CN115260955B - Silver conductive adhesive containing conductive additive and preparation method and application thereof - Google Patents
Silver conductive adhesive containing conductive additive and preparation method and application thereof Download PDFInfo
- Publication number
- CN115260955B CN115260955B CN202210887872.9A CN202210887872A CN115260955B CN 115260955 B CN115260955 B CN 115260955B CN 202210887872 A CN202210887872 A CN 202210887872A CN 115260955 B CN115260955 B CN 115260955B
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- China
- Prior art keywords
- silver
- conductive
- parts
- epoxy resin
- complex
- Prior art date
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 77
- 239000000853 adhesive Substances 0.000 title claims abstract description 74
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 74
- 239000004332 silver Substances 0.000 title claims abstract description 72
- 239000002482 conductive additive Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000003822 epoxy resin Substances 0.000 claims abstract description 50
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 239000000654 additive Substances 0.000 claims abstract description 30
- 239000011231 conductive filler Substances 0.000 claims abstract description 22
- 239000003085 diluting agent Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- 229940100890 silver compound Drugs 0.000 claims abstract description 15
- 150000003379 silver compounds Chemical class 0.000 claims abstract description 15
- 239000008139 complexing agent Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 21
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000007822 coupling agent Substances 0.000 claims description 15
- -1 glycidyl ester Chemical class 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- SESYNEDUKZDRJL-UHFFFAOYSA-N 3-(2-methylimidazol-1-yl)propanenitrile Chemical compound CC1=NC=CN1CCC#N SESYNEDUKZDRJL-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 13
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 13
- 238000004806 packaging method and process Methods 0.000 claims description 13
- 239000012745 toughening agent Substances 0.000 claims description 13
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 238000003825 pressing Methods 0.000 claims description 12
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 claims description 8
- 230000003078 antioxidant effect Effects 0.000 claims description 8
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 8
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 8
- 229930185605 Bisphenol Natural products 0.000 claims description 7
- 150000001412 amines Chemical class 0.000 claims description 7
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 7
- 239000003446 ligand Substances 0.000 claims description 7
- 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 6
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- YAXXOCZAXKLLCV-UHFFFAOYSA-N 3-dodecyloxolane-2,5-dione Chemical compound CCCCCCCCCCCCC1CC(=O)OC1=O YAXXOCZAXKLLCV-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-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
- 229910052796 boron Inorganic materials 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 6
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 6
- 229940071536 silver acetate Drugs 0.000 claims description 6
- 229910001923 silver oxide Inorganic materials 0.000 claims description 6
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 claims description 6
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-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
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 claims description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 235000012207 sodium gluconate Nutrition 0.000 claims description 5
- 239000000176 sodium gluconate Substances 0.000 claims description 5
- 229940005574 sodium gluconate Drugs 0.000 claims description 5
- 229960002317 succinimide Drugs 0.000 claims description 5
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 5
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 5
- 238000011282 treatment Methods 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 4
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- 101000823183 Alcaligenes faecalis Aralkylamine dehydrogenase heavy chain Proteins 0.000 claims description 3
- 101000823182 Alcaligenes faecalis Aralkylamine dehydrogenase light chain Proteins 0.000 claims description 3
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 claims description 3
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229920003986 novolac Polymers 0.000 claims description 3
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004100 electronic packaging Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 150000008065 acid anhydrides Chemical class 0.000 claims 1
- 238000001723 curing Methods 0.000 description 33
- 229920005989 resin Polymers 0.000 description 24
- 239000011347 resin Substances 0.000 description 24
- 239000011159 matrix material Substances 0.000 description 21
- 235000006708 antioxidants Nutrition 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000009461 vacuum packaging Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002313 adhesive film Substances 0.000 description 5
- 239000002518 antifoaming agent Substances 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 229920000459 Nitrile rubber Polymers 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 2
- KWYJDIUEHHCHCZ-UHFFFAOYSA-N 3-[2-[bis(2-carboxyethyl)amino]ethyl-(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCN(CCC(O)=O)CCC(O)=O KWYJDIUEHHCHCZ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 2
- MQNVHUZWFZKETG-UHFFFAOYSA-N P1(OCCCCCO1)=O.NCCNCCN Chemical compound P1(OCCCCCO1)=O.NCCNCCN MQNVHUZWFZKETG-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002042 Silver nanowire Substances 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- STNSYZSNIYTNMI-UHFFFAOYSA-N azane;[2-[bis(phosphonomethyl)amino]ethyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound N.OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O STNSYZSNIYTNMI-UHFFFAOYSA-N 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229940071106 ethylenediaminetetraacetate Drugs 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 229960003151 mercaptamine Drugs 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 2
- 229910000161 silver phosphate Inorganic materials 0.000 description 2
- 229940019931 silver phosphate Drugs 0.000 description 2
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 2
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 2
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 description 2
- 235000019832 sodium triphosphate Nutrition 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- BDZBKCUKTQZUTL-UHFFFAOYSA-N triethyl phosphite Chemical compound CCOP(OCC)OCC BDZBKCUKTQZUTL-UHFFFAOYSA-N 0.000 description 2
- OQILSTRGJVCFAG-UHFFFAOYSA-N 1-(oxiran-2-ylmethoxy)butan-1-ol Chemical compound CCCC(O)OCC1CO1 OQILSTRGJVCFAG-UHFFFAOYSA-N 0.000 description 1
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 229930091371 Fructose Natural products 0.000 description 1
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 1
- 239000005715 Fructose Substances 0.000 description 1
- 239000004944 Liquid Silicone Rubber Substances 0.000 description 1
- CMQAMENQCKNUPB-UHFFFAOYSA-N NC1CCOP(=O)O1 Chemical compound NC1CCOP(=O)O1 CMQAMENQCKNUPB-UHFFFAOYSA-N 0.000 description 1
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- SNCZNSNPXMPCGN-UHFFFAOYSA-N butanediamide Chemical compound NC(=O)CCC(N)=O SNCZNSNPXMPCGN-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
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- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
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- 150000002367 halogens Chemical class 0.000 description 1
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- 235000021317 phosphate Nutrition 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
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- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- 235000019165 vitamin E Nutrition 0.000 description 1
- 229940046009 vitamin E Drugs 0.000 description 1
- 239000011709 vitamin E Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- 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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- 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
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- 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)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a silver conductive adhesive containing a conductive additive and a preparation method thereof, wherein the silver conductive adhesive comprises the following components in parts by weight: 5-16 parts of epoxy resin; 0-2 parts of diluent; 0.5 to 14 parts of curing agent; 0.01-5 parts of conductive additive; 72-84 parts of conductive filler; 0-1 part of additive. According to the invention, on the basis of the conductive adhesive formed by the epoxy resin and the conductive filler, the complex of the silver compound with specific content is added, and the diluent, the curing agent and the additive with specific content are added, so that the prepared silver conductive adhesive not only can reduce the use amount of the conductive filler, but also has obviously improved conductive performance and shear strength.
