JPH03133006A - Silver-copper alloy group conductive paste and conductor using same - Google Patents
Silver-copper alloy group conductive paste and conductor using sameInfo
- Publication number
- JPH03133006A JPH03133006A JP1269026A JP26902689A JPH03133006A JP H03133006 A JPH03133006 A JP H03133006A JP 1269026 A JP1269026 A JP 1269026A JP 26902689 A JP26902689 A JP 26902689A JP H03133006 A JPH03133006 A JP H03133006A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- conductive paste
- copper alloy
- weight
- thermosetting 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
- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 37
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000004020 conductor Substances 0.000 title description 4
- 239000000843 powder Substances 0.000 claims abstract description 47
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 30
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 17
- -1 alkyl dicarboxylic acid Chemical compound 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000853 adhesive Substances 0.000 claims description 5
- 230000001070 adhesive effect Effects 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000007650 screen-printing Methods 0.000 claims description 3
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 32
- 239000004332 silver Substances 0.000 abstract description 32
- 238000013508 migration Methods 0.000 abstract description 15
- 230000005012 migration Effects 0.000 abstract description 14
- 229910052751 metal Inorganic materials 0.000 abstract description 6
- 239000002184 metal Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 32
- 239000003822 epoxy resin Substances 0.000 description 20
- 229920000647 polyepoxide Polymers 0.000 description 20
- 238000000576 coating method Methods 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 11
- 239000005011 phenolic resin Substances 0.000 description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 229920000877 Melamine resin Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004640 Melamine resin Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920003986 novolac Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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
- 239000003990 capacitor Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000001307 helium Substances 0.000 description 3
- 229910052734 helium Inorganic materials 0.000 description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 229920003987 resole Polymers 0.000 description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical class [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000002390 adhesive tape Substances 0.000 description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000001630 malic acid Substances 0.000 description 2
- 235000011090 malic acid Nutrition 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920003217 poly(methylsilsesquioxane) Polymers 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- ZQXCQTAELHSNAT-UHFFFAOYSA-N 1-chloro-3-nitro-5-(trifluoromethyl)benzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC(C(F)(F)F)=C1 ZQXCQTAELHSNAT-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- MBHRHUJRKGNOKX-UHFFFAOYSA-N [(4,6-diamino-1,3,5-triazin-2-yl)amino]methanol Chemical class NC1=NC(N)=NC(NCO)=N1 MBHRHUJRKGNOKX-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229960000448 lactic acid Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229960004708 noscapine Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
本発明は、導電性に優れ、かつ耐酸化性が良く、恨マイ
グレーションに優れた特性を有する銀銅合金糸導電性ペ
ーストに関するものであり、電磁波シールド、ＩＣダイ
ボンディングペースト、コンデンサー用電極、導電性接
着剤、接点材料、導電回路用ペーストとして応用できる
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silver-copper alloy thread conductive paste that has excellent conductivity, good oxidation resistance, and excellent anti-migration properties. It can be used as electromagnetic shielding, IC die bonding paste, capacitor electrodes, conductive adhesives, contact materials, and conductive circuit pastes.
従来、導電性を有する材料として、カーボン、銅、アル
ミニウムや、銅、パラジウム等の貴金属、銀メツキ複合
粉が用いられており、これら導電性の粉末をエポキシ、
フェノール、メラミン、熱硬化性アクリルメラミン樹脂
等の熱硬化性樹脂と溶剤、必要に応じて添加剤を加え分
散させたペーストが公知である。Conventionally, carbon, copper, aluminum, precious metals such as copper and palladium, and silver plating composite powder have been used as conductive materials.
A paste prepared by dispersing a thermosetting resin such as phenol, melamine, or thermosetting acrylic melamine resin, a solvent, and additives as necessary is known.
〔発明が解決しようとする課題］
公知導電性ペーストとして用いられているカーボン、銅
、銀及び貴金属粉末、恨メツキ複合粉は以下の欠点があ
る。銅は安価であるが、酸化により塗膜の導電性が低下
しやすい。また、銀は高価であり、電場中、特に高湿度
下で銀がマイグレーションを起こし絶縁不良を起こしや
すい。銀メツキ粉末は、ペーストとする場合、剥がれが
生じやすく、銀のマイグレーションを完全に防止するに
は至っていない。カーボン粉末を用いたペーストは導電
性が劣るという欠点を有している。[Problems to be Solved by the Invention] Carbon, copper, silver, noble metal powders, and granmetsuki composite powders used as known conductive pastes have the following drawbacks. Copper is inexpensive, but the conductivity of the coating film tends to decrease due to oxidation. Furthermore, silver is expensive and tends to migrate in an electric field, especially under high humidity, resulting in poor insulation. When the silver plating powder is made into a paste, it tends to peel off and cannot completely prevent silver migration. Pastes using carbon powder have the disadvantage of poor electrical conductivity.
本発明は、導電性に優れ、かつ長期にわたり耐酸化性に
優れ、恨マイグレーションを起こさない銀銅合金糸導電
性ペーストとその応用に関するものである。The present invention relates to a silver-copper alloy thread conductive paste that has excellent conductivity, long-term oxidation resistance, and does not cause migration, and its applications.
即ち、本発明は、
１、熱硬化性樹脂と、銀銅合金粉末とからなる導電性ペ
ーストにおいて、銀銅合金粉末９重量部に対して、熱硬
化性樹脂工ないし９重量部を有する銅銀合金系導電性ペ
ースト。That is, the present invention provides the following features: 1. In a conductive paste consisting of a thermosetting resin and a silver-copper alloy powder, a thermosetting resin or a copper-silver alloy having 9 parts by weight based on 9 parts by weight of a silver-copper alloy powder is provided. Alloy-based conductive paste.
