JP2005056778A - Conductive paste and printed circuit using it - Google Patents
Conductive paste and printed circuit using it Download PDFInfo
- Publication number
- JP2005056778A JP2005056778A JP2003288646A JP2003288646A JP2005056778A JP 2005056778 A JP2005056778 A JP 2005056778A JP 2003288646 A JP2003288646 A JP 2003288646A JP 2003288646 A JP2003288646 A JP 2003288646A JP 2005056778 A JP2005056778 A JP 2005056778A
- Authority
- JP
- Japan
- Prior art keywords
- conductive paste
- resistance
- silver powder
- resin
- polyester 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.)
- Granted
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 36
- 229920001225 polyester resin Polymers 0.000 claims description 36
- 239000004645 polyester resin Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 13
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 9
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 238000013508 migration Methods 0.000 abstract description 17
- 230000005012 migration Effects 0.000 abstract description 17
- 238000003780 insertion Methods 0.000 abstract description 13
- 230000037431 insertion Effects 0.000 abstract description 13
- 238000000605 extraction Methods 0.000 abstract description 5
- 230000000903 blocking effect Effects 0.000 abstract description 4
- 238000005452 bending Methods 0.000 description 32
- 239000002245 particle Substances 0.000 description 24
- -1 isocyanate compound Chemical class 0.000 description 23
- 238000000034 method Methods 0.000 description 14
- 239000012948 isocyanate Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- 238000001723 curing Methods 0.000 description 11
- 229920005862 polyol Polymers 0.000 description 11
- 150000003077 polyols Chemical class 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052709 silver Inorganic materials 0.000 description 8
- 239000004332 silver Substances 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002356 laser light scattering Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 4
- 239000004970 Chain extender Substances 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000003822 epoxy resin Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 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 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 3
- 239000000539 dimer Substances 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- 150000002460 imidazoles Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 2
- AAAWJUMVTPNRDT-UHFFFAOYSA-N 2-methylpentane-1,5-diol Chemical compound OCC(C)CCCO AAAWJUMVTPNRDT-UHFFFAOYSA-N 0.000 description 2
- SXFJDZNJHVPHPH-UHFFFAOYSA-N 3-methylpentane-1,5-diol Chemical compound OCCC(C)CCO SXFJDZNJHVPHPH-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 229920008347 Cellulose acetate propionate Polymers 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XDODWINGEHBYRT-UHFFFAOYSA-N [2-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCCC1CO XDODWINGEHBYRT-UHFFFAOYSA-N 0.000 description 2
- LUSFFPXRDZKBMF-UHFFFAOYSA-N [3-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCCC(CO)C1 LUSFFPXRDZKBMF-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- FOTKYAAJKYLFFN-UHFFFAOYSA-N decane-1,10-diol Chemical compound OCCCCCCCCCCO FOTKYAAJKYLFFN-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000007646 gravure printing Methods 0.000 description 2
- 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 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 150000002483 hydrogen compounds Chemical class 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 150000007974 melamines Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
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- 238000002360 preparation method Methods 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000000790 scattering method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 2
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- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- 229940051269 1,3-dichloro-2-propanol Drugs 0.000 description 1
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical class C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
本発明は導電性ペーストに関するものであり、さらに詳しくは導電性ペーストをフィルムまたは基板上に塗布または印刷、硬化することにより導電性を与え、回路を形成したり、電子部品の端子やリード線の接着を行ったり、電子装置を電磁波障害（ＥＭＩ）から保護することに利用する導電性ペーストに関わるものであり、特に高い導電性と耐屈曲性の要求される回路用に適した導電ペーストに関する。 The present invention relates to a conductive paste. More specifically, the conductive paste is applied, printed, or cured on a film or a substrate to impart conductivity, thereby forming a circuit, or a terminal or lead wire of an electronic component. The present invention relates to a conductive paste used for bonding or protecting an electronic device from electromagnetic interference (EMI), and particularly relates to a conductive paste suitable for a circuit requiring high conductivity and bending resistance.
ＰＥＴフィルムなどに導電性ペーストを印刷したメンブレン回路は低コストで軽量であり、キーボードやスイッチなどに広く使用されている。しかしながら、印刷パターンのファイン化により、年々要求特性は厳しくなってきており、従来以上の高度の耐屈曲性と導電性、耐マイグレーション性が望まれており、さらには表面平滑性、コネクター使用時の耐挿抜性、耐ブロッキング性なども、従来技術では充分でなく改良が望まれている。
例えば特許文献１ではフレーク状の銀粉とポリエステル系樹脂とブロック化イソシアネート化合物を結合剤に使用したメンブレン回路用の銀ペーストについて記載されている。しかしながらこの導電性は比較的良好であるが現状の要求には不足しており、また、耐マイグレーション性、耐屈曲性、耐コネクター挿抜性もファインパターン化した現代の要求に対しては不足している。また、特許文献２では導電粉として３次元高次構造の銀粉を使用したメンブレン回路用の銀ペーストが提案されているが、耐屈曲性、導電性共には現代の要求には不足している。
For example, Patent Document 1 describes a silver paste for a membrane circuit using flaky silver powder, a polyester resin, and a blocked isocyanate compound as a binder. However, this conductivity is relatively good, but it is not enough for the current requirements, and it is not enough for the modern requirements with a fine pattern of migration resistance, bending resistance and connector insertion / removal. Yes. Further, Patent Document 2 proposes a silver paste for a membrane circuit that uses silver powder having a three-dimensional higher order structure as conductive powder. However, both flex resistance and conductivity are insufficient for modern demands.
本発明の課題は、これら従来の導電性ペーストが抱えている耐マイグレーション性の改良が望まれており、さらには低抵抗で、表面平滑性、コネクター使用時の耐挿抜性、耐ブロッキング性を改良するものであり、特に高度の耐屈曲性を付与した導電性ペーストを低コストで提供することである。 The object of the present invention is to improve the migration resistance possessed by these conventional conductive pastes, and further, with low resistance, improved surface smoothness, resistance to insertion / removal when using connectors, and blocking resistance. In particular, it is to provide a conductive paste imparted with a high degree of bending resistance at low cost.
以上のような問題を解決するために、鋭意検討した結果、ハロゲン元素を含有する有機樹脂と平均の厚さが１３００オングストローム以下のフレーク状銀粉を主体とする導電粉を使用することにより、驚くべきことに非常に低抵抗で、耐屈曲性が向上し、さらには耐マイグレーション性が向上することを見出し本発明に到達した。また、この導電粉を用いることにより、公知のポリマー型導電性ペーストに使用されるフレーク状銀粉と比較して硬質な結合剤を用いた場合でも、良好な耐屈曲性を得られるため、耐屈曲性と耐コネクターブロッキング性及び挿抜性の両立も可能となる。さらに、ブロック化イソシアネート化合物などの硬化剤を配合しない場合においても良好な耐屈曲性が得られるため、従来技術より低温速硬化が可能となる。また、膜厚が１〜３μｍ程度の薄い領域においても良好な導電性が得られるため、基材フィルムにグラビア印刷などで薄く印刷し電磁波シールド用として有用である。 As a result of intensive studies to solve the above problems, it is surprising to use a conductive powder mainly composed of an organic resin containing a halogen element and a flaky silver powder having an average thickness of 1300 angstroms or less. In particular, the inventors have found that the resistance is very low, the bending resistance is improved, and further the migration resistance is improved. In addition, by using this conductive powder, even when a hard binder is used compared to the flaky silver powder used in known polymer type conductive paste, it is possible to obtain a good bending resistance. Compatibility with connector blocking resistance and insertion / removal properties is also possible. In addition, even when a curing agent such as a blocked isocyanate compound is not blended, good bending resistance can be obtained, so that low temperature rapid curing can be achieved as compared with the prior art. Moreover, since favorable electroconductivity is obtained also in a thin area | region with a film thickness of about 1-3 micrometers, it prints thinly by gravure printing etc. on a base film, and is useful as an electromagnetic wave shield.
さらには、フレーク状銀粉と塩化ビニル＝酢酸ビニル共重合体などのハロゲン元素含有有機樹脂とを組み合わせることにより、高価な銀粉などの導電性フィラーの充填量を大幅に低減しても低い抵抗値を維持し、塗膜比重が低下することにより、カバレージ（ペースト１ｋｇ当たりの塗布面積）を低減することなく、大幅なコストダウンが可能となる。さらに、低温硬化条件においても良好な素材に対する密着性、硬化性が得られる。
すなわち、本発明は、以下の導電性ペースト及びこれを用いた印刷回路に関する。
Furthermore, by combining flaky silver powder and halogen element-containing organic resin such as vinyl chloride = vinyl acetate copolymer, low resistance is achieved even if the amount of conductive filler such as expensive silver powder is drastically reduced. By maintaining and reducing the specific gravity of the coating film, it is possible to significantly reduce the cost without reducing the coverage (application area per 1 kg of paste). Further, good adhesion to the material and curability can be obtained even under low temperature curing conditions.
That is, the present invention relates to the following conductive paste and a printed circuit using the same.
（１）形状がフレーク状であり、かつ厚さが１３００オングストローム以下である銀粉（Ａ）、バインダー樹脂としてハロゲン元素含有有機樹脂（Ｂ）を含む導電性ペースト。 (1) A conductive paste containing silver powder (A) having a flake shape and a thickness of 1300 angstroms or less, and a halogen element-containing organic resin (B) as a binder resin.
（２）ハロゲン元素含有有機樹脂（Ｂ）が塩化ビニル＝酢酸ビニル共重合体である（１）に記載の導電性ペースト。 (2) The conductive paste according to (1), wherein the halogen element-containing organic resin (B) is vinyl chloride = vinyl acetate copolymer.