Description
Technical Field
The invention belongs to the technical field of conductive adhesive, and particularly relates to silver conductive adhesive containing a conductive additive, and a preparation method and application thereof.
Background
The conductive adhesive is used as a novel green environment-friendly electronic adhesive, has the advantages of low operation temperature, simple process and the like, and has been widely applied to the fields of microelectronic packaging, IC packaging, LED packaging and the like. Conductive paste has some disadvantages compared to conventional tin-lead solder. In terms of performance, the conductivity, the heat conductivity and the like of the conductive adhesive are lower than those of tin-lead solder; in the aspect of storage, tin-lead solder does not need to be stored at low temperature, but commercial single-component conductive adhesive needs to be stored at low temperature, so that great inconvenience is caused to the transportation of the conductive adhesive; in application, tin-lead solder gradually develops towards a lead-free and VOC-free direction, which puts higher demands on the VOC content of the conductive adhesive.
The conductive adhesive mainly comprises a resin matrix and conductive fillers, wherein the resin matrix provides mechanical properties for the conductive adhesive, and the conductive fillers form a conductive network to provide conductive properties for the conductive adhesive. In view of the excellent comprehensive properties of epoxy resins, epoxy resins are generally used for the resin matrix at present. Silver powder has excellent conductivity and chemical stability, and even if oxidized, silver oxide has certain conductivity. Therefore, silver powder is often used as a filler for high-reliability conductive paste. In order to improve the electrical conductivity of the conductive adhesive, new methods and techniques have been developed gradually, for example, chinese patent (single radium etc., a preparation method of high thermal conductivity conductive die bond adhesive, CN 11386911 a [ p ], 2021) destroy the organic insulating material on the surface of silver powder by organic diacid, chinese patent (Zhang Lijiang, a conductive adhesive for chip packaging and preparation method thereof, CN 108864979 a [ p ], 2018) increase the electrical conductivity of the conductive adhesive by adding conductive materials such as silver nanowires, nano silver powder, graphene, etc., document (Cheng Y,Cui X,Zhang Z,et al.Fractal dendrite-based electrically conductive composites for laser-scribed flexible circuits[J].Nature Communications,2015,6(8150):10.) and chinese patent (Yang Cheng, cui Xiaoya, zhang Zhexu) a conductive composite material and preparation method thereof, preparation method of conductive lines, CN 105006270 a [ p ], 2015) increase the electrical conductivity of the conductive adhesive after curing by applying dendrite, chinese patent (Yang Cheng, etc., metal powder with sponge microstructure and preparation method thereof, conductive material, CN 1063302 a [ p ], 2016) introduce silver halide, chinese patent (Tian Yanqing, a conductive adhesive film, a solid conductive adhesive and preparation method thereof, and application, CN 113831876 a [ p ], 2018) add conductive polymer, etc., and so as to increase the electrical conductivity of the conductive adhesive. However, some of the above additives for enhancing conductivity are expensive (e.g., silver nanowires, nano silver powder), some are not industrialized (e.g., graphene and dendritic silver powder), some may cause a decrease in mechanical properties (e.g., organic dibasic acid and conductive polymer), and some may introduce halogen element into the product, so that further researches on the formulation of silver conductive paste and the preparation method thereof are necessary.
The current known conductive adhesive enterprises are mainly concentrated in few developed countries such as America, japanese, germany and the like, the research and development forces are large, and almost the whole high-end product market is monopoly. Compared with developed countries, the conductive adhesive technology in China starts late, and has a certain gap between the product performance and overseas products, and is mainly applied to middle-low end products. As the manufacturing industry of the electronic industry, the demand of China for silver conductive adhesive is huge and increases year by year. In order to meet the needs of practical application and accelerate the localization of silver conductive adhesive applied to high-end product markets, further researches on the formula of silver conductive adhesive and the preparation method thereof are necessary to be continued, and novel silver conductive adhesive is prepared so as to improve the international competitiveness of the electronic product packaging industry in China.
Disclosure of Invention
In order to solve the technical problems in the art, it is a primary object of the present invention to provide a conductive paste containing a conductive additive having significantly improved conductive properties and shear strength.
The invention also aims to provide a preparation method of the silver conductive adhesive containing the conductive additive.