２、熱硬化性樹脂と銀銅合金粉末の合計１００重量部に
対して、熱硬化性樹脂の溶剤を５重量部〜１００重量部
含有することを特徴とする導電性ペースト。2. A conductive paste containing 5 to 100 parts by weight of a thermosetting resin solvent based on a total of 100 parts by weight of the thermosetting resin and silver-copper alloy powder.
３、 上記１または２に記載の導電性ペーストに、炭素
数１２以上の脂肪酸あるいはその塩、アルキルジカルボ
ン酸、アラルキルジカルボン酸、オキシカルボン酸、キ
レート形成剤、フェノール化合物の１種以上を前期銀銅
合金粉末１００重量部にたいして０．１〜２５重量部を
含有させたことを特徴とする導電性ペースト。3. Add one or more of a fatty acid having 12 or more carbon atoms or a salt thereof, an alkyl dicarboxylic acid, an aralkyl dicarboxylic acid, an oxycarboxylic acid, a chelate forming agent, or a phenol compound to the conductive paste described in 1 or 2 above. A conductive paste containing 0.1 to 25 parts by weight per 100 parts by weight of alloy powder.
４、 上記１，２または３に記載の導電性ペーストから
なる導電性接着剤。4. A conductive adhesive comprising the conductive paste described in 1, 2 or 3 above.
５、上記１．２または３に記載の導電性ペーストを、加
熱硬化したプリント電子回路用導線。5. A conductive wire for a printed electronic circuit obtained by heating and curing the conductive paste described in 1.2 or 3 above.
６、上記２または３に記載の導電性ペーストからなるス
クリーン印刷用導電性ペースト。6. A conductive paste for screen printing comprising the conductive paste described in 2 or 3 above.
７、 上記２または３に記載の導電性ペーストを加熱硬
化処理した電磁波シールド膜である。7. An electromagnetic shielding film obtained by heating and curing the conductive paste described in 2 or 3 above.
本発明に用いる銀銅合金粉末は、少量の銀（該合金１重
量部中の０．０１〜０．４重量部）を含み、かつ内部か
ら表面に向かって、銀濃度が増加する領域を有し、かつ
表面の銀濃度が平均の銀濃度の２．１倍以上になってい
ることを特徴とするものであり、高い導電性、耐酸化性
、低銀マイグレーション性を有する。The silver-copper alloy powder used in the present invention contains a small amount of silver (0.01 to 0.4 parts by weight per 1 part by weight of the alloy) and has a region where the silver concentration increases from the inside toward the surface. It is characterized in that the surface silver concentration is 2.1 times or more the average silver concentration, and has high electrical conductivity, oxidation resistance, and low silver migration.
本発明で用いる銀銅合金粉末の好ましい範囲は、ＡｇＸ
Ｃｕ＋−ｘ （ただし、Ｘは重量単位で０．０１〜０．
４）で表され、かつ、内部より表面に向けて恨の濃度が
増加する領域を有し、かつ、表面の銀濃度が平均の銀濃
度の２．１倍以上である銀銅合金粉末（以下、銀銅合金
粉末と略記する）であり、その製造方法は、さきに同一
出願人により出願した特開平１２０５５６９号において
詳細に説明されているが、高圧ガスアトマイズ法を用い
るのが好ましい。それによれば、該組成の銀、銅を混合
し、不活性ガス中、るつぼ等で高周波誘導加熱を用いて
融解する。さらに、るつぼ先端より融液を不活性ガス中
へ噴出する。噴出と同時に高圧の不活性ガスを断熱膨張
させて発生した高速気流を融液に向かって噴出してアト
マイズ化し、微粒子を作製する方法等が挙げられる。The preferred range of the silver-copper alloy powder used in the present invention is AgX
Cu+-x (where X is 0.01 to 0.0 in weight unit)
4), and has a region in which the concentration increases from the inside toward the surface, and the silver concentration on the surface is 2.1 times or more than the average silver concentration (hereinafter referred to as silver-copper alloy powder) , abbreviated as silver-copper alloy powder), and its manufacturing method is described in detail in Japanese Patent Laid-Open No. 1205569 previously filed by the same applicant, but it is preferable to use a high-pressure gas atomization method. According to this, silver and copper having the above composition are mixed and melted in a crucible or the like in an inert gas using high frequency induction heating. Furthermore, the melt is jetted into the inert gas from the tip of the crucible. Examples include a method in which a high-speed airflow generated by adiabatically expanding a high-pressure inert gas at the same time as the ejection is ejected toward the melt to atomize it to produce fine particles.
本発明で用いられる銀銅合金粉末の平均粒径は、１〜１
００μｍが好ましく、１００μｍを越えると印刷適正が
悪く、また、１μｍ未満では導電性が劣り、１〜３０μ
ｍがさらに好ましく、５〜１５μｍが最も好ましい。形
状は球状、鱗片状およびそれらの混合物が好ましく、な
かでも、それらの混合物が好ましい。鱗片状粉末の形状
は、径／厚み比が３以上であるのが好ましい。The average particle size of the silver-copper alloy powder used in the present invention is 1 to 1
00 μm is preferable; if it exceeds 100 μm, printing properties are poor; if it is less than 1 μm, conductivity is poor;
m is more preferable, and 5 to 15 μm is most preferable. Preferably, the shape is spherical, scaly, or a mixture thereof, and a mixture thereof is particularly preferable. It is preferable that the shape of the scaly powder has a diameter/thickness ratio of 3 or more.
