JP2003045228A - Conductive paste - Google Patents
Conductive pasteInfo
- Publication number
- JP2003045228A JP2003045228A JP2001233714A JP2001233714A JP2003045228A JP 2003045228 A JP2003045228 A JP 2003045228A JP 2001233714 A JP2001233714 A JP 2001233714A JP 2001233714 A JP2001233714 A JP 2001233714A JP 2003045228 A JP2003045228 A JP 2003045228A
- Authority
- JP
- Japan
- Prior art keywords
- conductive paste
- powder
- conductive
- weight
- epoxy resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000843 powder Substances 0.000 claims abstract description 88
- 239000011230 binding agent Substances 0.000 claims abstract description 41
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 26
- 230000009477 glass transition Effects 0.000 claims abstract description 13
- 230000005484 gravity Effects 0.000 claims abstract description 13
- 229920005989 resin Polymers 0.000 claims abstract description 13
- 239000011347 resin Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 8
- 239000011812 mixed powder Substances 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 52
- 239000003822 epoxy resin Substances 0.000 claims description 45
- 229920000647 polyepoxide Polymers 0.000 claims description 45
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 44
- 239000005011 phenolic resin Substances 0.000 claims description 41
- 229910052709 silver Inorganic materials 0.000 claims description 40
- 239000004332 silver Substances 0.000 claims description 40
- 239000002245 particle Substances 0.000 claims description 30
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- 229920003987 resole Polymers 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 239000004593 Epoxy Substances 0.000 claims description 5
- 238000009835 boiling Methods 0.000 claims description 5
- 238000010494 dissociation reaction Methods 0.000 claims description 4
- 230000005593 dissociations Effects 0.000 claims description 4
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 description 36
- 239000000853 adhesive Substances 0.000 description 34
- 230000001070 adhesive effect Effects 0.000 description 34
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 230000005012 migration Effects 0.000 description 10
- 238000013508 migration Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 8
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical group CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 8
- 239000004020 conductor Substances 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- TYOXIFXYEIILLY-UHFFFAOYSA-N 5-methyl-2-phenyl-1h-imidazole Chemical compound N1C(C)=CN=C1C1=CC=CC=C1 TYOXIFXYEIILLY-UHFFFAOYSA-N 0.000 description 5
- CJMZLCRLBNZJQR-UHFFFAOYSA-N ethyl 2-amino-4-(4-fluorophenyl)thiophene-3-carboxylate Chemical compound CCOC(=O)C1=C(N)SC=C1C1=CC=C(F)C=C1 CJMZLCRLBNZJQR-UHFFFAOYSA-N 0.000 description 5
- 229910000679 solder Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 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 description 4
- 239000000463 material Substances 0.000 description 4
- -1 nitrogen-containing compound Chemical class 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000010079 rubber tapping Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 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 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- DZCLVBQEPZQZNN-UHFFFAOYSA-N copper;phenol Chemical compound [Cu].OC1=CC=CC=C1 DZCLVBQEPZQZNN-UHFFFAOYSA-N 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical group CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical group CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920003986 novolac Polymers 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001275 scanning Auger electron spectroscopy Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000013008 thixotropic agent Substances 0.000 description 2
- 230000009974 thixotropic effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical group CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIPRQQHINVWJCH-UHFFFAOYSA-N 1-ethoxypropan-2-yl acetate Chemical group CCOCC(C)OC(C)=O LIPRQQHINVWJCH-UHFFFAOYSA-N 0.000 description 1
- QBDAFARLDLCWAT-UHFFFAOYSA-N 2,3-dihydropyran-6-one Chemical compound O=C1OCCC=C1 QBDAFARLDLCWAT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical group CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- MTVLEKBQSDTQGO-UHFFFAOYSA-N 2-(2-ethoxypropoxy)propan-1-ol Chemical compound CCOC(C)COC(C)CO MTVLEKBQSDTQGO-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical group COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical compound CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- YCUKMYFJDGKQFC-UHFFFAOYSA-N 2-(octan-3-yloxymethyl)oxirane Chemical compound CCCCCC(CC)OCC1CO1 YCUKMYFJDGKQFC-UHFFFAOYSA-N 0.000 description 1
- HJEORQYOUWYAMR-UHFFFAOYSA-N 2-[(2-butylphenoxy)methyl]oxirane Chemical compound CCCCC1=CC=CC=C1OCC1OC1 HJEORQYOUWYAMR-UHFFFAOYSA-N 0.000 description 1
- CUFXMPWHOWYNSO-UHFFFAOYSA-N 2-[(4-methylphenoxy)methyl]oxirane Chemical compound C1=CC(C)=CC=C1OCC1OC1 CUFXMPWHOWYNSO-UHFFFAOYSA-N 0.000 description 1
- HPILSDOMLLYBQF-UHFFFAOYSA-N 2-[1-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COC(CCC)OCC1CO1 HPILSDOMLLYBQF-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical group CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- YTWBFUCJVWKCCK-UHFFFAOYSA-N 2-heptadecyl-1h-imidazole Chemical compound CCCCCCCCCCCCCCCCCC1=NC=CN1 YTWBFUCJVWKCCK-UHFFFAOYSA-N 0.000 description 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- RILGFINHPYGNPC-UHFFFAOYSA-N 3-methoxy-1-(3-methoxy-3-methylbutoxy)-3-methylbutane Chemical group COC(C)(C)CCOCCC(C)(C)OC RILGFINHPYGNPC-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical group COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical group CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- VQAJOWJEGHKRHX-UHFFFAOYSA-N CCOCC(C)OCC(C)OC(C)C Chemical compound CCOCC(C)OCC(C)OC(C)C VQAJOWJEGHKRHX-UHFFFAOYSA-N 0.000 description 1
- SWCIBYZQKLHRHZ-UHFFFAOYSA-N COCC(C)OCC(C)OC(C)C Chemical compound COCC(C)OCC(C)OC(C)C SWCIBYZQKLHRHZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007718 adhesive strength test Methods 0.000 description 1
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 description 1
- 239000004844 aliphatic epoxy resin Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 239000001191 butyl (2R)-2-hydroxypropanoate Chemical group 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229930003836 cresol Natural products 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- ZZTCPWRAHWXWCH-UHFFFAOYSA-N diphenylmethanediamine Chemical compound C=1C=CC=CC=1C(N)(N)C1=CC=CC=C1 ZZTCPWRAHWXWCH-UHFFFAOYSA-N 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- NXPPAOGUKPJVDI-UHFFFAOYSA-N naphthalene-1,2-diol Chemical compound C1=CC=CC2=C(O)C(O)=CC=C21 NXPPAOGUKPJVDI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011134 resol-type phenolic resin Substances 0.000 description 1
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical group COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Powder Metallurgy (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Conductive Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子部品、回路配
線材料、電極材料、導電性接合材料、導電性接着剤とし
て使用される導電ペーストに関する。TECHNICAL FIELD The present invention relates to a conductive paste used as an electronic component, a circuit wiring material, an electrode material, a conductive bonding material, and a conductive adhesive.
【０００２】[0002]
【従来の技術】電子部品を回路基板などへ実装するに
は、鉛を含むはんだを用いた接合法が広く知られてい
る。しかし近年、環境問題への認識の高まりから、はん
だに代わって鉛を含まない鉛フリーはんだや導電ペース
トが注目されるようになってきた。導電ペーストは、貴
金属を含むため鉛フリーはんだより高価ではあるが、実
装温度の低温化、接合部の柔軟性等の多くの利点が兼ね
備えられている。2. Description of the Related Art A bonding method using a solder containing lead is widely known for mounting electronic components on a circuit board or the like. However, in recent years, due to increasing awareness of environmental problems, lead-free solders and conductive pastes that do not contain lead have been attracting attention in place of solders. The conductive paste is more expensive than lead-free solder because it contains a noble metal, but it has many advantages such as a lower mounting temperature and flexibility of the joint.
【０００３】従来の導電ペーストは、電子材料、１９９
４年１０月号の４２〜４６頁に記載されているように、
金、銀、銅、カーボン等の導電性粉末を用い、それにバ
インダ、有機溶剤及び必要に応じて添加剤を加えてペー
スト状に混合して作製していた。特に高導電性が要求さ
れる分野では、金粉又は銀粉を用いることが一般的に知
られていた。A conventional conductive paste is an electronic material, 199.
As described on pages 42-46 of the October 4 issue,
A conductive powder such as gold, silver, copper, or carbon is used, and a binder, an organic solvent and, if necessary, additives are added thereto and mixed in a paste form. It has been generally known to use gold powder or silver powder particularly in the field where high conductivity is required.
【０００４】最近導電ペーストは、価格、実績及び導電
性の観点から導電性粉末として銀又は銅を用いるのが一
般的である。銀粉を含有する導電ペーストは、導電性が
良好なことから印刷配線板、電子部品等の電気回路や電
極の形成に使用されているが、これらは高温多湿の雰囲
気下で電解が印可されると、電気回路や電極にマイグレ
ーションと称する銀の電析が生じ電極間又は配線間が短
絡するという欠点が生じる。このマイグレーションを防
止するための方策はいくつか行われており、導体の表面
に防湿塗料を塗布するか又は導電ペーストに含窒素化合
物などの腐食抑制剤を添加するなどの方策が検討されて
いるが十分な効果の得られるものではなかった。Recently, the conductive paste generally uses silver or copper as a conductive powder from the viewpoints of price, performance and conductivity. Conductive paste containing silver powder is used for forming electric circuits and electrodes of printed wiring boards, electronic parts, etc. because of its good conductivity, but when these are electrolyzed in a hot and humid atmosphere. However, there is a drawback in that electroplating of silver called migration occurs in an electric circuit or an electrode and a short circuit occurs between electrodes or between wirings. Several measures have been taken to prevent this migration, and measures such as applying a moisture-proof coating to the surface of the conductor or adding a corrosion inhibitor such as a nitrogen-containing compound to the conductive paste have been studied. It was not a sufficient effect.
【０００５】また、導通抵抗の良好な導体を得るには銀
粉の配合量を増加しなければならず、銀粉が高価である
ことから導電ペーストも高価になるという欠点があっ
た。銀被覆銅粉を使用すればマイグレーションを改善で
き、これを用いれば安価な導電ペーストが得られること
になる。しかし銀被覆を均一に、かつ厚く被覆するとマ
イグレーションの改善効果はない。Further, in order to obtain a conductor having good conduction resistance, the amount of silver powder blended must be increased, and there is a drawback that the conductive paste is expensive because silver powder is expensive. If silver-coated copper powder is used, migration can be improved, and if this is used, an inexpensive conductive paste can be obtained. However, if the silver coating is applied uniformly and thickly, there is no effect of improving migration.
【０００６】一方、銅粉を使用した導電ペーストは、加
熱硬化後の銅の被酸化性が大きいため、空気中及びバイ
ンダ中に含まれる酸素と銅粉が反応し、その表面に酸化
膜を形成し、導電性を著しく低下させる。そのため、各
種添加剤を加えて、銅粉の酸化を防止し、導電性が安定
した銅ペーストが開示されているが、その導電性は銀ペ
ーストには及ばず、また保存安定性にも欠点があった。
現在使用している導電ペーストでは、導電性、接着強
度、作業性及びマイグレーション性に優れ、かつ価格の
観点から鉛はんだに対抗できる導電ペーストが見あたら
ないのが現状である。On the other hand, in the conductive paste using copper powder, the oxygen contained in the air and the binder reacts with the copper powder because the copper is highly oxidizable after being heated and hardened, and an oxide film is formed on the surface thereof. However, the conductivity is significantly reduced. Therefore, various additives are added to prevent oxidation of the copper powder, and a stable copper paste is disclosed, but its conductivity does not reach that of the silver paste, and there is also a drawback in storage stability. there were.
