JP6509770B2 - Conductive metal powder paste - Google Patents
Conductive metal powder paste Download PDFInfo
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- JP6509770B2 JP6509770B2 JP2016073343A JP2016073343A JP6509770B2 JP 6509770 B2 JP6509770 B2 JP 6509770B2 JP 2016073343 A JP2016073343 A JP 2016073343A JP 2016073343 A JP2016073343 A JP 2016073343A JP 6509770 B2 JP6509770 B2 JP 6509770B2
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- 239000000843 powder Substances 0.000 title claims description 50
- 239000002184 metal Substances 0.000 title claims description 49
- 229910052751 metal Inorganic materials 0.000 title claims description 49
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 47
- -1 halide ion Chemical class 0.000 claims description 37
- 239000011347 resin Substances 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 26
- 238000000576 coating method Methods 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 24
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 125000003884 phenylalkyl group Chemical group 0.000 claims description 17
- 125000001624 naphthyl group Chemical group 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 125000003342 alkenyl group Chemical group 0.000 claims description 15
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 15
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 15
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims description 14
- 238000010304 firing Methods 0.000 claims description 8
- 150000001450 anions Chemical class 0.000 claims description 7
- 230000009477 glass transition Effects 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 239000011354 acetal resin Substances 0.000 claims description 4
- 229920006324 polyoxymethylene Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 229920006397 acrylic thermoplastic Polymers 0.000 claims description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003275 alpha amino acid group Chemical group 0.000 claims 1
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims 1
- 239000010949 copper Substances 0.000 description 26
- 229910052802 copper Inorganic materials 0.000 description 25
- 150000001412 amines Chemical class 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 239000000945 filler Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000010419 fine particle Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical group CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical group C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 2
- QDZOFZFDBDYWJX-UHFFFAOYSA-N 2-ethoxy-n-(2-ethoxyethyl)ethanamine Chemical group CCOCCNCCOCC QDZOFZFDBDYWJX-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical group C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 229920000084 Gum arabic Polymers 0.000 description 2
- 241000978776 Senegalia senegal Species 0.000 description 2
- 239000000205 acacia gum Substances 0.000 description 2
- 235000010489 acacia gum Nutrition 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 2
- 239000002826 coolant Substances 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003966 growth inhibitor Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- MXYATHGRPJZBNA-KRFUXDQASA-N isopimaric acid Chemical compound [C@H]1([C@](CCC2)(C)C(O)=O)[C@@]2(C)[C@H]2CC[C@@](C=C)(C)CC2=CC1 MXYATHGRPJZBNA-KRFUXDQASA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical group C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- MHVJRKBZMUDEEV-UHFFFAOYSA-N (-)-ent-pimara-8(14),15-dien-19-oic acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)C=C1CC2 MHVJRKBZMUDEEV-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical compound CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 1
- MXYATHGRPJZBNA-UHFFFAOYSA-N 4-epi-isopimaric acid Natural products C1CCC(C(O)=O)(C)C2C1(C)C1CCC(C=C)(C)CC1=CC2 MXYATHGRPJZBNA-UHFFFAOYSA-N 0.000 description 1
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 1
- 229940073608 benzyl chloride Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000010332 dry classification Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007649 pad printing Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- 239000002562 thickening agent Substances 0.000 description 1
- 238000001269 time-of-flight mass spectrometry Methods 0.000 description 1
- 238000001195 ultra high performance liquid chromatography Methods 0.000 description 1
- 238000004704 ultra performance liquid chromatography Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
Description
本発明は、導電性金属粉ペーストに関する。 The present invention relates to a conductive metal powder paste.
スクリーン印刷での回路形成が近年注目されている。スクリーン印刷では、基材に必要な分だけ、必要量の回路材料を印刷する。基材としては、Siウェハー、ガラス、樹脂フィルムが挙げられる。回路材料としては、金属フィラーと溶剤、必要に応じて樹脂を含む導電性ペーストが使用されている。主な金属フィラーとしては銀粉、銀めっき銅粉、銅粉が挙げられる。導電性ペーストにはその成分によって、樹脂硬化型と焼成型がある。こうした導電性ペーストは配線用途以外では、導電性接着剤、接合材としての使用が増えている。 Circuit formation by screen printing has attracted attention in recent years. In screen printing, only the necessary amount of circuit material is printed on the substrate. As a base material, Si wafer, glass, and a resin film are mentioned. As the circuit material, a conductive paste containing a metal filler and a solvent, and optionally a resin is used. The main metal fillers include silver powder, silver-plated copper powder and copper powder. The conductive paste may be of a resin curing type or a baking type depending on its components. Such conductive pastes are increasingly used as conductive adhesives and bonding materials except for wiring applications.
樹脂硬化型ペーストは、金属フィラーと溶剤に加えて、フェノール等の樹脂、イミダゾール等の硬化促進剤、必要に応じて増粘剤、基板との密着性向上剤等から構成される。金属フィラーは1〜10μm程度のフレーク状のものが採用されている。このタイプのペーストの特徴は300℃以下、製品によっては200℃以下の焼成で、100μΩcm以下の比抵抗が得られるので、配線用途には使いにくい高い比抵抗ではあるが、プリント配線板での接着剤用途には広く採用されている。焼成体中では金属フィラー間での焼結は起こっておらず、導電性が発現する主な要因はフィラー間の接触であるとされている。一般に後述する焼成タイプのペーストよりも安価である。 The resin-curable paste is composed of a resin such as phenol, a curing accelerator such as imidazole, a thickener, if necessary, an adhesive improver with a substrate, and the like in addition to the metal filler and the solvent. The metal filler is in the form of flakes of about 1 to 10 μm. The characteristic of this type of paste is that baking at a temperature of 300 ° C or less and 200 ° C or less depending on the product gives a specific resistance of 100μΩcm or less, so it is difficult to use for wiring applications. Are widely used in chemical applications. Sintering between metal fillers does not occur in the sintered body, and the main factor for developing conductivity is considered to be contact between the fillers. Generally, it is cheaper than the baking type paste described later.
一方、焼成型ペーストは、一般にフィラーとしての金属ナノ粒子と、溶媒から構成される。低温でナノ粒子を焼結させるとき、樹脂は焼結障害となるために、ペーストには添加されない。焼成型ペーストの特徴は300℃以下、製品によっては200℃以下の焼成で、20μΩcm以下、場合により5μΩcm以下という低い比抵抗が得られることである。また、フィラーの大きさが100nm以下であるために、焼成体表面が平坦となる。焼成型ペーストとして、銀粉ペーストが知られている(特許文献1、特許文献2、特許文献3)。 On the other hand, the fired paste is generally composed of metal nanoparticles as a filler and a solvent. When sintering nanoparticles at low temperatures, the resin is not added to the paste as it becomes a sintering obstacle. The characteristic of the baking type paste is that a specific resistance as low as 20 μΩcm or less, sometimes 5 μΩcm or less can be obtained by baking at 300 ° C. or less and 200 ° C. or less depending on the product. Moreover, since the size of the filler is 100 nm or less, the surface of the sintered body becomes flat. Silver powder paste is known as a baking type paste (patent document 1, patent document 2, patent document 3).