本発明に用いる熱硬化性樹脂は、エポキシ樹脂、フェノ
ール樹脂、メラミン樹脂、アルキッド樹脂、ポリウレタ
ン樹脂、ポリエステル樹脂、熱硬化性アクリル樹脂及び
それらの変性樹脂の１種以上の組合せがあげられる。中
でもエポキシ樹脂、フェノール樹脂の１種あるいは２種
以上の組合せが好ましい。エポキシ樹脂としては、分子
量３８０〜８０００のビスフェノールＡ型エポキシ樹脂
、ノボラック型エポキシ樹脂、ブロム化ビスフェノール
Ａ型エポキシ樹脂、およびそれらの変性樹脂や樹脂酸変
性エポキシ樹脂などが挙げられる。フェノール樹脂とし
ては、ノボラック型、レゾール型フェノール樹脂、ロジ
ン変性フェノール樹脂を単独あるいはエポキシ樹脂の架
橋剤として用いるのが好ましい。メラミン樹脂としては
、例えばメチロール化メラミンあるいはアルキル化メチ
ロールメラミン樹脂等をエポキシ樹脂の架橋剤して混ぜ
合わせて用いるのが好ましい。エポキシ樹脂の熱硬化剤
としては、上述の樹脂、有機ポリアミン、酸無水物、ジ
シアンジアミド、三弗化はう素などの公知の硬化剤など
が用いられる。The thermosetting resin used in the present invention includes one or more combinations of epoxy resin, phenol resin, melamine resin, alkyd resin, polyurethane resin, polyester resin, thermosetting acrylic resin, and modified resins thereof. Among these, one type or a combination of two or more of epoxy resins and phenol resins are preferred. Examples of the epoxy resin include bisphenol A type epoxy resins, novolak type epoxy resins, brominated bisphenol A type epoxy resins, modified resins thereof, and acid-modified epoxy resins having a molecular weight of 380 to 8000. As the phenol resin, it is preferable to use a novolac type phenol resin, a resol type phenol resin, or a rosin-modified phenol resin alone or as a crosslinking agent for an epoxy resin. As the melamine resin, it is preferable to use, for example, methylolated melamine or alkylated methylolmelamine resin as a crosslinking agent for the epoxy resin. As the thermosetting agent for the epoxy resin, the above-mentioned resins, organic polyamines, acid anhydrides, dicyandiamide, fluorine trifluoride, and other known curing agents are used.
本発明の銀銅合金系導電性ペーストは、銀銅合金粉末／
熱硬化性樹脂の重量比が１〜９であり、好ましくは３〜
８である。９を越える場合は塗膜中の導電性金属粉末を
結合させておくに充分な樹脂量がなく、導電性、機械的
強度を低下させる。The silver-copper alloy-based conductive paste of the present invention comprises silver-copper alloy powder/
The weight ratio of the thermosetting resin is 1 to 9, preferably 3 to 9.
It is 8. If it exceeds 9, there is not enough resin to bind the conductive metal powder in the coating, resulting in a decrease in conductivity and mechanical strength.
また、１未満では、導電性金属分の量が足りず充分な導
電性が得られない。さらに、熱硬化性樹脂の溶剤を銀銅
合金粉末と熱硬化性樹脂の合計１００重量部に対して５
〜１００重量部を含有することが好ましい。Further, if it is less than 1, the amount of conductive metal is insufficient and sufficient conductivity cannot be obtained. Furthermore, add 5 parts by weight of the thermosetting resin solvent to 100 parts by weight of the silver-copper alloy powder and the thermosetting resin.
It is preferable to contain up to 100 parts by weight.
本発明で用いる熱硬化性樹脂の溶剤は、公知の溶剤で構
わない。例えばトルエン、キシレンなどの芳香族溶剤、
メチルエチルケトン、メチルイソブチルケトン、酢酸ブ
チル、ブチルセロソルブ、エチルセロソルブ、ブチルカ
ルピトール、ブチルカルピトールアセテート、α−テル
ベノール、イソプロパツール等を１種以上含むものなど
が好ましり、ｖＡ銅合金粉末と熱硬化性樹脂合計１００
重量部に対して５〜１００重量部を含有させる。含有量
が１００重量部を超える場合は印刷ににじみ等が生じ導
電性を損ね、また、５重量部未満の場合には粘度が高す
ぎて印刷適性を向上する効果が少ない。１０〜３０重量
部が好ましい。The solvent for the thermosetting resin used in the present invention may be any known solvent. For example, aromatic solvents such as toluene and xylene,
Preferably, those containing one or more of methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, butyl cellosolve, ethyl cellosolve, butyl carpitol, butyl carpitol acetate, α-terbenol, isopropanol, etc., and vA copper alloy powder and thermosetting. Total resin: 100
It is contained in an amount of 5 to 100 parts by weight. When the content exceeds 100 parts by weight, bleeding occurs in printing and impairs conductivity, and when the content is less than 5 parts by weight, the viscosity is too high and there is little effect in improving printability. 10 to 30 parts by weight is preferred.