In the current state of the art, there is no electrically conductive paste that is excellent in electrical conductivity, adhesive strength, workability and migration property, and that can counter lead solder in terms of cost.
【０００７】[0007]
【発明が解決しようとする課題】請求項１及び２記載の
発明は、導電性、接着強度、作業性に優れる導電ペース
トを提供するものである。請求項３記載の発明は、導電
性の向上効果及びマイグレーション性に優れる導電ペー
ストを提供するものである。請求項４及び５記載の発明
は、導電性、接着強度及び作業性のバランスに優れる導
電ペーストを提供するものである。The invention described in claims 1 and 2 provides a conductive paste having excellent conductivity, adhesive strength and workability. The invention according to claim 3 provides a conductive paste excellent in conductivity improving effect and migration property. The inventions according to claims 4 and 5 provide a conductive paste having an excellent balance of conductivity, adhesive strength and workability.
【０００８】請求項６及び７記載の発明は、導電性の向
上効果及び導電ペーストの保存安定性に優れる導電ペー
ストを提供するものである。請求項８及び９記載の発明
は、接着強度、作業性、導電ペーストの保存安定性の向
上効に優れる導電ペ−ストを提供するものである。請求
項１０記載の発明は、導電性、接着強度のバランスに優
れる導電ペ−ストを提供するものである。The inventions according to claims 6 and 7 provide a conductive paste which is excellent in conductivity improving effect and storage stability of the conductive paste. The inventions according to claims 8 and 9 provide a conductive paste which is excellent in improving the adhesive strength, workability, and storage stability of the conductive paste. The tenth aspect of the present invention provides a conductive paste having an excellent balance of conductivity and adhesive strength.
【０００９】請求項１１記載の発明は、作業性の向上効
果に優れる導電ペ−ストを提供するものである。請求項
１２記載の発明は、導電性、接着強度、作業性のバラン
スに優れる導電ペ−ストを提供するものである。請求項
１３記載の発明は、作業性の向上効果に優れる導電ペ−
ストを提供するものである。請求項１４記載の発明は、
導電性、作業性の向上効果及び接合部の柔軟性に優れる
導電ペーストを提供するものである。The eleventh aspect of the present invention provides a conductive paste excellent in workability improving effect. The invention according to claim 12 provides a conductive paste having an excellent balance of conductivity, adhesive strength and workability. The invention according to claim 13 is a conductive sheet excellent in the workability improving effect.
It provides a strike. The invention according to claim 14 is
The purpose of the present invention is to provide a conductive paste which is excellent in conductivity and workability and is excellent in flexibility of a joint.
【００１０】[0010]
【課題を解決するための手段】本発明は、導電粉、バイ
ンダ及び有機溶剤を含み、かつ導電粉が球状若しくは略
球状と扁平状との混合粉又は球状、略球状、扁平状のい
ずれか１種の単独粉であり、バインダの主成分が熱硬化
性樹脂及びその硬化剤を含み、比重が３〜７．５及び導
電ペースト硬化物のガラス転移点が４０〜１８０℃であ
る導電ペーストに関する。また、本発明は、有機溶剤
が、１種又は２種以上の混合溶剤である導電ペーストに
関する。また、本発明は、導電粉が、銅粉又は銅合金粉
の一部を露出して、表面が大略銀で被覆された銀被覆銅
粉又銀被覆銅合金粉であり、かつ銀の被覆量が５〜２５
重量％及び銅粉又は銅合金粉の露出面積が１０〜６０％
である導電ペーストに関する。According to the present invention, conductive powder, a binder and an organic solvent are contained, and the conductive powder is spherical or a mixed powder of substantially spherical and flat or spherical, substantially spherical or flat. The present invention relates to a conductive paste that is a single powder of a seed, contains a thermosetting resin and a curing agent thereof as a main component of a binder, has a specific gravity of 3 to 7.5, and a cured glass of the conductive paste having a glass transition point of 40 to 180 ° C. The present invention also relates to a conductive paste in which the organic solvent is one kind or a mixed solvent of two or more kinds. Further, the present invention is a conductive powder, a part of the copper powder or copper alloy powder is exposed, the surface is a silver-coated copper powder or silver-coated copper alloy powder substantially coated with silver, and the coating amount of silver Is 5 to 25
Weight% and exposed area of copper powder or copper alloy powder is 10 to 60%
Which is a conductive paste.
【００１１】また、本発明は、球状又は略球状の導電粉
が、長径の平均粒径が１〜２０μｍ、アスペクト比が１
〜１．５、タップ密度が４．５〜６．２ｇ／ｃｍ３、相
対密度が５０〜６８％及び比表面積が０．１〜１．０ｍ
２／ｇである導電ペーストに関する。また、本発明は、
扁平状の導電粉が、長径の平均粒径が５〜３０μｍ、ア
スペクト比が３〜２０、タップ密度が２．５〜５．８ｇ
／ｃｍ３、相対密度が２７〜６３％及び比表面積が０．
４〜１．３ｍ２／ｇである導電ペーストに関する。According to the present invention, the spherical or substantially spherical conductive powder has an average major axis diameter of 1 to 20 μm and an aspect ratio of 1.
˜1.5, tap density 4.5 to 6.2 g / cm 3 , relative density 50 to 68% and specific surface area 0.1 to 1.0 m.
2 / g for a conductive paste. Further, the present invention is
The flat conductive powder has an average major particle diameter of 5 to 30 μm, an aspect ratio of 3 to 20, and a tap density of 2.5 to 5.8 g.
/ Cm 3 , relative density of 27 to 63% and specific surface area of 0.
It relates to a conductive paste that is 4 to 1.3 m 2 / g.
【００１２】また、本発明は、熱硬化性樹脂が、エポキ
シ樹脂及びフェノール樹脂である導電ペーストに関す
る。また、本発明は、エポキシ樹脂が、常温で液状のエ
ポキシ樹脂及びフェノール樹脂が、アルコキシ基含有レ
ゾール型フェノール樹脂である導電ペーストに関する。
また、本発明は、エポキシ樹脂が、エポキシ当量が１６
０〜３３０ｇ／ｅｑ及びフェノール樹脂が、アルコキシ
基の炭素数が１〜６、アルコキシ化率が５〜９５％、重
量平均分子量が５００〜２００，０００である導電ペー
ストに関する。また、本発明は、エポキシ樹脂の硬化剤
が、融点が４０〜２４０℃及びフェノール樹脂の硬化剤
が、官能基がマスキングされており解離温度が６０〜１
４０℃である導電ペーストに関する。また、本発明は、
エポキシ樹脂とフェノール樹脂の配合割合が、重量比で
エポキシ樹脂：フェノール樹脂が１０：９０〜９５：５
である導電ペーストに関する。The present invention also relates to a conductive paste in which the thermosetting resin is an epoxy resin or a phenol resin. The present invention also relates to a conductive paste in which the epoxy resin is a liquid epoxy resin at normal temperature and the phenol resin is an alkoxy group-containing resol-type phenol resin.
Further, in the present invention, the epoxy resin has an epoxy equivalent of 16
0-330 g / eq and phenol resin relates to a conductive paste having an alkoxy group having 1 to 6 carbon atoms, an alkoxylation rate of 5 to 95%, and a weight average molecular weight of 500 to 200,000. Further, in the present invention, the epoxy resin curing agent has a melting point of 40 to 240 ° C. and the phenol resin curing agent has a functional group masked so that the dissociation temperature is 60 to 1
It relates to a conductive paste that is 40 ° C. Further, the present invention is
The epoxy resin and the phenol resin are mixed in a weight ratio of epoxy resin: phenol resin of 10:90 to 95: 5.
Which is a conductive paste.
【００１３】また、本発明は、有機溶剤が、蒸発速度が
３０以下（０を除く）であり、沸点が１５０〜２６０℃
である導電ペーストに関する。また、本発明は、導電粉
とバインダの配合割合が、導電ペーストの固形分に対し
て重量比で導電粉：バインダが８３：１７〜９７：３及
び体積比で導電粉：バインダが２８：７２〜８４：１６
である導電ペーストに関する。また、本発明は、有機溶
剤が、導電ペーストに対して２〜１０重量％含有してな
る導電ペーストに関する。さらに、本発明は、粘度が１
００〜７，０００ｄｐａ・ｓ及びチキソ値が１．８〜
7．３である導電ペーストに関する。In the present invention, the organic solvent has an evaporation rate of 30 or less (excluding 0) and a boiling point of 150 to 260 ° C.
Which is a conductive paste. Further, in the present invention, the mixing ratio of the conductive powder and the binder is 83:17 to 97: 3 by weight and the conductive powder: binder is 28:72 by volume with respect to the solid content of the conductive paste. ~ 84: 16
Which is a conductive paste. The present invention also relates to a conductive paste containing an organic solvent in an amount of 2 to 10% by weight based on the conductive paste. Further, the present invention has a viscosity of 1
00-7,000 dpa · s and thixo value of 1.8-
7.3 conductive paste.
【００１４】[0014]
【発明の実施の形態】本発明に用いられる導電粉の形状
は、球状若しくは略球状と扁平状との混合粉又は球状、
略球状、扁平状のいずれか１種の単独粉とされるが、こ
れらの導電粉は導電ペーストの粘度、塗布面積、膜厚、
接合部材等の接合の仕様や要求特性により、組み合わせ
や比率が異なってくる。例えば、平面方向の導電性は、
導電粉同士の接触面積、配向等の点から扁平状の導電粉
が好ましく、断面方向の導電性は断面方向に対する単一
粒子が占める体積が増えるので球状又は略球状の導電粉
を用いることが好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The shape of the conductive powder used in the present invention is spherical or a mixed powder of spherical and substantially spherical, or spherical,
It is a single powder of either a substantially spherical shape or a flat shape. These conductive powders include the conductive paste viscosity, coating area, film thickness,
Combinations and ratios vary depending on the specifications and required characteristics of joining members and the like. For example, the conductivity in the plane direction is
A flat conductive powder is preferable in terms of contact area between conductive powders, orientation, etc., and conductivity in the cross-sectional direction is preferably spherical or substantially spherical because the volume occupied by a single particle in the cross-sectional direction increases. .
【００１５】また、接着強度についても、接合の仕様に
よって異なるが、一般的に基材に対して平滑に塗布した
導電ペーストでは、扁平状の導電粉の方が球状又は略球
状の導電粉より高い値を示す。例えば図１に示すよう
に、導電ペースト２を用いて銅箔１にリードフレーム３
を接合する場合、導電性、接着強度、作業性、信頼性等
の点から球状又は略球状の導電粉と扁平状の導電粉との
比率が、重量比で球状又は略球状の導電粉：扁平状の導
電粉が４０：６０〜９８：２の範囲で良好な結果が得ら
れている。The adhesive strength also varies depending on the bonding specifications, but in the conductive paste applied to the base material evenly, the flat conductive powder is generally higher than the spherical or substantially spherical conductive powder. Indicates a value. For example, as shown in FIG. 1, the lead frame 3 is formed on the copper foil 1 using the conductive paste 2.
In the case of joining, the ratio of spherical or substantially spherical conductive powder to flat conductive powder in terms of conductivity, adhesive strength, workability, reliability, etc. is spherical or substantially spherical conductive powder by weight ratio: flat. Good results have been obtained in the range of 40:60 to 98: 2 of the conductive powder.