上述のように、樹脂硬化型ペーストは配線用途、放熱用途としての接合材としては比抵抗が高い。また、フィラーが数μmの大きさであるため、塗膜が平坦とならない。これはパワーモジュールにおけるチップの接合材としては障害となる可能性がある。 As described above, the resin-curable paste has a high resistivity as a bonding material for wiring applications and heat radiation applications. In addition, since the filler has a size of several μm, the coating does not become flat. This may be an obstacle as a chip bonding material in the power module.
一方、焼成型ペーストは配線用途、放熱用途としては十分に低い比抵抗が得られるが、合成試薬、合成時間を要するため、高価となる。また、放熱用途では接合層を厚くする必要があるのに対して、焼成型ペーストは樹脂を加えていなのでチクソ性に劣り、厚い塗膜を形成することができない。 On the other hand, although the baking type paste can obtain a sufficiently low specific resistance for wiring applications and heat radiation applications, it requires a synthesis reagent and a synthesis time, and is therefore expensive. Moreover, while it is necessary to thicken the bonding layer in heat radiation applications, the baking type paste is poor in thixotropy since a resin is added, and a thick coating film can not be formed.
そこで、樹脂硬化型ペーストのように厚い塗膜を形成できて、同時に、焼成型ペーストのように比較的に低温で低い比抵抗を得ることができて、平坦な塗膜を形成できる、導電性金属粉ペーストが求められていた。 Therefore, it is possible to form a thick coating film like a resin-curable paste, and at the same time obtain a low specific resistance at a relatively low temperature like a baking type paste and form a flat coating film. A metal powder paste has been sought.
したがって、本発明の目的は、樹脂を導入して厚い塗膜を形成可能としつつ、低温焼成できて低い比抵抗を達成可能である、導電性金属粉ペーストを提供することにある。 Therefore, an object of the present invention is to provide a conductive metal powder paste which can be fired at a low temperature and can achieve low specific resistance while introducing a resin to form a thick coating film.
本発明者は、鋭意研究の結果、銅粉又は銀粉にアミン処理を行って、アミン処理された銅粉又は銀粉に対して、特定の樹脂を使用することによって、樹脂が導入されつつ、低温焼結できて低い比抵抗を達成可能な導電性金属粉ペーストを得られることを見出して、本発明に到達した。 As a result of earnest research, the inventors of the present invention performed amine treatment on copper powder or silver powder and used a specific resin for amine-treated copper powder or silver powder while introducing a resin, while low temperature baking was performed. The present invention has been achieved by finding that a conductive metal powder paste can be obtained that can be consolidated and can achieve low specific resistance.
したがって、本発明は以下の(1)以下を含む。
(1)
窒素含有有機物が表面に付着した、銅粉又は銀粉を60〜90質量%含有し、
Tg(ガラス転移点)が50℃〜200℃の範囲にある樹脂を0.1〜10質量%含有する、導電性金属粉ペーストであって、
前記窒素含有有機物が、
アミノ酸;又は
以下のいずれかの基:
−CH(OH)−CH2−NR1R2基
(ただし、R1及びR2はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基である。)
又は
−CH(OH)−CH2−[N+R1R2R3]X1 -基
(ただし、R1、R2及びR3はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基であり、
X1 -は、ハロゲン化物イオン、CH3SO4 -からなる群から選択された1価のアニオンである)
を1個以上有するアミン化合物である、導電性金属粉ペースト。
(2)
窒素含有有機物が、次の式I:
R基は、以下のいずれかの基である:
−NR1R2基
(ただし、R1及びR2はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基である。)
又は
−[N+R1R2R3]X1 -基
(ただし、R1、R2及びR3はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基であり、
X1 -は、ハロゲン化物イオン、CH3SO4 -からなる群から選択された1価のアニオンである))
で表される窒素含有有機物である、(1)に記載の導電性金属粉ペースト。
(3)
Tg(ガラス転移点)が50℃〜200℃の範囲にある樹脂が、ポリビニルアセタール系樹脂、ロジン、アクリル、ポリビニルアルコール、及びポリビニルピロリドンよりなる群から選択された1種以上の樹脂である、(1)〜(2)のいずれかに記載の導電性金属粉ペースト。
(4)
金属粉の比表面積が0.1m2g-1以上である、(1)〜(3)のいずれかに記載の導電性金属粉ペースト。
(5)
さらに溶媒を含有する、(1)〜(4)のいずれかに記載の導電性金属粉ペースト。
(6)
(1)〜(5)のいずれかに記載の導電性金属粉ペーストを、焼成して、焼成体を得る工程、
を含む、導電性焼成体の製造方法。
(7)
(1)〜(5)のいずれかに記載の導電性金属粉ペーストを、塗工して、塗膜を得る工程、
得られた塗膜を焼成して、焼成体を得る工程、
を含む、導電性焼成体の製造方法。
(8)
焼成の温度が、220℃〜300℃の範囲の温度である、(6)〜(7)のいずれかに記載の方法。 Therefore, the present invention includes the following (1):
(1)
60-90 mass% of copper powder or silver powder which nitrogen-containing organic substance adhered to the surface,
A conductive metal powder paste comprising 0.1 to 10% by mass of a resin having a Tg (glass transition point) in the range of 50 ° C. to 200 ° C.,
The nitrogen-containing organic substance is
An amino acid; or any of the following groups:
-CH (OH) -CH 2 -NR 1 R 2 group (wherein R 1 and R 2 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- It is a group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group. )
Or -CH (OH) -CH 2- [N + R 1 R 2 R 3 ] X 1 - group (however, R 1 , R 2 and R 3 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- A group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group,
X 1 - is a halide ion, CH 3 SO 4 - is a monovalent anion selected from the group consisting of)
Conductive metal powder paste which is an amine compound having one or more.
(2)
The nitrogen-containing organic compound has the following formula I:
(Wherein, n is an integer of 1 to 8,
The R group is any of the following groups:
An -NR 1 R 2 group (provided that R 1 and R 2 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- It is a group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group. )
Or-[N + R 1 R 2 R 3 ] X 1 - group (with the proviso that R 1 , R 2 and R 3 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- A group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group,
X 1 - is a halide ion, CH 3 SO 4 - is a monovalent anion selected from the group consisting of))
The electroconductive metal-powder paste as described in (1) which is nitrogen-containing organic substance represented by these.