（３）塩化ビニル＝酢酸ビニル共重合体が極性基を有することを特徴とする（２）に記載の導電性ペースト。 (3) The conductive paste according to (2), wherein the vinyl chloride = vinyl acetate copolymer has a polar group.
（４）さらに、バインダー樹脂として数平均分子量３０００以上のポリエステル樹脂及び／または変性ポリエステル樹脂（Ｃ）を含むことを特徴とする（１）〜（３）のいずれかに記載の導電性ぺースト。 (4) The conductive paste according to any one of (1) to (3), further comprising a polyester resin having a number average molecular weight of 3000 or more and / or a modified polyester resin (C) as a binder resin.
（５）全ジカルボン酸、グリコール成分の合計をそれぞれ１００モル％としたとき、ポリエステル樹脂及び／または変性ポリエステル樹脂（Ｃ）が、酸成分として芳香族ジカルボン酸及び／または脂環族ジカルボン酸を５０モル％以上、かつグリコール成分としてネオペンチルグリコール、炭素数５〜１０の脂肪族ジオールからなる群より選ばれる少なくとも１種以上を２０モル％以上共重合されている（４）に記載の導電性ペースト。 (5) When the total of all dicarboxylic acids and glycol components is 100 mol%, the polyester resin and / or modified polyester resin (C) contains 50 aromatic dicarboxylic acids and / or alicyclic dicarboxylic acids as acid components. The conductive paste according to (4), wherein at least one selected from the group consisting of mol% or more and neopentyl glycol as a glycol component and an aliphatic diol having 5 to 10 carbon atoms is copolymerized in an amount of 20 mol% or more. .
（６）さらに、導電性微粉末としてカーボンブラック及び／またはグラファイト微粉末を含む（１）〜（５）のいずれかに記載の導電性ペースト。 (6) The conductive paste according to any one of (1) to (5), further including carbon black and / or graphite fine powder as the conductive fine powder.
（７）（１）〜（６）のいずれかに記載の導電性ペーストが基材上に印刷されていることを特徴とする印刷回路。 (7) A printed circuit, wherein the conductive paste according to any one of (1) to (6) is printed on a substrate.
本発明の導電性ペーストにより、低抵抗で耐屈曲性を大幅に向上でき、さらには優れた耐屈曲性、耐マイグレーション性、耐コネクター挿抜性をも合わせ持つ優れた回路材料を作成することが可能となる。 With the conductive paste of the present invention, it is possible to significantly improve the bending resistance with low resistance, and furthermore, it is possible to create an excellent circuit material that has excellent bending resistance, migration resistance, and connector insertion / removal resistance. It becomes.
本発明で用いる銀粉（Ａ）はその形状がフレーク状である必要がある。ここで言うフレーク状とは、レーザー光散乱法により測定した５０％平均粒子径を後述する電子顕微鏡で測定した平均厚さで徐した値（アスペクト比）が２以上のものを示す。より具体的には、５０％平均粒子径は銀粉をミクロスパテラで１〜２杯、１００ｍｌトールビーカーに採り、イソプロピルアルコールを６０ｍｌ入れ、超音波ホモジナイザーで１分間分散し、粒度分布計（マイクロトラックＦＲＡ型（日機装（株））で測定することができる。測定時間は、３０秒で２回測定して、５０％の累積径の平均値を平均粒径とする。測定条件は、粒子の光透過性（Ｔ、Ｐ）；ＹＥＳ、粒子の形状（Ｓ、Ｐ）；ＮＯ、粒子屈折率（Ｐｒｉ）；２．２５、分散媒屈折率（Ｃｒｉ）；１．３７とする。平均厚さは、具体的には次の方法で測定できる。銀粉２ｇを水溶性エポキシ樹脂（Ｑｕｅｔｏｌ６５１（日新ＥＭ（株）製））１０ｃｃとよく混合し、６０℃の恒温槽中で１時間３０分静置後、注射器（ニプロシリンジ１ｍｌ（ニプロ（株）製））でサンプルを吸い出し、注射器に入れたまま６０℃の恒温槽中に８時間置いた。硬化した樹脂を、注射器より取り出し、ミクロトームで面出し加工を行い、カーボン蒸着後、電解放射型走査型電子顕微鏡（日立（株）製Ｓ４５００型）で５０００倍又は１００００倍の倍率で写真を撮影し、銀粉の厚みを測定した。測定個数５０個の平均値で表した。 The silver powder (A) used in the present invention needs to have a flake shape. The flaky shape referred to here indicates that the 50% average particle diameter measured by the laser light scattering method is a value (aspect ratio) obtained by grading with an average thickness measured with an electron microscope, which will be described later, of 2 or more. More specifically, the 50% average particle diameter is 1 to 2 cups of silver powder in a microspatella, taken in a 100 ml tall beaker, 60 ml of isopropyl alcohol, dispersed with an ultrasonic homogenizer for 1 minute, and a particle size distribution meter (Microtrac FRA). It can be measured with a mold (Nikkiso Co., Ltd.) The measurement time is measured twice in 30 seconds, and the average value of 50% cumulative diameter is taken as the average particle diameter. (T, P): YES, particle shape (S, P): NO, particle refractive index (Pri): 2.25, dispersion medium refractive index (Cri): 1.37 The average thickness is Specifically, it can be measured by the following method: 2 g of silver powder is mixed well with 10 cc of a water-soluble epoxy resin (Quetol 651 (manufactured by Nissin EM Co., Ltd.)) and left in a constant temperature bath at 60 ° C. for 1 hour 30 minutes. , Syringe (Nipro Syringe 1 1 (made by Nipro Co., Ltd.) was sucked out and placed in a syringe for 8 hours in a thermostatic bath at 60 ° C. The cured resin was taken out of the syringe, surfaced with a microtome, and carbon deposited. Then, a photograph was taken with an electrolytic emission scanning electron microscope (S4500, manufactured by Hitachi, Ltd.) at a magnification of 5000 times or 10000 times, and the thickness of the silver powder was measured.
本発明において用いられる銀粉（Ａ）は、さらに平均厚さが１３００Å以下である必要がある。驚くべきことに、形状がフレーク状で平均厚さが１３００Å以下とすることにより、低抵抗で著しく良好な耐屈曲性が得られる。さらには、従来技術のフレーク状銀粉、その他の形状の銀粉と比較して耐マイグレーション性、耐コネクター挿抜性を向上できる。 The silver powder (A) used in the present invention needs to have an average thickness of 1300 mm or less. Surprisingly, when the shape is flaky and the average thickness is 1300 mm or less, extremely good bending resistance can be obtained with low resistance. Furthermore, migration resistance and connector insertion / removal resistance can be improved as compared with conventional flaky silver powder and other shapes of silver powder.
平均厚さのより好ましい上限は１１００Å、さらに好ましくは９００Åである。下限は特に限定されないが、１００Åが好ましい。上限が１３００Å超では、耐マイグレーション性、耐屈曲性、導電性などが低下する。下限が１００Å未満では銀粉の吸油量が大きくなる傾向があり、密着性や耐屈曲性などが低下したり、印刷性が悪化するおそれがある。 A more preferable upper limit of the average thickness is 1100 mm, and more preferably 900 mm. Although a minimum is not specifically limited, 100 tons is preferable. If the upper limit is more than 1300 mm, the migration resistance, the bending resistance, the conductivity and the like are lowered. If the lower limit is less than 100%, the oil absorption of the silver powder tends to increase, and adhesion and bending resistance may decrease, or printability may deteriorate.
本発明において用いられる銀粉（Ａ）の厚さを１３００オングストローム以下にする方法としては、硝酸銀の還元により作成される１次銀粒子のレーザー光散乱法による５０％平均粒子径が好ましくは５μｍ以下、より好ましくは３μｍ以下、下限は好ましくは０．０１μｍ以上のものを、滑剤の存在下、湿式法でビーズミル、ボールミルもしくはアトライターなど公知の装置を用いて高速でミリングすることにより得られる。分散に用いるビーズは直径が３ｍｍ以下が好ましく、より好ましくは２ｍｍ以下が好ましい。最も好ましくは１．５ｍｍ以下、下限は０．１ｍｍ以上の小径のジルコニアあるいはシリカビーズが好ましい。 As a method of making the thickness of the silver powder (A) used in the present invention 1300 angstroms or less, the 50% average particle diameter by laser light scattering of primary silver particles prepared by reduction of silver nitrate is preferably 5 μm or less, More preferably, it is obtained by milling a material having a size of 3 μm or less and a lower limit of preferably 0.01 μm or more at a high speed using a known apparatus such as a bead mill, a ball mill or an attritor in the presence of a lubricant by a wet method. The beads used for dispersion preferably have a diameter of 3 mm or less, more preferably 2 mm or less. Most preferably, zirconia or silica beads having a small diameter of 1.5 mm or less and a lower limit of 0.1 mm or more are preferred.
分散機としては、ビーズミルが高いシェアをかけられるため好ましく、商品名としてはダイノーミル（ＷＩＬＬＹ Ａ．ＢＡＣＨＯＦＥＮ ＡＧ製）、Ｋシリーズ（ビューラー（株）製）などが挙げられる。 As the disperser, a bead mill is preferable because it can take a high share, and as a trade name, dyno mill (manufactured by WILLY A. BACHOFE AG), K series (manufactured by Buehler Co., Ltd.) and the like can be mentioned.