It is still another object of the present invention to provide the use of the above-mentioned conductive paste containing a conductive additive.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the silver conductive adhesive containing the conductive auxiliary agent comprises the following components in parts by weight:
In some preferred technical schemes, the silver conductive adhesive containing the conductive additive comprises the following components in parts by weight:
In some preferred embodiments, the epoxy resin is selected from one or more of liquid bisphenol a type epoxy resin, bisphenol F type epoxy resin, and phenolic type epoxy resin; the bisphenol A type epoxy resin is selected from bisphenol E44 epoxy resin and/or bisphenol E51 epoxy resin; the phenolic epoxy resin is selected from novolac F44 and/or F51 epoxy resins.
In some preferred embodiments, the diluent is selected from one or more of monoglycidyl ether, diglycidyl ether, polyfunctional glycidyl amine, polyfunctional glycidyl ester in reactive diluent. It will be appreciated that a great advantage of the silver conductive paste of the present invention is a solvent-free silver conductive paste. Compared with silver conductive adhesive with solvent, the silver conductive adhesive of the invention reduces VOC generated in the application process to the maximum extent, and is more environment-friendly.
In some preferred technical schemes, the curing agent is selected from one or more of amine curing agents, anhydride curing agents, imidazole curing agents and boron amine complex curing agents; the amine curing agent is one or more selected from dicyandiamide DICY, diamino diphenyl sulfone DDS, diamino diphenyl methane DDM and adipic acid dihydrazide AADH; the anhydride curing agent is one or more selected from methyl tetrahydrophthalic anhydride (MeTHPA), methyl hexahydrophthalic anhydride (MeHHPA), methyl Nadic Anhydride (MNA) and dodecyl succinic anhydride (DDSA); the imidazole curing agent is one or more selected from 2-methylimidazole 2MZ, 2-ethyl-4 methylimidazole 2E4MZ, 1-cyanoethyl-2-methylimidazole 2MZ-CN and 1-cyanoethyl-2-ethyl-4-methylimidazole 2E4 MZ-CN; the boron amine complex curing agent is one or more selected from triethylamine-BF 3 complex, aniline-BF 3 complex and monoethylamine-BF 3 complex.
In some preferred embodiments, the conductive aid is a complex of a silver compound consisting of a silver compound, an organic ligand, and a complexing agent; wherein the silver compound is one or more selected from silver nitrate, silver acetate, silver oxide, silver lactate, silver phosphate, silver acetylacetonate and silver organic complex; the organic ligand is selected from one or more of NH 3, triphenylphosphine, triethoxy phosphine, succinimide, phthalimide, glutarimide, maleimide, N-bromosuccinimide, a compound containing-CN, a compound containing-SCN and a compound containing S 2O3 -; the complexing agent is selected from one or more of sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, diethanolamine, triethanolamine, ethylenediamine tetrapropionic acid, triethylenetetramine, ethylenediamine tetraacetate EDTA, aminotriacetate NTA, diethylenetriamine pentacarboxylate DTPA, tartaric acid, citric acid, heptonate, sodium gluconate, sulfosalicylic acid, dimercaptopropanol, mercaptoethylamine, thioglycollic acid, tributyl phosphate, ethylenediamine tetramethylene sodium EDTMPS, diethylenetriamine pentamethylene phosphonate DETPMPS, aminotrimethylene phosphonate, thiourea and thioacetamide. The complexing agent is used as one of the components of the complex of the silver compound, plays a role in regulating the release of silver atoms in the complex of the silver compound, and enables the silver atoms to be released under specific conditions so as to meet the use process requirements under different application scenes. Therefore, the complex of the silver compound is suitable for silver conductive adhesive with different formulas and application scenes of various using processes by adjusting the release condition of silver atoms in the complex of the silver compound.
In some preferred technical schemes, the conductive auxiliary agent is selected from one or more of a complex formed by ① silver acetate and a ligand of succinimide and/or 1-cyanoethyl-2-methylimidazole, a complex formed by a complexing agent of tributyl phosphate and/or triethanolamine, a complex formed by ② silver oxide and maleimide and/or 1-cyanoethyl-2-methylimidazole, a complex formed by a complexing agent of dimercaptopropanol and/or thioacetamide, a complex formed by ③ silver acetylacetonate and triphenylphosphine and/or phthalimide, a complexing agent of diethanolamine and/or triethylenetetramine, a complex formed by ④ silver nitrate and a ligand of 1-cyanoethyl-2-methylimidazole and/or glutarimide, and a complexing agent of sodium gluconate and/or citric acid.
In some preferred embodiments, the conductive filler is selected from the group consisting of surface fatty acid modified plate-like silver powder and/or spherical silver powder; preferably silver micro-flakes, micro-silver powder or nano-silver powder; the additive is one or more selected from antioxidant, defoamer, coupling agent and toughening agent.
In some preferred technical schemes, the antioxidant is selected from one or more of phosphite esters, vitamins, thioesters and reducing saccharides;
in some preferred embodiments, the defoamer is selected from one or more of phosphates, silicones, fatty acids and fatty acid esters;
in some preferred technical schemes, the coupling agent is selected from one or more of silane coupling agents, titanate coupling agents and zirconium aluminate coupling agents;
In some preferred technical schemes, the toughening agent is selected from one or more of liquid hydroxyl-terminated nitrile rubber, polyimide, liquid silicone rubber, polysulfide rubber, nano titanium oxide, white carbon black and organic bentonite.