(3)
The resin having a Tg (glass transition temperature) in the range of 50 ° C. to 200 ° C. is one or more resins selected from the group consisting of polyvinyl acetal resins, rosins, acrylics, polyvinyl alcohol, and polyvinyl pyrrolidone 1) Conductive metal powder paste in any one of-2).
(4)
The electroconductive metal-powder paste in any one of (1)-(3) whose specific surface area of metal powder is 0.1 m < 2 > g < -1 > or more.
(5)
The conductive metal powder paste according to any one of (1) to (4), further containing a solvent.
(6)
A step of firing the conductive metal powder paste according to any one of (1) to (5) to obtain a fired body,
A method for producing a conductive fired body, comprising:
(7)
A step of applying the conductive metal powder paste according to any one of (1) to (5) to obtain a coated film,
Baking the obtained coating film to obtain a fired body,
A method for producing a conductive fired body, comprising:
(8)
The method in any one of (6)-(7) whose temperature of baking is temperature of the range of 220 degreeC-300 degreeC.
本発明によれば、樹脂を導入して厚い塗膜を形成可能としつつ、低温焼成できて低い比抵抗を達成可能な導電性金属粉ペーストを得ることができる。 According to the present invention, it is possible to obtain a conductive metal powder paste which can be fired at low temperature and can achieve low specific resistance while introducing a resin to form a thick coating film.
以下に本発明を実施の態様をあげて詳細に説明する。本発明は以下にあげる具体的な実施の態様に限定されるものではない。 Hereinafter, the present invention will be described in detail by way of embodiments. The present invention is not limited to the specific embodiments described below.
[導電性金属粉ペースト]
本発明の導電性金属粉ペーストは、窒素含有有機物が表面に付着した、銅粉又は銀粉を60〜90質量%含有し、Tg(ガラス転移点)が50℃〜200℃の範囲にある樹脂を0.1〜10質量%含有する。
[Conductive metal powder paste]
The conductive metal powder paste of the present invention contains 60 to 90% by mass of copper powder or silver powder with a nitrogen-containing organic substance attached to the surface, and a resin having a Tg (glass transition point) in the range of 50 ° C to 200 ° C. It contains 0.1 to 10% by mass.
[窒素含有有機物]
上記窒素含有有機物は、
アミノ酸;又は
以下のいずれかの基:
−CH(OH)−CH2−NR1R2基
(ただし、R1及びR2はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基である。)
又は
−CH(OH)−CH2−[N+R1R2R3]X1 -基
(ただし、R1、R2及びR3はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基であり、
X1 -は、ハロゲン化物イオン、CH3SO4 -からなる群から選択された1価のアニオンである)
を1個以上有するアミン化合物である。
[Nitrogen-containing organic matter]
The above nitrogen-containing organic substance is
An amino acid; or any of the following groups:
-CH (OH) -CH 2 -NR 1 R 2 group (wherein R 1 and R 2 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- It is a group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group. )
Or -CH (OH) -CH 2- [N + R 1 R 2 R 3 ] X 1 - group (however, R 1 , R 2 and R 3 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- A group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group,
X 1 - is a halide ion, CH 3 SO 4 - is a monovalent anion selected from the group consisting of)
Or an amine compound having one or more.
好適な実施の態様において、上記窒素含有有機物は、次の式I:
R基は、以下のいずれかの基である:
−NR1R2基
(ただし、R1及びR2はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基である。)
又は
−[N+R1R2R3]X1 -基
(ただし、R1、R2及びR3はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基であり、
X1 -は、ハロゲン化物イオン、CH3SO4 -からなる群から選択された1価のアニオンである))
で表される窒素含有有機物である。 In a preferred embodiment, the nitrogen-containing organic compound has the following formula I:
(Wherein, n is an integer of 1 to 8,
The R group is any of the following groups:
An -NR 1 R 2 group (provided that R 1 and R 2 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- It is a group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group. )
Or-[N + R 1 R 2 R 3 ] X 1 - group (with the proviso that R 1 , R 2 and R 3 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- A group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group,
X 1 - is a halide ion, CH 3 SO 4 - is a monovalent anion selected from the group consisting of))
It is a nitrogen-containing organic substance represented by
好適な実施の態様において、これらの置換基(R1、R2、R3)は、アミン化合物が全体として水溶性を有するように、選択される。 In a preferred embodiment, these substituents (R 1 , R 2 , R 3 ) are selected such that the amine compound as a whole has water solubility.
アルキル基は、例えばC1〜C8(炭素数1個から8個)、C1〜C6、C1〜C3、C1〜C2とできる。ヒドロキシアルキル基は、例えばC1〜C8、C1〜C6、C1〜C3、C1〜C2とできる。アルコキシアルキル基は、例えばC1〜C8、C1〜C6、C1〜C3、C1〜C2とでき、例えばメトキシアルキル基、エトキシアルキル基、プロポキシアルキル基とできる。フェニルアルキル基は、例えばC7〜C10、C7〜C8とでき、フェニルアルキル基のフェニル基が置換又は無置換のフェニル基であってもよく、例えばフェニルアルキル基のフェニル基は、C1〜C3のアルキル基によって1個又は2個置換されていてもよい。フェニル基は、例えばC6〜C8、C6〜C7とでき、置換又は無置換のフェニル基であってもよく、例えばC1〜C3のアルキル基によって1個又は2個置換されていてもよい。ナフチル基は、例えばC12〜C16、C12〜C14とでき、置換又は無置換のナフチル基であってもよく、例えばC1〜C3のアルキル基によって1個又は2個置換されていてもよい。アルケニル基は、例えばC3〜C8、C3〜C6、C3〜C4とでき、直鎖又は分枝の骨格を有していてもよい。 The alkyl group can be, for example, C1 to C8 (having 1 to 8 carbon atoms), C1 to C6, C1 to C3 and C1 to C2. The hydroxyalkyl group can be, for example, C1-C8, C1-C6, C1-C3, C1-C2. The alkoxyalkyl group can be, for example, C1 to C8, C1 to C6, C1 to C3, or C1 to C2, and can be, for example, a methoxyalkyl group, an ethoxyalkyl group, or a propoxyalkyl group. The phenylalkyl group can be, for example, C7 to C10 and C7 to C8, and the phenyl group of the phenylalkyl group may be a substituted or unsubstituted phenyl group, for example, the phenyl group of the phenylalkyl group is a C1 to C3 alkyl It may be substituted one or two by a group. The phenyl group may be, for example, C6 to C8 or C6 to C7, and may be a substituted or unsubstituted phenyl group, and may be substituted, for example, one or two by a C1 to C3 alkyl group. The naphthyl group may be, for example, C12 to C16 and C12 to C14, and may be a substituted or unsubstituted naphthyl group, and may be substituted, for example, by one or two C1 to C3 alkyl groups. The alkenyl group can be, for example, C3 to C8, C3 to C6, or C3 to C4, and may have a linear or branched skeleton.
