CN112992404B - High-conductivity conductive slurry - Google Patents
High-conductivity conductive slurry Download PDFInfo
- Publication number
- CN112992404B CN112992404B CN202110488790.2A CN202110488790A CN112992404B CN 112992404 B CN112992404 B CN 112992404B CN 202110488790 A CN202110488790 A CN 202110488790A CN 112992404 B CN112992404 B CN 112992404B
- Authority
- CN
- China
- Prior art keywords
- glycol
- epoxy resin
- diisocyanate
- isocyanate
- conductive paste
- 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.)
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- 239000002002 slurry Substances 0.000 title abstract description 10
- 239000003094 microcapsule Substances 0.000 claims abstract description 84
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 55
- 239000002245 particle Substances 0.000 claims abstract description 50
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000003822 epoxy resin Substances 0.000 claims abstract description 26
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 26
- 239000000843 powder Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 15
- 239000002775 capsule Substances 0.000 claims abstract description 13
- 239000003085 diluting agent Substances 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000002612 dispersion medium Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 88
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 48
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 42
- 239000012948 isocyanate Substances 0.000 claims description 42
- 150000002513 isocyanates Chemical class 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 40
- 239000012071 phase Substances 0.000 claims description 38
- -1 polybutylene adipate Polymers 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 35
- 239000007764 o/w emulsion Substances 0.000 claims description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 27
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000003921 oil Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 20
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 20
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 19
- 239000002270 dispersing agent Substances 0.000 claims description 17
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 16
- MTHSVFCYNBDYFN-UHFFFAOYSA-N anhydrous diethylene glycol Natural products OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 16
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 16
- 239000004970 Chain extender Substances 0.000 claims description 15
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 15
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 15
- 229920005906 polyester polyol Polymers 0.000 claims description 15
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 15
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 11
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 11
- 238000002360 preparation method Methods 0.000 claims description 10
- 229910052709 silver Inorganic materials 0.000 claims description 10
- 239000004332 silver Substances 0.000 claims description 10
- 239000013638 trimer Substances 0.000 claims description 10
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 9
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 9
- OEOIWYCWCDBOPA-UHFFFAOYSA-N 6-methyl-heptanoic acid Chemical compound CC(C)CCCCC(O)=O OEOIWYCWCDBOPA-UHFFFAOYSA-N 0.000 claims description 8
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 8
- 239000007822 coupling agent Substances 0.000 claims description 8
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 239000004632 polycaprolactone Substances 0.000 claims description 8
- 239000013008 thixotropic agent Substances 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical class C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229920001213 Polysorbate 20 Polymers 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- 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 6
- 239000004359 castor oil Substances 0.000 claims description 6
- 235000019438 castor oil Nutrition 0.000 claims description 6
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 6
- 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 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 6
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 claims description 6
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 claims description 6
- 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 5
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 5
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 claims description 4
- OQZDJLFNMXRJHZ-UHFFFAOYSA-N 1-benzyl-2-ethylimidazole Chemical group CCC1=NC=CN1CC1=CC=CC=C1 OQZDJLFNMXRJHZ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims description 4
- 150000002460 imidazoles Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- RLJWTAURUFQFJP-UHFFFAOYSA-N propan-2-ol;titanium Chemical compound [Ti].CC(C)O.CC(C)O.CC(C)O.CC(C)O RLJWTAURUFQFJP-UHFFFAOYSA-N 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N tetraisopropyl titanate Substances CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- QKVROWZQJVDFSO-UHFFFAOYSA-N 2-(2-methylimidazol-1-yl)ethanamine Chemical group CC1=NC=CN1CCN QKVROWZQJVDFSO-UHFFFAOYSA-N 0.000 claims description 3
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical group CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical group CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 2-phenyl-1h-imidazole Chemical group C1=CNC(C=2C=CC=CC=2)=N1 ZCUJYXPAKHMBAZ-UHFFFAOYSA-N 0.000 claims description 3
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical class N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 claims description 3
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical group CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 2
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 claims description 2
- AZYRZNIYJDKRHO-UHFFFAOYSA-N 1,3-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC(C(C)(C)N=C=O)=C1 AZYRZNIYJDKRHO-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- CDMDQYCEEKCBGR-UHFFFAOYSA-N 1,4-diisocyanatocyclohexane Chemical compound O=C=NC1CCC(N=C=O)CC1 CDMDQYCEEKCBGR-UHFFFAOYSA-N 0.000 claims description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 claims description 2
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 2
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical class C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims description 2
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 claims description 2
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 claims description 2
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 2
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- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 claims description 2
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- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 2
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- 125000005442 diisocyanate group Chemical group 0.000 claims description 2
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- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
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- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 2
- 239000002070 nanowire Substances 0.000 claims description 2
- 239000004843 novolac epoxy resin Substances 0.000 claims description 2
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 6
- 238000004132 cross linking Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 47
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000007639 printing Methods 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000009775 high-speed stirring Methods 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- XFUOBHWPTSIEOV-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) cyclohexane-1,2-dicarboxylate Chemical compound C1CCCC(C(=O)OCC2OC2)C1C(=O)OCC1CO1 XFUOBHWPTSIEOV-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000002009 diols Chemical class 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000921 polyethylene adipate Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- DCKDPDONFMIQBA-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diol;phthalic acid Chemical compound OCC(C)(C)CO.OC(=O)C1=CC=CC=C1C(O)=O DCKDPDONFMIQBA-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- KMHIOVLPRIUBGK-UHFFFAOYSA-N butane-1,4-diol;hexane-1,6-diol Chemical compound OCCCCO.OCCCCCCO KMHIOVLPRIUBGK-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a high-conductivity conductive paste, which comprises conductive powder, resin, a liquid microcapsule type curing agent, an active diluent, a solvent, an additive and the like, wherein the content of the conductive powder is 85-95%, the liquid microcapsule type curing agent comprises microcapsule particles and a dispersion medium epoxy resin, the capsule wall of the microcapsule particles is polyurethane resin containing closed isocyanate end groups, and the capsule core is an imidazole substance and can be uniformly mixed with the epoxy resin. In the high-temperature curing process of the slurry, the capsule wall of the microcapsule is softened, the imidazole substance in the capsule core is released to react with the epoxy resin, and the active isocyanate functional group released by the capsule wall of the microcapsule reacts with the hydroxyl group of the epoxy resin, so that the conductive slurry is high in crosslinking density and low in resistivity after being cured. The conductive paste has good room temperature storage performance, can be quickly cured at high temperature, has excellent conductive performance after being cured, and can be applied to the field with high requirements on the conductive performance, such as solar cell grids.