本発明の導電性ペースト中の銀銅合金粉末の分散性を向
上させるため、粉末表面の銅酸化物を除去あるいは還元
するなどのため添加剤を加えても良い。In order to improve the dispersibility of the silver-copper alloy powder in the conductive paste of the present invention, additives may be added to remove or reduce copper oxides on the powder surface.
本発明に用いる添加剤としては、銅酸化物の還元剤、溶
解剤など銅粉末の公知な添加剤が用いられる。特に炭素
数１０以上、好ましくは炭素数１６〜１８の飽和あるい
は不飽和脂肪酸及びそれらの金属塩、オキシカルボン酸
（例えばりんご酸、グルコース酸、グリセリン酸、乳酸
、酒石酸、クエン酸、マンデル酸、サリチル酸）、銅金
属キレート形成剤、或はハイドロキノン、ピロカテコー
ル、フェノール及びその誘導体などのフェノール化合物
が好ましい。添加量としては、銀銅合金粉末１００重量
部に対して０．１〜２５重量部が必要である。添加量が
２５重量部を超える場合には導電体の特性に悪影響がで
き、また、０．１重量部未満では、効果が充分でない。As the additives used in the present invention, known additives for copper powder such as copper oxide reducing agents and dissolving agents are used. In particular, saturated or unsaturated fatty acids having 10 or more carbon atoms, preferably 16 to 18 carbon atoms, and their metal salts, oxycarboxylic acids (e.g. malic acid, glucose acid, glyceric acid, lactic acid, tartaric acid, citric acid, mandelic acid, salicylic acid) ), copper metal chelating agents, or phenolic compounds such as hydroquinone, pyrocatechol, phenol and its derivatives are preferred. The amount added is 0.1 to 25 parts by weight per 100 parts by weight of silver-copper alloy powder. If the amount added exceeds 25 parts by weight, the properties of the conductor may be adversely affected, and if it is less than 0.1 part by weight, the effect is not sufficient.
好ましくは２〜１０重量部であり、さらに２〜５重量部
が好ましい。Preferably it is 2 to 10 parts by weight, and more preferably 2 to 5 parts by weight.
本発明の導電性ペーストに用いる銀銅合金粉末は、粉体
表面に銀が多量に濃縮されているため高い導電性を有す
ると考えているが、前述の添加剤を加えることで分散性
さらには導電性を向上できる効果がある。It is believed that the silver-copper alloy powder used in the conductive paste of the present invention has high conductivity because a large amount of silver is concentrated on the powder surface, but by adding the above-mentioned additives, the dispersibility and It has the effect of improving conductivity.
本発明の導電性ペーストは、電子回路用等の導電性材料
として有用である。例えば、電子回路素子へのあるいは
素子間の導線、ＩＣダイポンディング、抵抗体、コンデ
ンサー等の素子の電極、導電性接着剤、電磁波シールド
膜等が好適な用途例である。The conductive paste of the present invention is useful as a conductive material for electronic circuits and the like. For example, suitable applications include conductive wires to or between electronic circuit elements, IC die bonding, electrodes of elements such as resistors and capacitors, conductive adhesives, and electromagnetic shielding films.
本発明の導電性ペーストを電子回路、電子機器などに適
用する方法としては、スクリーン印刷、スプレー法、刷
毛、バーコード法などの印刷、塗布法などの公知な方法
でよい。さらに、加熱して、熱硬化性樹脂を硬化させる
のが好ましい。加熱温度は熱硬化性樹脂の公知の加熱硬
化温度を適用できる。熱硬化性樹脂の硬化剤はあらかじ
め熱硬化性樹脂に混合しておいても良いしく−液性熱硬
化性樹脂）、熱硬化のさいに加えても良い（二液性熱硬
化性樹脂）。As a method for applying the conductive paste of the present invention to electronic circuits, electronic devices, etc., known methods such as screen printing, spraying, brushing, barcode printing, coating, and other methods may be used. Furthermore, it is preferable to heat the thermosetting resin to harden it. As the heating temperature, a known heating curing temperature for thermosetting resins can be applied. The curing agent for the thermosetting resin may be mixed with the thermosetting resin in advance (liquid thermosetting resin), or may be added during thermosetting (two-component thermosetting resin).
（実施例） 以下に実施例を示す。(Example) Examples are shown below.
実施例１
銀粉（高純度化学製、純度：９９．９％以上）５ｇと銅
粉（高純度化学製、純度： ９９．９％以上）６３ｇと
を黒鉛るつぼにいれ、高周波誘導加熱でヘリウム雰囲気
中１，３００°Ｃで溶解した。融解後、ヘリウム雰囲気
中にるつぼ先端に取り付けたノズルより融液を噴出した
。この時、融液に対してヘリウムガス１００ Ｋ／Ｇを
ガスノズルより断熱膨張させ発生した高速ガス（ガス線
速度２００ｍ／秒）を噴出し、急冷凝固した（ガス質量
速度／融液質量速度＝４５）。Example 1 5 g of silver powder (manufactured by Kojundo Kagaku, purity: 99.9% or more) and 63 g of copper powder (manufactured by Kojundo Kagaku, purity: 99.9% or more) were placed in a graphite crucible, and heated in a helium atmosphere by high-frequency induction heating. It was dissolved at 1,300°C. After melting, the melt was spouted into a helium atmosphere from a nozzle attached to the tip of the crucible. At this time, high-speed gas (gas linear velocity 200 m/s) generated by adiabatically expanding helium gas 100 K/G from a gas nozzle was ejected against the melt, and the melt was rapidly solidified (gas mass velocity/melt mass velocity = 45 ).