The invention also provides a preparation method of the silver conductive adhesive, which comprises the following steps:
s1, weighing epoxy resin, a diluent, a curing agent, a conductive auxiliary agent, a conductive filler and an additive according to a proportion of ingredients, and performing pretreatment;
S2, loading the pretreated raw materials into a high-speed dispersion mixer to be mixed and dispersed for 30 seconds to 2 hours;
and S3, defoaming treatment, pressing and packaging to obtain the silver conductive adhesive.
In some preferred embodiments, in step S1, the epoxy resin, the conductive filler and the additive need to be heat-pretreated.
In some preferred embodiments, in step S2, the high-speed dispersion mixer is a planetary dispersion method.
In some preferred embodiments, in step S3, the defoaming treatment is selected from centrifugal defoaming or vacuum defoaming. The defoaming treatment mode of the silver conductive adhesive in the invention is optimally selected to be vacuum defoaming, and other defoaming modes are not particularly limited.
In some preferred embodiments, in step S3, the packaging may be vacuum packaging, or may be non-vacuum packaging. The vacuum packaging mode in the invention is the optimal choice, and other packaging modes are not particularly limited herein. It should be noted that the pressing and vacuum packaging may be performed by a separate process or a combined process, which is not particularly limited herein.
The invention also provides application of the silver conductive adhesive in electronic packaging.
Compared with the prior art, the invention has the following technical effects:
1) According to the invention, on the basis of the conductive adhesive formed by the epoxy resin and the conductive filler, the conductive additive with specific content is added, and the diluent, the curing agent and the additive with specific content are added, so that the prepared conductive adhesive containing the conductive additive not only can reduce the use amount of the conductive filler, but also has obviously improved conductive performance and shear strength.
2) The preparation method disclosed by the invention is simple in process, low in cost, free of VOC and environment-friendly, the prepared silver conductive adhesive is stored for more than 1 month at room temperature, and cured for 1h at 170 ℃, the volume resistivity after curing is up to 0.27 multiplied by 10 -4 ohm cm, and the shearing strength can be up to 28.9MPa.
Drawings
FIG. 1 is a cross-sectional view of an example-80.5% Ag conductive paste without conductive additive;
FIG. 2 is a cross-sectional view of an example-80.5% Ag conductive paste without conductive additive;
FIG. 3 is a cross-sectional view of a conductive paste of example II containing an Ag content of 80.5% by weight of a conductive additive;
FIG. 4 is a cross-sectional view of a conductive paste of example II containing an Ag content of 80.5% by weight of a conductive additive;
FIG. 5 is a cross-sectional view of a conductive paste of example III containing 0.09 parts of a conductive additive and 79.5% Ag;
FIG. 6 is a cross-sectional view of a conductive paste of example III containing 0.09 parts of a conductive additive and 79.5% Ag;
FIG. 7 is a cross-sectional view of a conductive paste of example IV containing 1.7 parts of a conductive additive and 72.8% Ag;
fig. 8 is a cross-sectional view of a conductive paste of example four containing 1.7 parts of a conductive additive and 72.8% ag.
Detailed Description
The invention is described in further detail below with reference to the drawings and examples. It is to be understood that the specific embodiments described herein are merely illustrative of the invention and are not limiting thereof. It should be further noted that, for convenience of description, only some, but not all of the structures related to the present invention are shown in the drawings.
Various embodiments of the invention are disclosed below, and for purposes of clarity, numerous practical details are set forth in the following description. However, it should be understood that these practical details are not to be taken as limiting the invention. That is, in some embodiments of the invention, these practical details are unnecessary.
The heat-curable conductive adhesive and the preparation method thereof according to the embodiment of the application are specifically described below.
The silver conductive adhesive containing the conductive auxiliary agent comprises the following components in parts by weight:
5 to 16 parts of epoxy resin, 0 to 2 parts of diluent, 0.5 to 14 parts of curing agent, 0.01 to 5 parts of conductive additive, 72 to 84 parts of conductive filler and 0 to 1 part of additive.
As an example, the epoxy resin accounts for 5 to 16 parts by weight of the raw material, and may be, for example, 5 parts, 6 parts, 6.5 parts, 7 parts, 7.4 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 12.5 parts, 13 parts, 14.5 parts, 15.6 parts, 16 parts, or the like.
In some embodiments, the epoxy resin is selected from one or more of a liquid bisphenol a type epoxy resin, a bisphenol F type epoxy resin, and a phenolic type epoxy resin. The bisphenol A type epoxy resin is one or two of bisphenol E44 epoxy resin and bisphenol E51 epoxy resin, and the phenolic aldehyde type epoxy resin is one or two of novolac F44 and F51 epoxy resin. For example, 7.8 parts by weight of bisphenol E44 epoxy resin is used.
Illustratively, the diluent may comprise 0 to 2 parts by weight of the raw materials, for example, 0 part, 0.1 part, 0.2 part, 0.3 part, 0.4 part, 0.5 part, 0.8 part, 0.9 part, 1 part, 1.2 part, 1.3 part, 1.5 part, 1.7 part, 1.8 part, or 2 parts, etc.
In some embodiments, the diluent is selected from one or more of a monoglycidyl ether, a diglycidyl ether, a multifunctional glycidyl amine, and a multifunctional glycidyl ester in a reactive diluent. For example, 1.5 parts by weight of butyl glycidyl ether are used.
Illustratively, the curing agent may comprise 0.5 to 14 parts by weight of the raw materials, for example, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.8 parts, 2.7 parts, 3.4 parts, 4.6 parts, 5.9 parts, 6.2 parts, 7.1 parts, 8.0 parts, 9.5 parts, 10.3 parts, 11.2 parts, 13.1 parts, or 14.0 parts, etc.