Description
Technical Field
The invention belongs to the technical field of conductive paste, and particularly relates to high-filling, room-temperature storage, high-temperature rapid curing and high-conductivity conductive paste.
Background
The conductive paste is prepared by dispersing conductive powder in a high polymer resin (mainly epoxy resin) system, and a required conductive pattern is prepared by screen printing, drying and curing. The development of high-performance conductive paste has two problems to be solved: (1) based on market demands, it is required to develop a slurry with high conductivity. The conductivity of the slurry is related to the addition amount of the conductive powder, and the conductivity is improved as the addition amount of the powder is increased. However, when the amount of the powder added is large, it is difficult to uniformly disperse the powder in the polymer resin, and the viscosity of the slurry also increases rapidly, which is not favorable for screen printing. (2) The conductive paste needs to have good operability, that is, the paste can be stored at normal temperature for a long time and can be rapidly cured after printing, which is mainly realized by adding a latent curing agent. The common latent curing agents for epoxy resin mainly comprise dicyandiamide, modified imidazole, modified urea, microcapsules and the like. Dicyandiamide, modified imidazole, and modified urea are generally solid powders and are difficult to uniformly disperse in highly filled conductive pastes. The microcapsule curing agent can achieve the effects of long-term storage at normal temperature and rapid curing at high temperature, but most of the microcapsule curing agents sold in the market are solid powder, and most of capsule wall materials are thermoplastic polymers and cannot react with epoxy resin, so that the curing shrinkage rate of a resin system is reduced, and the high-conductivity slurry is not easy to obtain.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides the high-conductivity conductive paste which is high in filling, stored at room temperature and quickly cured at high temperature.
The conductive slurry comprises, by mass, 85% -95% of conductive powder, 2.0% -13.0% of resin, 0.3% -3.0% of liquid microcapsule type curing agent, 0.1% -1.0% of active diluent, 0.2% -3.0% of solvent and 0.05% -1.5% of additive.
In the conductive paste, the conductive powder is selected from one or more of silver powder, copper powder, silver-coated aluminum powder, silver-coated nickel powder and silver-coated glass powder, the conductive powder is in the shape of one or more of a nanowire, a sheet, an irregular particle and a sphere, and the particle size of the conductive powder is 50 nm-15 mu m. Preferably, two or more than two kinds of powder with different shapes and different grain diameters are matched for use so as to realize optimal conductive connection.
In the conductive paste, the resin is preferably a low-viscosity epoxy resin having a viscosity of 100 to 5000 mPas (measured at 10rpm and 25 ℃ C., hereinafter referred to as 10rpm @25 ℃ C.), and is specifically selected from any one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, alicyclic epoxy resin, low-molecular-weight glycidyl ether, low-molecular-weight glycidyl ester, low-molecular-weight glycidyl amine and the like
In the conductive paste, the liquid microcapsule type curing agent comprises microcapsule particles and a dispersion medium, wherein the capsule wall of the microcapsule particles is polyurethane resin containing blocked isocyanate end groups, the capsule core is an imidazole substance, and the dispersion medium is epoxy resin. The preparation method of the liquid microcapsule type curing agent comprises the following steps:
(1) uniformly mixing polyester polyol, isocyanate, a chain extender and a catalyst, controlling the molar ratio of-NCO groups contained in the isocyanate to-OH groups contained in the polyester polyol and the chain extender to be 1.05/1-2.0/1, and controlling the addition amount of the catalyst to be 0.05-0.3 percent of the total mass of the polyester polyol, the isocyanate and the chain extender to react at 70-100 ℃ to obtain the polyurethane resin with the terminal groups of isocyanate groups. Wherein the polyester polyol is selected from any one of polyethylene adipate glycol, polypropylene adipate glycol, polybutylene adipate glycol, polyhexamethylene adipate glycol, polydiethylene phthalate glycol, poly-1, 6-hexanediol phthalate, polydiethylene phthalate glycol, polycaprolactone butanediol glycol, polycaprolactone neopentyl glycol diol, polycaprolactone diethylene glycol diol, polycaprolactone hexanediol diol, polyhexamethylene carbonate glycol, poly-1, 6-hexanediol carbonate glycol, polybuthylene carbonate glycol, poly-1, 4-butanediol-1, 6-hexanediol carbonate glycol and the like, preferably polyethylene adipate glycol, polypropylene adipate glycol, polybutylene carbonate glycol-1, 4-butanediol-1, 6-hexanediol carbonate glycol and the like, Any one of polypropylene glycol adipate glycol, polybutylene glycol adipate glycol and polyhexamethylene glycol adipate glycol; the isocyanate is selected from any one of Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, TDI dimer, TDI trimer, HDI dimer, IPDI trimer, triphenylmethane triisocyanate, dimethyltriphenylmethane tetraisocyanate, etc., preferably any one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate trimer, hexamethylene diisocyanate trimer, and isophorone diisocyanate trimer; the chain extender is any one polyurethane chain extender selected from ethylene glycol, 1, 4-butanediol, diethylene glycol, 1, 6-hexanediol and the like; the catalyst is selected from any one of triethylene diamine, bis (dimethylaminoethyl) ether, cyclohexyl methyl tertiary amine, N-dimethyl benzylamine, dimethyl ethanolamine, 1, 4-dimethyl piperazine, N-methyl morpholine, N-ethyl morpholine, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, potassium isooctanoate, tin isooctanoate, bismuth isooctanoate, tetrabutyl titanate, tetraisopropyl titanate, etc., preferably any one of cyclohexyl methyl tertiary amine, N-dimethyl benzylamine, N-methyl morpholine, dibutyltin dilaurate, stannous octoate, bismuth isooctanoate, tetraisopropyl titanate, etc.
(2) And adding methyl ethyl ketoxime into the polyurethane resin with the end group of isocyanate group, and reacting at 70-90 ℃ until isocyanate is completely blocked to obtain the polyurethane resin with the blocked isocyanate end group.