生成した粉末は、走査型電子顕微鏡で１００個の粒子の
平均径より求めると、平均径は３０μｍの球状粉であっ
た。そのうち１０μｍ以下の球状粉を分級し、ボールミ
ル中１０戒のミネラルスピリットを加えて、ステンレス
球（１０ｍｍ）１００個とともに粉砕した。得られた粉
末を同様に走査型電子顕微鏡で観測したところ、平均長
径３０μｍ、平均厚さ１．５μｍの鱗片状銀銅合金粉末
であった。The produced powder was found to be a spherical powder with an average diameter of 30 μm, as determined from the average diameter of 100 particles using a scanning electron microscope. Among them, spherical powder with a diameter of 10 μm or less was classified, and mineral spirit of 10 precepts was added in a ball mill, and the powder was ground together with 100 stainless steel balls (10 mm). When the obtained powder was similarly observed with a scanning electron microscope, it was found to be a scaly silver-copper alloy powder with an average major axis of 30 μm and an average thickness of 1.5 μm.
粉末の表面の銀、銅の組成比をＸＰＳ （Ｘ線光電子
分析装置、ＸＳＡＭ８００、クラトス社製）を用いて下
記要領で測定した。The composition ratio of silver and copper on the surface of the powder was measured using XPS (X-ray photoelectron spectrometer, XSAM800, manufactured by Kratos) in the following manner.
試料：試料台に両面接着テープをはりつけ、試料粉末を
両面接着テープ上を完全に覆うようにイ」着させた。Sample: A double-sided adhesive tape was attached to the sample stand, and the sample powder was applied so as to completely cover the double-sided adhesive tape.
エツチング条件：アルゴンイオンガンを加速電圧３ ｋ
ｅＶで用い、アルゴンイオンビームの試料面に対する入
射各４５度、室内圧力１０−’ｔｏｒｒで毎回１０分間
行った。Etching conditions: Acceleration voltage of argon ion gun 3K
eV, the argon ion beam was incident at 45 degrees on the sample surface, and the chamber pressure was 10-'torr for 10 minutes each time.
銀濃度の測定条件：マグネシウムのにα線（電圧１２ｋ
ｖ、電流１０ｍＡ）を入射させ、光電子の取り出し角は
試料面に対し９０度、室内圧力１０−８Ｌｏｒｒで行っ
た。銀濃度の測定はエンチング、ついで４１１定を５回
繰り返し、最初の２回の測定の平均値を表面の銀濃度と
した。Measurement conditions for silver concentration: alpha rays of magnesium (voltage 12k)
(V, current 10 mA), the photoelectron extraction angle was 90 degrees with respect to the sample surface, and the room pressure was 10 −8 Lorr. The silver concentration was measured by enching and then by repeating 411 constant five times, and the average value of the first two measurements was taken as the surface silver concentration.
平均の銀濃度の測定は、試料を濃硝酸中で溶解し、ＩＣ
Ｐ （高周波誘導型プラズマ発光分析計）を用いて測
定した。To measure the average silver concentration, the sample was dissolved in concentrated nitric acid and the IC
Measured using P (high frequency induction type plasma emission spectrometer).
ＸＰＳを用いた測定の結果、測定値へｇ／ （Ａｇ ＋
Ｃｕ）（原子比）は表面より内部に向かって０．４．
０．３４゜０．３１．０．２７．０．２２であり、表面
の銀濃度は定義により最初のふたつの測定値の平均値０
．３７であった。As a result of measurement using XPS, the measured value is g/ (Ag +
Cu) (atomic ratio) is 0.4 from the surface toward the inside.
0.34°0.31.0.27.0.22, and the surface silver concentration is, by definition, the average value of the first two measurements, 0.
．． It was 37.
ＩＣＰで測定した平均の銀濃度は０．０４８であり、表
面の銀濃度は平均銀濃度の８．３倍であった。The average silver concentration measured by ICP was 0.048, and the surface silver concentration was 8.3 times the average silver concentration.
上記で得られた鱗片状銀銅合金粉末５ｇ、レヅール型フ
ェノール樹脂２ｇ及びブチルカルピトールアセテート２
ｇを良く練り合わせペースト状とした。得られたペース
トをガラス・エポキシ樹脂基板上へ幅１０鵬、長さ３０
ｍｍの塗膜を作製し、１６０°Ｃ，１時間加熱硬化した
（膜厚２０μｍ）。硬化膜の抵抗率は、４Ｘ１０−’Ω
・ｃｍであった。また、温度４０°Ｃ５湿度９５％中に
、ｔ 、 ｏｏｏ時間放置後の抵抗率は、殆ど変化がな
っかた。また、銀のマイグレーションを測定するために
、膜間１ ＋ｎｍの２本の塗膜（幅ｌＯ胴、長さ３０世
）を作製した。塗膜間に０．２ ｍｌの純水を滴下し、
電位差３■を印可し、電流計で銀の移行現象を測定した
。１時間経過後の電流値は２ｇ八未満と殆ど認められな
かった。5 g of scaly silver-copper alloy powder obtained above, 2 g of rezul type phenol resin and 2 g of butyl carpitol acetate
g was well kneaded to form a paste. The resulting paste was spread onto a glass/epoxy resin substrate with a width of 10 mm and a length of 30 mm.
