-06-16 | 2021-06-16 | Reworkable epoxy conductive adhesive composition, preparation method thereof and reworking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110665806.2A CN113292956A (en) | 2021-06-16 | 2021-06-16 | Reworkable epoxy conductive adhesive composition, preparation method thereof and reworking method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113292956A true CN113292956A (en) | 2021-08-24 |
Family
ID=77328424
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110665806.2A Pending CN113292956A (en) | 2021-06-16 | 2021-06-16 | Reworkable epoxy conductive adhesive composition, preparation method thereof and reworking method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113292956A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939999A (en) * | 2005-09-27 | 2007-04-04 | 上海特视精密仪器有限公司 | Sliver-powder conducting glue and its production |
| US20160237322A1 (en) * | 2013-08-08 | 2016-08-18 | Boe Technology Group Co., Ltd. | Silver conductive adhesive and preparation method |
| CN110272686A (en) * | 2019-05-22 | 2019-09-24 | 北京蓝海黑石科技有限公司 | A kind of low halogen rapid-curing conductive composition and preparation method thereof |
| CN110724486A (en) * | 2019-09-20 | 2020-01-24 | 北京蓝海黑石科技有限公司 | Recyclable LED packaging conductive adhesive composition and preparation method thereof |
| CN112920379A (en) * | 2021-03-26 | 2021-06-08 | 蓝赛夫(上海)电子材料有限公司 | Epoxy resin monomer and intermediate thereof, preparation method, epoxy resin and recovery method |
-
2021
- 2021-06-16 CN CN202110665806.2A patent/CN113292956A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1939999A (en) * | 2005-09-27 | 2007-04-04 | 上海特视精密仪器有限公司 | Sliver-powder conducting glue and its production |
| US20160237322A1 (en) * | 2013-08-08 | 2016-08-18 | Boe Technology Group Co., Ltd. | Silver conductive adhesive and preparation method |
| CN110272686A (en) * | 2019-05-22 | 2019-09-24 | 北京蓝海黑石科技有限公司 | A kind of low halogen rapid-curing conductive composition and preparation method thereof |
| CN110724486A (en) * | 2019-09-20 | 2020-01-24 | 北京蓝海黑石科技有限公司 | Recyclable LED packaging conductive adhesive composition and preparation method thereof |
| CN112920379A (en) * | 2021-03-26 | 2021-06-08 | 蓝赛夫(上海)电子材料有限公司 | Epoxy resin monomer and intermediate thereof, preparation method, epoxy resin and recovery method |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7718090B2 (en) | Conductive paste | |
| CN106914710B (en) | Resin flux paste and mounting structure | |
| CN102086364A (en) | Conductive silver paste for microelectronic packaging and preparation method thereof | |
| US20050230667A1 (en) | Conductive adhesive and circuit using the same | |
| CN110272686B (en) | Low-halogen fast-curing conductive adhesive composition and preparation method thereof | |
| JP4235887B2 (en) | Conductive paste | |
| JP7083474B2 (en) | Recyclable LED packaging conductive adhesive composition and its manufacturing method | |
| CN104822789A (en) | Conductive adhesive composition and electronic element using same | |
| JP3837858B2 (en) | Conductive adhesive and method of using the same | |
| JP4235888B2 (en) | Conductive paste | |
| CN110607150A (en) | Conductive adhesive composition capable of being stored at normal temperature and preparation method thereof | |
| CN104629643B (en) | Conducting resinl, its preparation method and wiring board | |
| CN117487496B (en) | Conductive silver adhesive based on modified silver powder and preparation method thereof | |
| JP2000290617A (en) | Electroconductive adhesive and usage thereof | |
| CN113292956A (en) | Reworkable epoxy conductive adhesive composition, preparation method thereof and reworking method | |
| JP4224771B2 (en) | Conductive paste | |
| JP2000192000A (en) | Electrically conductive adhesive | |
| CN101402838B (en) | Silver staining palladium alloy microsphere conductive adhesive and method of producing the same | |
| TWI706856B (en) | Conductive composition, conductive film, and circuit board using the same | |
| JP4235885B2 (en) | Conductive paste | |
| CN112543548B (en) | Conductive composition, conductive layer using same and circuit board | |
| JP4224772B2 (en) | Conductive paste | |
| CN117625106A (en) | High-temperature-resistant silver conductive adhesive and preparation method thereof | |
| Inada et al. | Fundamental study on adhesive strength of electrical conductive adhesives (ECAs) | |
| JP4224774B2 (en) | Conductive paste |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210824 |