(3) Dissolving an imidazole substance and polyurethane resin containing blocked isocyanate end groups into acetone to obtain an oil phase solution with the mass fraction of 1% -10%, wherein the mass ratio of the imidazole substance to the polyurethane resin containing blocked isocyanate end groups is 5/95-50/50; dissolving a hydrophilic dispersant in water to obtain an aqueous phase solution with the mass fraction of 0.2-1.2%; mixing the oil phase solution and the water phase solution according to the volume ratio of 1: 3-1: 7, and stirring to form an oil-in-water emulsion; adding the formed oil-in-water emulsion into a polyvinyl alcohol aqueous solution with the mass concentration of 1%, wherein the volume ratio of the oil-in-water emulsion to the polyvinyl alcohol aqueous solution is 60/40-98/2, stirring and heating to volatilize acetone, and obtaining microcapsule particles. Wherein the imidazole substance is selected from any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 1-benzyl-2-ethylimidazole, 1-aminoethyl-2-methylimidazole, 1-cyanoethyl substituted imidazole, 2-phenyl-4-methylimidazole and benzimidazole; the hydrophilic dispersant is any one of sodium dodecyl sulfate and tween-20.
(4) And mixing the microcapsule particles with epoxy resin according to the mass ratio of 5/95-95/5, and uniformly stirring and dispersing to obtain the liquid microcapsule curing agent. Wherein the epoxy resin is liquid epoxy resin selected from any one of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, alicyclic epoxy resin and novolac epoxy resin; the viscosity of the epoxy resin is 3000-50000 mPas (10 rpm @25 ℃).
In the step (1) of the preparation method of the liquid microcapsule-type curing agent, polyester polyol, isocyanate, a chain extender and a catalyst are preferably uniformly mixed, the molar ratio of-NCO groups contained in the isocyanate to-OH groups contained in the polyester polyol and the chain extender is controlled to be 1.2/1-1.5/1, the addition amount of the catalyst is 0.06-0.15 percent of the total mass of the polyester polyol, the isocyanate and the chain extender, and the polyurethane resin with the end group of isocyanate groups is obtained by reaction at 80-90 ℃.
In the step (2) of the preparation method of the liquid microcapsule type curing agent, methyl ethyl ketoxime is preferably added into the polyurethane resin with the terminal group of isocyanate group, and the reaction is carried out at 75-85 ℃ until isocyanate is completely blocked, so as to obtain the polyurethane resin with the blocked isocyanate terminal group.
In the step (3) of the preparation method of the liquid microcapsule type curing agent, imidazole substances and polyurethane resin containing blocked isocyanate end groups are preferably dissolved in acetone to obtain an oil phase solution with the mass fraction of 4-7%, wherein the mass ratio of the imidazole substances to the polyurethane resin containing blocked isocyanate end groups is 20/80-40/60; dissolving a hydrophilic dispersant in water to obtain an aqueous phase solution with the mass fraction of 0.5-1%; mixing the oil phase solution and the water phase solution according to the volume ratio of 1: 5-1: 6, and stirring to form an oil-in-water emulsion; adding the formed oil-in-water emulsion into a polyvinyl alcohol aqueous solution with the mass concentration of 1%, wherein the volume ratio of the oil-in-water emulsion to the polyvinyl alcohol aqueous solution is 75/25-85/15, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
In the step (4) of the preparation method of the liquid microcapsule type curing agent, preferably, microcapsule particles and epoxy resin are mixed according to a mass ratio of 30/70-70/30, and the mixture is uniformly stirred and dispersed to obtain the liquid microcapsule type curing agent.
In the conductive paste, the reactive diluent includes a monofunctional reactive diluent and a bifunctional reactive diluent. Wherein the monofunctional reactive diluent is selected from one or more of butyl glycidyl ether, 2-ethylhexyl glycidyl ether, o-cresol glycidyl ether, phenyl glycidyl ether, p-methylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether and the like, and the difunctional reactive diluent is selected from one or more of neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, cyclohexyl dimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, ethylene glycol diglycidyl ether and the like. The viscosity of the reactive diluent is 1-1500 mPa & s (10 rpm @25 ℃), and the main functions are to adjust the viscosity of the conductive paste and toughen the resin cured body.
In the conductive paste, the solvent is one or more selected from naphtha, DBE, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, dimethyl succinate, dimethyl glutarate, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diacetone alcohol, 3-methoxy butyl acetate, 3-methoxy butyl propionate, propylene carbonate, butyl acetate and diethylene glycol diacetate.
In the conductive paste, the additive comprises at least one of a dispersant, a thixotropic agent, a leveling agent, a coupling agent and the like, wherein the dispersant is selected from any one or more of Silok-7423, Silok-7421, Silok-7455H, Silok-7631, Silok-7096, Silok-7160, BYK-111, BYK-2155, BYK-2008, BYK-170, BYK-2025, BYK-220S, BYK-106, BYK-370, BYK-388, Demoded D9850, Cure 983, Demoded 904S, Demoded 910, Demoded 912, Demoded 929, DARNC-N and Beacon 4803, the thixotropic agent is selected from any one or more of polyethylene wax, gas phase silica, organic bentonite and castor oil, and the leveling agent is selected from any one or more of organosilicon leveling agent, organic fluorine leveling agent and acrylate leveling agent, the coupling agent is selected from any one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent.
The preparation method of the conductive paste comprises the following steps: respectively weighing the conductive powder, the resin, the liquid microcapsule curing agent, the active diluent, the solvent and the additive according to the mass percentage, uniformly stirring, and rolling by a three-roller mill to prepare the slurry with the fineness of less than or equal to 10 mu m.
The invention has the following beneficial effects:
1. the conductive powder content in the conductive paste is 85% -95%, and the conductive powder is uniformly dispersed in an organic system by matching with low-viscosity epoxy resin, an active diluent, a solvent and a liquid microcapsule type curing agent. The viscosity of the conductive paste is 120-200 Pa.s (10 rpm @25 ℃), and the conductive paste is suitable for screen printing.
2. The liquid microcapsule type curing agent in the conductive paste can be uniformly mixed with epoxy resin, and in the high-temperature curing process of the paste, the capsule wall of the microcapsule is softened, the capsule core imidazole substance is released to react with the epoxy resin, and the capsule wall of the microcapsule releases active isocyanate functional groups to react with the hydroxyl groups of the epoxy resin. Therefore, the conductive paste prepared by the liquid microcapsule type curing agent has high crosslinking density and low resistivity after curing.