[窒素含有有機物の表面への付着]
窒素含有有機物、例えば上記アミン化合物の水溶液を、銅粉又は銀粉と混合して、銅粉又は銀粉の表面に付着させることができる。窒素含有有機物が表面に付着した銅粉又は銀粉の全体の質量に対して、付着した窒素含有有機物の質量は、例えば0.03質量%〜70質量%、2質量%〜60質量%の範囲とすることができる。所望により、銅粉又は銀粉をアミン化合物の水溶液と混合した後に、公知の手段によって溶液から残渣を分離して、必要に応じて乾燥や解砕を行って、その後の導電性金属粉ペーストの製造に適した形態としてもよい。
[Attachment of nitrogen-containing organic matter to the surface]
An aqueous solution of a nitrogen-containing organic matter, such as the above-mentioned amine compound, can be mixed with copper powder or silver powder and deposited on the surface of copper powder or silver powder. The mass of the nitrogen-containing organic substance attached is, for example, in the range of 0.03 mass% to 70 mass% and 2 mass% to 60 mass% with respect to the total mass of the copper powder or silver powder to which the nitrogen-containing organic substance is attached can do. Optionally, after mixing copper powder or silver powder with an aqueous solution of an amine compound, the residue is separated from the solution by a known means, dried and disintegrated if necessary, and thereafter producing a conductive metal powder paste. It may be in a form suitable for
[銅粉又は銀粉の表面に付着したアミンの分析]
銅粉又は銀粉の表面へ付着した窒素含有有機物は、上述のアミン化合物とすることができる。表面処理された銅粉又は銀粉の表面のアミンの定量方法は、例えば、超高速液体クロマトグラフ飛行時間型質量分析(UPLC/TOF−MS)であれば、アミンの分子量、分子構造が同定されるので、ダイレクトに定性、半定量ができる。一方、液体クロマトグラフィーであっても、間接的に定性、半定量が可能である。
[Analysis of amine attached to the surface of copper powder or silver powder]
The nitrogen-containing organic substance attached to the surface of the copper powder or silver powder can be the above-mentioned amine compound. The method of determining the amine on the surface of the surface-treated copper powder or silver powder is, for example, ultra high performance liquid chromatography time-of-flight mass spectrometry (UPLC / TOF-MS), whereby the molecular weight and molecular structure of the amine are identified. Because it can be direct qualitative and semi-quantitative. On the other hand, even with liquid chromatography, qualitative and semi-quantitative determination is possible indirectly.
[樹脂]
Tg(ガラス転移点)が50℃〜200℃の範囲にある樹脂として、例えば、ポリビニルアセタール系樹脂、ロジン、アクリル、ポリビニルアルコール、及びポリビニルピロリドンよりなる群から選択された1種以上の樹脂を使用できる。ポリビニルアセタール系樹脂としては、例えばポリビニルブチラール(ブチラール樹脂ともいう)をあげることができる。アクリル(アクリル系樹脂)には、アクリル酸エステルの重合体あるいはメタクリル酸エステルの重合体が含まれ、例えばポリメタクリル酸メチルがあげられる。ロジンは、ロジン酸(アビエチン酸、パラストリン酸、イソピマール酸等)を主成分とする天然樹脂である。
[resin]
As a resin having a Tg (glass transition point) in the range of 50 ° C. to 200 ° C., for example, at least one resin selected from the group consisting of polyvinyl acetal resin, rosin, acrylic, polyvinyl alcohol, and polyvinyl pyrrolidone is used it can. Examples of polyvinyl acetal resins include polyvinyl butyral (also referred to as butyral resin). Acrylic (acrylic resin) includes polymers of acrylic acid esters or polymers of methacrylic acid esters, and examples thereof include poly (methyl methacrylate). Rosin is a natural resin containing as a main component rosin acid (abietic acid, parastoric acid, isopimaric acid, etc.).
[金属粉]
金属粉としては、公知の方法によって製造された銅粉又は銀粉が使用される。好適な実施の態様において、例えば、湿式法によって製造された銅粉又は銀粉、乾式法によって製造された銅粉又は銀粉を使用できる。好ましくは、湿式法によって製造された銅粉、例えば、不均化法、化学還元法等によって製造された銅粉を使用できる。
[Metal powder]
As metal powder, the copper powder or silver powder manufactured by the well-known method is used. In a preferred embodiment, for example, copper powder or silver powder produced by a wet method, copper powder or silver powder produced by a dry method can be used. Preferably, copper powder produced by a wet method, for example, copper powder produced by a disproportionation method, a chemical reduction method or the like can be used.
[金属粉の比表面積]
金属粉の比表面積は、例えば0.1m2g-1以上、0.5m2g-1以上とすることができ、例えば15m2g-1以下、10m2g-1以下とすることができる。
[Specific surface area of metal powder]
The specific surface area of the metal powder can be, for example, 0.1 m 2 g −1 or more, 0.5 m 2 g −1 or more, and for example, 15 m 2 g −1 or less, 10 m 2 g −1 or less .
[溶媒]
好適な実施の態様において、導電性金属粉ペーストは、窒素含有有機物が表面に付着した銅粉又は銀粉と、樹脂に加えて、さらに溶媒を含有する。溶媒の含有量は、例えば窒素含有有機物が表面に付着した銅粉又は銀粉の含有量と、樹脂の含有量の和の残余の質量%とすることができる。導電性金属粉ペーストにその他の添加剤を添加した場合には、これらの含有量と、銅粉又は銀粉の含有量と、樹脂の含有量の和の残余の質量%とすることができる。
[solvent]
In a preferred embodiment, the conductive metal powder paste further contains a copper powder or silver powder having a nitrogen-containing organic substance attached to the surface, and a solvent, in addition to the resin. The content of the solvent can be, for example, the mass% of the remainder of the sum of the content of the copper powder or silver powder with the nitrogen-containing organic substance adhering to the surface and the content of the resin. When other additives are added to the conductive metal powder paste, the content can be made to be the remaining mass% of the sum of the content of the copper powder or the silver powder and the content of the resin.