【００１６】なお、扁平状の導電粉を主として用いた場
合、導電ペーストの粘度は高くなり、反面、球状又は略
球状の導電粉を主として用いた場合、扁平状の導電粉を
主とて用いた場合より粘度が低くなり作業性がよくな
る。また球状又は略球状の導電粉を主として用いた場合
と扁平状の導電粉を主として用いた場合の導電ペースト
の粘度を同一にする場合は、球状又は略球状の導電粉の
比率を扁平状の導電粉の比率より高くすることができ
る。When the flat conductive powder is mainly used, the viscosity of the conductive paste is high. On the other hand, when the spherical or substantially spherical conductive powder is mainly used, the flat conductive powder is mainly used. The viscosity is lower than in the case and workability is improved. When the viscosity of the conductive paste is the same when the spherical or substantially spherical conductive powder is mainly used and when the flat conductive powder is mainly used, the ratio of the spherical or substantially spherical conductive powder is flat. It can be higher than the powder ratio.
【００１７】本発明になる導電ペーストの比重は、３〜
７．５、好ましくは３．５〜６．５の範囲とされ、比重
が３未満であると導電粉の比率が低いため高導電性が得
られない。一方、７．５を超えると導電粉の比率は高い
がバインダの比率が低くなるため、接着強度が低くな
る。導電ペーストの比重を上記の範囲にするためには、
導電粉とバインダの比率を導電ペーストの固形分に対し
て重量比で導電粉：バインダが８３：１７〜９７：３及
び体積比で導電粉：バインダが２８：７２〜８４：１６
の範囲にすることが好ましく、重量比で導電粉：バイン
ダが８５：１５〜９５：５及び体積比で導電粉：バイン
ダが３５：６５〜６５：３５の範囲にすることがさらに
好ましい。The specific gravity of the conductive paste according to the present invention is 3 to.
It is set to 7.5, preferably 3.5 to 6.5, and if the specific gravity is less than 3, high conductivity cannot be obtained because the ratio of the conductive powder is low. On the other hand, when it exceeds 7.5, the ratio of the conductive powder is high, but the ratio of the binder is low, so that the adhesive strength is low. In order to make the specific gravity of the conductive paste within the above range,
The weight ratio of the conductive powder to the binder is 83:17 to 97: 3 for the conductive powder: binder and 28:72 to 84:16 for the conductive powder: binder in the volume ratio.
The conductive powder: binder is preferably in the range of 85:15 to 95: 5 in weight ratio and the conductive powder: binder is in the range of 35:65 to 65:35 in volume ratio.
【００１８】導電ペースト硬化物のガラス転移点は、４
０〜１８０℃、好ましくは７０〜１８０℃の範囲とさ
れ、導電ペースト硬化物のガラス転移点が４０℃未満で
あると導電性、接着強度、接合部の柔軟性等他の特性と
のバランスの良い導電ペーストの作製が非常に困難であ
るか又は作製できない場合がある。１８０℃を超えると
エポキシ樹脂の比率を低下させなければならず、そのた
め接着強度が低下する。The glass transition point of the conductive paste cured product is 4
It is set in the range of 0 to 180 ° C., preferably 70 to 180 ° C., and when the glass transition point of the conductive paste cured product is less than 40 ° C., the balance with other properties such as conductivity, adhesive strength, and flexibility of the joint is obtained. Making a good conductive paste can be very difficult or impossible. If the temperature exceeds 180 ° C, the ratio of the epoxy resin has to be reduced, so that the adhesive strength is reduced.
【００１９】本発明に用いられる導電粉は、銅粉又は銅
合金粉の一部を露出して、表面が大略銀で被覆された銀
被覆銅粉又は銀被覆銅合金粉を用いることが好ましい。
もし銅粉又は銅合金粉の一部を露出させないで全面に銀
を被覆したものを用いるとマイグレーション性が悪くな
る傾向がある。銅粉又は銅合金粉の露出面積は、マイグ
レ−ション性、露出部の酸化、導電性等の点から１０〜
６０％の範囲が好ましく、１０〜５５％の範囲がさらに
好ましい。As the conductive powder used in the present invention, it is preferable to use a silver-coated copper powder or a silver-coated copper alloy powder in which a part of the copper powder or the copper alloy powder is exposed and the surface is substantially coated with silver.
If a copper powder or a copper alloy powder whose whole surface is covered with silver without exposing a part thereof is used, the migration property tends to deteriorate. The exposed area of the copper powder or the copper alloy powder is 10 to 10 in terms of the migration property, the oxidation of the exposed portion, the conductivity, and the like.
The range of 60% is preferable, and the range of 10-55% is more preferable.
【００２０】銅粉又は銅合金粉は、アトマイズ法で作製
された粉体を用いることが好ましく、その粒径は小さい
ほど好ましい。例えば平均粒径が１〜２０μｍの範囲の
粉体を用いることが好ましく、１〜１０μｍの範囲の粉
体を用いることがさらに好ましい。銅粉又は銅合金粉の
表面に銀を被覆するには、置換めっき、電気めっき、無
電解めっき等の方法があり、銅粉又は銅合金粉と銀の付
着力が高いこと及びランニングコストが安価であること
から、置換めっきで被覆することが好ましい。銅粉又は
銅合金粉の表面への銀の被覆量は、耐マイグレーション
性、コスト、導電性向上等の点から銅粉に対して５〜２
５重量％の範囲が好ましく、１０〜２３重量％の範囲が
さらに好ましい。As the copper powder or the copper alloy powder, it is preferable to use a powder produced by an atomizing method, and the smaller the particle size, the more preferable. For example, it is preferable to use a powder having an average particle size in the range of 1 to 20 μm, and it is more preferable to use a powder in the range of 1 to 10 μm. To coat silver on the surface of copper powder or copper alloy powder, there are methods such as displacement plating, electroplating, electroless plating, etc., high adhesion of copper powder or copper alloy powder and silver, and low running cost. Therefore, it is preferable to cover with displacement plating. The coating amount of silver on the surface of the copper powder or the copper alloy powder is 5 to 2 with respect to the copper powder from the viewpoint of migration resistance, cost, improvement of conductivity, and the like.
The range of 5% by weight is preferable, and the range of 10 to 23% by weight is more preferable.
【００２１】さらに、本発明に用いられる導電粉のうち
球状又は略球状の導電粉は、長径の平均粒径が１〜２０
μｍ、アスペクト比が１〜１．５、タップ密度が４．５
〜６．２ｇ／ｃｍ３、相対密度が５０〜６８％及び比表
面積が０．１〜１．０ｍ２／ｇの範囲のものを用いるこ
とが好ましい。一方、扁平状の導電粉は、長径の平均粒
径が５〜３０μｍ、アスペクトが比３〜２０、タップ密
度が２．５〜５．８ｇ／ｃｍ３、相対密度が２７〜６３
％及び比表面積が０．４〜１．３ｍ２／ｇの範囲のもの
を用いることが好ましい。Further, among the conductive powders used in the present invention, the spherical or substantially spherical conductive powders have an average major particle diameter of 1 to 20.
μm, aspect ratio 1 to 1.5, tap density 4.5
~6.2g / cm 3, a relative density is 50 to 68% and the specific surface area is preferably used in the range of 0.1~1.0m 2 / g. On the other hand, the flat conductive powder has an average major axis particle diameter of 5 to 30 μm, an aspect ratio of 3 to 20, a tap density of 2.5 to 5.8 g / cm 3 , and a relative density of 27 to 63.
% And a specific surface area of 0.4 to 1.3 m 2 / g are preferably used.
【００２２】なお、上記でいう平均粒径は、マスターサ
イザー・レーザー散乱型粒度分布測定装置（マルバン社
製）を用いて測定し、比表面積はガス吸着式比表面積・
細孔径分布測定装置（ユアサアイオニクス社製）を用い
て測定して求めることができる。また、上記に示すタッ
プ密度は、メスシリンダーに適量の導電粉を投入し、１
０００回タッピングを行い、投入した重量と１０００回
タッピング後のメスシリンダーが示す体積から換算して
求めることができる。また、相対密度は次式から求める
ことができる。The average particle size referred to above is measured by using a master sizer / laser scattering particle size distribution measuring device (manufactured by Malvan Co.), and the specific surface area is a gas adsorption specific surface area.
It can be determined by measurement using a pore size distribution measuring device (manufactured by Yuasa Ionics Inc.). In addition, the tap density shown above is 1
The tapping can be performed 000 times, and it can be calculated by converting the weight input and the volume indicated by the graduated cylinder after 1000 tappings. The relative density can be calculated from the following equation.
【００２３】[0023]
【数１】 相対密度（％）＝（タップ密度／真密度）×ｆ×１００ ただしｆは実測値による補正係数である。[Equation 1] Relative density (%) = (tap density / true density) × f × 100 However, f is a correction coefficient based on an actual measurement value.
【００２４】本発明におけるアスペクト比とは、導電粉
の粒子の長径と短径の比率（長径／短径）をいう。本発
明においては、粘度の低い硬化性樹脂中に導電粉の粒子
をよく混合し、静置して粒子を沈降させるとともにその
まま樹脂を硬化させ、得られた硬化物を垂直方向に切断
し、その切断面に現れる粒子の形状を電子顕微鏡で拡大
して観察し、少なくとも１００の粒子について一つ一つ
の粒子の長径／短径を求め、それらの平均値をもってア
スペクト比とする。The aspect ratio in the present invention means the ratio of the major axis to the minor axis of the particles of the conductive powder (major axis / minor axis). In the present invention, particles of conductive powder are mixed well in a curable resin having a low viscosity, the resin is cured as it is while the particles are allowed to settle by allowing it to stand, and the resulting cured product is cut in the vertical direction. The shape of the particles appearing on the cut surface is magnified and observed with an electron microscope, the major axis / minor axis of each particle is obtained for at least 100 particles, and the average value thereof is used as the aspect ratio.
【００２５】ここで、短径とは、前記切断面に現れる粒
子について、その粒子の外側に接する二つの平行線の組
み合わせ粒子を挟むように選択し、それらの組み合わせ
のうち最短間隔になる二つの平行線の距離である。一
方、長径とは、前記短径を決する平行線に直角方向の二
つの平行線であって、粒子の外側に接する二つの平行線
の組み合わせのうち、最長間隔になる二つの平行線の距
離である。これらの四つの線で形成される長方形は、粒
子がちょうどその中に納まる大きさとなる。なお、本発
明において行った具体的方法については後述するHere, the minor axis is selected so that a particle appearing on the cut surface sandwiches a combination particle of two parallel lines in contact with the outside of the particle, and two particles having the shortest interval among the combinations are selected. The distance between parallel lines. On the other hand, the major axis is the distance between the two parallel lines that are the longest distance among the two parallel lines that are in contact with the outside of the particle and are the two parallel lines that are perpendicular to the parallel lines that determine the minor axis. is there. The rectangle formed by these four lines is the size that the particles will fit within. The specific method used in the present invention will be described later.
【００２６】本発明における、バインダの主成分は熱硬
化性樹脂及びその硬化剤であり、このうち熱硬化性樹脂
としては、エポキシ樹脂及びフェノール樹脂を用いるこ
とが好ましい。エポキシ樹脂は、常温で液状のものが好
ましい。常温で結晶化するものは液状物と混合すること
で結晶化を回避できる。本発明における常温で液状エポ
キシ樹脂とは、例えば常温で固形のものでも常温で液状
のエポキシ樹脂と混合することで常温で安定して液状と
なるものも含む。なお、本発明において常温とは温度が
約２５℃を示すものを意味する。常温で液状のエポキシ
樹脂を使用した導電ペーストは、固形のエポキシ樹脂を
使用した場合と比較し、粘度を低くすることができ、そ
のため作業性がよくなるので好ましい。The main component of the binder in the present invention is a thermosetting resin and its curing agent, and among these, it is preferable to use an epoxy resin and a phenol resin as the thermosetting resin. The epoxy resin is preferably liquid at room temperature. Those that crystallize at room temperature can be avoided by mixing with a liquid material. The liquid epoxy resin at room temperature in the present invention includes, for example, a solid resin at normal temperature and a resin which becomes stable liquid at normal temperature when mixed with an epoxy resin liquid at normal temperature. In addition, in this invention, normal temperature means what shows a temperature of about 25 degreeC. A conductive paste using a liquid epoxy resin at room temperature is preferable because it can have a lower viscosity than that of a solid epoxy resin and therefore improves workability.