本発明に用いられる銀粉（Ａ）のその他の粉末特性としては、タップ密度が２．５ｇ／ｃｍ3以下、比表面積が１．２ｍ2／ｇ以上、レーザー光散乱法のよる５０％平均粒子径が２０μｍ以下が好ましい。タップ密度はより好ましくは２．０ｇ／ｍ3以下、下限は特に定めるものではないが１．０ｇ／ｃｍ3以上が好ましい。比表面積はより好ましくは１．５ｍ2／ｇ以上で、上限は特に定めるものではないが４ｍ2／ｇ以下が好ましく、より好ましくは３ｍ2／ｇ以下である。５０％平均粒子径はより好ましくは１５μｍ以下、最も好ましくは１０μｍ以下である。下限は特に定めるものではないが、導電性、密着性の面より１μｍ以上が好ましい。タップ密度が２．２ｇ／ｃｍ3を越えたり、比表面積が１．５ｍ2／ｇ未満であったり、５０％平均粒子径１μｍ未満であると、フレーク状銀粉の厚さが１３００オングストロームを越える可能性があり、導電性、耐屈曲性、耐マイグレーション性などが低下する場合がある。 As other powder characteristics of the silver powder (A) used in the present invention, the tap density is 2.5 g / cm 3 or less, the specific surface area is 1.2 m 2 / g or more, and the 50% average particle diameter by the laser light scattering method. Is preferably 20 μm or less. The tap density is more preferably 2.0 g / m 3 or less, and the lower limit is not particularly defined but is preferably 1.0 g / cm 3 or more. The specific surface area is more preferably 1.5 m 2 / g or more, and the upper limit is not particularly defined, but is preferably 4 m 2 / g or less, more preferably 3 m 2 / g or less. The 50% average particle diameter is more preferably 15 μm or less, and most preferably 10 μm or less. The lower limit is not particularly defined, but is preferably 1 μm or more from the viewpoint of conductivity and adhesion. If the tap density exceeds 2.2 g / cm 3 , the specific surface area is less than 1.5 m 2 / g, or the 50% average particle diameter is less than 1 μm, the thickness of the flaky silver powder can exceed 1300 angstroms. In some cases, the electrical conductivity, the bending resistance, the migration resistance and the like may be deteriorated.
本発明に使用するその他の導電粉としては、特性を低下しない範囲で公知のフレーク状銀粉、球状銀粉、３次元高次構造の銀粉、樹枝状銀粉、グラファイト粉、カーボン粉、ニッケル粉、銅粉、金粉、パラジウム粉、アルミ粉、インジウム粉などを併用しても良いが、形状がフレーク状で厚さが１３００Å以下の銀粉（Ａ）を少なくとも全導電粉量の２０重量％以上、より好ましくは３０重量％以上、さらに好ましくは５０重量％以上、最も好ましくは７０重量％以上含むことが好ましい。公知の導電粉の内、好ましいものとしては、公知のフレーク状銀粉、グラファイト粉、導電性カーボンブラックが挙げられる。特に、導電性カーボンブラックを少量併用することが、導電性、コスト面より好ましい。この他、ペースト粘性を調整する目的などでシリカ粉、ヒュームドシリカ、コロイダルシリカ、タルク、硫酸バリウムなどの非導電性フィラーを少量配合しても良い。 Other conductive powders used in the present invention include known flaky silver powder, spherical silver powder, three-dimensional higher order silver powder, dendritic silver powder, graphite powder, carbon powder, nickel powder, copper powder as long as the characteristics are not deteriorated. , Gold powder, palladium powder, aluminum powder, indium powder, etc. may be used together, but silver powder (A) having a flake shape and a thickness of 1300 mm or less is at least 20% by weight or more of the total conductive powder amount, more preferably It is preferable to contain 30% by weight or more, more preferably 50% by weight or more, and most preferably 70% by weight or more. Among the known conductive powders, preferred are flaky silver powder, graphite powder, and conductive carbon black. In particular, it is preferable to use a small amount of conductive carbon black in view of conductivity and cost. In addition, a small amount of non-conductive filler such as silica powder, fumed silica, colloidal silica, talc, and barium sulfate may be blended for the purpose of adjusting paste viscosity.
本発明の導電性ペーストは、銀粉（Ａ）とバインダー樹脂としてハロゲン元素含有有機樹脂（Ｂ）を組み合わせて使用される。ハロゲン元素含有有機樹脂を銀粉（Ａ）と組み合わせて使用することにより、導電性がさらに向上でき、また、銀粉の充填量を低減しても良好な導電性が維持できるため、コストダウンが可能となる。ハロゲン元素含有有機樹脂（Ｂ）としては、汎用の有機溶剤に溶解するものが好ましく、塩化ビニル＝酢酸ビニル共重合体、ブロム化エポキシ樹脂、塩素化ポリプロピレン、変性ポリフッ化ビニリデンなどが挙げられるが、ＰＥＴフィルムなどの基材への密着性、耐屈曲性の面より、塩化ビニル＝酢酸ビニル共重合体が特に好ましい。 The conductive paste of the present invention is used in combination with silver powder (A) and a halogen element-containing organic resin (B) as a binder resin. By using a halogen element-containing organic resin in combination with silver powder (A), the conductivity can be further improved, and good conductivity can be maintained even if the filling amount of silver powder is reduced. Become. The halogen element-containing organic resin (B) is preferably one that dissolves in a general-purpose organic solvent, and examples include vinyl chloride = vinyl acetate copolymer, brominated epoxy resin, chlorinated polypropylene, and modified polyvinylidene fluoride. From the viewpoints of adhesion to a substrate such as a PET film and bending resistance, vinyl chloride = vinyl acetate copolymer is particularly preferable.
さらには、塩化ビニル＝酢酸ビニル共重合体において、溶解性と塗膜物性よりポリマー中の塩化ビニルの含有量は８５〜９５％のものが好ましい。また、塩化ビニル、酢酸ビニル以外のモノマーとして、マレイン酸、ビニルアルコールなどを少量共重合して極性基を導入してもよい。マレイン酸によりカルボキシル基を導入すると金属に対する密着性が向上し、ビニルアルコールにより水酸基を導入するとイソシアネート化合物を硬化剤として使用できる。さらに、基材への密着性、分散性などの面より、アミノ基、スルホン酸金属塩基、リン酸塩基などの極性基を含むことも好ましい。 Further, in the vinyl chloride = vinyl acetate copolymer, the content of vinyl chloride in the polymer is preferably 85 to 95% from the viewpoint of solubility and physical properties of the coating film. Further, a polar group may be introduced by copolymerizing a small amount of maleic acid, vinyl alcohol or the like as a monomer other than vinyl chloride or vinyl acetate. When a carboxyl group is introduced with maleic acid, adhesion to a metal is improved, and when a hydroxyl group is introduced with vinyl alcohol, an isocyanate compound can be used as a curing agent. Furthermore, it is preferable that polar groups, such as an amino group, a sulfonate metal base, and a phosphate group, are included from the surface of adhesiveness to a base material, dispersibility, etc.
ハロゲン元素含有有機樹脂（Ｂ）は耐屈曲性の面から数平均分子量が３０００以上が好ましく、より好ましくは８０００以上である。数平均分子量が３０００未満であると良好な耐屈曲性が得にくく、また、ペースト粘度が低下し、印刷性の低下する虞がある。上限はペースト粘度等作業性を考慮すると６００００未満が好ましい。 The halogen element-containing organic resin (B) has a number average molecular weight of preferably 3000 or more, more preferably 8000 or more, from the viewpoint of bending resistance. When the number average molecular weight is less than 3,000, good flex resistance is difficult to obtain, and the paste viscosity is lowered and printability may be lowered. In consideration of workability such as paste viscosity, the upper limit is preferably less than 60000.
また、ハロゲン元素含有有機樹脂（Ｂ）の他に、別の有機樹脂を併用することができる。その他の有機樹脂としては、ポリエステル樹脂、ウレタン変性ポリエステル樹脂、エポキシ変性ポリエステル樹脂、アクリル変性ポリエステルなどの各種変性ポリエステル樹脂、ポリエーテルウレタン樹脂、ポリカーボネートウレタン樹脂、エポキシ樹脂、フェノール樹脂、アクリル樹脂、ポリアミドイミド、ニトロセルロース、セルロース・アセテート・ブチレート（ＣＡＢ）、セルロース・アセテート・プロピオネート（ＣＡＰ）などの変性セルロース類などが挙げられる。 In addition to the halogen element-containing organic resin (B), another organic resin can be used in combination. Other organic resins include polyester resins, urethane modified polyester resins, epoxy modified polyester resins, various modified polyester resins such as acrylic modified polyester, polyether urethane resins, polycarbonate urethane resins, epoxy resins, phenol resins, acrylic resins, polyamideimides And modified celluloses such as nitrocellulose, cellulose acetate butyrate (CAB), and cellulose acetate propionate (CAP).
このうち、可撓性の不要な導電性接着剤、リジット基板の回路用導電ペースト、スルーホール用導電性ペーストなどの用途にはエポキシ樹脂、フェノール樹脂でも使用できるが、ＰＥＴフィルム、ＩＴＯ蒸着ＰＥＴフィルム、ポリイミドフィルムなどのフレキシブルで比較的難接着性の基材を用いる場合は、耐屈曲性と基材に対する密着性の面から、ポリエステル樹脂、上記の変性ポリエステル樹脂が好ましく、最も好ましくは、ポリエステル樹脂および／または変性ポリエステル樹脂（Ｃ）であり、特にこのようなフレキシブルな基材に用いた時にその特徴が発揮できる。 Of these, epoxy resin and phenolic resin can be used for applications such as flexible conductive adhesives, rigid circuit board conductive pastes, and through-hole conductive pastes. In the case of using a flexible and relatively difficult-to-adhere base material such as a polyimide film, a polyester resin and the above-described modified polyester resin are preferable, and most preferably a polyester resin, from the viewpoint of flexibility and adhesion to the base material. And / or a modified polyester resin (C), and its characteristics can be exhibited particularly when used for such a flexible substrate.