溶媒としては、使用する樹脂の溶剤となる公知の溶媒であって、上記のTgの範囲内又はそれ以下の温度で揮発する公知の溶媒を使用できる。例えば沸点が100〜300℃の範囲、120〜250℃の範囲の溶媒を使用できる。好適な実施の態様において、溶媒として、ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート、ポリエチレングリコール、プロピレングリコール、エチルカルビトール、ブチルセロソルブアセテート、ブチルセロソルブ、ジアセトンアルコール、ビネン、シクロヘキサノン、テレビン油、プロピレングリコールモノメチルエーテルアセテート、キシレン、エチルセロソルブ、及びプロピレングリコールモノメチルエーテルからなる群から選択された溶媒を使用でき、好ましくはターピネオール、ブチルカルビトールをあげることができる。 As the solvent, a known solvent which becomes a solvent of the resin to be used, and which volatilizes at a temperature within the range of the above Tg or lower can be used. For example, a solvent having a boiling point in the range of 100 to 300 ° C. and in the range of 120 to 250 ° C. can be used. In a preferred embodiment, terpineol, butyl carbitol, butyl carbitol acetate, polyethylene glycol, propylene glycol, ethyl carbitol, butyl cellosolve acetate, butyl cellosolve, diacetone alcohol, binene, cyclohexanone, turpentine oil, propylene glycol monomethyl ether as a solvent A solvent selected from the group consisting of acetate, xylene, ethyl cellosolve and propylene glycol monomethyl ether can be used, preferably terpineol and butyl carbitol.
[塗膜]
本発明の導電性金属粉ペーストは、樹脂を含有しているために、チクソ性に優れ、十分に厚い塗膜を形成することができる。塗膜は、導電性金属粉ペーストを塗工することによって形成できる。塗工の手段として、例えばスクリーン印刷、インクジェット印刷、インクジェット印刷、メタルマスク印刷、マイクロコンタクト法、パッド印刷等をあげることができる。好適な実施の態様において、塗膜の厚さは、例えば10〜500μmの範囲、20〜200μmの範囲とすることができる。塗膜は、所望により適宜乾燥して、その後の焼成を行うことができる。好適な実施の態様において、乾燥後の塗膜の厚さは、例えば20〜500μmの範囲とすることができる。
[Coating]
The conductive metal powder paste of the present invention, which contains a resin, is excellent in thixotropy and can form a sufficiently thick coating film. The coating film can be formed by applying a conductive metal powder paste. Examples of the coating method include screen printing, inkjet printing, inkjet printing, metal mask printing, microcontact method, pad printing and the like. In a preferred embodiment, the thickness of the coating can be, for example, in the range of 10 to 500 μm and in the range of 20 to 200 μm. The coating can be dried as appropriate, if desired, and then fired. In a preferred embodiment, the thickness of the coating after drying can be, for example, in the range of 20 to 500 μm.
[焼成]
導電性金属粉ペーストの塗膜は、低温焼成できて、低い比抵抗の焼成体を得ることができる。焼成の温度は、上記のTgの範囲よりも大きな温度とすることができ、例えば220℃〜300℃の範囲とすることができる。
[Firing]
The coating film of the conductive metal powder paste can be fired at a low temperature, and a fired body with low specific resistance can be obtained. The firing temperature can be a temperature higher than the above Tg range, for example, can be in the range of 220 ° C. to 300 ° C.
[接合強度]
導電性金属粉ペーストは、塗膜の焼成によって、十分に大きな接合強度によって部材を接合することができる。そのために、低い比抵抗を達成できることとあわせて、例えばパワーモジュールにおけるチップの接合材として好適に使用できる。好適な実施の態様において、接合強度は、例えば0MPa以上、1MPa以上とすることができ、例えば0MPa〜5MPaの範囲、0MPa〜3MPaの範囲とすることができる。
Bonding strength
The conductive metal powder paste can bond the members with sufficiently high bonding strength by firing the coating. Therefore, combined with the ability to achieve low specific resistance, it can be suitably used, for example, as a bonding material for chips in power modules. In a preferred embodiment, the bonding strength can be, for example, 0 MPa or more and 1 MPa or more, and can be, for example, in the range of 0 MPa to 5 MPa, and in the range of 0 MPa to 3 MPa.
[比抵抗]
導電性金属粉ペーストの焼成体は、十分に低い比抵抗を備える。好適な実施の態様において、比抵抗は、例えば1.7〜100μΩcmの範囲、5〜50μΩcmの範囲とすることができる。このような低い比抵抗は、従来の導電性金属粉ペーストが樹脂を含有していた場合には、達成できなかった範囲のものである。
[Resistance]
The fired body of the conductive metal powder paste has a sufficiently low specific resistance. In a preferred embodiment, the specific resistance can be, for example, in the range of 1.7 to 100 μΩcm, in the range of 5 to 50 μΩcm. Such low specific resistance is in the range which could not be achieved when the conventional conductive metal powder paste contained a resin.
[雰囲気]
焼成は、例えば非酸化性雰囲気下又は還元性雰囲気下で行うことができる。非酸化性雰囲気下とは、酸化性気体が含まれない又は低減された雰囲気をいい、例えば酸素が完全又は十分に除去された雰囲気をいう。還元性雰囲気は、雰囲気中にCO、H2S、SO2、H2、HCHO、HCOOH、H2O等の還元性気体が、0.5vol%以上、好ましくは1.0vol%以上で含まれる雰囲気をいう。還元性雰囲気としては、例えば、大気圧の気体窒素及び気体水素を含む雰囲気を挙げることができる。
[atmosphere]
The firing can be performed, for example, in a non-oxidizing atmosphere or a reducing atmosphere. The non-oxidizing atmosphere means an atmosphere containing no or reduced oxidizing gas, such as an atmosphere in which oxygen is completely or sufficiently removed. The reducing atmosphere contains a reducing gas such as CO, H 2 S, SO 2 , H 2 , HCHO, HCOOH, H 2 O, etc. at 0.5 vol% or more, preferably 1.0 vol% or more. I say the atmosphere. As a reducing atmosphere, for example, an atmosphere containing gaseous nitrogen and gaseous hydrogen at atmospheric pressure can be mentioned.
[焼成体]
本発明は、上記導電性金属粉ペーストにもあり、導電性金属粉ペーストが塗工されてなる塗膜及び乾燥塗膜にもあり、塗膜が焼成されてなる焼成体にもあり、この製造方法にもある。この焼成体は、低い比抵抗を有しており、優れた電極であり、優れた接合材である。本発明は、これらの電極、接合材及びその製造方法にもある。
[Sintered body]
The present invention also relates to the above-mentioned conductive metal powder paste, and to a coating film and a dried coating film formed by coating the conductive metal powder paste, and also to a fired body formed by baking the coating film, There is also a way. This sintered body has a low specific resistance, is an excellent electrode, and is an excellent bonding material. The present invention also resides in these electrodes, a bonding material, and a method of manufacturing the same.
以下に実施例をあげて、本発明をさらに詳細に説明する。本発明は、以下の実施例に限定されるものではない。 The present invention will be described in more detail by way of the following examples. The present invention is not limited to the following examples.