【００２７】本発明に用いられるエポキシ樹脂は公知の
ものが用いられ、分子量中にエポキシ基を２個以上含有
する化合物、例えばビスフェノールＡ、ビスフェノール
ＡＤ、ビスフェノールＦ、ノボラック、クレゾールノボ
ラック類とエピクロルヒドリンとの反応により得られる
ポリグリシジルエーテル、ジヒドロキシナフタレンジグ
リシジルエーテル、ブタンジオールジグリシジルエーテ
ル、ネオペンチルグリコールジグリシジルエーテル等の
脂肪族エポキシ樹脂やジグリシジルヒダントイン等の複
素環式エポキシ、ビニルシクロヘキセンジオキサイド、
ジシクロペンタンジエンジオキサイド、アリサイクリッ
クジエポキシアジペイトのような脂環式エポキシ樹脂が
挙げられる。As the epoxy resin used in the present invention, known epoxy resins are used, and compounds having two or more epoxy groups in the molecular weight such as bisphenol A, bisphenol AD, bisphenol F, novolac, cresol novolaks and epichlorohydrin are used. Polyglycidyl ether obtained by the reaction, dihydroxynaphthalene diglycidyl ether, butanediol diglycidyl ether, heterocyclic epoxy such as aliphatic epoxy resin such as neopentyl glycol diglycidyl ether and diglycidyl hydantoin, vinylcyclohexenedioxide,
Examples thereof include alicyclic epoxy resins such as dicyclopentanediene dioxide and alicyclic diepoxy adipate.
【００２８】また、エポキシ樹脂は、エポキシ当量が１
６０〜３３０ｇ／ｅｑの範囲であることが好ましく、１
６０〜２５０ｇ／ｅｑの範囲であることがさらに好まし
い。１６０ｇ／ｅｑ未満のエポキシ樹脂は作製が困難で
あり、３３０ｇ／ｅｑを超えるエポキシ樹脂を使用した
導電ペーストは、粘度が高くなる傾向がある。これらの
エポキシ樹脂は、単独又は２種以上を混合して用いるこ
とができる。The epoxy resin has an epoxy equivalent of 1
It is preferably in the range of 60 to 330 g / eq, and 1
More preferably, it is in the range of 60 to 250 g / eq. Epoxy resin with less than 160 g / eq is difficult to produce, and conductive paste using epoxy resin with more than 330 g / eq tends to have high viscosity. These epoxy resins may be used alone or in combination of two or more.
【００２９】本発明においては、必要に応じて可撓性付
与剤を併用することができる。可撓性付与剤は公知のも
のが用いられ、分子量中にエポキシ基を１個だけ有する
化合物、例えばｎ−ブチルグリシジルエーテル、バーサ
ティック酸グリシジルエステル、スチレンオキサイド、
エチルヘキシルグリシジルエーテル、フェニルグリシジ
ルエーテル、クレジルグリシジルエーテル、ブチルフェ
ニルグリシジルエーテル等のような通常のエポキシ樹脂
が挙げられる。可撓性付与剤の併用割合は、バインダに
対して重量比で６０％以下（０も含む）の範囲が好まし
く、３０％以下（０も含む）の範囲がさらに好ましい。
これらの可撓性付与剤は、単独又は２種以上を混合して
用いることができる。In the present invention, a flexibility-imparting agent may be used in combination if necessary. Known flexibility-imparting agents are used, and compounds having only one epoxy group in the molecular weight, such as n-butyl glycidyl ether, versatic acid glycidyl ester, styrene oxide,
Usual epoxy resins such as ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, butyl phenyl glycidyl ether and the like can be mentioned. The proportion of the flexibility-imparting agent used in combination is preferably 60% or less (including 0) by weight, and more preferably 30% or less (including 0).
These flexibility-imparting agents can be used alone or in admixture of two or more.
【００３０】本発明に用いられるフェノール樹脂は、ア
ルコキシ基含有レゾール型フェノール樹脂が好ましい。
フェノール樹脂を使用した導電ペーストはエポキシ樹脂
を使用した導電ペーストより高い導電性が得られる。一
方、エポキシ樹脂を使用した導電ペーストはフェノール
樹脂を使用した導電ペーストより高い接着強度が得られ
る。The phenol resin used in the present invention is preferably an alkoxy group-containing resol type phenol resin.
The conductive paste using the phenol resin has higher conductivity than the conductive paste using the epoxy resin. On the other hand, the conductive paste using the epoxy resin has higher adhesive strength than the conductive paste using the phenol resin.
【００３１】高導電性が要求される導電ペーストにフェ
ノール樹脂は不可欠であるが、導電ペーストの粘度が高
くなり作業性が悪くなるが、アルコキシ基含有レゾール
型フェノール樹脂を使用することによりこの問題を解決
することができる。アルコキシ基含有レゾール型フェノ
ール樹脂としては、これを使用した導電ペーストの導電
性及び作業性の点から、特に炭素数１〜６のアルコキシ
基で置換されたレゾール型フェノール樹脂が好ましい。
レゾール型フェノール樹脂のアルコキシ化率、即ち全メ
チロール基のアルコキシ化されている割合は、導電ペー
ストの導電性及び作業性の点から、５〜９５％の範囲が
好ましく、１０〜８５％の範囲がさらに好ましい。Phenolic resin is indispensable for the conductive paste which is required to have high conductivity, but the viscosity of the conductive paste becomes high and the workability deteriorates. However, this problem is solved by using the alkoxy group-containing resol type phenol resin. Can be resolved. As the alkoxy group-containing resol type phenol resin, a resol type phenol resin substituted with an alkoxy group having 1 to 6 carbon atoms is particularly preferable from the viewpoint of the conductivity and workability of the conductive paste using the same.
From the viewpoint of conductivity and workability of the conductive paste, the alkoxylation rate of the resol-type phenol resin, that is, the proportion of all the methylol groups that are alkoxylated is preferably in the range of 5 to 95%, and in the range of 10 to 85%. More preferable.
【００３２】また、レゾール型フェノール樹脂中のアル
コキシ基は、ベンゼン環１個当たりのアルコキシ基が
０．１〜２個の範囲が好ましく、０．３〜１．５個の範
囲がより好ましく、０．５〜１．２個の範囲がさらに好
ましい。なお、アルコキシ化率及びアルコキシ基の数は
核磁気共鳴スペクトル分析に基づいて測定することがで
きる。本発明におけるアルコキシ基含有レゾール型フェ
ノール樹脂の重量平均分子量は導電ペーストの導電性、
作業性及びポットライフの点から５００〜２００，００
０の範囲が好ましく、７００〜１２０，０００の範囲が
さらに好ましい。なお、重量平均分子量は、ゲルパーミ
エーションクロマトグラフィー法により測定し、標準ポ
リスチレン換算することにより求めることができる。The alkoxy group in the resol-type phenol resin preferably has a range of 0.1 to 2 alkoxy groups per benzene ring, more preferably 0.3 to 1.5, and more preferably 0. The range of 0.5 to 1.2 is more preferable. The alkoxylation rate and the number of alkoxy groups can be measured based on nuclear magnetic resonance spectrum analysis. The weight average molecular weight of the alkoxy group-containing resol type phenol resin in the present invention is the conductivity of the conductive paste,
500-200,00 from the viewpoint of workability and pot life
The range of 0 is preferable, and the range of 700 to 120,000 is more preferable. The weight average molecular weight can be determined by measuring by gel permeation chromatography and converting to standard polystyrene.
【００３３】エポキシ樹脂の硬化剤としては、例えばメ
ンセンジアミン、イソフオロンジアミン、メタフェニレ
ンジアミン、ジアミノジフェニルメタン、ジアミノジフ
ェニルスルホン、メチレンジアニリン等のアミン類、無
水フタル酸、無水トリメリット酸、無水ピロメリット酸、
無水コハク酸、テトラヒドロ無水フタル酸等の酸無水
物、イミダゾール、ジシアンジアミド等の化合物系硬化
剤、ポリアミド樹脂、フェノール樹脂、尿素樹脂等の樹脂
系硬化剤が用いられるが、必要に応じて、潜在性アミン
硬化剤等の硬化剤と併用して用いてもよく、また３級ア
ミン、イミダゾール類、トリフェニルホスフィン、テト
ラフェニルホスフェニルボレート等といった一般にエポ
キシ樹脂とフェノ−ル系硬化剤との硬化促進剤として知
られている化合物を添加してもよい。Examples of the curing agent for the epoxy resin include amines such as menthenediamine, isophoronediamine, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone and methylenedianiline, phthalic anhydride, trimellitic anhydride, and anhydrous pyromethylene. Meritic acid,
Acid anhydrides such as succinic anhydride and tetrahydrophthalic anhydride, compound-based curing agents such as imidazole and dicyandiamide, and resin-based curing agents such as polyamide resins, phenolic resins, urea resins, etc. are used. It may be used in combination with a curing agent such as an amine curing agent, and is generally a curing accelerator for an epoxy resin and a phenolic curing agent such as tertiary amine, imidazoles, triphenylphosphine, tetraphenylphosphenyl borate and the like. Compounds known as
【００３４】エポキシ樹脂の硬化剤は、熱処理条件及び
ポットライフの点から、融点が４０〜２４０℃の範囲が
好ましく、６０〜２２０℃の範囲がさらに好ましい。そ
の代表的なものとしては、２−メチルイミダゾール、２
−ヘプタデシルイミダゾール、２−フェニル−４−メチ
ルイミダゾール等が挙げられる。From the viewpoint of heat treatment conditions and pot life, the epoxy resin curing agent preferably has a melting point of 40 to 240 ° C, more preferably 60 to 220 ° C. Typical examples thereof include 2-methylimidazole and 2
-Heptadecyl imidazole, 2-phenyl-4-methyl imidazole and the like.
【００３５】一方、フェノール樹脂の硬化剤としては、
熱処理条件及びポットライフの点から官能基がマスキン
グされており解離温度が６０〜１４０℃の範囲が好まし
く、６５〜１３５℃の範囲がさらに好ましい。その代表
的なものとしては、ジノニルナフタレンスルホン酸、ジ
ノニルナフタレンジスルホン酸、ドデシルベンゼンスル
ホン酸のブロックタイプ等が挙げられる。On the other hand, as a curing agent for phenol resin,
From the viewpoint of heat treatment conditions and pot life, the functional group is masked, and the dissociation temperature is preferably in the range of 60 to 140 ° C, more preferably in the range of 65 to 135 ° C. Typical examples thereof include block types of dinonylnaphthalene sulfonic acid, dinonyl naphthalene disulfonic acid, dodecylbenzene sulfonic acid, and the like.
【００３６】これらの硬化剤の含有量は、熱処理条件及
びポットライフの点で熱硬化性樹脂１００重量部に対し
て０．０５〜２０重量部の範囲であることが好ましく、
０．１〜１０重量部の範囲であることがさらに好まし
い。またこれらの硬化剤は必要に応じて２種以上組み合
わせて用いてもよい。The content of these curing agents is preferably in the range of 0.05 to 20 parts by weight with respect to 100 parts by weight of the thermosetting resin in terms of heat treatment conditions and pot life.
It is more preferably in the range of 0.1 to 10 parts by weight. Moreover, you may use these hardening | curing agents in combination of 2 or more types as needed.