3. The conductive paste can be stored for a long time at room temperature, can be quickly cured at high temperature, has excellent conductive performance and high conductivity after being cured, and can be applied to the field with high requirement on the conductivity, such as solar cell grids.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to these examples.
Example 1
Synthesis of liquid microcapsule type curing agent:
(1) 980g (0.98 mol) of polyethylene glycol adipate having a number average molecular weight of 1000, 226.2g (1.3 mol) of Toluene Diisocyanate (TDI), 1.8g (0.02 mol) of 1, 4-butanediol and 1.25g of dibutyltin dilaurate were uniformly mixed, and reacted at 90 ℃ for 3 hours with the molar ratio of isocyanate/hydroxyl being controlled to 1.3:1, to obtain a polyurethane resin having an isocyanate group as a terminal group.
(2) 53.07g (0.61 mol) of methyl ethyl ketone oxime is added into the polyurethane resin with the terminal group of isocyanate group obtained in the step 1, and the methyl ethyl ketone oxime and the isocyanate group are reacted at 80 ℃ until the isocyanate is completely blocked, so that the polyurethane resin with the blocked isocyanate terminal group is obtained.
(3) 3g of 2-methylimidazole and 37g of a polyurethane resin containing blocked isocyanate end groups were dissolved in 760g of acetone to obtain an oil-phase solution having a mass fraction of 5%. 2g of sodium dodecyl sulfate was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 40mL of oil phase solution with 200mL of water phase solution, and stirring at high speed to form an oil-in-water emulsion; adding the formed oil-in-water emulsion into 60mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
(4) 30g of microcapsule particles and 70g of bisphenol A epoxy resin with the viscosity of 10000 mPas (10 rpm @25 ℃) are mixed and uniformly dispersed by high-speed stirring to obtain the liquid microcapsule curing agent HX-01.
Weighing 45g of spherical silver powder (the particle size is 200-500 nm), 45g of flake silver powder (2.0-6.0 mu m), 5.4g of bisphenol F epoxy resin with the viscosity of 1500mPa & s (10 rpm @25 ℃), 0.25g of p-methylphenyl glycidyl ether with the viscosity of 7.5mPa & s (10 rpm @25 ℃), HX-011.3 g of liquid microcapsule curing agent, 2.5g of diethylene glycol butyl ether acetate, KH-5600.05 g of silane coupling agent, BYK-1110.25 g of dispersing agent and 0.25g of thixotropic agent hydrogenated castor oil, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
Example 2
Synthesis of liquid microcapsule type curing agent:
(1) 1940g (0.97 mol) of polybutylene adipate diol having a number average molecular weight of 2000, 375g (1.5 mol) of diphenylmethane diisocyanate (MDI), 2.7g (0.03 mol) of 1, 4-butanediol and 1.8g N, N-dimethylbenzylamine were uniformly mixed, the molar ratio of isocyanate/hydroxyl was controlled to be 1.5:1, and a reaction was carried out at 80 ℃ for 2.8 hours to obtain a polyurethane resin having an isocyanate group as a terminal group.
(2) And (2) adding 95.7g (1.1 mol) of methyl ethyl ketoxime to the polyurethane resin with the terminal group of isocyanate group obtained in the step (1), and reacting the methyl ethyl ketoxime with the isocyanate group at 75 ℃ until the isocyanate is completely blocked to obtain the polyurethane resin with the blocked isocyanate terminal group.
(3) 5g of 2-ethyl-4-methylimidazole and 35g of polyurethane resin containing blocked isocyanate end groups are dissolved in 760g of acetone to obtain an oil phase solution with the mass fraction of 5%. 2g of sodium dodecyl sulfate was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 36.4mL of the oil phase solution with 200mL of the water phase solution, stirring at high speed to form an oil-in-water emulsion, adding the formed oil-in-water emulsion into 78.8mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining the microcapsule particles.
(4) 40g of microcapsule particles and 60g of bisphenol A epoxy resin with the viscosity of 20000 mPas (10 rpm @25 ℃) are mixed and uniformly dispersed by high-speed stirring to obtain the liquid microcapsule curing agent HX-02.
Weighing 30g of spherical silver powder (with the particle size of 200-500 nm), 58g of flake silver powder (3.0-8.0 mu m), 5.3g of bisphenol F epoxy resin with the viscosity of 1500 mPas (10 rpm @25 ℃), 2.6g of hexahydrophthalic acid diglycidyl ester with the viscosity of 500 mPas (10 rpm @25 ℃), 0.15g of p-tert-butylphenyl glycidyl ether with the viscosity of 25 mPas (10 rpm @25 ℃), 0.8978 g of liquid microcapsule curing agent HX-022.0 g, 1.15g of diethylene glycol butyl ether acetate, KH-5500.05 g of silane coupling agent, BYK-21550.2 g of dispersant, 0.3g of thixotropic agent hydrogenated castor oil and 0.25g of organic silicon flatting agent, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
Example 3
Synthesis of liquid microcapsule type curing agent:
(1) 1960g (0.98 mol) of polyethylene terephthalate glycol having a number average molecular weight of 2000, 235.2g (1.4 mol) of Hexamethylene Diisocyanate (HDI), 0.9g (0.01 mol) of 1, 4-butanediol and 1.8g of stannous octoate were uniformly mixed, the molar ratio of isocyanate/hydroxyl group was controlled to be 1.4:1, and the reaction was carried out at 90 ℃ for 4 hours to obtain a polyurethane resin having an isocyanate group as a terminal group.
(2) 71.34g (0.82 mol) of methyl ethyl ketone oxime is added into the polyurethane resin with the terminal group of isocyanate group obtained in the step 1, and the methyl ethyl ketone oxime and the isocyanate group are reacted at 85 ℃ until the isocyanate is completely blocked, so that the polyurethane resin with the blocked isocyanate terminal group is obtained.
(3) 4g of 2-ethylimidazole and 36g of polyurethane resin containing blocked isocyanate end groups were dissolved in 760g of acetone to give an oil-phase solution with a mass fraction of 5%. 2g of sodium dodecyl sulfate was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 40mL of oil phase solution with 200mL of water phase solution, stirring at high speed to form an oil-in-water emulsion, adding the formed oil-in-water emulsion into 42.4mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
(4) 50g of the microcapsule particles and 50g of bisphenol F epoxy resin with the viscosity of 5000mPa & s (10 rpm @25 ℃) are mixed and uniformly dispersed by high-speed stirring to obtain a liquid type microcapsule curing agent HX-03.