ポリエステル樹脂および／または変性ポリエステル樹脂（Ｃ）は、さらに具体的には、数平均分子量３０００以上であることが好ましく、非常に優れた耐屈曲性、基材への密着性が得られる。耐屈曲性の観点から数平均分子量は８０００以上が好ましく、より好ましくは１００００以上である。数平均分子量が３、０００未満であると良好な耐屈曲性が得られないことがあり、また、ペースト粘度が低下し、印刷性に劣る場合がある。上限はペースト粘度等作業性を考慮すると５００００未満が望ましい。耐屈曲性と硬度の面からガラス転移点温度は−２０℃以上が好ましく、より好ましくは−１０℃以上である。耐屈曲性の観点から好ましい上限は７０℃以下が好ましく、より好ましくは５０℃以下、最も好ましくは２０℃以下である。本発明のポリエステル樹脂は公知の方法により常圧または減圧下で重縮合して得られたものを使用できる。ポリエステル樹脂は飽和ポリエステルが好ましい。また、ポリエステル樹脂を重合後、１８０〜２３０℃でε−カプロラクトンなどの環状エステルを後付加（開環付加）してブロック化したり、無水トリメリット酸、無水フタル酸などの酸無水物を後付加してカルボキシル基をポリエステル分子末端に付与してもよい。 More specifically, the polyester resin and / or the modified polyester resin (C) preferably has a number average molecular weight of 3000 or more, and very excellent bending resistance and adhesion to a substrate can be obtained. From the viewpoint of bending resistance, the number average molecular weight is preferably 8000 or more, more preferably 10,000 or more. When the number average molecular weight is less than 3,000, good bending resistance may not be obtained, and the paste viscosity may be lowered and printability may be poor. The upper limit is preferably less than 50000 considering workability such as paste viscosity. The glass transition temperature is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, in terms of bending resistance and hardness. The upper limit is preferably 70 ° C. or less, more preferably 50 ° C. or less, and most preferably 20 ° C. or less from the viewpoint of bending resistance. As the polyester resin of the present invention, those obtained by polycondensation by a known method under normal pressure or reduced pressure can be used. The polyester resin is preferably a saturated polyester. In addition, after polymerizing the polyester resin, a cyclic ester such as ε-caprolactone is post-added (ring-opening addition) at 180 to 230 ° C. to form a block, or an acid anhydride such as trimellitic anhydride or phthalic anhydride is post-added. Then, a carboxyl group may be imparted to the polyester molecule terminal.
本発明に用いられる樹脂及び／または変性ポリエステル樹脂（Ｃ）に共重合するジカルボン酸は、テレフタル酸、イソフタル酸、オルソフタル酸、２，６−ナフタレンジカルボン酸などの芳香族ジカルボン酸、コハク酸、グルタル酸、アジピン酸、セバシン酸、ドデカンジカルボン酸、アゼライン酸などの脂肪族ジカルボン酸、炭素数１２〜２８の二塩基酸、１，４−シクロヘキサンジカルボン酸、１，３−シクロヘキサンジカルボン酸、１，２−シクロヘキサンジカルボン酸、４−メチルヘキサヒドロ無水フタル酸、３−メチルヘキサヒドロ無水フタル酸、２−メチルヘキサヒドロ無水フタル酸、ジカルボキシ水素添加ビスフェノールＡ、ジカルボキシ水素添加ビスフェノールＳ、ダイマー酸、水素添加ダイマー酸、水素添加ナフタレンジカルボン酸、トリシクロデカンジカルボン酸などの脂環族ジカルボン酸が挙げられる。また、発明の内容を損なわない範囲で、無水トリメリット酸、無水ピロメリット酸などの多価のカルボン酸、フマール酸などの不飽和ジカルボン酸、さらに、５−スルホイソフタル酸ナトリウム塩などのスルホン酸金属塩基含有ジカルボン酸を併用してもよい。具体的には、全ジカルボン酸量を１００モル％としたとき、芳香族ジカルボン酸及び／または脂環族ジカルボン酸を５０モル％以上共重合されたものが、硬度、密着性などの塗膜物性および耐湿性の点より好ましい。またより好ましくは６０モル％以上である。 The dicarboxylic acid copolymerized with the resin and / or the modified polyester resin (C) used in the present invention is an aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, orthophthalic acid, or 2,6-naphthalenedicarboxylic acid, succinic acid, or glutar. Acids, adipic acid, sebacic acid, dodecanedicarboxylic acid, azelaic acid and other aliphatic dicarboxylic acids, dibasic acids having 12 to 28 carbon atoms, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2 -Cyclohexanedicarboxylic acid, 4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 2-methylhexahydrophthalic anhydride, dicarboxy hydrogenated bisphenol A, dicarboxy hydrogenated bisphenol S, dimer acid, hydrogen Added dimer acid, hydrogenated naphthalene Carboxylic acid, alicyclic dicarboxylic acids such as tricyclodecane acid. Further, within the scope of not impairing the contents of the invention, polyvalent carboxylic acids such as trimellitic anhydride and pyromellitic anhydride, unsaturated dicarboxylic acids such as fumaric acid, and sulfonic acids such as sodium 5-sulfoisophthalic acid A metal base-containing dicarboxylic acid may be used in combination. Specifically, when the total amount of dicarboxylic acid is 100 mol%, a copolymer obtained by copolymerizing 50 mol% or more of aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid has properties such as hardness and adhesion. From the viewpoint of moisture resistance. More preferably, it is 60 mol% or more.
本発明のポリエステル樹脂及び変性ポリエステル樹脂（Ｃ）に使用されるグリコールは、エチレングリコール、プロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、１，５−ペンタンジオール、ネオペンチルグリコール、１，６−ヘキサンジオール、３−メチル−１，５−ペンタンジオール、２−メチル−１，５−ペンタンジオール、２，２−ジエチル−１，３−プロパンジオール、２−ブチル−２−エチル−１，３−プロパンジオール、１，９−ノナンジオール、１，１０−デカンジオール、１，４−シクロヘキサンジメタノール、１，３−シクロヘキサンジメタノール、１，２−シクロヘキサンジメタノール、ダイマージオールなどが挙げられる。また、発明の内容を損なわない範囲でトリメチロールエタン、トリメチロールプロパン、グリセリン、ペンタエリスリトール、ポリグリセリンなどの多価ポリオールを併用してもよい。これらのうち、耐湿性の面より、全グリコール成分量１００モル％としたとき、ネオペンチルグリコール、脂環族グリコール、主鎖の炭素数５〜１０の脂肪族ジオールからなる群より選ばれる少なくとも１種以上を２０モル％以上共重合されたものが耐加水分解性の点より好ましい。またより好ましくは３０モル％以上、最も好ましくは４０モル％以上である。ここで言う主鎖の炭素数５〜１０のグリコールとしては具体的には、１，５−ペンタンジオール、３−メチル−１，５−ペンタンジオール、２−メチル−１，５−ペンタンジオール、１，６−ヘキサンジオール、１，９−ノナンジオール、１，１０−デカンジオールなどが挙げられる。脂環族グリコールとしては、１，４−シクロヘキサンジメタノール、１，３−シクロヘキサンジメタノール、１，２−シクロヘキサンジメタノールなどが挙げられる。 The glycol used in the polyester resin and modified polyester resin (C) of the present invention is ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, 2,2-diethyl-1,3-propanediol, 2-butyl-2-ethyl- 1,3-propanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol, dimer diol, etc. It is done. Moreover, you may use together polyhydric polyols, such as a trimethylol ethane, a trimethylol propane, glycerol, a pentaerythritol, a polyglycerol, in the range which does not impair the content of invention. Among these, from the viewpoint of moisture resistance, when the total glycol component amount is 100 mol%, at least one selected from the group consisting of neopentyl glycol, alicyclic glycol, and aliphatic diol having 5 to 10 carbon atoms in the main chain. What copolymerized 20 mol% or more of seed | species or more is preferable from the point of hydrolysis resistance. More preferably, it is 30 mol% or more, and most preferably 40 mol% or more. Specific examples of the main chain glycol having 5 to 10 carbon atoms include 1,5-pentanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,5-pentanediol, , 6-hexanediol, 1,9-nonanediol, 1,10-decanediol and the like. Examples of the alicyclic glycol include 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,2-cyclohexanedimethanol and the like.
また、本発明の導電ペーストに使用するポリエステル樹脂はウレタン変性、エポキシ変性、（メタ）アクリレート変性、（メタ）アクリルグラフト変性など公知の方法により変性して使用できる。このうち、耐屈曲性、密着性の面よりウレタン変性が特に好ましい。ウレタン変性樹脂は公知の方法により、ポリエステルポリオールと必要に応じて鎖延長剤を用いてイソシアネート化合物と反応させて合成したものを使用できる。 Moreover, the polyester resin used for the electrically conductive paste of this invention can be modified | denatured and used by well-known methods, such as urethane modification, epoxy modification, (meth) acrylate modification, and (meth) acryl graft modification. Of these, urethane modification is particularly preferred from the viewpoint of bending resistance and adhesion. A urethane-modified resin synthesized by a known method by reacting with an isocyanate compound using a polyester polyol and, if necessary, a chain extender can be used.
ウレタン変性ポリエステル樹脂に使用するポリオールには前述したポリエステルポリオールを使用するが、この他にポリエーテルポリオール、（メタ）アクリルポリオール、ポリカーボネートジオール、ポリブタジエンポリオール、その他のポリオールを併用してもよい。その他のポリオールとしては、接着性、耐屈曲性、耐久性よりポリカーボネートジオールが特に好ましい。鎖延長剤として使用するポリオールとしてはネオペンチルグリコール、１，６−ヘキサンジオール、エチレングリコール、ＨＰＮ（ネオペンチルグリコールのヒドロキシピバリン酸エステル）、トリメチロールプロパン、グリセリンなどの公知のポリオールが挙げられる。さらにジメチロールプロピオン酸のようなカルボキシル基含有ポリオールなども鎖延長剤として使用できる。 As the polyol used in the urethane-modified polyester resin, the above-described polyester polyol is used, but in addition to this, polyether polyol, (meth) acryl polyol, polycarbonate diol, polybutadiene polyol, and other polyols may be used in combination. As other polyols, polycarbonate diol is particularly preferable in view of adhesiveness, flex resistance, and durability. Examples of the polyol used as the chain extender include known polyols such as neopentyl glycol, 1,6-hexanediol, ethylene glycol, HPN (hydroxypivalate ester of neopentyl glycol), trimethylolpropane, and glycerin. Furthermore, carboxyl group-containing polyols such as dimethylolpropionic acid can also be used as chain extenders.