【００３７】エポキシ樹脂とフェノ−ル樹脂の配合割合
は、接着強度、作業性、導電性及び抵抗値バラツキの点
で、重量比でエポキシ樹脂：フェノ−ル樹脂が１０：９
０〜９５：５の範囲であることが好ましく、重量比で１
５：８５〜８５：１５の範囲であることがさらに好まし
い。The mixing ratio of the epoxy resin and the phenol resin is 10: 9 by weight of the epoxy resin: phenol resin in terms of adhesive strength, workability, conductivity and resistance value variation.
The weight ratio is preferably in the range of 0 to 95: 5.
The range of 5:85 to 85:15 is more preferable.
【００３８】溶剤を含有している導電ペーストは、溶剤
を含有していない導電ペーストより、印刷塗布したとき
と熱処理を行い硬化させた後の導電ペーストの体積減少
量が溶剤を含んでいるだけ大きい。また熱処理を行う過
程で溶剤を含有している導電ペーストの方が、導電ペー
ストの粘度が大きく低下し、導電ペーストに含まれてい
る導電粉が導電体層内で緻密になる。これらの要因のた
め、溶剤を含有している導電ペーストは溶剤を含有して
いない導電ペーストより導電性が良好になりバラツキも
少なくなると考えられる。The conductive paste containing a solvent has a larger volume reduction amount than the conductive paste not containing a solvent, because the conductive paste has a reduced volume when printed and applied and after being cured by heat treatment. . Further, in the process of performing the heat treatment, the conductive paste containing the solvent has a much lower viscosity, and the conductive powder contained in the conductive paste becomes denser in the conductive layer. Due to these factors, it is considered that the conductive paste containing the solvent has better conductivity and less variation than the conductive paste containing no solvent.
【００３９】また、溶剤は、熱処理の導電ペーストの粘
度低下が大きい溶剤ほど好ましく、逆に乾燥性が速く熱
処理時溶剤の乾燥が進み導電ペーストの粘度が大きく低
下しない溶剤は好ましくない。本発明に用いられる有機
溶剤は、含有する溶剤の蒸発速度が３０以下（０を除
く）であることが好ましく、２５以下（０を除く）であ
ることがさらに好ましい。蒸発速度が３０を超える溶剤
を用いると、印刷塗布後の導電ペートに含まれる溶剤の
乾燥が速い。即ち印刷塗布〜熱処理工程中の溶剤のス乾
燥が速いため導電ペーストの粘度が大きく低下しない。
そのため導電粉が導電体層内で緻密にならず、熱処理後
の導電性が低下しバラツキが大きくなる傾向がある。Further, the solvent is preferably a solvent in which the viscosity of the conductive paste in the heat treatment is large, and conversely, a solvent which has a fast drying property and in which the solvent is dried during the heat treatment so that the viscosity of the conductive paste is not largely reduced is not preferable. The organic solvent used in the present invention preferably has an evaporation rate of the solvent contained of 30 or less (excluding 0), and more preferably 25 or less (excluding 0). When a solvent having an evaporation rate of more than 30 is used, the solvent contained in the conductive paste after printing is dried quickly. That is, the viscosity of the conductive paste is not significantly reduced because the solvent is quickly dried during the printing and heat treatment steps.
Therefore, the conductive powder does not become dense in the conductor layer, and the conductivity after heat treatment tends to decrease and the variation tends to increase.
【００４０】なお、本発明において蒸発速度とは、温度
が２５℃及び相対湿度が５５％ＲＨのときの酢酸ブチル
の単位時間あたりの重量減少量を１００とした場合の相
対速度を示す。蒸発速度は、本発明で用いる溶剤１０ｇ
を直径が９０ｍｍのガラスシャーレに滴下し、これを常
温常圧の雰囲気に１時間放置し、１時間後の溶剤乾燥重
量減少量をＡとし、また酢酸ブチル１０ｇを前記と同
様、直径９０ｍｍのガラスシャーレに滴下し、これを常
温常圧の雰囲気に１時間放置し、１時間後の溶剤乾燥重
量減少量をＢとして、次式により求めることができる。In the present invention, the evaporation rate means a relative rate when the weight loss of butyl acetate per unit time at a temperature of 25 ° C. and a relative humidity of 55% RH is 100. The evaporation rate is 10 g of the solvent used in the present invention.
Was dropped into a glass petri dish having a diameter of 90 mm, and this was allowed to stand in an atmosphere at room temperature and normal pressure for 1 hour, and the solvent dry weight reduction amount after 1 hour was defined as A, and 10 g of butyl acetate was used in the same manner as described above for a glass having a diameter of 90 mm. It can be determined by the following equation, where it is dropped on a petri dish and left in an atmosphere of normal temperature and normal pressure for 1 hour, and the amount of solvent dry weight reduction after 1 hour is B.
【００４１】[0041]
【数２】蒸発速度＝Ａ×１００／Ｂ[Equation 2] Evaporation rate = A × 100 / B
【００４２】また、本発明に用いられる有機溶剤の沸点
は、１５０〜２６０℃の範囲であることが好ましく、１
７０〜２４０℃の範囲であることがさらに好ましい。沸
点が１５０℃未満であると蒸発速度が３０を超える場合
と同様の理由、即ち熱処理後の導電性が低下しバラツキ
が大きくなる傾向があり、沸点が２６０℃を超えると溶
剤の乾燥速度が遅いため短時間の熱処理工程に不向きで
ある。The boiling point of the organic solvent used in the present invention is preferably in the range of 150 to 260 ° C.
More preferably, it is in the range of 70 to 240 ° C. If the boiling point is less than 150 ° C, the evaporation rate exceeds 30, for the same reason, that is, the conductivity after heat treatment tends to decrease and the dispersion tends to increase. If the boiling point exceeds 260 ° C, the drying rate of the solvent is slow. Therefore, it is not suitable for a short-time heat treatment process.
【００４３】使用される溶剤としては、例えばジプロピ
レングリコールメチルエーテル、ジプロピレングリコー
ルエチルエーテル、ジプロピレングリコールブチルエー
テル、ジプロピレングリコールイソプロピルメチルエー
テル、ジプロピレングリコールイソプロピルエチルエー
テル、トリプロピレングリコールメチルエーテル、プロ
ピレングリコールターシャリーブチルエーテル、プロピ
レングリコールエチルエーテルアセテート、エチレング
リコールエチルエーテルアセテート、エチレングリコー
ルブチルエーテル、ジエチレングリコールメチルエーテ
ル、トリエチレングリコールメチルエーテル、ジエチレ
ングリコールエチルエーテル、エチレングリコールブチ
ルエーテル、ジエチレングリコールブチルエーテル、３
−メチル−３−メトキシブタノール、３−メチル−３−
メトキシブチルエーテル、乳酸エチル、乳酸ブチルなど
が挙げられる。Examples of the solvent used include dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, dipropylene glycol isopropyl methyl ether, dipropylene glycol isopropyl ethyl ether, tripropylene glycol methyl ether, propylene glycol. Tertiary butyl ether, propylene glycol ethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol butyl ether, diethylene glycol methyl ether, triethylene glycol methyl ether, diethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol butyl ether, 3
-Methyl-3-methoxybutanol, 3-methyl-3-
Methoxybutyl ether, ethyl lactate, butyl lactate and the like can be mentioned.
【００４４】含有させる溶剤は１種又は必要に応じて２
種以上の溶剤を混合した溶剤を使用し、溶剤の含有量は
導電性及び作業性から導電ペーストに対して２〜１０重
量％の範囲が好ましく、２〜７．５重量％の範囲がさら
に好ましい。The solvent to be contained is one kind or two if necessary.
A solvent in which two or more kinds of solvents are mixed is used, and the content of the solvent is preferably in the range of 2 to 10% by weight, more preferably 2 to 7.5% by weight based on the conductive paste from the viewpoint of conductivity and workability. .
【００４５】本発明になる導電ペーストは、上記に示す
材料の他に必要に応じてチキソ剤、カップリング剤、消
泡剤、粉末表面処理剤、沈降防止剤等と共にらいかい
機、ニーダー、三本ロール等で均一に混合、分散して得
ることができる。必要に応じて添加されるチキソ剤、カ
ップリング剤、消泡剤、粉末表面処理剤、沈降防止剤等
は、公知のものでよく、その含有量は、導電ペーストに
対して０．０１〜１重量％の範囲であることが好まし
く、０．０３〜０．５重量％の範囲であることがさらに
好ましい。The conductive paste according to the present invention may be combined with a thixotropic agent, a coupling agent, a defoaming agent, a powder surface treating agent, an anti-settling agent, etc., if necessary, in addition to the above-mentioned materials. It can be obtained by uniformly mixing and dispersing with a main roll or the like. The thixotropic agent, the coupling agent, the defoaming agent, the powder surface treatment agent, the anti-settling agent and the like which are added as necessary may be known ones, and the content thereof is 0.01 to 1 with respect to the conductive paste. It is preferably in the range of wt%, and more preferably in the range of 0.03 to 0.5 wt%.
【００４６】本発明になる導電ペーストは、作業性の点
から、粘度が１００〜７，０００ｄＰａ・ｓ及びチキソ
値が１．８〜７．３の範囲が好ましく、粘度が３５０〜
５，０００ｄＰａ・ｓ及びチキソ値が１．９〜５．０の
範囲がさらに好ましい。粘度が１００ｄＰａ・ｓ未満で
あると塗布後の導電ペーストが滲み易くなる傾向があ
り、７，０００ｄＰａ・ｓを超えると作業性が悪くなる
傾向がある。一方、チキソ値が１．８未満であると塗布
後の導電ペーストが滲み易くなる傾向があり、７．３を
超えると滲みは発生しなくなるが作業性が悪くなる傾向
があると共に塗布した導電ペースト表面の平滑性が悪く
なる傾向がある。From the viewpoint of workability, the conductive paste according to the present invention preferably has a viscosity of 100 to 7,000 dPa · s and a thixotropic value of 1.8 to 7.3, and a viscosity of 350 to 350.
The range of 5,000 dPa · s and thixo value is more preferably 1.9 to 5.0. If the viscosity is less than 100 dPa · s, the conductive paste after application tends to bleed, and if it exceeds 7,000 dPa · s, workability tends to deteriorate. On the other hand, when the thixo value is less than 1.8, the conductive paste after application tends to bleed, and when it exceeds 7.3, bleeding does not occur but workability tends to deteriorate and the conductive paste applied Surface smoothness tends to deteriorate.
【００４７】上記に示す導電ペーストの粘度は、ブルッ
クフィールド社製の粘度計ＨＢＴ型を用いて測定を行
い、１０min−１の値を次式から求めることができる。The viscosity of the above conductive paste can be measured by using a Brookfield viscometer HBT type, and a value of 10 min -1 can be obtained from the following equation.
【００４８】[0048]
【数３】 粘度（ｄＰａ・ｓ）＝１０min−１の値×ｆ１０ ただし、ｆ１０は１０min−１の補正係数である。## EQU00003 ## Viscosity (dPa.s) = value of 10 min −1 × f 10 where f 10 is a correction coefficient of 10 min −1 .
【００４９】また、チキソ値は、ブルックフィールド社
製の粘度計ＨＢＴ型を用いて測定を行い、１０min−１
及び１００min−１の値を次式から求めることができ
る。The thixo value was measured using a viscometer HBT type manufactured by Brookfield Co., and 10 min -1
And the value of 100 min −1 can be obtained from the following equation.
【００５０】[0050]
【数４】チキソ値＝１０min−１の値×ｆ１０／１００m
in−１の値×ｆ１００
ただし、ｆ１００は１０min−１の補正係数である。[Number 4] value of thixotropic value = 10min -1 × f 10 / 100m
value of in −1 × f 100 However, f 100 is a correction coefficient of 10 min −1 .