A coating film of mm thickness was prepared and cured by heating at 160°C for 1 hour (film thickness: 20 μm). The resistivity of the cured film is 4X10-'Ω
・It was cm. Further, the resistivity after being left for t,ooo hours at a temperature of 40° C. and a humidity of 95% hardly changed. In addition, in order to measure the migration of silver, two coating films (width 10 mm, length 30 cm) with a film spacing of 1 + nm were prepared. Drop 0.2 ml of pure water between the coatings,
A potential difference of 3 cm was applied, and the silver migration phenomenon was measured with an ammeter. The current value after 1 hour was less than 2g8, which was hardly noticeable.
実施例２
実施例１で得られた鱗片状銀銅合金１５〕末５ｇ、エポ
キシ樹脂１ｇ、メラミン樹脂１．２ｇ、メチルエチルケ
トンＩｇ及びブチルカルピトールアセテート１ｇを混合
した後、リルン酸０．２ｇを添加し、よく練り合わせペ
ースト化した。作製したペーストを実施例１と同様に、
ガラス・エポキシ樹脂基板上へ幅１０ｍｍ、長さ３０ｍ
ｍの膜を作製し、１６０°Ｃ１１時間空気中で加熱硬化
した（膜厚１８μｍ）。硬化膜の抵抗率は、３Ｘ１０−
’Ω・ｃｍであり、温度４０°Ｃ，湿度９５％中に１
、０００時間放置しても抵抗率変化は殆どなかった。実
施例１と同様に銀のマイグレーションを測定するために
膜間１０の２木の塗膜を作製した。０．２１成の純水を
塗膜間に滴下し、電位差３Ｖを印可し、電流計で銀のマ
イグレーションを測定したところ１時間後の電流値は２
ｇ八未満であった。Example 2 After mixing 5 g of flaky silver-copper alloy 15 obtained in Example 1, 1 g of epoxy resin, 1.2 g of melamine resin, 1 g of methyl ethyl ketone Ig and 1 g of butyl carpitol acetate, 0.2 g of lylunic acid was added. Then, knead it well to make a paste. The prepared paste was prepared in the same manner as in Example 1,
Width 10mm, length 30m onto glass/epoxy resin substrate
A film of m was prepared and cured by heating in air at 160° C. for 11 hours (film thickness: 18 μm). The resistivity of the cured film is 3X10-
'Ω・cm, and 1 at a temperature of 40°C and a humidity of 95%.
There was almost no change in resistivity even after being left for ,000 hours. In the same manner as in Example 1, two wood coatings with a film gap of 10 were prepared in order to measure silver migration. 0.21 pure water was dropped between the coating films, a potential difference of 3V was applied, and silver migration was measured with an ammeter.The current value after 1 hour was 2.
It was less than g8.
実施例３
実施例１で得られた鱗片状銀銅合金粉末５ｇ、ノボラッ
ク型フェノール樹脂１ｇ、エポキシ樹脂１ｇ１ブチルセ
ロソルブ２ｇ及びリンゴ酸０．１５ｇを良く練り合わせ
ペースト化した。得られたペーストをガラス・エポキシ
樹脂基板上へ実施例１と同様に塗布し、１５０“Ｃ１２
時間加熱硬化した（硬化膜厚２５μｍ）。硬化膜の抵抗
率は２Ｘ１０−’Ω・ｃｍであった。また、温度４０°
Ｃ１湿度９５％中に１ 、０００時間放置後の抵抗率は
殆ど変化がなかった。Example 3 5 g of the flaky silver-copper alloy powder obtained in Example 1, 1 g of novolac type phenol resin, 1 g of epoxy resin, 2 g of butyl cellosolve, and 0.15 g of malic acid were thoroughly kneaded to form a paste. The obtained paste was applied onto a glass epoxy resin substrate in the same manner as in Example 1, and a 150"C12
It was cured by heating for hours (cured film thickness: 25 μm). The resistivity of the cured film was 2×10 −′Ω·cm. Also, the temperature is 40°
There was almost no change in resistivity after being left in C1 humidity of 95% for 1,000 hours.
さらに、実施例１と同様に銀のマイグレーションを測定
したところ、１時間後の電流値は２μＡ未満と殆ど観測
されなかった。Furthermore, when silver migration was measured in the same manner as in Example 1, the current value after 1 hour was less than 2 μA, which was hardly observed.
実施例４
実施例１で得られた鱗片状銀銅合金粉末５ｇ、エポキシ
樹脂２ｇ１ジシアンジアミド０．２ｇ、ブチルカルピト
ールアセテート２ｇ及びオレイン酸０．３ｇをよく練り
合わせペースト化し、実施例１と同様に塗膜を作製し、
１４０°Ｃ１３０分間加熱硬化した（膜厚２０μｍ）ｏ
硬化膜の抵抗率は、６ Ｘ １０−’Ω・ｃｍであった
。また、温度４０°Ｃ１湿度９５％中に１．０００時間
放置後の抵抗率は殆ど変化がなかった。さらに、恨のマ
イグレーション試験を同様の方法でおこなったところ、
１時間後の電流値は２ｇ八未満であった。Example 4 5 g of the flaky silver-copper alloy powder obtained in Example 1, 2 g of epoxy resin, 0.2 g of dicyandiamide, 2 g of butylcarpitol acetate, and 0.3 g of oleic acid were thoroughly kneaded to form a paste, and coated in the same manner as in Example 1. Create a membrane,
Cured by heating at 140°C for 130 minutes (film thickness 20 μm) o
The resistivity of the cured film was 6 x 10-'Ω·cm. Moreover, there was almost no change in resistivity after being left at a temperature of 40° C. and a humidity of 95% for 1,000 hours. Furthermore, when we conducted a grudge migration test using the same method, we found that
The current value after 1 hour was less than 2g8.