(例1:アミンの合成(A1〜A6))
窒素含有有機物(有機物)として以下の手順でアミン化合物(A1〜A6)を合成した。
エポキシ化合物(デナコールEX−521(ナカセケムテックス株式会社製))10.0gとジエタノールアミン5.72gを三口フラスコに投入し、ドライアイス−メタノールを冷却媒体とした冷却管を用意して、60℃で3時間反応を行い、ジエタノールアミンで変性した化合物を得た。得られたジエタノールアミン化合物の構造は下記の通りである。
(Example 1: Synthesis of amine (A1 to A6))
The amine compounds (A1 to A6) were synthesized as nitrogen-containing organic substances (organic substances) according to the following procedure.
A three-necked flask was charged with 10.0 g of an epoxy compound (Denacol EX-521 (manufactured by Nakase ChemteX Co., Ltd.)) and 5.72 g of diethanolamine, and a cooling pipe using dry ice-methanol as a cooling medium was prepared. The reaction was carried out for 3 hours to obtain a diethanolamine-modified compound. The structure of the obtained diethanolamine compound is as follows.
同様にして、ビス(2−エトキシエチル)アミン、ジベンジルアミン、ジフェニルアミン、ジアリルアミン、ジメチルアミンでそれぞれ変性した化合物を経た。FT−IR、1H−NMR、13C−NMRで生成物の構造を特定した。以下、ジエタノールアミン化合物、ジメチルアミン化合物、ビス(2−エトキシエチル)アミン化合物、ジベンジルアミン化合物、ジフェニルアミン化合物、ジアリルアミン化合物をそれぞれA1〜A6と表記する。 Similarly, compounds modified with bis (2-ethoxyethyl) amine, dibenzylamine, diphenylamine, diallylamine, and dimethylamine, respectively, were obtained. The structure of the product was identified by FT-IR, 1 H-NMR and 13 C-NMR. Hereinafter, the diethanolamine compound, the dimethylamine compound, the bis (2-ethoxyethyl) amine compound, the dibenzylamine compound, the diphenylamine compound, and the diallylamine compound are respectively represented as A1 to A6.
(例2:アミンの合成(B1〜B6))
窒素含有有機物(有機物)として以下の手順でアミン化合物(B1〜B6)を合成した。
エポキシ化合物(デナコールEX−521(ナカセケムテックス株式会社製))10.0gとジエタノールアミン5.72gを三口フラスコに投入し、ドライアイス−メタノールを冷却媒体とした冷却管を用意して、60℃で3時間反応を進行させた。その後、冷却管を取り外して、窒素ガスを反応液に吹き込んで余剰のジエタノールアミンを除去した。最後にベンジルクロライドを6.88g反応液に追加し、100℃で3時間反応を行った。FT−IR、1H−NMR、13C−NMRで生成物の構造を特定した。得られたジエタノールアミン化合物の構造は下記の通りである。
(Example 2: Synthesis of amine (B1 to B6))
The amine compounds (B1 to B6) were synthesized as nitrogen-containing organic substances (organic substances) by the following procedure.
A three-necked flask was charged with 10.0 g of an epoxy compound (Denacol EX-521 (manufactured by Nakase ChemteX Co., Ltd.)) and 5.72 g of diethanolamine, and a cooling pipe using dry ice-methanol as a cooling medium was prepared. The reaction was allowed to proceed for 3 hours. Thereafter, the cooling pipe was removed, and nitrogen gas was blown into the reaction solution to remove excess diethanolamine. Finally, 6.88 g of benzyl chloride was added to the reaction solution, and the reaction was performed at 100 ° C. for 3 hours. The structure of the product was identified by FT-IR, 1 H-NMR and 13 C-NMR. The structure of the obtained diethanolamine compound is as follows.
同様にして、ビス(2−エトキシエチル)アミン、ジベンジルアミン、ジフェニルアミン、ジアリルアミン、ジメチルアミンでそれぞれ変性した化合物を経た。FT−IR、1H−NMR、13C−NMRで生成物の構造を特定した。以下、ジエタノールアミン化合物、ジメチルアミン化合物、ビス(2−エトキシエチル)アミン化合物、ジベンジルアミン化合物、ジフェニルアミン化合物、ジアリルアミン化合物をそれぞれB1〜B6と表記する。 Similarly, compounds modified with bis (2-ethoxyethyl) amine, dibenzylamine, diphenylamine, diallylamine, and dimethylamine, respectively, were obtained. The structure of the product was identified by FT-IR, 1 H-NMR and 13 C-NMR. Hereinafter, the diethanolamine compound, the dimethylamine compound, the bis (2-ethoxyethyl) amine compound, the dibenzylamine compound, the diphenylamine compound, and the diallylamine compound are respectively described as B1 to B6.
上記合成した化合物A1〜A6及びB1〜B6の構造は、以下の式Iにおいて、n=3であり、R基がそれぞれ下記の表1の通りに置換された構造式である。 The structures of the synthesized compounds A1 to A6 and B1 to B6 are structural formulas in which n = 3 in the following formula I, and R groups are substituted as shown in the following table 1, respectively.
式I:
(例3:実施例1〜3、5〜21、比較例2)
1Lビーカー内に亜酸化銅粉50gと保護剤(粒成長抑制剤)としてアラビアゴムまたは魚から精製した動物性ニカワを0.25gを350mLの純水に分散させ、そこに体積比率25%の希硫酸100mLを添加し、不均化反応を行った。このスラリーからデカンテーション、水洗を繰り返し、比表面積3.5m2/g(D50 0.2μm)の銅微粒子20gを得た。この銅微粒子20gと、有機物(窒素含有有機物)として各種アミンを所定量含む水溶液100mLを300rpmで1時間混合した後、銅微粉を回収した。その後、窒素中で70℃で1時間乾燥させた後、解砕し、表面処理された銅微粒子を得た。この銅微粒子を金属比率が85%となるように、各種樹脂を所定量、残部が溶剤としてターピネオールを加えてミキサーで混ぜた後、3本ロールでペーストを調整した。樹脂としてはアクリル樹脂(綜研化学 SPB−K113)、ロジン(和光純薬工業)、ブチラール(積水化学 S−LEC SV−02)、ポリビニルアルコール(積水化学 SELVOL)、ポリビニルピロリドン(日本触媒 K−85)、セルロース(和光純薬工業 エチルセルロース)を用いた。これらのペーストをスクリーン印刷で乾燥塗膜厚で約50μmで乾燥塗膜厚で約10μmとなるように銅板上にスクリーン印刷をした。この乾燥塗膜の上に3mm角の銅板を載せ、2%H2−N2中で、250℃、5分、1MPaで加圧焼成した(接合条件1)。得られた接合サンプルの3mm角の銅板に横から力を加え、接合強度を測定した。
(Example 3: Examples 1 to 3, 5 to 21, Comparative Example 2)
In a 1 L beaker, 50 g of copper suboxide powder and 0.25 g of animal glue purified from gum arabic or fish as a protective agent (grain growth inhibitor) are dispersed in 350 mL of pure water and diluted there with 25% volume ratio 100 mL of sulfuric acid was added to carry out disproportionation reaction. Decantation and water washing were repeated from this slurry to obtain 20 g of copper fine particles having a specific surface area of 3.5 m 2 / g (D50 0.2 μm). After mixing 20 g of this copper fine particle and 100 mL of an aqueous solution containing a predetermined amount of various amines as an organic substance (nitrogen-containing organic substance) at 300 rpm for 1 hour, copper fine powder was recovered. Then, after drying at 70 ° C. in nitrogen for 1 hour, it was crushed to obtain surface-treated copper fine particles. A predetermined amount of each resin was added to the copper fine particles, and terpineol was added as a solvent in a predetermined amount, and the remainder was mixed with a mixer as a solvent, and then the paste was adjusted with a triple roll. As resin, acrylic resin (SOKEN CHEMICAL SPB-K113), rosin (Wako Pure Chemical Industries, Ltd.), butyral (Sekisui Chemical S-LEC SV-02), polyvinyl alcohol (Sekisui Chemical SELVOL), polyvinyl pyrrolidone (Nippon Catalyst K-85) And cellulose (Wako Pure Chemical Industries ethylcellulose) were used. These pastes were screen-printed on a copper plate by screen printing to a dry film thickness of about 50 μm and a dry film thickness of about 10 μm. A copper plate of 3 mm square was placed on this dried coating, and pressed and fired in 2% H 2 -N 2 at 250 ° C. for 5 minutes at 1 MPa (bonding condition 1). A lateral force was applied to a 3 mm square copper plate of the obtained bonded sample to measure the bonding strength.