【００５１】[0051]
【実施例】以下、本発明を実施例により説明する。
実施例１
ブトキシ基含有レゾール型フェノール樹脂（当社試作
品、ブトキシ化率６５％、重量平均分子量１，２００）
４０重量部、エポキシ樹脂（三井化学（株）製、商品名
１４０Ｃ エポキシ当量１９５〜２１５ｇ／ｅｑ）５５
重量部、２−フェニル−４−メチル−イミダゾール（四
国化成（株）製、キュアゾール２Ｐ４ＭＺ、融点１７４
〜１８４℃）４重量部及びジノニルナフタレンスルホン
酸のブロックタイプ（楠本化成(株)製、商品名Ｘ４９−
１１０、解離温度９０℃）１重量部を均一に混合してバ
インダとした。
なお、フェノール樹脂とエポキシ樹脂の割合は、重量比
でフェノール樹脂：エポキシ樹脂が４２．１：５７．９
であった。EXAMPLES The present invention will be described below with reference to examples. Example 1 Butoxy group-containing resol-type phenolic resin (our prototype, butoxylation rate 65%, weight average molecular weight 1,200)
40 parts by weight, epoxy resin (Mitsui Chemicals, Inc., trade name 140C epoxy equivalent 195-215 g / eq) 55
Parts by weight, 2-phenyl-4-methyl-imidazole (manufactured by Shikoku Kasei Co., Ltd., Cureazole 2P4MZ, melting point 174)
Block type of 4 parts by weight and dinonylnaphthalene sulfonic acid (Kusumoto Kasei Co., Ltd., trade name X49-
1 part by weight (110, dissociation temperature 90 ° C.) was uniformly mixed to obtain a binder. The weight ratio of the phenol resin to the epoxy resin is 42.1: 57.9 for phenol resin: epoxy resin.
Met.
【００５２】次に、アトマイズ法で作製した平均粒径が
５．１μｍの球状銅粉（日本アトマイズ加工（株）製、
商品名ＳＦＲ−Ｃｕ）を希塩酸及び純水で洗浄した後、
水1リットルあたりＡｇＣＮ ８０ｇ及びＮａＣＮ７５ｇ
含むめっき溶液で球状銅粉に対して銀の被覆量が１８重
量％になるように置換めっきを行い、水洗、乾燥して銀
めっき銅粉を得た。Next, spherical copper powder having an average particle size of 5.1 μm produced by the atomizing method (manufactured by Nippon Atomizing Co., Ltd.,
After washing the product name SFR-Cu) with diluted hydrochloric acid and pure water,
80 g of AgCN and 75 g of NaCN per liter of water
Displacement plating was performed using a plating solution containing silver so that the amount of silver coated on the spherical copper powder was 18% by weight, washed with water, and dried to obtain silver-plated copper powder.
【００５３】この後、２リットルのボールミル容器内に
上記で得た銀めっき銅粉７５０ｇ及び直径が５ｍｍのジ
ルコニアボール３ｋｇを投入し、４０分間回転させて、１
０００回のタッピングによるタップ密度が５．９３ｇ／
ｃｍ３、相対密度が９３％、比表面積が０．２６ｍ２／
ｇ、アスペクト比が平均１．３及び長径の平均粒径が
５．５μｍの略球状銀被覆銅粉を得た。得られた略球状
銀被覆銅粉の粒子を５個取り出し、走査型オージェ電子
分光分析装置で定量分析して銅の露出面積について調べ
たところ、１０〜５０％の範囲で平均が２０％であっ
た。Thereafter, 750 g of the silver-plated copper powder obtained above and 3 kg of zirconia balls having a diameter of 5 mm were placed in a 2 liter ball mill container and rotated for 40 minutes to 1
Tap density after tapping 000 times is 5.93 g /
cm 3 , relative density 93%, specific surface area 0.26 m 2 /
A substantially spherical silver-coated copper powder having an average particle size of g, an average aspect ratio of 1.3 and an average major particle diameter of 5.5 μm was obtained. Five particles of the obtained substantially spherical silver-coated copper powder were taken out and quantitatively analyzed by a scanning Auger electron spectroscopy analyzer to examine the exposed area of copper. The average was 20% in the range of 10 to 50%. It was
【００５４】一方、２リットルのボールミル容器内に上
記で得た銀めっき銅粉７５０ｇ及び直径が１０ｍｍのジ
ルコニアボール３ｋｇを投入し、８時間回転させて、１０
００回のタッピングによるタップ密度が３．７９ｇ／ｃ
ｍ３、相対密度が４８％、比表面積が０．７７ｍ２／ｇ
アスペクト比が平均５．２及び長径の平均粒径が７．７
μｍの扁平状銀被覆銅粉を得た。得られた扁平状銀被覆
銅粉の粒子を５個取り出し、走査型オージェ電子分光分
析装置で定量分析して銅の露出面積について調べたとこ
ろ、１０〜６０％の範囲で平均が４１％であった。On the other hand, 750 g of the silver-plated copper powder obtained above and 3 kg of zirconia balls having a diameter of 10 mm were placed in a 2 liter ball mill container and rotated for 8 hours to give 10
Tap density of 3.79 g / c after tapping 00 times
m 3 , relative density 48%, specific surface area 0.77 m 2 / g
The average aspect ratio is 5.2 and the average diameter of major axis is 7.7.
A flat silver-coated copper powder of μm was obtained. Five particles of the obtained flat silver-coated copper powder were taken out and quantitatively analyzed by a scanning Auger electron spectroscopy analyzer to examine the exposed area of copper. The average was 41% in the range of 10 to 60%. It was
【００５５】次に、上記で得たバインダ５０ｇ、略球状
銀被覆銅粉２７０ｇ及び扁平状銀被覆銅粉１８０ｇに、
溶剤としてエチルカルビトール（蒸発速度１未満）１１
ｇを加えて、撹拌らいかい機及び三本ロールで均一に混
合、分散して比重が５．２、粘度が１０５０ｄｐａ・
ｓ、チキソ値が２．９及び硬化物のガラス転移点が１４
２℃の導電ペーストを得た。
なお、導電粉とバインダの割合は、導電ペーストの固形
分に対して重量比で導電粉：バインダが９０：１０であ
り、溶剤の含有量は導電ペーストに対して２．９％であ
った。Next, to 50 g of the binder obtained above, 270 g of substantially spherical silver-coated copper powder and 180 g of flat silver-coated copper powder,
Ethyl carbitol as solvent (evaporation rate less than 1) 11
g, and uniformly mixed and dispersed with a stirrer and a triple roll to have a specific gravity of 5.2 and a viscosity of 1050 dpa.
s, thixo value is 2.9, and glass transition point of cured product is 14
A conductive paste of 2 ° C. was obtained. The ratio of the conductive powder to the binder was 90:10 by weight ratio of the conductive powder: binder to the solid content of the conductive paste, and the content of the solvent was 2.9% with respect to the conductive paste.
【００５６】次に、上記で得た導電ペーストを用いて、
厚さが１．０ｍｍの紙フェノール銅張積層板（日立化成
工業（株）製、商品名ＭＣＬ−４３７Ｆ）の銅箔をエッ
チングにより除去した面に図２に示すような形状に塗布
し、１７０℃９０分間加熱処理して導電体５を得た。得
られた導電体５の比抵抗は１．７μΩ・ｍであった。な
お図２において、４は紙フェノール銅張積層板である。
また、引張せん断接着強さはＪＩＳＫ６８５０「引張せ
ん断接着強さ試験方法」に準じて引張せん断接着強さを
調べた。その結果、引張せん断接着強さは１２．２ＭＰ
ａであった。Next, using the conductive paste obtained above,
A paper phenol copper-clad laminate having a thickness of 1.0 mm (Hitachi Kasei Kogyo KK, trade name MCL-437F) was applied on the surface of the copper foil removed by etching in a shape as shown in FIG. Heat treatment was performed at 90 ° C. for 90 minutes to obtain a conductor 5. The specific resistance of the obtained conductor 5 was 1.7 μΩ · m. In FIG. 2, 4 is a paper phenol copper clad laminate.
For the tensile shear adhesive strength, the tensile shear adhesive strength was examined according to JIS K 6850 "Tensile shear adhesive strength test method". As a result, the tensile shear adhesive strength is 12.2MP
It was a.
【００５７】なお、本実施例におけるアスペクト比の具
体的測定法を以下に示す。低粘度のエポキシ樹脂（ビュ
ーラー社製）の主剤（Ｎｏ．１０−８１３０）８ｇと硬
化剤（Ｎｏ．１０−８１３２）２ｇを混合し、ここへ導
電粉２ｇを混合して良く分散させ、そのまま３０℃で真
空脱泡した後、１０時間３０℃で静置して粒子を沈降さ
せ硬化させた。その後、得られた硬化物を垂直方向に切断
し、切断面を電子顕微鏡で１０００倍に拡大して切断面
に現れた１５０個の粒子について長径／短径を求め、そ
れらの平均値をもって、アスペクト比とした。A specific method for measuring the aspect ratio in this embodiment is shown below. 8 g of a main component (No. 10-8130) of a low-viscosity epoxy resin (manufactured by Buehler) and 2 g of a curing agent (No. 10-8132) are mixed, and 2 g of conductive powder is mixed therein and well dispersed. After vacuum degassing at 0 ° C, the particles were allowed to settle by standing at 30 ° C for 10 hours to cure. After that, the obtained cured product is cut in the vertical direction, the cut surface is magnified 1000 times with an electron microscope, and the major axis / minor axis of 150 particles appearing on the cut surface is determined. Ratio.
【００５８】実施例２
実施例１で用いたブトキシ基含有レゾール型フェノール
樹脂２０重量部、エポキシ樹脂７５重量部、２−フェニ
ル−４−メチル−イミダゾール４．５重量部及びジノニ
ルナフタレンスルホン酸のブロックタイプ０．５重量部
を均一に混合してバインダとした。
なお、フェノール樹脂とエポキシ樹脂の割合は、重量比
でフェノール樹脂：エポキシ樹脂が２１．１：７８．９
であった。Example 2 20 parts by weight of butoxy group-containing resol type phenol resin used in Example 1, 75 parts by weight of epoxy resin, 4.5 parts by weight of 2-phenyl-4-methyl-imidazole and dinonylnaphthalene sulfonic acid were used. 0.5 parts by weight of the block type was uniformly mixed to obtain a binder. The weight ratio of phenol resin to epoxy resin is 21.1: 78.9 for phenol resin: epoxy resin.
Met.
【００５９】次に、上記で得たバインダ６０ｇ、実施例
１と同様の工程を経て得たタップ密度が５．２２ｇ／ｃ
ｍ３、相対密度が９１％、比表面積が０．２９ｍ２／
ｇ、アスペクト比が平均１．４及び長径の平均粒径が
５．６μｍの略球状銀被覆銅粉３５０ｇ並びにタップ密
度が３．２９ｇ／ｃｍ３、相対密度が４４％、比表面積
が０．７４ｍ２／ｇ、％、アスペクト比が平均６．１及
び長径の平均粒径が７．５μｍの扁平状銀被覆銅粉９０
ｇに、溶剤として実施例１で用いたエチルカルビトール
１１ｇを加えて、撹拌らいかい機及び三本ロールで均一
に混合、分散して比重が４．７、粘度が８６０ｄｐａ・
ｓ、チキソ値が３．２及び硬化物のガラス転移点が１１
９℃の導電ペーストを得た。Next, 60 g of the binder obtained above and the tap density obtained through the same steps as in Example 1 were 5.22 g / c.
m3, the relative density of 91%, a specific surface area of 0.29 m 2 /
g, 350 g of an approximately spherical silver-coated copper powder having an average aspect ratio of 1.4 and an average major particle diameter of 5.6 μm, a tap density of 3.29 g / cm 3 , a relative density of 44%, and a specific surface area of 0.74 m. 2 / g,%, flat aspect silver-covered copper powder 90 having an average aspect ratio of 6.1 and major axis average particle size of 7.5 μm
11 g of ethyl carbitol used in Example 1 as a solvent was added to g and uniformly mixed and dispersed with a stirrer and a triple roll to have a specific gravity of 4.7 and a viscosity of 860 dpa.
s, thixo value is 3.2, and glass transition point of the cured product is 11
A conductive paste having a temperature of 9 ° C. was obtained.