Weighing 45g of spherical silver powder (with the particle size of 200-500 nm), 48g of sheet silver powder (with the particle size of 2.0-5.0 mu m), 3.0g of hydrogenated bisphenol A epoxy resin with the viscosity of 750 mPas (10 rpm @25 ℃), 1.2g of hexahydrophthalic acid diglycidyl ester with the viscosity of 500 mPas (10 rpm @25 ℃), 0.2g of p-tert-butylphenyl glycidyl ether with the viscosity of 25 mPas (10 rpm @25 ℃), 0.8g of liquid microcapsule curing agent HX-031.0 g, 1.0g of diethylene glycol butyl ether acetate, 0.5g of ethylene glycol butyl ether acetate and 0.32 g of dispersant BYK-20080.1 g, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
Example 4
Synthesis of liquid microcapsule type curing agent:
(1) 2910g (0.97 mol) of polydiethylene glycol adipate diol having a number average molecular weight of 3000, 293.04g (1.32 mol) of isophorone diisocyanate (IPDI), 3.54g (0.03 mol) of 1, 6-hexanediol, and 2.1g of bismuth isooctanoate were uniformly mixed, the molar ratio of isocyanate/hydroxyl group was controlled to be 1.32:1, and the mixture was reacted at 90 ℃ for 3.5 hours to obtain a polyurethane resin having an isocyanate group as a terminal group.
(2) 56.55g (0.65 mol) of methyl ethyl ketoxime is added into the polyurethane resin with the terminal group of isocyanate group obtained in the step 1, and the methyl ethyl ketoxime and the isocyanate group are reacted at 85 ℃ until the isocyanate is completely blocked, so that the polyurethane resin with the blocked isocyanate terminal group is obtained.
(3) 7g of 2-phenylimidazole and 33g of a polyurethane resin containing blocked isocyanate end groups were dissolved in 760g of acetone to give an oil phase solution having a mass fraction of 5%. 2g of sodium dodecyl sulfate was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 40mL of oil phase solution with 200mL of water phase solution, stirring at high speed to form an oil-in-water emulsion, adding the formed oil-in-water emulsion into 60mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
(4) 40g of microcapsule particles and 60g of bisphenol F epoxy resin with the viscosity of 5500 mPas (10 rpm @25 ℃) are mixed and uniformly dispersed by high-speed stirring to obtain the liquid microcapsule curing agent HX-04.
Weighing 40g of spherical silver-coated copper powder (with the particle size of 200-600 nm), 50g of flake silver powder (with the particle size of 2.0-7.0 mu m), 5.4g of bisphenol F epoxy resin with the viscosity of 1500mPa & s (10 rpm @25 ℃), 0.25g of p-tert-butylphenyl glycidyl ether with the viscosity of 7.5mPa & s (10 rpm @25 ℃), HX-041.3 g of liquid microcapsule curing agent, 2.5g of ethylene glycol butyl ether acetate, KH-5600.05 g of silane coupling agent, Silok-70960.25 g of dispersing agent and 0.25g of thixotropic agent castor oil, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
Example 5
Synthesis of liquid microcapsule type curing agent:
(1) 900g (0.9 mol) of polybutylene adipate diol with the number average molecular weight of 1000, 344.1g (1.55 mol) of isophorone diisocyanate (IPDI), 10.6g (0.1 mol) of diethylene glycol and 1.0g N-methylmorpholine are mixed uniformly, the molar ratio of isocyanate/hydroxyl is controlled to be 1.55:1, and the mixture is reacted for 4 hours at 90 ℃ to obtain the polyurethane resin with the end group of isocyanate.
(2) Adding 104.4g (1.2 mol) of methyl ethyl ketoxime into the polyurethane resin with the terminal group of isocyanate group obtained in the step 1, and reacting the methyl ethyl ketoxime with the isocyanate group at 78 ℃ until the isocyanate is completely blocked to obtain the polyurethane resin with the blocked isocyanate terminal group.
(3) 10g of 1-benzyl-2-ethylimidazole and 30g of polyurethane resin containing blocked isocyanate end groups are dissolved in 760g of acetone to obtain an oil phase solution with the mass fraction of 5%. 2g of Tween-20 was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 30.8mL of oil phase solution with 200mL of water phase solution, stirring at high speed to form an oil-in-water emulsion, adding the formed oil-in-water emulsion into 57.7mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining the microcapsule particles.
(4) 35g of microcapsule particles and 65g of bisphenol A epoxy resin with viscosity of 15500 mPas (10 rpm @25 ℃) are mixed and uniformly dispersed by high-speed stirring to obtain a liquid microcapsule curing agent HX-05.
Weighing 20g of spherical silver-coated copper powder (with the particle size of 200-600 nm), 20g of spherical silver powder (with the particle size of 200-800 nm), 50g of flake silver powder (with the particle size of 2.0-7.0 mu m), 2.8g of hydrogenated bisphenol F epoxy resin with the viscosity of 750mPa & s (10 rpm @25 ℃), 2.7g of bisphenol F epoxy resin with the viscosity of 1500mPa & s (10 rpm @25 ℃), 0.25g of p-methylphenyl glycidyl ether with the viscosity of 7.5mPa & s (10 rpm @25 ℃), HX-051.3 g of liquid microcapsule curing agent, 2.5g of diethylene glycol butyl ether acetate, KH-5600.05 g of silane coupling agent, Silok-74230.2 g of dispersing agent and 0.2g of thixotropic agent hydrogenated castor oil, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
Example 6
Synthesis of liquid microcapsule type curing agent:
(1) 1900g (0.95 mol) of neopentyl glycol phthalate glycol having a number average molecular weight of 2000, 312.5g (1.25 mol) of diphenylmethane diisocyanate (MDI), 5.9g (0.05 mol) of 1, 6-hexanediol and 1.8g of dimethylethanolamine were mixed uniformly, the molar ratio of isocyanate/hydroxyl group was controlled to be 1.25:1, and the reaction was carried out at 90 ℃ for 2.6 hours to obtain a polyurethane resin having an isocyanate group as a terminal group.