In some embodiments, the curing agent is selected from one or more of an amine curing agent, an anhydride curing agent, an imidazole curing agent, and a boron amine complex curing agent; the amine curing agent is one or more selected from dicyandiamide DICY, diamino diphenyl sulfone DDS, diamino diphenyl methane DDM and adipic acid dihydrazide AADH; the anhydride curing agent is one or more selected from methyl tetrahydrophthalic anhydride (MeTHPA), methyl hexahydrophthalic anhydride (MeHHPA), methyl Nadic Anhydride (MNA) and dodecyl succinic anhydride (DDSA); the imidazole curing agent is one or more selected from 2-methylimidazole 2MZ, 2-ethyl-4 methylimidazole 2E4MZ, 1-cyanoethyl-2-methylimidazole 2MZ-CN and 1-cyanoethyl-2-ethyl-4-methylimidazole 2E4 MZ-CN; the boron amine complex curing agent is selected from triethylamine-BF 3 complex and/or aniline-BF 3 complex. For example, 0.8 parts by weight of 1-cyanoethyl-2-ethyl-4-methylimidazole (2E 4 MZ-CN) is selected.
As an example, the conductive auxiliary agent accounts for 0.01 to 5 parts by weight of the raw material, and may be, for example, 0.01 part, 0.02 part, 0.04 part, 0.05 part, 0.07 part, 0.09 part, 1.0 part, 1.1 part, 1.7 part, 2.3 parts, 2.7 parts, 3.0 parts, 3.4 parts, 4.0 parts, 4.75 parts, or 5.0 parts, or the like.
In some embodiments, the conductive aid is a complex of a silver compound consisting of a silver compound, an organic ligand, and a complexing agent; wherein the silver compound is one or more selected from silver nitrate, silver acetate, silver oxide, silver lactate, silver phosphate, silver acetylacetonate and silver organic complex; the organic ligand is selected from one or more of NH 3, triphenylphosphine, triethoxy phosphine, succinimide, phthalimide, glutarimide, maleimide, N-bromosuccinimide, a compound containing-CN, a compound containing-SCN and a compound containing S 2O3 -; the complexing agent is selected from one or more of sodium tripolyphosphate, sodium pyrophosphate, sodium hexametaphosphate, diethanolamine, triethanolamine, ethylenediamine tetrapropionic acid, triethylenetetramine, ethylenediamine tetraacetate EDTA, aminotriacetate NTA, diethylenetriamine pentacarboxylate DTPA, tartaric acid, citric acid, heptonate, sodium gluconate, sulfosalicylic acid, dimercaptopropanol, mercaptoethylamine, thioglycollic acid, tributyl phosphate, ethylenediamine tetramethylene sodium EDTMPS, diethylenetriamine pentamethylene phosphonate DETPMPS, amine trimethophosphate, thiourea and thioacetamide. For example, the silver complex with the butanediamide complexing agent as tributyl phosphate is selected from one or more of ① silver acetate and the ligand butanediimide and/or 1-cyanoethyl-2-methylimidazole, the complexing agent tributyl phosphate and/or triethanolamine, the complex of ② silver oxide and maleimide and/or 1-cyanoethyl-2-methylimidazole, the complexing agent dimercaptopropanol and/or thioacetamide, the complex of ③ silver acetylacetonate and triphenylphosphine and/or phthalimide, the complexing agent diethanolamine and/or triethylenetetramine, ④ silver nitrate and the ligand 1-cyanoethyl-2-methylimidazole and/or glutarimide, and the complexing agent sodium gluconate and/or citric acid.
The conductive filler accounts for 72 to 84 weight parts of the raw materials. For example, 72 parts, 72.8 parts, 73 parts, 76 parts, 79.3 parts, 80 parts, 81.7 parts, 82 parts, 82.1 parts, 83.8 parts, 84 parts, or the like may be used.
In some embodiments, the conductive filler is selected from one or a mixture of both of surface fatty acid modified plate-like silver powder and spherical silver powder. For example, 80.8 parts by weight of silver micro-flakes are selected.
The weight of the additive is 0-1. For example, 0 part, 0.01 part, 0.15 part, 0.18 part, 0.2 part, 0.34 part, 0.4 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, 1 part, or the like may be used.
In some embodiments, the additive is selected from one or more of an antioxidant, a defoamer, a coupling agent, a toughening agent. For example, 0.5 parts by weight of liquid hydroxyl-terminated nitrile rubber is selected as the toughening agent.
A preparation method of a silver conductive adhesive containing a conductive additive comprises the following steps:
s1, weighing epoxy resin, a diluent, a curing agent, a conductive auxiliary agent, a conductive filler and an additive according to a proportion of ingredients, and performing pretreatment;
S2, loading the pretreated raw materials into a high-speed dispersion mixer to be mixed and dispersed for 30 seconds to 2 hours;
and S3, defoaming treatment, pressing and packaging to obtain the silver conductive adhesive.
The epoxy resin, the conductive filler and the additive in step S1 need to be heat-pretreated. For example, the conductive filler is pretreated by heating at 170 ℃ for 1 hour.
The high-speed dispersion mixer in the step S2 adopts a planetary dispersion mode. For example, a planetary high-speed disperser is used.
The dispersion time in step S3 is 30 seconds to 2 hours. For example, 30 seconds, 42 seconds, 50 seconds, 60 seconds, 120 seconds, 180 seconds, 230 seconds, 300 seconds, 360 seconds, 480 seconds, 600 seconds, 1200, 1800 seconds, 2400 seconds, 3000 seconds, 1 hour, 10 minutes, 1 hour, 20 minutes, 1.5 hours, 1 hour, 40 minutes, 1 hour, 50 minutes, 2 hours may be used.