【００６０】なお、実施例１と同様の方法で銅の露出面
積を調べたところ、略球状銀被覆銅粉は１０〜５０％の
範囲で平均が２７％及び扁平状銀被覆銅粉は１０〜６２
％の範囲で平均が４６％であった。
また、導電粉とバインダの割合は、導電ペーストの固形
分に対して重量比で導電粉：バインダが８８：１２であ
り、溶剤の含有量は、導電ペーストに対して２．２％で
あった。
さらに、実施例1と同様の方法で比抵抗及び引張せん断
接着強さを調べた結果、比抵抗は２．６μΩ・ｍ及び引
張せん断接着強さは１７．６ＭＰａであった。When the exposed area of copper was examined in the same manner as in Example 1, the average spherical spherical silver-coated copper powder was 27% in the range of 10 to 50% and the flat silver-coated copper powder was 10 to 50%. 62
In the range of%, the average was 46%. Further, the ratio of the conductive powder and the binder was 88:12 in the conductive powder: binder by weight ratio with respect to the solid content of the conductive paste, and the content of the solvent was 2.2% with respect to the conductive paste. . Further, as a result of examining the specific resistance and the tensile shear adhesive strength in the same manner as in Example 1, the specific resistance was 2.6 μΩ · m and the tensile shear adhesive strength was 17.6 MPa.
【００６１】実施例３
実施例１で用いたブトキシ基含有レゾール型フェノール
樹脂６０重量部、エポキシ樹脂３５重量部、２−フェニ
ル−４−メチル−イミダゾール３．５重量部及びジノニ
ルナフタレンスルホン酸のブロックタイプ１．５重量部
を均一に混合してバインダとした。
なお、フェノール樹脂とエポキシ樹脂の割合は、重量比
でフェノール樹脂：エポキシ樹脂が６３．２：３６．８
であった。Example 3 60 parts by weight of the butoxy group-containing resol type phenol resin used in Example 1, 35 parts by weight of an epoxy resin, 3.5 parts by weight of 2-phenyl-4-methyl-imidazole and dinonylnaphthalene sulfonic acid were used. A block type of 1.5 parts by weight was uniformly mixed to obtain a binder. The weight ratio of the phenol resin to the epoxy resin is 63.2: 36.8 for phenol resin: epoxy resin.
Met.
【００６２】次に、上記で得たバインダ４５ｇ及び実施
例１で得た略球状銀被覆銅粉４５５ｇに、溶剤として実
施例１で用いたエチルカルビトール１４ｇを加えて、撹
拌らいかい機及び三本ロールで均一に混合、分散して比
重が５．５、粘度が１０１０ｄｐａ・ｓ、チキソ値が
３．３及び硬化物のガラス転移点が１５２℃の導電ペー
ストを得た。Next, to 45 g of the binder obtained above and 455 g of the substantially spherical silver-coated copper powder obtained in Example 1, 14 g of ethyl carbitol used in Example 1 was added as a solvent, and a stirring and stirring machine and a mixer were used. By uniformly mixing and dispersing with this roll, a conductive paste having a specific gravity of 5.5, a viscosity of 1010 dpa · s, a thixo value of 3.3, and a glass transition point of the cured product of 152 ° C. was obtained.
【００６３】なお、導電粉とバインダの割合は、導電ペ
ーストの固形分に対して重量比で導電粉：バインダが９
１：９であり、溶剤の含有量は、導電ペーストに対して
２．７％であった。
また、実施例1と同様の方法で比抵抗及び引張せん断接
着強さを調べた結果、比抵抗は１．３μΩ・ｍ及び引張
せん断接着強さは１０．１ＭＰａであった。The ratio of conductive powder to binder is 9 by weight of conductive powder: binder with respect to the solid content of the conductive paste.
It was 1: 9, and the content of the solvent was 2.7% with respect to the conductive paste. Further, as a result of examining the specific resistance and the tensile shear adhesive strength in the same manner as in Example 1, the specific resistance was 1.3 μΩ · m and the tensile shear adhesive strength was 10.1 MPa.
【００６４】実施例４
実施例１で得たバインダ５０ｇ及び実施例１で得た扁平
状銀被覆銅粉４５０ｇに、溶剤として実施例１で用いた
エチルカルビトール１５ｇを加えて、撹拌らいかい機及
び三本ロールで均一に混、分散して比重が５．１、粘度
が１８７０ｄｐａ・ｓ、チキソ値が３．８及び硬化物の
ガラス転移点が１４２℃の導電ペーストを得た。Example 4 To 50 g of the binder obtained in Example 1 and 450 g of the flat silver-coated copper powder obtained in Example 1, 15 g of ethyl carbitol used in Example 1 as a solvent was added, and the mixture was stirred and stirred. Then, a conductive paste having a specific gravity of 5.1, a viscosity of 1870 dpa · s, a thixo value of 3.8, and a glass transition point of 142 ° C. of the cured product was obtained by uniformly mixing and dispersing with a triple roll.
【００６５】なお、導電粉とバインダの割合は、導電ペ
ーストの固形分に対して重量比で導電粉：バインダが９
０：１０であり、溶剤の含有量は、導電ペーストに対し
て２．９％であった。
また、実施例1と同様の方法で比抵抗及び引張せん断接
着強さを調べた結果、比抵抗は１．１μΩ・ｍ及び引張
せん断接着強さは１４．１ＭＰａであった。The ratio of the conductive powder to the binder is 9% by weight of the conductive powder to the solid content of the conductive paste.
It was 0:10, and the content of the solvent was 2.9% with respect to the conductive paste. Further, as a result of examining the specific resistance and the tensile shear adhesive strength in the same manner as in Example 1, the specific resistance was 1.1 μΩ · m and the tensile shear adhesive strength was 14.1 MPa.
【００６６】比較例１
実施例１で得たバインダ１５ｇ、実施例１で得た略球状
銀被覆銅粉２９１ｇ及び実施例１で得た扁平状銀被覆銅
粉１９４ｇに、溶剤として実施例１で用いたエチルカル
ビトール１５ｇを加えて、撹拌らいかい機及び三本ロー
ルで均一に混合、分散して比重が７．８、粘度が５５１
０ｄｐａ・ｓ、チキソ値が５．３及び硬化物のガラス転
移点が１４２℃の導電ペーストを得た。Comparative Example 1 15 g of the binder obtained in Example 1, 291 g of the substantially spherical silver-coated copper powder obtained in Example 1 and 194 g of the flat silver-coated copper powder obtained in Example 1 were used in Example 1 as a solvent. 15 g of the ethyl carbitol used was added, and the mixture was uniformly mixed and dispersed with a stirrer and a triple roll to have a specific gravity of 7.8 and a viscosity of 551.
A conductive paste having 0 dpa · s, a thixo value of 5.3, and a cured product having a glass transition point of 142 ° C. was obtained.
【００６７】なお、導電粉とバインダの割合は、導電ペ
ーストの固形分に対して重量比で導電粉：バインダが９
７：３であり、溶剤の含有量は、導電ペーストに対して
２．９％であった。
また、実施例1と同様の方法で比抵抗及び引張せん断接
着強さを調べた結果、比抵抗は１．０μΩ・ｍと良好で
あったが、引張せん断接着強さは４．８ＭＰａと低い値
であった。The ratio of the conductive powder to the binder is 9% by weight of the conductive powder to the solid content of the conductive paste.
It was 7: 3, and the content of the solvent was 2.9% with respect to the conductive paste. Moreover, as a result of examining the specific resistance and the tensile shear adhesive strength in the same manner as in Example 1, the specific resistance was good at 1.0 μΩ · m, but the tensile shear adhesive strength was a low value of 4.8 MPa. Met.
【００６８】比較例２
実施例１で得たバインダ１００ｇ、実施例１で得た略球
状銀被覆銅粉２４０ｇ及び実施例１で得た扁平状銀被覆
銅粉１６０ｇに、溶剤として実施例１で用いたエチルカ
ルビトール１５ｇを加えて、撹拌らいかい機及び三本ロ
ールで均一に混合、分散して比重が２．８、粘度が３４
０ｄｐａ・ｓ、チキソ値が２．８及び硬化物のガラス転
移点が１４５℃の導電ペーストを得た。Comparative Example 2 100 g of the binder obtained in Example 1, 240 g of the substantially spherical silver-coated copper powder obtained in Example 1 and 160 g of the flat silver-coated copper powder obtained in Example 1 were used as a solvent in Example 1. 15 g of the ethyl carbitol used was added and uniformly mixed and dispersed with a stirrer and a triple roll to have a specific gravity of 2.8 and a viscosity of 34.
A conductive paste having 0 dpa · s, a thixo value of 2.8, and a glass transition point of the cured product of 145 ° C. was obtained.
【００６９】なお、導電粉とバインダの割合は、導電ペ
ーストの固形分に対して重量比で導電粉：バインダが８
０：２０であり、溶剤の含有量は、導電ペーストに対し
て２．９％であった。
また、実施例1と同様の方法で比抵抗及び引張せん断接
着強さを調べた結果、比抵抗は４１．７μΩ・ｍと導電
性としては悪い値を示したが、引張せん断接着強さは２
３．２ＭＰａであった。The ratio of the conductive powder to the binder is 8 by weight of the conductive powder to the solid content of the conductive paste.
It was 0:20, and the content of the solvent was 2.9% with respect to the conductive paste. Further, as a result of examining the specific resistance and the tensile shear adhesive strength in the same manner as in Example 1, the specific resistance was 41.7 μΩ · m, which was a poor value for conductivity, but the tensile shear adhesive strength was 2
It was 3.2 MPa.
【００７０】比較例３
実施例１で用いたブトキシ基含有レゾール型フェノール
樹脂９２重量部、エポキシ樹脂３重量部、２−フェニル
−４−メチル−イミダゾール０．５重量部及びジノニル
ナフタレンスルホン酸のブロックタイプ４．５重量部を
均一に混合してバインダとした。
なお、フェノール樹脂とエポキシ樹脂の割合は、重量比
でフェノール樹脂：エポキシ樹脂が9６．８：３．２で
あった。Comparative Example 3 92 parts by weight of the butoxy group-containing resol type phenol resin used in Example 1, 3 parts by weight of an epoxy resin, 0.5 parts by weight of 2-phenyl-4-methyl-imidazole and dinonylnaphthalene sulfonic acid were used. A block type of 4.5 parts by weight was uniformly mixed to obtain a binder. The weight ratio of the phenol resin to the epoxy resin was 96.8: 3.2 of phenol resin: epoxy resin.
【００７１】次に、上記で得たバインダ５０ｇ、実施例
１で得た略球状銀被覆銅粉２７０ｇ及び実施例１で得た
扁平状銀被覆銅粉１８０ｇに、溶剤として実施例１で用
いたエチルカルビトール１５ｇを加えて、撹拌らいかい
機及び三本ロールで均一に混合、分散して比重が５．
３、粘度が５１１０ｄｐａ・ｓ、チキソ値が３．１及び
硬化物のガラス転移点が１８７℃の導電ペーストを得
た。Next, 50 g of the binder obtained above, 270 g of the substantially spherical silver-coated copper powder obtained in Example 1 and 180 g of the flat silver-coated copper powder obtained in Example 1 were used as a solvent in Example 1. Add 15 g of ethyl carbitol, mix and disperse evenly with a stirrer and a triple roll to obtain a specific gravity of 5.