ウレタン変性に使用するジイソシアネート化合物は、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、水素化ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネートなどが挙げられる。 Examples of the diisocyanate compound used for urethane modification include tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, and isophorone diisocyanate.
変性ポリエステル樹脂（Ｃ）としてのポリエステルウレタン樹脂のウレタン基濃度は下限は、密着性、耐屈曲性の面から５００当量／１０6ｇ以上が好ましく、上限は溶解性の面から４０００当量／１０6ｇ以下が好ましい。 The lower limit of the urethane group concentration of the polyester urethane resin as the modified polyester resin (C) is preferably 500 equivalents / 10 6 g or more from the viewpoint of adhesion and flex resistance, and the upper limit is 4000 equivalents / 10 6 from the viewpoint of solubility. g or less is preferable.
本発明に使用するハロゲン元素含有有機樹脂（Ｂ）、ポリエステル樹脂及び／または変性ポリエステル樹脂（Ｃ）は硬化剤を配合して使用しても良い。これらの樹脂に反応し得る硬化剤は、種類は限定しないが接着性、耐屈曲性、硬化性などからイソシアネート化合物が特に好ましい。さらに、これらのイソシアネート化合物はブロック化して使用することが貯蔵安定性から好ましい。イソシアネート化合物以外の硬化剤としては、メチル化メラミン、ブチル化メラミン、ベンゾグアナミン、尿素樹脂などのアミノ樹脂、酸無水物、イミダゾール類、エポキシ樹脂、フェノール樹脂などの公知の化合物が挙げられる。 The halogen element-containing organic resin (B), polyester resin and / or modified polyester resin (C) used in the present invention may be used by blending a curing agent. The curing agent capable of reacting with these resins is not particularly limited, but an isocyanate compound is particularly preferable from the viewpoint of adhesion, flex resistance, curability, and the like. Further, these isocyanate compounds are preferably used after being blocked from the viewpoint of storage stability. Examples of curing agents other than isocyanate compounds include known compounds such as amino resins such as methylated melamine, butylated melamine, benzoguanamine, and urea resin, acid anhydrides, imidazoles, epoxy resins, and phenol resins.
イソシアネート化合物としては、芳香族、脂肪族のジイソシアネート、３価以上のポリイソシアネートがあり、低分子化合物、高分子化合物のいずれでもよい。例えば、テトラメチレンジイソシアネート、ヘキサメチレンジイソシアネート、トルエンジイソシアネート、ジフェニルメタンジイソシアネート、水素化ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、水素化キシリレンジイソシアネート、イソホロンジイソシアネートあるいはこれらのイソシアネート化合物の３量体、及びこれらのイソシアネート化合物の過剰量と、例えばエチレングリコール、プロピレングリコール、トリメチロールプロパン、グリセリン、ソルビトール、エチレンジアミン、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン等の低分子活性水素化合物または各種ポリエステルポリオール類、ポリエーテルポリオール類、ポリアミド類の高分子活性水素化合物などと反応させて得られる末端イソシアネート基含有化合物が挙げられる。 Examples of the isocyanate compound include aromatic and aliphatic diisocyanates and trivalent or higher polyisocyanates, which may be either low molecular compounds or high molecular compounds. For example, tetramethylene diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hydrogenated diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate or trimers of these isocyanate compounds, and excess of these isocyanate compounds Amount of low molecular active hydrogen compounds such as ethylene glycol, propylene glycol, trimethylolpropane, glycerin, sorbitol, ethylenediamine, monoethanolamine, diethanolamine, triethanolamine or various polyester polyols, polyether polyols, polyamides Obtained by reacting with polymer active hydrogen compounds Terminal isocyanate group-containing compounds to be.
イソシアネート基のブロック化剤としては、例えばフェノール、チオフェノール、メチルチオフェノール、エチルチオフェノール、クレゾール、キシレノール、レゾルシノール、ニトロフェノール、クロロフェノールなどのフェノール類、アセトキシム、メチルエチルケトオキシム、シクロヘキサノンオキシムなどのオキシム類、メタノール、エタノール、プロパノール、ブタノールなどのアルコール類，エチレンクロルヒドリン、１，３−ジクロロ−２−プロパノールなどのハロゲン置換アルコール類、ｔ−ブタノール、ｔ−ペンタノールなどの第三級アルコール類、ε−カプロラクタム、δ−バレロラクタム、γ−ブチロラクタム、β−プロピロラクタムなどのラクタム類が挙げられ、その他にも芳香族アミン類、イミド類、アセチルアセトン、アセト酢酸エステル、マロン酸エチルエステルなどの活性メチレン化合物、メルカプタン類、イミン類、イミダゾール類、尿素類、ジアリール化合物類、重亜硫酸ソーダ等も挙げられる。このうち、硬化性よりオキシム類、イミダゾール類、アミン類がとくに好ましい。 Examples of the isocyanate group blocking agent include phenols such as phenol, thiophenol, methylthiophenol, ethylthiophenol, cresol, xylenol, resorcinol, nitrophenol, chlorophenol, oximes such as acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime, Alcohols such as methanol, ethanol, propanol and butanol; halogen-substituted alcohols such as ethylene chlorohydrin and 1,3-dichloro-2-propanol; tertiary alcohols such as t-butanol and t-pentanol; -Lactams such as caprolactam, δ-valerolactam, γ-butyrolactam, β-propylolactam and the like, and other aromatic amines, imides, acetylacetates Emissions, acetoacetic ester, active methylene compounds such as malonic acid ethyl ester, mercaptans, imines, imidazoles, ureas, diaryl compounds, sodium bisulfite, etc. can be mentioned. Of these, oximes, imidazoles, and amines are particularly preferable from the viewpoint of curability.
これらの架橋剤には、その種類に応じて選択された公知の触媒あるいは促進剤を併用することもできる。 These crosslinking agents may be used in combination with known catalysts or accelerators selected according to the type.
本発明の導電性ペーストは、銀粉（Ａ）とハロゲン元素含有有機樹脂（Ｂ）を使用することにより、硬化剤を配合しなくても良好な耐屈曲性、密着性を得ることができる。硬化剤を配合しない場合（熱可塑タイプ）は熱硬化タイプより低温での乾燥が可能であるが、従来技術の熱可塑タイプでは耐屈曲性が不良であった。本発明の導電性ペーストは従来技術の熱可塑タイプと比較して著しく優れた耐屈曲性が得られる。 By using the silver powder (A) and the halogen element-containing organic resin (B), the conductive paste of the present invention can obtain good bending resistance and adhesion without blending a curing agent. When the curing agent is not blended (thermoplastic type), drying at a lower temperature is possible than the thermosetting type, but the conventional thermoplastic type has poor bending resistance. The conductive paste of the present invention can provide significantly superior bending resistance as compared with the thermoplastic type of the prior art.
本発明の導電性ペーストに用いるに溶剤はその種類に制限はなく、エステル系、ケトン系、エーテルエステル系、塩素系、アルコール系、エーテル系、炭化水素系などが挙げられる。このうち、スクリーン印刷する場合はエチルカルビトールアセテート、ブチルセロソルブアセテート、イソホロン、シクロヘキサノン、γ−ブチロラクトンなどの高沸点溶剤が好ましい。 There is no restriction | limiting in the kind in the solvent used for the electrically conductive paste of this invention, Ester type | system | group, ketone type | system | group, ether ester type | system | group, chlorine type | system | group, alcohol type | system | group, ether type | system | group, hydrocarbon type etc. are mentioned. Among these, in the case of screen printing, high boiling point solvents such as ethyl carbitol acetate, butyl cellosolve acetate, isophorone, cyclohexanone, and γ-butyrolactone are preferable.
本発明の導電性ペーストはスクリーン印刷、グラビア印刷、転写印刷、ロールコート、フローコート、ディスペンサー、スプレー塗装等公知の方法で、ＰＥＴフィルム（シート）を始めとするプラスチックフィルムに印刷してキーボードやスイッチに用いられるメンブレン回路等に使用できる。また、導電性接着剤としても使用できる。 The conductive paste of the present invention is printed on a plastic film such as a PET film (sheet) by a known method such as screen printing, gravure printing, transfer printing, roll coating, flow coating, dispenser, spray coating, etc. It can be used for the membrane circuit etc. It can also be used as a conductive adhesive.
以下、本発明を実施例を用いて説明する。実施例中、単に部とあるものは重量部を示す。また、各測定項目は以下の方法に従った。 Hereinafter, the present invention will be described using examples. In the examples, “parts” simply means “parts by weight”. Each measurement item followed the following method.
１．分子量
ＧＰＣによりポリスチレン換算の数平均分子量を測定した。測定溶媒はテトラヒドロフランを使用した。
1. Molecular weight The number average molecular weight in terms of polystyrene was measured by GPC. Tetrahydrofuran was used as a measurement solvent.
２．ガラス転移点温度（Ｔｇ）
示差走査熱量計（ＤＳＣ）を用いて、２０℃／分の昇温速度で測定した。サンプルは試料５ｍｇをアルミニウム押え蓋型容器に入れ、クリンプした。
2. Glass transition temperature (Tg)
It measured with the temperature increase rate of 20 degree-C / min using the differential scanning calorimeter (DSC). As a sample, 5 mg of a sample was placed in an aluminum press-lid container and crimped.