実施例５
実施例１で得られた鱗片状銀銅合金粉末５ｇ、ノボラッ
ク型フェノール樹脂２ｇ、ブチルカルピトール２ｇ及び
ヘキサメチレンテトラミン０．５ｇをよく練り合わせペ
ースト化した。実施例１と同様に塗膜を作製し、１５０
°Ｃ１１時間加熱硬化した（膜厚２３μｍ）。硬化膜の
抵抗率は４．５ Ｘｌ０−’Ω・印であり、また温度４
０°Ｃ１湿度９５％中に１ 、０００時間放置後の抵抗
率は殆ど変化がなかった。Example 5 5 g of the flaky silver-copper alloy powder obtained in Example 1, 2 g of novolac type phenol resin, 2 g of butylcarpitol, and 0.5 g of hexamethylenetetramine were thoroughly kneaded to form a paste. A coating film was prepared in the same manner as in Example 1, and 150
The film was cured by heating at °C for 11 hours (film thickness: 23 μm). The resistivity of the cured film is 4.5
After being left at 0°C and 95% humidity for 1,000 hours, there was almost no change in resistivity.
さらに、銀のマイグレーション試験を実施例１と同様に
しておこなったところ電流値は２ｇ八未満であった。Furthermore, when a silver migration test was conducted in the same manner as in Example 1, the current value was less than 2g8.
比較例１
市販の電解銅粉末（〜１５μｍ、樹木状）５ｇ、レゾー
ル型フェノール樹脂２ｇ及びブチルカルピトールアセテ
ート２ｇをよく練り合わせペースト化した。得られたペ
ーストをガラス・エポキシ樹脂基板上べ幅１０離、長さ
３０唾の塗膜を作製し、１６０°Ｃ１１時間加熱硬化し
た（膜厚２０μｍ）。硬化膜の抵抗率は５ＸＩＯ−３Ω
・ｃｍであった。また、温度４０°Ｃ，湿度９５％中に
１，０００時間放置後の抵抗率は８Ｘ１０−’Ω・ｃｍ
と６０％近く抵抗率が増加していた。Comparative Example 1 5 g of commercially available electrolytic copper powder (~15 μm, tree-like), 2 g of resol type phenol resin, and 2 g of butyl carpitol acetate were thoroughly kneaded to form a paste. A coating film with a width of 10 cm and a length of 30 cm was prepared from the obtained paste on a glass epoxy resin substrate, and the film was cured by heating at 160° C. for 11 hours (film thickness: 20 μm). The resistivity of the cured film is 5XIO-3Ω
・It was cm. In addition, the resistivity after being left for 1,000 hours at a temperature of 40°C and a humidity of 95% is 8X10-'Ω・cm.
The resistivity increased by nearly 60%.
比較例２
市販の銀粉末（平均５μｍ）５ｇ、レゾール型フェノー
ル樹脂２ｇ及びブチルカルピトールアセテート２ｇをよ
く練り合わせペースト化した。得られたペーストをガラ
ス・エポキシ樹脂基板上八幡１０ｍｍ、長さ３０１０ｍ
の塗膜を作製し、１６０°Ｃ１１時間加熱硬化した（膜
厚２５μｍ）。硬化膜の抵抗率はｌＸｌ０−’Ω・ｃｍ
であった。また、銀のマイグレーシン試験をしたところ
、薬５分間で電流値が１００ｍＡを越え、恨のマイグレ
ーションが観測された。Comparative Example 2 5 g of commercially available silver powder (5 μm on average), 2 g of resol type phenol resin, and 2 g of butylcarpitol acetate were thoroughly kneaded to form a paste. The resulting paste was placed on a glass epoxy resin substrate with a thickness of 10 mm and a length of 3010 m.
A coating film was prepared and cured by heating at 160°C for 11 hours (film thickness: 25 μm). The resistivity of the cured film is lXl0-'Ω・cm
Met. In addition, when a silver migracin test was conducted, the current value exceeded 100 mA in 5 minutes, and significant migration was observed.
比較例３
実施例１で得られた鱗片状銀銅合金粉末５ｇ、エポキシ
樹脂０．２ｇ、ジシアンジアミｌ”０．０２ｇ及びプチ
ルカルビトールアテテート０．２ｇを良く練り合わせペ
ースト化した。実施例１と同様に塗膜化し、１６０ ”
Ｃ１１時間加熱硬化した。硬化膜は表面が粗く、簡単に
膜が剥がれてしまった。Comparative Example 3 5 g of the scaly silver-copper alloy powder obtained in Example 1, 0.2 g of epoxy resin, 0.02 g of dicyandiamyl and 0.2 g of butylcarbitol atetate were well kneaded to form a paste. Similarly, it was made into a coating film and 160"
C. Heat curing was performed for 11 hours. The cured film had a rough surface and peeled off easily.
比較例４
実施例１で得られた鱗片状銀銅合金粉末５ｇ、エポキシ
樹脂２ｇ及びブチルカルピトールアセテートＬｏｇを練
り合わせペースト化した。実施例１と同様に塗膜を作製
し、１６０°Ｃで１時間加熱硬化した。硬化時にペース
トのにしめが生し、また、導電性も４ Ｘ １０−”Ω
・Ｃｌ１１と高かった。Comparative Example 4 5 g of the flaky silver-copper alloy powder obtained in Example 1, 2 g of epoxy resin, and butylcarpitol acetate Log were kneaded to form a paste. A coating film was prepared in the same manner as in Example 1 and cured by heating at 160°C for 1 hour. The paste wrinkles when hardened, and the conductivity is 4 x 10-”Ω.