3, a conductive paste having a viscosity of 5110 dpa · s, a thixo value of 3.1, and a glass transition point of the cured product of 187 ° C. was obtained.
【００７２】なお、導電粉とバインダの割合は、導電ペ
ーストの固形分に対して重量比で導電粉：バインダが９
０：１０であり、溶剤の含有量は、導電ペーストに対し
て２．９％であった。
また、実施例1と同様の方法で比抵抗及び引張せん断接
着強さを調べた結果、比抵抗は１．３μΩ・ｍと良好で
あったが、引張せん断接着強さは６．１ＭＰａと低い値
であった。The ratio of the conductive powder to the binder is 9% by weight of the conductive powder to the solid content of the conductive paste.
It was 0:10, and the content of the solvent was 2.9% with respect to the conductive paste. Further, as a result of examining the specific resistance and the tensile shear adhesive strength in the same manner as in Example 1, the specific resistance was good at 1.3 μΩ · m, but the tensile shear adhesive strength was as low as 6.1 MPa. Met.
【００７３】なお、本発明者らは、ガラス転移点が４０
℃未満の導電ペーストの製造を試みたが、困難製を伴い
途中で製造を中止した。The inventors of the present invention have a glass transition point of 40.
An attempt was made to produce a conductive paste having a temperature of less than 0 ° C, but the production was stopped halfway due to difficulty in production.
【００７４】[0074]
【発明の効果】請求項１及び２記載の導電ペーストは、
導電性、接着強度、作業性に優れる。請求項３記載の導
電ペーストは、導電性の向上効果及びマイグレーション
性に優れる。請求項４及び５記載の導電ペーストは、導
電性、接着強度及び作業性のバランスに優れる。請求項
６及び７記載の導電ペーストは、導電性の向上効果及び
導電ペーストの保存安定性に優れる。請求項８及び９記
載の導電ペーストは、接着強度、作業性、導電ペースト
の保存安定性の向上効に優れる。The conductive paste according to claims 1 and 2 is
Excellent conductivity, adhesive strength and workability. The conductive paste according to claim 3 is excellent in conductivity improving effect and migration property. The conductive paste according to claims 4 and 5 is excellent in the balance of conductivity, adhesive strength, and workability. The conductive paste according to claims 6 and 7 is excellent in the effect of improving conductivity and the storage stability of the conductive paste. The conductive paste according to claims 8 and 9 is excellent in improving the adhesive strength, workability, and storage stability of the conductive paste.
【００７５】請求項１０記載の導電ペーストは、導電
性、接着強度のバランスに優れる。請求項１１記載の導
電ペーストは、作業性の向上効果に優れる。請求項１２
記載の導電ペーストは、導電性、接着強度、作業性のバ
ランスに優れる。請求項１３記載の導電ペーストは、作
業性の向上効果に優れる。請求項１４記載の導電ペース
トは、導電性、作業性の向上効果及び、接合部の柔軟性
に優れる。The conductive paste according to claim 10 is excellent in the balance between conductivity and adhesive strength. The conductive paste according to claim 11 has an excellent effect of improving workability. Claim 12
The described conductive paste has an excellent balance of conductivity, adhesive strength, and workability. The conductive paste according to claim 13 has an excellent effect of improving workability. The conductive paste according to claim 14 is excellent in conductivity, workability improving effect, and flexibility of the joint portion.
【図１】導電ペーストを使用して、部品を接着する手段
を示す断面図である。FIG. 1 is a cross-sectional view showing a means for adhering parts using a conductive paste.
【図２】紙フェノール銅張積層板上に導電体を形成した
状態を示す平面図である。FIG. 2 is a plan view showing a state in which a conductor is formed on a paper phenol copper clad laminate.
１ 銅箔 ２ 導電ペースト ３ リードフレーム ４ 紙フェノール銅張積層板 ５ 導電体 1 copper foil 2 Conductive paste 3 lead frame 4 Paper phenol copper clad laminate 5 conductor
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｊ 163/00 Ｃ０９Ｊ 163/00 Ｈ０１Ｂ 1/00 Ｈ０１Ｂ 1/00 Ｃ Ｈ Ｈ０５Ｋ 3/32 Ｈ０５Ｋ 3/32 Ｂ Ｆターム(参考） 4J037 AA04 AA06 CA03 CC22 CC23 DD01 DD05 DD07 DD09 DD10 DD13 DD30 EE03 EE43 FF11 FF13 4J040 EB031 EB032 EC001 EC002 EC021 EC022 EC061 EC062 EC261 EC262 HA06 KA16 KA23 KA32 LA02 LA04 LA09 NA19 5E319 AA03 BB11 CC61 CD26 GG15 5G301 DA03 DA06 DA55 DA57 DD01─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C09J 163/00 C09J 163/00 H01B 1/00 H01B 1/00 C H H05K 3/32 H05K 3/32 B F-term (reference) 4J037 AA04 AA06 CA03 CC22 CC23 DD01 DD05 DD07 DD09 DD10 DD13 DD30 EE03 EE43 FF11 FF13 4J040 EB031 EB032 EC001 EC002 EC021 EC022 EC061 EC062 EC261 EC262 HA06 NA19 5AB03 CC06 LA03E11 DA55 DA57 DD01
Claims (14)
かつ導電粉が球状若しくは略球状と扁平状との混合粉又
は球状、略球状、扁平状のいずれか１種の単独粉であ
り、バインダの主成分が熱硬化性樹脂及びその硬化剤を
含み、比重が３〜７．５及び導電ペースト硬化物のガラ
ス転移点が４０〜１８０℃である導電ペースト。1. A conductive powder, a binder and an organic solvent are included,
And the conductive powder is a mixed powder of spherical or substantially spherical and flat shape or spherical, substantially spherical, is any one kind of flat shape, the main component of the binder contains a thermosetting resin and its curing agent, An electrically conductive paste having a specific gravity of 3 to 7.5 and a glass transition point of the electrically conductive paste cured product of 40 to 180 ° C.
剤である請求項１記載の導電ペースト。2. The conductive paste according to claim 1, wherein the organic solvent is one kind or a mixed solvent of two or more kinds.
出して、表面が大略銀で被覆された銀被覆銅粉又は銀被
覆銅合金粉であり、かつ銀の被覆量が５〜２５重量％及
び銅粉又は銅合金粉の露出面積が１０〜６０％である請
求項１又は２記載の導電ペースト。3. The conductive powder is a silver-coated copper powder or a silver-coated copper alloy powder in which a part of the copper powder or the copper alloy powder is exposed and the surface is coated with silver, and the coating amount of silver is The conductive paste according to claim 1 or 2, wherein the exposed area of 5 to 25% by weight and the copper powder or the copper alloy powder is 10 to 60%.
粒径が１〜２０μｍ、アスペクト比が１〜１．５、タッ
プ密度が４．５〜６．２ｇ／ｃｍ３、相対密度が５０〜
６８％及び比表面積が０．１〜１．０ｍ２／ｇである請
求項１〜３のいずれかに記載の導電ペースト。4. The spherical or substantially spherical conductive powder has an average major particle diameter of 1 to 20 μm, an aspect ratio of 1 to 1.5, a tap density of 4.5 to 6.2 g / cm 3 , and a relative density of 50-
68% and specific surface area are 0.1-1.0 m < 2 > / g, The electrically conductive paste in any one of Claims 1-3.
〜３０μｍ、アスペクト比が３〜２０、タップ密度が
２．５〜５．８ｇ／ｃｍ３、相対密度が２７〜６３％及
び比表面積が０．４〜１．３ｍ２／ｇである請求項１〜
４のいずれかに記載の導電ペースト。5. The flat conductive powder has an average major diameter of 5
3. 30 μm, aspect ratio 3 to 20, tap density 2.5 to 5.8 g / cm 3 , relative density 27 to 63%, and specific surface area 0.4 to 1.3 m 2 / g. ~
4. The conductive paste according to any one of 4 above.
ノール樹脂である請求項１〜５のいずれかに記載の導電
ペースト。6. The conductive paste according to claim 1, wherein the thermosetting resin is an epoxy resin or a phenol resin.
樹脂及びフェノール樹脂が、アルコキシ基含有レゾール
型フェノール樹脂である請求項１〜６のいずれかに記載
の導電ペースト。7. The conductive paste according to claim 1, wherein the epoxy resin is a liquid epoxy resin at room temperature and the phenol resin is an alkoxy group-containing resol type phenol resin.
〜３３０ｇ／ｅｑ及びフェノール樹脂が、アルコキシ基
の炭素数が１〜６、アルコキシ化率が５〜９５％、重量
平均分子量が５００〜２００，０００である請求項１〜
７のいずれかに記載の導電ペースト。8. The epoxy resin has an epoxy equivalent of 160.
~ 330 g / eq and the phenol resin has 1 to 6 carbon atoms in the alkoxy group, an alkoxylation rate of 5 to 95%, and a weight average molecular weight of 500 to 200,000.
7. The conductive paste according to any one of 7.
２４０℃及びフェノール樹脂の硬化剤が、官能基がマス
キングされており解離温度が６０〜１４０℃である請求
項１〜８のいずれかに記載の導電ペースト。9. The epoxy resin curing agent has a melting point of 40 to 40.
The conductive paste according to any one of claims 1 to 8, wherein the curing agent of 240 ° C and the phenol resin has a functional group masked and a dissociation temperature of 60 to 140 ° C.
割合が、重量比でエポキシ樹脂：フェノール樹脂が１
０：９０〜９５：５である請求項１〜９のいずれかに記
載の導電ペースト。10. The compounding ratio of the epoxy resin and the phenol resin is such that the weight ratio of the epoxy resin to the phenol resin is 1.
It is 0: 90-95: 5, The electrically conductive paste in any one of Claims 1-9.
を除く）であり、沸点が１５０〜２６０℃である請求項
１〜１０のいずれかに記載の導電ペースト。11. An organic solvent having an evaporation rate of 30 or less (0
And the boiling point is 150 to 260 ° C. 11. The conductive paste according to claim 1.
ペーストの固形分に対して重量比で導電粉：バインダが
８３：１７〜９７：３及び体積比で導電粉：バインダが
２８：７２〜８４：１６である請求項１〜１１のいずれ
かに記載の導電ペースト。12. The blending ratio of the conductive powder and the binder is 83:17 to 97: 3 by weight of conductive powder: binder and 28:72 by weight of conductive powder: binder to the solid content of the conductive paste. It is 84:16, The electrically conductive paste in any one of Claims 1-11.
〜１０重量％含有してなる請求項１〜１２のいずれかに
記載の導電ペースト。13. The organic solvent is used in an amount of 2 with respect to the conductive paste.
The conductive paste according to any one of claims 1 to 12, containing 10 to 10% by weight.
及びチキソ値が１．８〜7．３である請求項１〜１３の
いずれかに記載の導電ペースト。14. The viscosity is 100 to 7,000 dpa · s.
And the thixo value is 1.8-7.3, The conductive paste in any one of Claims 1-13.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001233714A JP2003045228A (en) | 2001-08-01 | 2001-08-01 | Conductive paste |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001233714A JP2003045228A (en) | 2001-08-01 | 2001-08-01 | Conductive paste |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003045228A true JP2003045228A (en) | 2003-02-14 |
Family
ID=19065456
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2001233714A Pending JP2003045228A (en) | 2001-08-01 | 2001-08-01 | Conductive paste |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003045228A (en) |
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