３．酸価
試料０．２ｇを精秤し２０ｍｌのクロロホルムに溶解した。ついで、０．０１Ｎの水酸化カリウム（エタノール溶液）で滴定して求めた。指示薬には、フェノールフタレイン溶液を用いた。
3. Acid value 0.2 g of a sample was precisely weighed and dissolved in 20 ml of chloroform. Subsequently, it titrated with 0.01N potassium hydroxide (ethanol solution). A phenolphthalein solution was used as an indicator.
４．比表面積
銀粉１５ｇをサンプル管に採り、６０±５℃、６０±５分の条件で前処理をし、比表面積自動測定装置（マイクロネリティクス２３００津島製作所；ＢＥＴ法装置Ｎ2ガス吸着１点法）にて総表面積を測定した。総表面積をサンプル量で除いて１ｇ当たりの比表面積を算出した。
4). Specific surface area 15g of silver powder is taken into a sample tube and pretreated under conditions of 60 ± 5 ° C and 60 ± 5 minutes, and a specific surface area automatic measuring device (Micronellitic 2300 Tsushima Seisakusho; BET method device N 2 gas adsorption one point method ) To measure the total surface area. The specific surface area per gram was calculated by removing the total surface area by the sample amount.
５．タップ密度
銀粉１００ｇをはかり、ロートで１００ｃｃメスシリンダーに静かに落した。タップ密度測定機にのせ、落差距離２０ｍｍ・６０回／分の速さで６００回落下させ、圧縮した銀粉の容積を測定し、銀粉の重量と容積より算出した。
5). Tap density 100 g of silver powder was weighed and gently dropped into a 100 cc graduated cylinder with a funnel. The sample was placed on a tap density measuring machine, dropped 600 times at a drop distance of 20 mm and a speed of 60 times / minute, the volume of the compressed silver powder was measured, and calculated from the weight and volume of the silver powder.
６．レーザー光散乱法による平均粒子径（５０％Ｄ）の測定
銀粉をミクロスパテラで１〜２杯、１００ｍｌトールビーカーに採り、イソプロピルアルコールを約６０ｍｌ入れ、超音波ホモジナイザーで１分間分散し、粒度分布計（マイクロトラックＦＲＡ型（日機装（株））で測定した。測定時間は、３０秒で２回測定して、５０％の累積径の平均値を平均粒径とした。測定条件は、
粒子の光透過性（Ｔ、Ｐ）；ＹＥＳ
粒子の形状 （Ｓ、Ｐ）；ＮＯ
粒子屈折率 （Ｐｒｉ）；２．２５
分散媒屈折率 （Ｃｒｉ）；１．３７
とした。
6). Measurement of average particle size (50% D) by laser light scattering method Take 1 to 2 cups of silver powder with a microspatella and place in a 100 ml tall beaker, add about 60 ml of isopropyl alcohol, and disperse with an ultrasonic homogenizer for 1 minute. (Measured with a Microtrac FRA type (Nikkiso Co., Ltd.) The measurement time was measured twice in 30 seconds, and the average value of 50% cumulative diameter was defined as the average particle diameter.
Light transmittance of particles (T, P); YES
Particle shape (S, P); NO
Particle refractive index (Pri); 2.25
Dispersion medium refractive index (Cri); 1.37
It was.
７．フレーク状銀粉の平均厚さの測定
銀粉２ｇを水溶性エポキシ樹脂（Ｑｕｅｔｏｌ６５１（日新ＥＭ（株）製））１０ｃｃとよく混合し、６０℃の恒温槽中で１時間３０分静置後、注射器（ニプロシリンジ１ｍｌ（ニプロ（株）製））でサンプルを吸い出し、注射器に入れたまま６０℃の恒温槽中に８時間置いた。硬化した樹脂を、注射器より取り出し、ミクロトームで面出し加工を行い、カーボン蒸着後、電解放射型走査型電子顕微鏡（日立（株）製Ｓ４５００型）で５０００倍又は１００００倍の倍率で写真を撮影し、銀粉の厚みを測定した。測定個数５０個の平均値で表した。
7). Measurement of average thickness of flaky silver powder 2 g of silver powder was mixed well with 10 cc of water-soluble epoxy resin (Quetol 651 (Nisshin EM Co., Ltd.)), left in a constant temperature bath at 60 ° C. for 1 hour and 30 minutes, and then syringe The sample was sucked out with 1 ml of Nipro Syringe (manufactured by Nipro Co., Ltd.) and placed in a constant temperature bath at 60 ° C. for 8 hours while being put in the syringe. Take out the cured resin from the syringe, chamfer the surface with a microtome, and after carbon deposition, take a picture at a magnification of 5000x or 10000x with an electrolytic emission scanning electron microscope (S4500, manufactured by Hitachi, Ltd.). The thickness of the silver powder was measured. It represented with the average value of 50 measurement numbers.
８．比抵抗
１５０℃で３０分間加熱硬化した導電性ペーストのシート抵抗を、４深針抵抗測定器を用いて測定し、シート抵抗と膜厚より比抵抗を算出した。
8). Specific resistance The sheet resistance of the conductive paste heated and cured at 150 ° C. for 30 minutes was measured using a 4 deep needle resistance measuring device, and the specific resistance was calculated from the sheet resistance and film thickness.
９．密着性
ＪＩＳ Ｋ５４００ ６−１５に準じて評価した。粘着テープは、セロハンテープＣＴ−１２（ニチバン（株）製）を用いた。
9. Adhesiveness It evaluated according to JIS K5400 6-15. Cellophane tape CT-12 (manufactured by Nichiban Co., Ltd.) was used as the adhesive tape.
１０．耐屈曲性
厚み１００μｍのアニ−ル処理ポリエステルフィルム上に導電性銀ペーストを線幅０．５ｍｍ、長さ７５ｍｍのパターンをスクリーン印刷し１５０℃／３０分加熱硬化（加熱乾燥）したものを試料とし、荷重５０ｇ／ｃｍ2、Ｒ＝０の条件で同一箇所で３６０°屈曲をくり返し、導体の抵抗値がＫΩオーダーに達するまでの回数で評価した。また、印刷パターンの乾燥膜厚は６〜８μｍで評価した。
10. Bending resistance A conductive silver paste screen-printed with a pattern of 0.5 mm line width and 75 mm length on an annealed polyester film with a thickness of 100 μm and heat-cured (heat-dried) at 150 ° C. for 30 minutes was used as a sample. Then, 360 ° bending was repeated at the same location under the conditions of a load of 50 g / cm 2 and R = 0, and the number of times until the resistance value of the conductor reached the KΩ order was evaluated. The dry film thickness of the printed pattern was evaluated at 6 to 8 μm.
１１．耐コネクター挿抜性
１０と同様に作成したテストピースの裏面に１２５μｍの補強フィルムを粘着したものにコネクターを１０回挿抜を繰り返し、導電ペースト塗膜の剥がれの程度で評価した。
○：剥がれなし
△：わずかに剥離する
×：剥離する
11. Connector Insertion / Removal Resistance The connector was inserted and removed 10 times on the back of a test piece prepared in the same manner as in Example 10 with a 125 μm reinforcing film adhered, and the degree of peeling of the conductive paste coating film was evaluated.
○: No peeling Δ: Slight peeling ×: Peeling
１２．耐マイグレーション性
厚み１００μｍのアニ−ル処理ポリエステルフィルム上に導電性銀ペーストを図１に示す中央に１．５ｍｍのギャップのある線幅２．０ｍｍ、長さ８５．５ｍｍのパターンを、乾燥膜厚が６〜８μｍになるようにスクリーン印刷し１５０℃／３０分加熱硬化（加熱乾燥）したものを試料とした。ついで上記ギャップ間に注射器（ニプロシリンジ１ｍｌ（ニプロ（株）製）で蒸留水０．０４ｍｌをゆるやかに滴下し定電圧電源（高砂製作所（株）製）で１０Ｖ印加し、デジタルマルチメーター（武田理研（株）製）で電流値を測定、電流値が０．１ｍＡになるまでの時間を測定し、５回の測定値の平均値で評価した。数値が大きいほど耐マイグレーション性は良好である。
12 Migration resistance A conductive silver paste on an annealed polyester film having a thickness of 100 μm, a pattern having a line width of 2.0 mm and a length of 85.5 mm with a gap of 1.5 mm in the center shown in FIG. The sample was screen-printed so as to be 6 to 8 μm and heat-cured (heat-dried) at 150 ° C./30 minutes. Next, 0.04 ml of distilled water was gently dropped with a syringe (Nipro syringe 1 ml (Nipro Co., Ltd.)) between the gaps, 10 V was applied with a constant voltage power source (Takasago Seisakusho Co., Ltd.), and a digital multimeter (Takeda Riken) The current value was measured by “Made by Co., Ltd.”, the time until the current value reached 0.1 mA was measured, and the average value of the five measured values was evaluated, and the larger the value, the better the migration resistance.