(2) 47.85g (0.55 mol) of methyl ethyl ketone oxime is added into the polyurethane resin with the terminal group of isocyanate group obtained in the step 1, and the methyl ethyl ketone oxime and the isocyanate group are reacted at 83 ℃ until the isocyanate is completely blocked, so that the polyurethane resin with the blocked isocyanate terminal group is obtained.
(3) 10g of 2-phenyl-4-methylimidazole and 30g of polyurethane resin containing blocked isocyanate end groups were dissolved in 760g of acetone to obtain an oil phase solution with a mass fraction of 5%. 2g of Tween-20 was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 30mL of oil phase solution with 180mL of water phase solution, stirring at high speed to form an oil-in-water emulsion, adding the formed oil-in-water emulsion into 70mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
(4) 50g of the microcapsule particles and 50g of bisphenol F epoxy resin with the viscosity of 7500 mPas (10 rpm @25 ℃) are mixed and uniformly dispersed by high-speed stirring to obtain the liquid microcapsule curing agent HX-06.
Weighing 20g of spherical silver-coated copper powder (with the particle size of 200-600 nm), 24g of spherical silver powder (with the particle size of 200-800 nm), 50g of flake silver powder (with the particle size of 2.0-7.0 mu m), 2.0g of hydrogenated bisphenol F epoxy resin with the viscosity of 750mPa & s (10 rpm @25 ℃), 1.8g of hexahydrophthalic acid diglycidyl ester with the viscosity of 500mPa & s (10 rpm @25 ℃), 0.2g of p-methylphenyl glycidyl ether with the viscosity of 7.5mPa & s (10 rpm @25 ℃), HX-060.8 g of liquid microcapsule curing agent, 0.5g of diethylene glycol butyl ether acetate, 0.5g of ethylene glycol butyl ether acetate and 0.5g of dispersing agent Silok-74210.2 g, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
Example 7
Synthesis of liquid microcapsule type curing agent:
(1) 1600g (0.8 mol) of 1, 6-hexanediol polycarbonate having a number average molecular weight of 2000, 412.5g (1.65 mol) of diphenylmethane diisocyanate (MDI), 18g (0.2 mol) of 1, 4-butanediol and 1.7g of dibutyltin dilaurate were mixed uniformly, and reacted at 90 ℃ for 3.5 hours while controlling the molar ratio isocyanate/hydroxyl to be 1.65:1, to obtain a polyurethane resin having an isocyanate group as a terminal group.
(2) 114.84g (1.32 mol) of methyl ethyl ketone oxime is added into the polyurethane resin with the terminal group of isocyanate group obtained in the step 1, and the methyl ethyl ketone oxime and the isocyanate group are reacted at 85 ℃ until the isocyanate is completely blocked, so that the polyurethane resin with the blocked isocyanate terminal group is obtained.
(3) 15g of 1-aminoethyl-2-methylimidazole and 25g of a polyurethane resin containing blocked isocyanate end groups were dissolved in 760g of acetone to give an oil-phase solution with a mass fraction of 5%. 2g of Tween-20 was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 36.4mL of the oil phase solution with 200mL of the water phase solution, stirring at high speed to form an oil-in-water emulsion, adding the formed oil-in-water emulsion into 59.1mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
(4) 45g of microcapsule particles and 55g of bisphenol A epoxy resin with the viscosity of 20000 mPas (10 rpm @25 ℃) are mixed and uniformly dispersed by high-speed stirring to obtain the liquid microcapsule curing agent HX-07.
Weighing 45g of spherical silver powder (the particle size is 200-800 nm), 49g of flake silver powder (2.0-7.0 mu m), 2.4g of hydrogenated bisphenol F epoxy resin with the viscosity of 600mPa & s (10 rpm @25 ℃), 1.8g of hexahydrophthalic acid diglycidyl ester with the viscosity of 500mPa & s (10 rpm @25 ℃), HX-071.0 g of liquid microcapsule curing agent, 0.7g of diethylene glycol monobutyl ether acetate and 0.1g of acrylate flatting agent, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
Example 8
Synthesis of liquid microcapsule type curing agent:
(1) 1760g (0.88 mol) of 1, 4-butanediol-1, 6-hexanediol polycarbonate diol having a number average molecular weight of 2000, 404.79g (1.545 mol) of dicyclohexylmethane diisocyanate, 12.72g (0.12 mol) of diethylene glycol and 1.8g of tin isooctanoate were mixed uniformly, and reacted at 80 ℃ for 4 hours while controlling the molar ratio of isocyanate/hydroxyl to be 1.545:1, to obtain a polyurethane resin having an isocyanate group as a terminal group.
(2) And (2) adding 95.7g (1.1 mol) of methyl ethyl ketoxime to the polyurethane resin with the terminal group of isocyanate group obtained in the step (1), and reacting the methyl ethyl ketoxime with the isocyanate group at 75 ℃ until the isocyanate is completely blocked to obtain the polyurethane resin with the blocked isocyanate terminal group.
(3) 15g of 1-benzyl-2-ethylimidazole and 25g of polyurethane resin containing blocked isocyanate end groups are dissolved in 760g of acetone to obtain an oil phase solution with the mass fraction of 5%. 2g of Tween-20 was dissolved in 198g of water to obtain an aqueous solution with a mass fraction of 1%. Mixing 40mL of oil phase solution with 200mL of water phase solution, stirring at high speed to form an oil-in-water emulsion, adding the formed oil-in-water emulsion into 67.7mL of polyvinyl alcohol aqueous solution with the mass fraction of 1%, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
(4) 65g of the microcapsule particles were mixed with 35g of bisphenol A epoxy resin having a viscosity of 4500 mPas (10 rpm @25 ℃), and uniformly dispersed with high-speed stirring to obtain a liquid type microcapsule curing agent HX-08.