(例4:実施例4)
実施例1のペーストを銅板上にスクリーン印刷し、塗膜を乾燥させずに、塗膜上に3mm角の銅板を載せ、2%H2−N2中で、250℃、60分、で無加圧焼成した(接合条件2)。得られた接合サンプルの3mm角の銅板に横から力を加え、接合強度を測定した。
(Example 4: Example 4)
The paste of Example 1 is screen-printed on a copper plate, a 3-mm square copper plate is placed on the coating without drying the coating, and 60% at 250 ° C. in 2% H 2 -N 2. It pressure-fired (joining condition 2). A lateral force was applied to a 3 mm square copper plate of the obtained bonded sample to measure the bonding strength.
(例5:実施例22)
日本アトマイズ加工製の銅フレーク粉AFS−Cu(比表面積0.4m2/g)をアルカリ洗、酸洗、水洗を行った後、例3の手順でアミン処理を行って表面処理銅微粒子、及びそのペーストを作製し、接合強度を測定した。
(Example 5: Example 22)
Alkaline copper foil powder AFS-Cu (specific surface area: 0.4 m 2 / g) manufactured by Nippon Atomizing Co., Ltd. is alkali-washed, pickled and washed with water, then amine-treated in the procedure of Example 3 to carry out surface-treated copper fine particles, The paste was produced and the bonding strength was measured.
(例6:実施例23)
特開2007−291513に従って製粉した。すなわち、0.8Lの純水に硝酸銀12.6gを溶解させ、25%アンモニア水を24mL、さらに硝酸アンモニウムを40g添加し、銀アンミン錯塩水溶液を調整した。これに0.5g/Lの割合でゼラチンを添加し、これを電解液とし、陽極、陰極ともにDSE極板を使用し、電流密度200A/m2、溶液温度20℃で電解し、電析した銀粒子を局番から掻き落としながら1時間電解した。こうして得られた銀粉をヌッチェでろ過し、純水、アルコールの順に洗浄を行い、70℃で12時間大気雰囲気下で乾燥させた。この銀粉を乾式分級し、最終的に比表面積2.3m2/g(D50 0.4μm)の銀粉を得た。この銀粉に例3の手順でアミン処理を行って表面処理銅微粒子、及びそのペーストを作製し、接合強度を測定した。
(Example 6: Example 23)
Milled according to JP-A-2007-291513. That is, 12.6 g of silver nitrate was dissolved in 0.8 L of pure water, 24 mL of 25% aqueous ammonia and 40 g of ammonium nitrate were further added to prepare a silver ammine complex salt aqueous solution. To this, gelatin was added at a ratio of 0.5 g / L, and this was used as an electrolyte, and both the anode and the cathode were electrodeposited at a current density of 200 A / m 2 and a solution temperature of 20 ° C using a DSE electrode plate. The silver particles were electrolyzed for 1 hour while being scraped off from the station number. The silver powder thus obtained was filtered with a Nutche, washed in order of pure water and alcohol, and dried at 70 ° C. for 12 hours in the air. The silver powder was subjected to dry classification to finally obtain a silver powder having a specific surface area of 2.3 m 2 / g (D50 0.4 μm). The silver powder was subjected to amine treatment according to the procedure of Example 3 to prepare surface-treated copper fine particles and a paste thereof, and the bonding strength was measured.
(例7:実施例24)
福田金属箔粉工業製の銀フレーク粉AgC−GS(比表面積0.4m2/g)を用い、アルカリ洗、酸洗、水洗を行った後、例3の手順でアミン処理を行って表面処理銅微粒子、及びそのペーストを作製し、接合強度を測定した。
(Example 7: Example 24)
Alkali washing, pickling and washing with silver flake powder AgC-GS (specific surface area: 0.4 m 2 / g) manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd., followed by amine treatment by the procedure of Example 3 for surface treatment Copper fine particles and a paste thereof were produced, and the bonding strength was measured.
(例8:比較例1)
1Lビーカー内に亜酸化銅粉50gと保護剤(粒成長抑制剤)としてアラビアゴム0.25gを350mLの純水に分散させ、そこに体積比率25%の希硫酸100mLを添加し、不均化反応を行った。このスラリーからデカンテーション、水洗を繰り返し、比表面積3.5m2/g(D50 0.2μm)の銅微粒子20gを回収した。この銅微粒子を、液温25℃、pH9.0の水酸化ナトリウム水溶液350mLと10分間混合し、デカンテーションにより銅微粒子を分離した。この銅微粒子とBTA0.2gを含む水溶液100mLと30分間混合し、吸引ろ過により銅微粒子を回収した。例3の手順で解砕された銅微粒子をペーストに加工し、接合強度を測定した。
(Example 8: Comparative Example 1)
50 g of cuprous oxide powder and 0.25 g of gum arabic as a protective agent (grain growth inhibitor) are dispersed in 350 mL of pure water in a 1 L beaker, and 100 mL of dilute sulfuric acid having a volume ratio of 25% is added thereto to disproportionate The reaction was done. Decantation and water washing were repeated from this slurry, and 20 g of copper microparticles having a specific surface area of 3.5 m 2 / g (D50 0.2 μm) were recovered. The copper particles were mixed with 350 mL of a sodium hydroxide aqueous solution having a liquid temperature of 25 ° C. and pH 9.0 for 10 minutes, and the copper particles were separated by decantation. The mixture was mixed with 100 mL of an aqueous solution containing this copper particulate and 0.2 g of BTA for 30 minutes, and the copper particulate was recovered by suction filtration. Copper fine particles crushed in the procedure of Example 3 were processed into a paste and the bonding strength was measured.