合成例１（ポリエステル樹脂Ｉ）
グビリュー精留塔を具備した四口フラスコにジメチルテレフタル酸１０１部、ジメチルイソフタル酸３５部、エチレングリコール９３部、ネオペンチルグリコール７３部、テトラブチルチタネート０．０６８部を仕込み、１８０℃、３時間エスエル交換を行なった。ついで、セバシン酸６１部を仕込み、さらにエステル化反応を行なった。次に、１ｍｍＨｇ以下まで徐々に減圧し、２４０℃、１時間重合した。得られた共重合ポリエステルの組成は、テレフタル酸／イソフタル酸／セバシン酸／／エチレングリコール／ネオペンチルグリコール＝５２／１８／３０／／５５／４５（モル比）、数平均分子量２２０００、酸価１．５ｍｇＫＯＨ／ｇ、Ｔｇ７℃であった。結果を表１に示す。
Synthesis example 1 (polyester resin I)
A four-necked flask equipped with a Gubileu fractionator is charged with 101 parts of dimethyl terephthalic acid, 35 parts of dimethyl isophthalic acid, 93 parts of ethylene glycol, 73 parts of neopentyl glycol, 0.068 parts of tetrabutyl titanate, and 180 ° C. for 3 hours. Exchange was performed. Subsequently, 61 parts of sebacic acid was added and esterification was further performed. Next, the pressure was gradually reduced to 1 mmHg or less, and polymerization was performed at 240 ° C. for 1 hour. The composition of the obtained copolyester was terephthalic acid / isophthalic acid / sebacic acid // ethylene glycol / neopentyl glycol = 52/18/30 // 55/45 (molar ratio), number average molecular weight 22000, acid value 1 It was 5 mgKOH / g and Tg7 ° C. The results are shown in Table 1.
合成例２〜４（ポリエステル樹脂II〜IV）
合成例１と同様に合成した。結果を表１に示す。
Synthesis Examples 2 to 4 (Polyester resins II to IV)
Synthesis was performed in the same manner as in Synthesis Example 1. The results are shown in Table 1.
合成例６（ウレタン変性ポリエステル樹脂Ｖ）
温度計、攪拌機、冷却器を具備した反応容器中に合成例のポリエステル樹脂IV１００部、鎖延長剤としてのネオペンチルグリコール３部、溶剤として酢酸エチルカルビトールを仕込み、８０℃で溶解後、ジフェニルメタンジイイソシアネート（ＭＤＩ）１９．４部及びジブチル錫ジラウレート０．０５部を仕込み、固形分濃度５０％、７０〜８０℃で３時間以上かけて残存イソシアネートが無くなるまで反応させた後、酢酸エチルカルビトールで固形分濃度３０％に希釈し、ウレタン変性ポリエステル樹脂Ｖを得た。数平均分子量は２５０００、酸価１．０ｍｇＫＯＨ／ｇ、ガラス転移点温度１５℃であった。
Synthesis Example 6 (urethane-modified polyester resin V)
In a reaction vessel equipped with a thermometer, a stirrer, and a cooler, 100 parts of polyester resin IV of synthesis example, 3 parts of neopentyl glycol as chain extender, ethyl carbitol acetate as a solvent were charged, dissolved at 80 ° C., and then diphenylmethane dii 19.4 parts of isocyanate (MDI) and 0.05 part of dibutyltin dilaurate were added and reacted at a solid concentration of 50% at 70 to 80 ° C. for 3 hours or more until there was no residual isocyanate, and then with ethyl carbitol acetate. Dilution to a solid content concentration of 30% yielded urethane-modified polyester resin V. The number average molecular weight was 25000, the acid value was 1.0 mgKOH / g, and the glass transition temperature was 15 ° C.
銀粉Ａ−１の調整
市販のタップ密度が２．８ｇ／ｃｍ3、比表面積が１．３ｍ2／ｇ、レーザー散乱法による平均粒子径が０．５μｍの球状の銀粉１００重量部、エチレングリコール６０重量部、滑剤としてオレイン酸を０．３重量部添加し直径１ｍｍのジルコニアビーズを用いてダイノーミルＫＤＬ−Ｓｐｅｃｉａｌ型（ＷＩＬＬＹ Ａ．ＢＡＣＨＯＦＥＮ ＡＧ製）を用いてシャフト速度３２００ｒｐｍ、アジテーターディスクの周速１６ｍ／ｓ（ディスク直径９６ｍｍ）で３パスミリングした。ついで、減圧濾過した後にメタノールで洗浄を２回くり返し、８０℃、２４時間減圧乾燥してフレーク状銀粉（Ａ−１）を得た。
得られたフレーク状銀粉の厚みを測定したところ６４０Åであった。また、タップ密度は１．７ｇ／ｃｍ3、比表面積は２．１ｍ2／ｇ、平均粒子径は５．５μｍ、アスペクト比８６であった。形状を図２に示す。
Preparation of silver powder A-1 Commercial tap density of 2.8 g / cm 3 , specific surface area of 1.3 m 2 / g, 100 parts by weight of spherical silver powder having an average particle size of 0.5 μm by laser scattering method, ethylene glycol 60 Parts by weight, 0.3 parts by weight of oleic acid as a lubricant, zirconia beads having a diameter of 1 mm and a dynomill KDL-special type (manufactured by WILLY A. BACHOFE AG), a shaft speed of 3200 rpm, an agitator disk peripheral speed of 16 m / Three pass milling was performed with s (disk diameter 96 mm). Next, after filtration under reduced pressure, washing was repeated twice with methanol, and dried under reduced pressure at 80 ° C. for 24 hours to obtain flaky silver powder (A-1).
The thickness of the obtained flaky silver powder was measured and found to be 640 mm. The tap density was 1.7 g / cm 3 , the specific surface area was 2.1 m 2 / g, the average particle size was 5.5 μm, and the aspect ratio was 86. The shape is shown in FIG.
銀粉Ａ−２の調整
市販のタップ密度が２．８ｇ／ｃｍ3、比表面積が１．３ｍ2／ｇ、レーザー散乱法による平均粒子径が０．１μｍの粒状の銀粉を用いて、銀粉（Ａ−１）と同様にミリング、洗浄、乾燥を行った。ただし、回転速度は２５００ｒｐｍで行った。
得られたフレーク状銀粉（Ａ−２）の厚みを測定したところ１０００Åであった。また、タップ密度は２．２ｇ／ｃｍ3、比表面積は１．８ｍ2／ｇ、平均粒子径は４．０μｍ、アスペクト比４０であった。
Adjustment of Silver Powder A-2 Using a granular silver powder having a commercially available tap density of 2.8 g / cm 3 , a specific surface area of 1.3 m 2 / g and an average particle diameter of 0.1 μm by a laser scattering method, silver powder (A Milling, washing and drying were performed in the same manner as in -1). However, the rotation speed was 2500 rpm.
It was 1000 と こ ろ when the thickness of the obtained flaky silver powder (A-2) was measured. The tap density was 2.2 g / cm 3 , the specific surface area was 1.8 m 2 / g, the average particle diameter was 4.0 μm, and the aspect ratio was 40.
銀粉Ａ−３の調整
市販のフレーク状銀粉（ＡｇＣ−Ａ、福田金属箔粉業（株）製）をそのまま用いた。銀フレークの厚みは１５４０Åであった。レーザー光散乱法による平均粒子径は４．５μｍ、比表面積０．７ｍ2／ｇであり、タップ密度は３．１ｇ／ｃｍ3、アスペクト比２９であった。
Adjustment of silver powder A-3 Commercially available flaky silver powder (AgC-A, manufactured by Fukuda Metal Foil Co., Ltd.) was used as it was. The thickness of the silver flakes was 1540 mm. The average particle diameter measured by the laser light scattering method was 4.5 μm, the specific surface area was 0.7 m 2 / g, the tap density was 3.1 g / cm 3 , and the aspect ratio was 29.
銀粉Ａ−４の調整
市販のフレーク状銀粉（ＳＦ７、フェロジャパン（株）製）をそのまま用いた。銀フレークの厚みは２５２０Åであった。レーザー光散乱法による平均粒子径は６．１μｍ、比表面積０．９４ｍ2／ｇであり、タップ密度は２．８ｇ／ｃｍ3、アスペクト比２４であった。
Adjustment of silver powder A-4 Commercially available flaky silver powder (SF7, manufactured by Ferro Japan Co., Ltd.) was used as it was. The thickness of the silver flakes was 2520 mm. The average particle diameter measured by the laser light scattering method was 6.1 μm, the specific surface area was 0.94 m 2 / g, the tap density was 2.8 g / cm 3 , and the aspect ratio was 24.
銀粉Ａ−５の調整
濃度３７％の硝酸銀水溶液２７５部と濃度１８％の水酸化ナトリウム水溶液２２０部とを４０〜５０℃において攪拌下で反応させ、反応終了後に蒸留水７０部を添加した。ついで、これに濃度２３％のホルマリン水溶液６０部を加え、３０〜４０℃で反応させた。反応終了後のｐＨは８であった。得られた銀粉を濾過し、水洗、脱水を繰り返した後、メタノールで洗浄した上で濾過し、８０℃で２４時間減圧乾燥した。
得られた銀粉は、球状の１次粒子が３次元状に結合した３次元高次構造であり、１次粒子の平均粒子径は走査型電子顕微鏡写真より０．５μｍであり、２次粒子の平均粒子径は光散乱法により測定したところ１１μｍ、比表面積１．６２ｍ2／ｇで、タップ密度は０．８ｇ／ｃｍ3、であった。ただし、この銀粉はフレーク状ではなく３次元高次構造であるので厚みは測定不可である。形状を図３に示す。
Preparation of silver powder A-5 275 parts of a 37% strength aqueous silver nitrate solution and 220 parts of a 18% strength aqueous sodium hydroxide solution were allowed to react at 40 to 50 ° C. with stirring, and 70 parts of distilled water was added after completion of the reaction. Subsequently, 60 parts of a 23% concentration formalin aqueous solution was added thereto and reacted at 30 to 40 ° C. The pH after completion of the reaction was 8. The obtained silver powder was filtered, washed with water and dehydrated repeatedly, then washed with methanol, filtered, and dried under reduced pressure at 80 ° C. for 24 hours.
The obtained silver powder has a three-dimensional higher order structure in which spherical primary particles are three-dimensionally bonded, and the average particle diameter of the primary particles is 0.5 μm from the scanning electron micrograph, The average particle diameter was 11 μm, the specific surface area was 1.62 m 2 / g, and the tap density was 0.8 g / cm 3 as measured by the light scattering method. However, since this silver powder has a three-dimensional higher order structure rather than a flake shape, the thickness cannot be measured. The shape is shown in FIG.