The silver conductive adhesive defoaming mode in the step S3 is vacuum defoaming.
It should be noted that in some embodiments, other defoaming and packaging methods are also used for the silver conductive paste. For example, centrifugal defoaming is selected.
The packaging process of the silver conductive adhesive in the step S3 comprises material pressing and vacuum packaging. For example, a vacuum press packaging integrated machine is selected.
The raw material information used in examples one to seven is as follows:
Conductive filler: micron silver powder, available from Kunming Norman electronic materials Co., ltd., PSP-440;
nanometer silver powder purchased from Kunming silver family electronic materials Co., ltd., ag-07;
the epoxy resins are E44, E51 and F44;
the diluent is butyl glycidyl ether, o-toluene glycidyl ether and butanediol glycidyl ether;
the curing agent is Dicyandiamide (DICY), diaminodiphenyl sulfone (DDS), methyl hexahydrophthalic anhydride (MeHHPA) and 1-cyanoethyl-2-ethyl-4-methylimidazole (2E 4 MZ-CN);
Conductive auxiliary agent: complex of silver compound: ① A complex formed by silver acetate and a ligand succinimide and/or 1-cyanoethyl-2-methylimidazole, and a complexing agent tributyl phosphate and/or triethanolamine;
③ Silver acetylacetonate, triphenylphosphine and/or phthalimide, and a complexing agent diethanolamine and/or triethylenetetramine;
Additive: coupling agent: silane coupling agent (KH 550, KH560, KH570, KH 580)
Titanate coupling agents (KR 238, 401);
an antioxidant: tributyl phosphite, vitamin E, vitamin C and fructose;
Defoaming agent: tributyl phosphate;
toughening agent: liquid hydroxyl-terminated nitrile rubber, nano titanium oxide, white carbon black and organic bentonite.
Example 1
80.5 Parts of micron silver powder is heat treated for 1 hour at 180 ℃, and then 0.5 part of coupling agent is added for high-speed dispersion, so that the micron silver powder is treated. 8.6 parts of epoxy resin, 0.5 part of diluent, 9.4 parts of curing agent and 0.5 part of other additives are subjected to heat treatment at 80 ℃ for 10 minutes to form a resin matrix, wherein the other additives comprise antioxidants, defoamers and toughening agents. And (3) putting the treated micrometer silver powder and the resin matrix into a high-speed dispersion mixer for mixing and dispersing, wherein the dispersing time is 20 minutes, and the dispersing speed is 1000 revolutions per minute. After being dispersed evenly at high speed, the silver conductive adhesive A is obtained by removing bubbles in vacuum, pressing and vacuum packaging. The cross-sectional view of the silver conductive paste a is shown in fig. 1 and 2, and it can be seen from fig. 1: the section has larger meteorite pits, which proves that the internal stress is extruded outside, the bearing parts are not dense, and the large block falling is shown; from FIG. 2, it can be seen that the silver powder is well dispersed with the resin, demonstrating that the formation of merle pits is not caused by uneven distribution of the filler and the resin matrix.
Example two
80.5 Parts of micron silver powder is heat treated for 1 hour at 180 ℃, and then 0.5 part of coupling agent is added for high-speed dispersion, so that the micron silver powder is treated. 8.4 parts of epoxy resin, 0.5 part of diluent, 9 parts of curing agent, 0.6 part of conductive additive and 0.5 part of other additives are subjected to heat treatment at 80 ℃ for 10 minutes to form a resin matrix, wherein the other additives comprise an antioxidant, a defoaming agent and a toughening agent. And (3) putting the treated micrometer silver powder and the resin matrix into a high-speed dispersion mixer for mixing and dispersing, wherein the dispersing time is 20 minutes, and the dispersing speed is 1000 revolutions per minute. After being dispersed evenly at high speed, the silver conductive adhesive B containing the conductive additive is obtained by vacuum defoaming, material pressing and vacuum packaging. The cross-sectional view of the silver conductive paste B is shown in fig. 3 and 4, and it can be seen from fig. 3: the section has smaller meteorite pits, which proves that the internal stress is denser under the external extrusion, the stress is dispersed, the mechanical property is improved, and small blocks are shown to fall off; from FIG. 4, it can be seen that the silver powder is well dispersed with the resin, demonstrating that the formation of merle pits is not caused by uneven distribution of the filler and the resin matrix.
Example III
79.5 Parts of the micron silver powder is heat treated at 140 ℃ for 15 minutes, and then 0.5 part of the coupling agent is added for high-speed dispersion, so that the micron silver powder is treated. 10.6 parts of epoxy resin, 0.4 part of diluent, 8.91 parts of curing agent, 0.09 part of conductive additive and 0.5 part of other additives are subjected to heat treatment at 50 ℃ for 30 minutes to form a resin matrix, wherein the other additives comprise antioxidants, defoamers and toughening agents. And (3) putting the treated micrometer silver powder and the resin matrix into a high-speed dispersion mixer for mixing and dispersing, wherein the dispersing time is 20 minutes, and the dispersing speed is 800 revolutions per minute. After being dispersed evenly at high speed, the silver conductive adhesive C containing the conductive additive is obtained by vacuum defoaming, material pressing and vacuum packaging. The cross-sectional views of the obtained silver conductive paste D are shown in fig. 5 and 6, and it can be seen from fig. 5: the section has a small amount of smaller meteorite pits, which proves that the internal stress is more dense in bearing parts under external extrusion, the stress is dispersed, the mechanical property is improved, and small blocks are shown to fall off; from FIG. 6, it can be seen that the silver powder is well dispersed with the resin, demonstrating that the formation of merle pits is not caused by uneven distribution of the filler and the resin matrix.