Weighing 10g of spherical silver-coated copper powder (with the particle size of 200-800 nm), 35g of spherical silver powder (with the particle size of 200-800 nm), 45g of flake silver powder (with the particle size of 2.0-7.0 mu m), 3.8g of bisphenol F epoxy resin with the viscosity of 1600 mPas (10 rpm @25 ℃), 2.0g of hydrogenated bisphenol A epoxy resin with the viscosity of 1500 mPas (10 rpm @25 ℃), 0.5g of p-methylphenyl glycidyl ether with the viscosity of 7.5 mPas (10 rpm @25 ℃), HX-081.5 g of liquid microcapsule curing agent, 2.0g of diethylene glycol butyl ether acetate, KH-5600.05 g of silane coupling agent and 0.15g of dispersing agent Silok-7455H, stirring and mixing uniformly, and preparing the conductive paste with the fineness of less than 10 mu m by a three-roll machine. Printing the conductive paste on a silicon wafer substrate, pre-drying at 120 ℃ for 5min, and heating at 150 ℃ for 10min to completely cure.
The conductive paste prepared in the above examples 1 to 8 was subjected to viscosity, printability, resistivity and long-term storage test, wherein the long-term storage test was conducted by placing the conductive paste at room temperature, testing the viscosity at different placing times, and characterizing the storage stability of the paste by viscosity change. The test data of the above examples are shown in table 1.
TABLE 1
| Conductive paste | Viscosity of the oil | Printability | Resistivity of | Viscosity of 7 days after standing at room temperature | Viscosity of 30 days after standing at room temperature | Standing at room temperature for 90d to obtain viscosity |
| Example 1 | 170Pa·s | Good effect | 7.3μΩ·cm | 171Pa·s | 175Pa·s | 182Pa·s |
| Example 2 | 160Pa·s | Good effect | 8.0μΩ·cm | 160Pa·s | 164Pa·s | 171Pa·s |
| Example 3 | 185Pa·s | Good effect | 6.0μΩ·cm | 187Pa·s | 190Pa·s | 197Pa·s |
| Example 4 | 168Pa·s | Good effect | 7.2μΩ·cm | 169Pa·s | 172Pa·s | 183Pa·s |
| Example 5 | 172Pa·s | Good effect | 7.0μΩ·cm | 173Pa·s | 178Pa·s | 186Pa·s |
| Example 6 | 190Pa·s | Good effect | 5.5μΩ·cm | 192Pa·s | 196Pa·s | 202Pa·s |
| Example 7 | 195Pa·s | Good effect | 5.3μΩ·cm | 197Pa·s | 200Pa·s | 205Pa·s |
| Example 8 | 175Pa·s | Good effect | 6.9μΩ·cm | 178Pa·s | 180Pa·s | 189Pa·s |
As can be seen from Table 1, the conductive paste of the present invention has good conductivity, and can be stored at room temperature for a long period of time and cured at high temperature for a short period of time (150 ℃/10 min).
Claims (10)
1. A high-conductivity conductive paste is characterized in that: the conductive paste consists of 85 to 95 percent of conductive powder, 2.0 to 13.0 percent of resin, 0.3 to 3.0 percent of liquid microcapsule type curing agent, 0.1 to 1.0 percent of active diluent, 0.2 to 3.0 percent of solvent and 0.05 to 1.5 percent of additive by mass percent;
the liquid microcapsule type curing agent comprises microcapsule particles and a dispersion medium, wherein the capsule wall of the microcapsule particles is polyurethane resin containing blocked isocyanate end groups, the capsule core is an imidazole substance, and the dispersion medium is epoxy resin; the liquid microcapsule type curing agent is prepared by the following method:
(1) uniformly mixing polyester polyol, isocyanate, a chain extender and a catalyst, controlling the molar ratio of-NCO groups contained in the isocyanate to-OH groups contained in the polyester polyol and the chain extender to be 1.05/1-2.0/1, and controlling the addition amount of the catalyst to be 0.05-0.3 percent of the total mass of the polyester polyol, the isocyanate and the chain extender to react at the temperature of 70-100 ℃ to obtain the polyurethane resin with the terminal groups of the isocyanate groups;
the polyester polyol is selected from any one of polyethylene glycol adipate glycol, polypropylene glycol adipate glycol, polybutylene adipate glycol, polyhexamethylene glycol adipate glycol, polydiethylene glycol phthalate glycol, poly-1, 6-hexanediol phthalate glycol, polydiethylene glycol phthalate glycol, polycaprolactone butanediol glycol, polycaprolactone neopentyl glycol diol, polycaprolactone diethylene glycol ester diol, polycaprolactone hexanediol glycol ester diol, polyhexamethylene carbonate glycol, polycarbonate-1, 6-hexanediol glycol, polybutylece carbonate diol, and polycarbonate-1, 4-butanediol-1, 6-hexanediol diol;
the isocyanate is selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, p-phenylene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethylm-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, tolylene diisocyanate dimer, tolylene diisocyanate trimer, hexamethylene diisocyanate dimer, isophorone diisocyanate trimer, tolylene diisocyanate trimer, and tolylene diisocyanate trimer, and isophorone diisocyanate trimer, Any one of triphenylmethane triisocyanate and dimethyltriphenylmethane tetraisocyanate;
the chain extender is any one of ethylene glycol, 1, 4-butanediol, diethylene glycol and 1, 6-hexanediol;
the catalyst is selected from any one of triethylene diamine, bis (dimethylaminoethyl) ether, cyclohexyl methyl tertiary amine, N-dimethyl benzylamine, dimethyl ethanolamine, 1, 4-dimethyl piperazine, N-methyl morpholine, N-ethyl morpholine, dibutyltin dilaurate, stannous octoate, dibutyltin diacetate, potassium isooctanoate, tin isooctanoate, bismuth isooctanoate, tetrabutyl titanate and tetraisopropyl titanate;
(2) adding methyl ethyl ketoxime into polyurethane resin with an end group of isocyanate group, and reacting at 70-90 ℃ until isocyanate is completely sealed to obtain polyurethane resin with a sealed isocyanate end group;
(3) dissolving an imidazole substance and polyurethane resin containing blocked isocyanate end groups into acetone to obtain an oil phase solution with the mass fraction of 1% -10%, wherein the mass ratio of the imidazole substance to the polyurethane resin containing blocked isocyanate end groups is 5/95-50/50; dissolving a hydrophilic dispersant in water to obtain an aqueous phase solution with the mass fraction of 0.2-1.2%; mixing the oil phase solution and the water phase solution according to the volume ratio of 1: 3-1: 7, and stirring to form an oil-in-water emulsion; adding the formed oil-in-water emulsion into a polyvinyl alcohol aqueous solution with the mass concentration of 1%, wherein the volume ratio of the oil-in-water emulsion to the polyvinyl alcohol aqueous solution is 60/40-98/2, stirring and heating to volatilize acetone, so as to obtain microcapsule particles;
the imidazole substance is selected from any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 1-benzyl-2-ethylimidazole, 1-aminoethyl-2-methylimidazole, 1-cyanoethyl substituted imidazole, 2-phenyl-4-methylimidazole and benzimidazole;
the hydrophilic dispersant is any one of sodium dodecyl sulfate and tween-20;
(4) mixing the microcapsule particles with epoxy resin according to a mass ratio of 5/95-95/5, and uniformly stirring and dispersing to obtain a liquid microcapsule curing agent;
the epoxy resin is liquid epoxy resin, and is selected from any one of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, alicyclic epoxy resin and novolac epoxy resin; the viscosity of the epoxy resin at 10rpm and 25 ℃ is 3000-50000 mPas.