実施例１
銀粉Ａ−１、８１部、塩化ビニル＝酢酸ビニル共重合体としてのＶＡＧＨ（ユニオンカーバイド（株）製）の酢酸エチルカルビトール溶液１６．１固形部、ブロックイソシアネート化合物（ヘキサメチレンジイソシアネートのビウレット３量体のメチルエチルケトオキシムブロック体、固形分８０％）２．９固形部、レべリング剤としてポリフローＳ（共栄社化学（株）製）０．５固形部、硬化触媒としてジブチルチンジラウレート０．０２重量部を配合し、充分プレミックスした後、チルド３本ロール混練り機で、３回通して分散した。得られた銀ペーストは銀粉の配合量が固形分中８１重量％と低いにもかかわらず、比抵抗３．２×１０-5Ω・ｃｍと低抵抗であり、耐屈曲性は１８回で良好であった。また、耐マイグレーション性が従来の銀粉を用いた場合より優れており、表面平滑性が良好であり、耐コネクター挿抜性も良好であった。結果を表２に示す。
Example 1
Silver powder A-1, 81 parts, vinyl chloride = vinyl acetate copolymer VAGH (manufactured by Union Carbide) 16.1 parts ethyl acetate carbitol solution, blocked isocyanate compound (hexamethylene diisocyanate biuret 3 quantity) 2.9 solid parts of methyl ethyl ketoxime block, solid content 80%), 0.5 solid part of polyflow S (manufactured by Kyoeisha Chemical Co., Ltd.) as a leveling agent, 0.02 part by weight of dibutyltin dilaurate as a curing catalyst Was mixed well and pre-mixed, and then dispersed three times with a chilled three-roll kneader. The obtained silver paste has a low specific resistance of 3.2 × 10 −5 Ω · cm and good bending resistance at 18 times, although the amount of silver powder is as low as 81% by weight in the solid content. Met. Further, the migration resistance was superior to the case of using conventional silver powder, the surface smoothness was good, and the connector insertion / extraction resistance was also good. The results are shown in Table 2.
実施例２〜５
実施例１と同様に評価した。結果を表２に示す。
Examples 2-5
Evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.
比較例１〜５
実施例１と同様に作成した。結果を表３に示す。
Comparative Examples 1-5
Prepared in the same manner as in Example 1. The results are shown in Table 3.
実施例１、２は塩化ビニル＝酢酸ビニル共重合体をバインダに用い、銀粉の配合量がそれぞれ８１％、７４％とかなり低い場合の例であるが、いずれも比抵抗は５×１０-5Ω・ｃｍ未満と良好であり、密着性を初め、耐屈曲性、耐マイグレーション性、耐コネクター挿抜性も非常に良好である。これに対して、比較銀粉を用いて同様の銀粉配合量で評価した比較例１、２では、比抵抗が著しく高く使用できない。 Examples 1 and 2 are examples in which vinyl chloride = vinyl acetate copolymer was used as a binder and the amount of silver powder blended was as low as 81% and 74%, respectively, but the specific resistance was 5 × 10 −5 in both cases. It is good at less than Ω · cm, and it has very good bending resistance, migration resistance and connector insertion / removal resistance as well as adhesion. On the other hand, in Comparative Examples 1 and 2 evaluated with the same amount of silver powder using comparative silver powder, the specific resistance is remarkably high and cannot be used.
実施例３、５は本発明の範囲内の銀粉とカーボン系導電粉を併用した例であるが、低い銀配合量においても非常に良好な比抵抗が得られている。この銀粉はカーボン系導電粉との併用が好ましいことが分かる。 Examples 3 and 5 are examples in which silver powder and carbon-based conductive powder within the scope of the present invention are used in combination, but very good specific resistance is obtained even at a low silver blending amount. It can be seen that this silver powder is preferably used in combination with carbon-based conductive powder.
実施例４は本発明の範囲内の銀粉を用いて、硬化剤のない乾燥タイプにした例であるが、
良好な密着性と乾燥タイプとしては良好な耐屈曲性を得ている。その他の物性も非常に良好である。乾燥タイプは１００〜１３０℃の低温乾燥が可能となる。
Example 4 is an example of using a silver powder within the scope of the present invention to make a dry type without a curing agent,
Good adhesion and good bending resistance as a dry type. Other physical properties are also very good. The drying type can be dried at a low temperature of 100 to 130 ° C.
比較例３は比較銀粉と塩化ビニル＝酢酸ビニル共重合体からなる熱硬化型の銀ペーストの例であるが、銀粉の充填量が多いためと思われるが、ＰＥＴフィルムへの密着性に劣り、耐屈曲性、耐マイグレーション性、耐コネクター挿抜性も劣る。 Comparative Example 3 is an example of a thermosetting silver paste composed of comparative silver powder and vinyl chloride = vinyl acetate copolymer, which seems to be due to the large amount of silver powder filled, but has poor adhesion to the PET film, Bending resistance, migration resistance, and connector insertion / extraction are also inferior.
比較例４は比較銀粉とポリエステル樹脂からなり、硬化剤を使用しない乾燥タイプにした例であるが、銀粉の充填量が多いので比較的良好な比抵抗を得ているが、耐屈曲性、耐マイグレーション性、耐コネクター挿抜性に劣る。 Comparative Example 4 is an example of a comparative silver powder and a polyester resin, which is a dry type that does not use a curing agent, but has a relatively good specific resistance because of the large amount of silver powder filled, Poor migration and connector insertion / extraction resistance.
比較例５は３次元高次構造の銀粉をウレタン変性ポリエステルと組み合わせて使用した例であるが、比抵抗がやや高く、同様に諸物性が劣る。 Comparative Example 5 is an example in which silver powder having a three-dimensional higher-order structure is used in combination with urethane-modified polyester, but the specific resistance is slightly high, and various physical properties are similarly inferior.
本発明の導電性ペーストにより、低抵抗で耐屈曲性を大幅に向上でき、さらには優れた耐屈曲性、耐マイグレーション性、耐コネクター挿抜性をも合わせ持つ優れた回路材料を作成することが可能となり、産業界に寄与することが大である。 With the conductive paste of the present invention, it is possible to significantly improve the bending resistance with low resistance, and furthermore, it is possible to create an excellent circuit material that has excellent bending resistance, migration resistance, and connector insertion / removal resistance. It is important to contribute to the industry.
１．ＰＥＴフィルム
２．スクリーン印刷パターン
1. 1. PET film Screen printing pattern
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100101842A1 (en) * | 2008-10-24 | 2010-04-29 | Toyo Boseki Kabushiki Kaisha | Low-temperature curable conductive paste for plating and electric wiring using the same |
| JP2010236039A (en) * | 2009-03-31 | 2010-10-21 | Dowa Electronics Materials Co Ltd | Flaky silver powder, its production method and conductive paste |
| JP2015069877A (en) * | 2013-09-30 | 2015-04-13 | 東洋紡株式会社 | Conductive paste, conductive film and touch panel |
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| JPS58108267A (en) * | 1981-12-17 | 1983-06-28 | イ−・アイ・デユポン・ド・ネモア−ス・アンド・コンパニ− | Screen printable conductive composition |
| JPH01159906A (en) * | 1987-12-14 | 1989-06-22 | Toyobo Co Ltd | Conductive paste |
| JPH05506876A (en) * | 1990-05-02 | 1993-10-07 | アチソン・インダストリーズ・インコーポレイテツド | Highly conductive polymeric thick film composition |
| JP2001261974A (en) * | 2000-03-13 | 2001-09-26 | Hitachi Chem Co Ltd | Paste composition |
| JP2002093238A (en) * | 2000-09-14 | 2002-03-29 | Toyobo Co Ltd | Conductive paste |
| JP2008171828A (en) * | 2008-03-26 | 2008-07-24 | Toyobo Co Ltd | Conductive paste, and printed circuit using it |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS58108267A (en) * | 1981-12-17 | 1983-06-28 | イ−・アイ・デユポン・ド・ネモア−ス・アンド・コンパニ− | Screen printable conductive composition |
| JPH01159906A (en) * | 1987-12-14 | 1989-06-22 | Toyobo Co Ltd | Conductive paste |
| JPH05506876A (en) * | 1990-05-02 | 1993-10-07 | アチソン・インダストリーズ・インコーポレイテツド | Highly conductive polymeric thick film composition |
| JP2001261974A (en) * | 2000-03-13 | 2001-09-26 | Hitachi Chem Co Ltd | Paste composition |
| JP2002093238A (en) * | 2000-09-14 | 2002-03-29 | Toyobo Co Ltd | Conductive paste |
| JP2008171828A (en) * | 2008-03-26 | 2008-07-24 | Toyobo Co Ltd | Conductive paste, and printed circuit using it |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100101842A1 (en) * | 2008-10-24 | 2010-04-29 | Toyo Boseki Kabushiki Kaisha | Low-temperature curable conductive paste for plating and electric wiring using the same |
| JP2010102988A (en) * | 2008-10-24 | 2010-05-06 | Toyobo Co Ltd | Low-temperature curable conductive paste for plating and electric wiring using the same |
| US8986575B2 (en) * | 2008-10-24 | 2015-03-24 | Toyo Boseki Kabushiki Kaisha | Low-temperature curable conductive paste for plating and electric wiring using the same |
| JP2010236039A (en) * | 2009-03-31 | 2010-10-21 | Dowa Electronics Materials Co Ltd | Flaky silver powder, its production method and conductive paste |
| JP2015069877A (en) * | 2013-09-30 | 2015-04-13 | 東洋紡株式会社 | Conductive paste, conductive film and touch panel |
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