・Cl was as high as 11.
比較例５
実施例１で得られた鱗片状銀銅合金粉末５ｇ、エポキシ
樹脂１０ｇ及びブチルカルピトールアセテート２ｇを練
り合わせペースト化化した。実施例１と同様に塗膜化し
、１６０°Ｃ，１時間加熱硬化した（膜厚２５μｍ）。Comparative Example 5 5 g of the flaky silver-copper alloy powder obtained in Example 1, 10 g of epoxy resin, and 2 g of butylcarpitol acetate were kneaded together to form a paste. A film was formed in the same manner as in Example 1, and cured by heating at 160°C for 1 hour (film thickness: 25 μm).
硬化膜の抵抗率はｌＸｌ０−１Ω・印と高かった。The resistivity of the cured film was as high as lXl0-1Ω.
［発明の効果］
本発明は、導電性が高く、耐酸化性に優れ、根のマイグ
レーションがない銀銅合金系導電性ペーストを提供する
ものであり、電磁波シールド、ＩＣグイボンディング、
コンデンサー電極、導電性接着剤、接点材料、導電回路
用ペースト等として応用できる。[Effects of the Invention] The present invention provides a silver-copper alloy-based conductive paste that has high conductivity, excellent oxidation resistance, and no root migration, and is useful for electromagnetic shielding, IC Gui bonding,
It can be used as capacitor electrodes, conductive adhesives, contact materials, pastes for conductive circuits, etc.
Claims (7)
ーストにおいて、銀銅合金粉末９重量部に対して、熱硬
化性樹脂１ないし９重量部を有する銅銀合金系導電性ペ
ースト。1. A conductive paste comprising a thermosetting resin and a silver-copper alloy powder, wherein the copper-silver alloy-based conductive paste contains 1 to 9 parts by weight of the thermosetting resin to 9 parts by weight of the silver-copper alloy powder.
対して、熱硬化性樹脂の溶剤５重量部〜１００重量部を
含有することを特徴とする導電性ペースト。2. A conductive paste characterized by containing 5 to 100 parts by weight of a thermosetting resin solvent to a total of 100 parts by weight of the thermosetting resin and silver-copper alloy powder.
ーストに、炭素数１２以上の脂肪酸あるいはその塩、ア
ルキルジカルボン酸、アラルキルジカルボン酸、オキシ
カルボン酸、キレート形成剤、フェノール化合物の１種
以上を銀銅合金粉末１００重量部にたいして０．１〜２
５重量部を含有させたことを特徴とする導電性ペースト
。3. The conductive paste according to claim 1 or 2 contains one or more of a fatty acid having 12 or more carbon atoms or a salt thereof, an alkyl dicarboxylic acid, an aralkyl dicarboxylic acid, an oxycarboxylic acid, a chelate forming agent, and a phenol compound. 0.1 to 2 parts by weight per 100 parts by weight of silver-copper alloy powder
A conductive paste characterized by containing 5 parts by weight.
ーストからなる導電性接着剤。4. A conductive adhesive comprising the conductive paste according to claim 1, 2 or 3.
ーストを、加熱硬化したプリント電子回路用導線。5. A conductive wire for a printed electronic circuit obtained by heating and curing the conductive paste according to claim 1, 2 or 3.
ストからなるスクリーン印刷用導電性ペースト。6. A conductive paste for screen printing comprising the conductive paste according to claim 2 or 3.
ストを加熱硬化処理した電磁波シールド膜。7. An electromagnetic shielding film obtained by heating and curing the conductive paste according to claim 2 or 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1269026A JPH03133006A (en) | 1989-10-18 | 1989-10-18 | Silver-copper alloy group conductive paste and conductor using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1269026A JPH03133006A (en) | 1989-10-18 | 1989-10-18 | Silver-copper alloy group conductive paste and conductor using same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03133006A true JPH03133006A (en) | 1991-06-06 |
Family
ID=17466643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1269026A Pending JPH03133006A (en) | 1989-10-18 | 1989-10-18 | Silver-copper alloy group conductive paste and conductor using same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03133006A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0762274A (en) * | 1993-08-25 | 1995-03-07 | Tatsuta Electric Wire & Cable Co Ltd | Electrically conductive coating having high adhesivity to formed metal oxide |
| WO2007040195A1 (en) * | 2005-10-03 | 2007-04-12 | Mitsui Mining & Smelting Co., Ltd. | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder |
-
1989
- 1989-10-18 JP JP1269026A patent/JPH03133006A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0762274A (en) * | 1993-08-25 | 1995-03-07 | Tatsuta Electric Wire & Cable Co Ltd | Electrically conductive coating having high adhesivity to formed metal oxide |
| WO2007040195A1 (en) * | 2005-10-03 | 2007-04-12 | Mitsui Mining & Smelting Co., Ltd. | Silver-copper composite powder having silver microparticule attached thereto, and method of production of the silver-copper composite powder |
| JP2007100155A (en) * | 2005-10-03 | 2007-04-19 | Mitsui Mining & Smelting Co Ltd | Silver nanoparticle-adhered silver-copper composite powder and method for producing the silver nanoparticle-adhered silver-copper composite powder |
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