2. The conductive paste of high conductivity according to claim 1, wherein: the conductive powder is selected from one or more of silver powder, copper powder, silver-coated aluminum powder, silver-coated nickel powder and silver-coated glass powder, the shape of the conductive powder is one or more of nano-wires, flakes, irregular particles and spheres, and the particle size of the conductive powder is 50 nm-15 mu m.
3. The conductive paste of high conductivity according to claim 1, wherein: the resin is selected from any one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol A epoxy resin, hydrogenated bisphenol F epoxy resin, alicyclic epoxy resin, low-molecular-weight glycidyl ether, low-molecular-weight glycidyl ester and low-molecular-weight glycidyl amine, and the viscosity of the resin at 10rpm and 25 ℃ is 100-5000 mPa & s.
4. The conductive paste of high conductivity according to claim 1, wherein: the reactive diluent is selected from one or more of butyl glycidyl ether, 2-ethylhexyl glycidyl ether, o-cresol glycidyl ether, phenyl glycidyl ether, p-methylphenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, neopentyl glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether and ethylene glycol diglycidyl ether; the viscosity of the reactive diluent is 1-1500 mPa.s at 10rpm and 25 ℃.
5. The conductive paste of high conductivity according to claim 1, wherein: the solvent is selected from one or more of naphtha, DBE, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, diethylene glycol butyl ether acetate, dimethyl succinate, dimethyl glutarate, dipropylene glycol methyl ether, dipropylene glycol butyl ether, diacetone alcohol, 3-methoxy butyl acetate, 3-methoxy butyl propionate, propylene carbonate, butyl acetate and diethylene glycol diacetate.
6. The conductive paste of high conductivity according to claim 1, wherein: the additive comprises at least one of a dispersant, a thixotropic agent, a leveling agent and a coupling agent; wherein the dispersant is selected from any one or more of Silok-7423, Silok-7421, Silok-7455H, Silok-7631, Silok-7096, Silok-7160, BYK-111, BYK-2155, BYK-2008, BYK-170, BYK-2025, BYK-220S, BYK-106, BYK-370, BYK-388, Delhi D9850, Delhi 983, Delhi 904S, Delhi 910, Delhi 912, Delhi 929, DARVANC-N and Xinyue 4803, the thixotropic agent is selected from any one or more of polyethylene wax, gas phase silica, organic bentonite and castor oil, the leveling agent is selected from any one or more of organosilicon leveling agent, organic fluorine leveling agent and acrylate leveling agent, and the coupling agent is selected from any one or more of silane coupling agent, titanate coupling agent and aluminate coupling agent.
7. The conductive paste of high conductivity according to claim 1, wherein: in the step (1) of the preparation method of the liquid microcapsule type curing agent, polyester polyol, isocyanate, a chain extender and a catalyst are uniformly mixed, the molar ratio of-NCO groups contained in the isocyanate to-OH groups contained in the polyester polyol and the chain extender is controlled to be 1.2/1-1.5/1, the addition amount of the catalyst is 0.06% -0.15% of the total mass of the polyester polyol, the isocyanate and the chain extender, and the reaction is carried out at the temperature of 80-90 ℃ to obtain the polyurethane resin with the end group of the isocyanate group; wherein the polyester polyol is selected from any one of polyethylene glycol adipate glycol, polypropylene glycol adipate glycol, polybutylene glycol adipate glycol and polyhexamethylene glycol adipate glycol; the isocyanate is selected from any one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, toluene diisocyanate tripolymer, hexamethylene diisocyanate tripolymer and isophorone diisocyanate tripolymer; the catalyst is selected from any one of cyclohexyl methyl tertiary amine, N-dimethyl benzylamine, N-methyl morpholine, dibutyltin dilaurate, stannous octoate, bismuth isooctanoate and tetraisopropyl titanate.
8. The conductive paste of high conductivity according to claim 1, wherein: in the step (2) of the preparation method of the liquid microcapsule type curing agent, methyl ethyl ketoxime is added into the polyurethane resin with the end group of isocyanate group, and the reaction is carried out at 75-85 ℃ until isocyanate is completely sealed, so as to obtain the polyurethane resin with the sealed isocyanate end group.
9. The conductive paste of high conductivity according to claim 1, wherein: in the step (3) of the preparation method of the liquid microcapsule type curing agent, imidazole substances and polyurethane resin containing blocked isocyanate end groups are dissolved in acetone to obtain an oil phase solution with the mass fraction of 4% -7%, wherein the mass ratio of the imidazole substances to the polyurethane resin containing blocked isocyanate end groups is 20/80-40/60; dissolving a hydrophilic dispersant in water to obtain an aqueous phase solution with the mass fraction of 0.5-1%; mixing the oil phase solution and the water phase solution according to the volume ratio of 1: 5-1: 6, and stirring to form an oil-in-water emulsion; adding the formed oil-in-water emulsion into a polyvinyl alcohol aqueous solution with the mass concentration of 1%, wherein the volume ratio of the oil-in-water emulsion to the polyvinyl alcohol aqueous solution is 75/25-85/15, stirring and heating to volatilize acetone, and obtaining microcapsule particles.
10. The conductive paste of high conductivity according to claim 1, wherein: in the step (4) of the preparation method of the liquid microcapsule type curing agent, microcapsule particles and epoxy resin are mixed according to the mass ratio of 30/70-70/30, and the mixture is stirred and uniformly dispersed to obtain the liquid microcapsule type curing agent.
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