Example IV
72.8 Parts of micron silver powder is heat treated for 20 minutes at 160 ℃, and then 0.1 part of coupling agent is added for high-speed dispersion, so that the micron silver powder is treated. 15.4 parts of epoxy resin, 9.6 parts of curing agent, 1.7 parts of conductive auxiliary agent and 0.4 part of other additives are subjected to heat treatment at 75 ℃ for 5 minutes to form a resin matrix, wherein the other additives comprise an antioxidant, a defoaming agent and a toughening agent. And (3) putting the treated micrometer silver powder and the resin matrix into a high-speed dispersion mixer for mixing and dispersing, wherein the dispersing time is 30 minutes, and the dispersing speed is 1000 revolutions per minute. After being dispersed evenly at high speed, the silver conductive adhesive D containing the conductive additive is obtained by vacuum defoaming, material pressing and vacuum packaging. The cross-sectional view of the silver conductive paste D obtained is shown in fig. 7 and 8, and it can be seen from fig. 7: the cross section basically has no meteorite pits, and the internal stress is proved to be denser under external extrusion, so that the stress is greatly dispersed, and the mechanical property is improved; from fig. 8, it can be seen that the silver powder is well dispersed with the resin.
Example five
78.8 Parts of micrometer silver powder was heat treated at 170℃for 30 minutes. 12.2 parts of epoxy resin, 1.6 parts of diluent, 1.5 parts of curing agent, 4.9 parts of conductive auxiliary agent and 1 part of other additives are subjected to heat treatment at 110 ℃ for 90 minutes to form a resin matrix, wherein the other additives comprise antioxidants, coupling agents, defoaming agents and toughening agents. And (3) putting the treated micrometer silver powder and the resin matrix into a high-speed dispersion mixer for mixing and dispersing, wherein the dispersing time is 10 minutes, and the dispersing speed is 1500 revolutions per minute. After being dispersed evenly at high speed, the silver conductive adhesive E containing the conductive additive is obtained by vacuum defoaming, material pressing and vacuum packaging.
Example six
83.8 Parts of micrometer silver powder and nanometer silver powder are subjected to heat treatment at 150 ℃ for 20 minutes, and then 0.5 part of coupling agent is added for high-speed dispersion, so that the micrometer silver powder is treated. 5.9 parts of epoxy resin, 0.5 part of diluent, 5.4 parts of curing agent, 3.75 parts of conductive additive and 0.15 part of other additives are subjected to heat treatment at 95 ℃ for 5 minutes to form a resin matrix, wherein the other additives comprise an antioxidant, a defoaming agent and a toughening agent. And (3) putting the treated micrometer silver powder and the resin matrix into a high-speed dispersion mixer for mixing and dispersing, wherein the dispersing time is 10 minutes, and the dispersing speed is 600 revolutions per minute. After being dispersed evenly at high speed, the silver conductive adhesive F containing the conductive additive is obtained by vacuum defoaming, material pressing and vacuum packaging.
Example seven
81.6 Parts of micron silver powder is heat treated for 20 minutes at 150 ℃, and then 0.1 part of coupling agent is added for high-speed dispersion, so that the micron silver powder is treated. 7.6 parts of epoxy resin, 0.2 part of diluent, 7.2 parts of curing agent, 2.65 parts of conductive additive and 0.65 part of other additives are subjected to heat treatment at 65 ℃ for 5 minutes to form a resin matrix, wherein the other additives comprise antioxidants, defoamers and toughening agents. And (3) putting the treated micrometer silver powder and the resin matrix into a high-speed dispersion mixer for mixing and dispersing, wherein the dispersing time is 10 minutes, and the dispersing speed is 600 revolutions per minute. After the silver conductive adhesive is uniformly dispersed at a high speed, pressing and packaging the silver conductive adhesive, and centrifugally defoamating the silver conductive adhesive to obtain the silver conductive adhesive G containing the conductive additive.
Test examples
The silver conductive paste provided in examples one to seven and commercially available product ABLESTIK 84-1LMISR4 conductive paste purchased from hangao were tested as follows:
Volume resistivity: the silver conductive adhesive of the first to seventh examples and a commercially available product were printed on a glass sheet to prepare a conductive adhesive film having a specification of 10mm×2mm×0.1mm, and after heat curing, the resistance was measured by a four-point probe method, and the volume resistivity was calculated.
Adhesive strength: and (3) preparing a sample by referring to the tensile shear strength of the standard GB-T7124-2008 adhesive, namely printing the silver conductive adhesive of the first embodiment to the seventh embodiment on a stainless steel sheet and preparing a conductive adhesive film with the specification of 25mm multiplied by 12.5mm multiplied by 0.05mm by a commercially available product, placing another stainless steel sheet on the conductive adhesive film, and forming a sandwich structure by the two layers of stainless steel sheets and the conductive adhesive film. And (3) after the sample is thermally cured, testing mechanical properties by using a universal material testing machine. The test results are shown in Table 1.
TABLE 1
As is clear from the results in Table 1, the silver conductive adhesive containing the conductive additive provided by the invention has low volume resistivity, about (0.2-2.7) multiplied by 10 -4 ohm cm, and the lowest 0.27 multiplied by 10 -4 ohm cm after heat curing, high bonding strength, and the shearing strength can be about (9.4-28.9) MPa, and the highest shearing strength is 28.9MPa, which is superior to the commercial products. The silver conductive adhesive prepared by the preparation method of the silver conductive adhesive containing the conductive additive has the advantages of low volume resistance, high bonding strength and the like.
From the results of the conductive additive-containing (example two) and conductive additive-free (example one) silver conductive pastes of table 1, it can be seen that the conductive additive-containing silver conductive pastes are superior to the conductive additive-free silver conductive pastes in both electrical and mechanical properties.
As can be seen from the results of examples two to seven in table 1, when the content of the conductive filler is low (example four), the silver conductive adhesive containing the conductive additive also has excellent electrical and mechanical properties, which proves that the conductive additive has a significant effect on improving the performance of the silver conductive adhesive.
In conclusion, the silver conductive adhesive containing the conductive additive realizes excellent mechanical and electrical properties by utilizing the complex of the silver compound, and the complex is compounded with the epoxy resin, so that the mechanical and electrical properties of a matrix material can be improved, and the use amount of the conductive filler can be reduced. The silver conductive adhesive is defoamed and packaged by adopting a vacuum defoamation and packaging technology, so that the influence of air and bubbles on the electrical and mechanical properties of a finished product can be avoided.
It should also be noted that the term "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a product or system that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such product or system. Without further limitation, the elements defined by the phrases "comprising … …" and "comprising … … below" do not exclude that additional identical elements are present in a commodity or system comprising the elements.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (8)
1. The silver conductive adhesive containing the conductive auxiliary agent comprises the following components in parts by weight:
5-16 parts of epoxy resin;
0-2 parts of a diluent;
0.5-14 parts of curing agent;
0.5-1.7 parts of conductive additive;
72-84 parts of conductive filler;
0-1 part of additive;
The conductive auxiliary agent is selected from one or more of a complex formed by ① silver acetate and a ligand succinimide and/or 1-cyanoethyl-2-methylimidazole, a complex formed by a complexing agent tributyl phosphate and/or triethanolamine, a complex formed by ② silver oxide and maleimide and/or 1-cyanoethyl-2-methylimidazole, a complex formed by a complexing agent dimercaptopropanol and/or thioacetamide, a complex formed by ③ silver acetylacetonate and triphenylphosphine and/or phthalimide, a complex formed by a complexing agent diethanolamine and/or triethylenetetramine, and a complex formed by ④ silver nitrate and a ligand 1-cyanoethyl-2-methylimidazole and/or glutarimide, and a complex formed by a complexing agent sodium gluconate and/or citric acid;
The complexing agent in the conductive additive is used as one of the components of the complex of the silver compound, plays a role in regulating the release of silver atoms in the complex of the silver compound, and enables the silver atoms to be released under specific conditions so as to meet the use process requirements under different application scenes.
2. The conductive assistant-containing silver conductive paste according to claim 1, wherein the epoxy resin is one or more selected from the group consisting of a liquid bisphenol a type epoxy resin, a bisphenol F type epoxy resin and a phenolic type epoxy resin; the bisphenol A type epoxy resin is selected from bisphenol E44 epoxy resin and/or bisphenol E51 epoxy resin; the phenolic epoxy resin is selected from novolac F44 and/or F51 epoxy resins.
3. The silver conductive paste according to claim 1, wherein the diluent is one or more selected from the group consisting of monoglycidyl ether, diglycidyl ether, polyfunctional glycidyl amine, and polyfunctional glycidyl ester in a reactive diluent.
4. The conductive assistant-containing silver conductive adhesive according to claim 1, wherein the curing agent is one or more selected from the group consisting of amine curing agents, acid anhydride curing agents, imidazole curing agents, and boron amine complex curing agents; the amine curing agent is one or more selected from dicyandiamide DICY, diamino diphenyl sulfone DDS, diamino diphenyl methane DDM and adipic acid dihydrazide AADH; the anhydride curing agent is one or more selected from methyl tetrahydrophthalic anhydride (MeTHPA), methyl hexahydrophthalic anhydride (MeHHPA), methyl Nadic Anhydride (MNA) and dodecyl succinic anhydride (DDSA); the imidazole curing agent is one or more selected from 2-methylimidazole 2MZ, 2-ethyl-4 methylimidazole 2E4MZ, 1-cyanoethyl-2-methylimidazole 2MZ-CN and 1-cyanoethyl-2-ethyl-4-methylimidazole 2E4 MZ-CN; the boron amine complex curing agent is one or more selected from triethylamine-BF 3 complex, aniline-BF 3 complex and monoethylamine-BF 3 complex.
5. The conductive assistant-containing silver conductive paste according to claim 1, wherein the conductive filler is selected from the group consisting of surface fatty acid-modified plate-like silver powder and/or spherical silver powder; the additive is one or more selected from antioxidant, defoamer, coupling agent and toughening agent.
6. The conductive paste as claimed in claim 5, wherein the plate-shaped silver powder and/or the spherical silver powder is a silver micro plate, a spherical micro silver powder or a spherical nano silver powder.
7. A method for preparing the conductive adhesive containing conductive auxiliary agent according to any one of claims 1 to 6, comprising the following steps:
s1, weighing epoxy resin, a diluent, a curing agent, a conductive auxiliary agent, a conductive filler and an additive according to a proportion of ingredients, and performing pretreatment;
s2, loading the pretreated raw materials into a high-speed dispersion mixer for mixing and dispersing for 30 seconds to 2 hours;
and S3, defoaming treatment, pressing and packaging to obtain the silver conductive adhesive.
8. Use of a silver conductive paste containing a conductive additive according to any one of claims 1 to 6 in electronic packaging.
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