(例9:実施例1、4)
例3の手順において、3mm角の銅板の接合面にカプトンテープを貼った。実施例1、4のペーストをそれぞれ例3、4の手順で銅板上に塗膜し、その上にカプトンテープが貼られた面を接合面として3mm角の銅板を載せ、それぞれの条件で焼成した。焼成後、3mm角の銅板を除去し、得られた焼成体の比抵抗を測定した。
(Example 9: Examples 1 and 4)
In the procedure of Example 3, Kapton tape was applied to the bonding surface of a 3 mm square copper plate. The pastes of Examples 1 and 4 were coated on the copper plate according to the procedures of Examples 3 and 4, respectively, and a copper plate of 3 mm square was placed on the copper plate with the surface on which the Kapton tape was attached as a bonding surface, and fired under each condition. . After firing, the 3 mm square copper plate was removed, and the specific resistance of the obtained fired body was measured.
(結果のまとめ)
実施例1〜24及び比較例1〜2に対して行った上記の実験の結果を、表2にまとめて示す。
(Summary of results)
The results of the above-described experiments performed on Examples 1 to 24 and Comparative Examples 1 and 2 are summarized in Table 2.
本発明は、樹脂を導入して厚い塗膜を形成可能としつつ、低温焼成できて低い比抵抗を達成可能な導電性金属粉ペーストを提供する。本発明は産業上有用な発明である。 The present invention provides a conductive metal powder paste that can be fired at low temperature and achieve low specific resistance while introducing a resin to form a thick coating film. The present invention is an industrially useful invention.
Claims (7)
Tg(ガラス転移点)が50℃〜200℃の範囲にある樹脂を、0.1〜10質量%含有する、導電性金属粉ペーストであって、
前記窒素含有有機物が、
アミノ酸;又は
以下のいずれかの基:
−CH(OH)−CH2−NR1R2基
(ただし、R1及びR2はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基である。)
又は
−CH(OH)−CH2−[N+R1R2R3]X1 -基
(ただし、R1、R2及びR3はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基であり、
X1 -は、ハロゲン化物イオン、CH3SO4 -からなる群から選択された1価のアニオンである)
を1個以上有するアミン化合物である、導電性金属粉ペーストであって、
Tg(ガラス転移点)が50℃〜200℃の範囲にある樹脂が、ポリビニルアセタール系樹脂、ロジン、アクリル、ポリビニルアルコール、及びポリビニルピロリドンよりなる群から選択された1種以上の樹脂である、導電性金属粉ペースト。 60 to 90% by mass of copper powder or silver powder with nitrogen-containing organic matter attached to the surface,
A conductive metal powder paste containing 0.1 to 10% by mass of a resin having a Tg (glass transition point) in the range of 50 ° C. to 200 ° C.,
The nitrogen-containing organic substance is
An amino acid; or any of the following groups:
-CH (OH) -CH 2 -NR 1 R 2 group (wherein R 1 and R 2 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- It is a group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group. )
Or -CH (OH) -CH 2- [N + R 1 R 2 R 3 ] X 1 - group (however, R 1 , R 2 and R 3 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- A group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group,
X 1 - is a halide ion, CH 3 SO 4 - is a monovalent anion selected from the group consisting of)
Conductive metal powder paste which is an amine compound having one or more of
The resin having a Tg (glass transition point) in the range of 50 ° C. to 200 ° C. is at least one resin selected from the group consisting of polyvinyl acetal resins, rosins, acrylics, polyvinyl alcohols, and polyvinyl pyrrolidones. Metal powder paste .
Tg(ガラス転移点)が50℃〜200℃の範囲にある樹脂を、0.1〜10質量%含有する、導電性金属粉ペーストであって、
前記窒素含有有機物が、
アミノ酸;又は
以下のいずれかの基:
−CH(OH)−CH 2 −NR 1 R 2 基
(ただし、R 1 及びR 2 はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基である。)
又は
−CH(OH)−CH 2 −[N + R 1 R 2 R 3 ]X 1 - 基
(ただし、R 1 、R 2 及びR 3 はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基であり、
X 1 - は、ハロゲン化物イオン、CH 3 SO 4 - からなる群から選択された1価のアニオンである)
を1個以上有するアミン化合物である、導電性金属粉ペーストであって、
窒素含有有機物が、次の式I:
(ただし、式中、nは、1〜8の整数であり、
R基は、以下のいずれかの基である:
−NR 1 R 2 基
(ただし、R 1 及びR 2 はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基である。)
又は
−[N + R 1 R 2 R 3 ]X 1 - 基
(ただし、R 1 、R 2 及びR 3 はそれぞれ独立に、
C1〜C8のアルキル基、C1〜C8のヒドロキシアルキル基、C2〜C8のアルコキシアルキル基、C7〜C10の置換又は無置換のフェニルアルキル基、C6〜C8の置換又は無置換のフェニル基、C12〜C16の置換又は無置換のナフチル基、C3〜C8の直鎖又は分枝のアルケニル基からなる群から選択された基であり、
X 1 - は、ハロゲン化物イオン、CH 3 SO 4 - からなる群から選択された1価のアニオンである))
で表される窒素含有有機物である、導電性金属粉ペースト。 60 to 90% by mass of copper powder or silver powder with nitrogen-containing organic matter attached to the surface,
A conductive metal powder paste containing 0.1 to 10% by mass of a resin having a Tg (glass transition point) in the range of 50 ° C. to 200 ° C.,
The nitrogen-containing organic substance is
Amino acid; or
One of the following groups:
-CH (OH) -CH 2 -NR 1 R 2 groups
(However, R 1 and R 2 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- It is a group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group. )
Or
-CH (OH) -CH 2 - [ N + R 1 R 2 R 3] X 1 - group
(However, R 1 , R 2 and R 3 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- A group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group,
X 1 - is a halide ion, CH 3 SO 4 - is a monovalent anion selected from the group consisting of)
Conductive metal powder paste which is an amine compound having one or more of
The nitrogen-containing organic compound has the following formula I:
(Wherein, n is an integer of 1 to 8,
The R group is any of the following groups:
-NR 1 R 2 group
(However, R 1 and R 2 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- It is a group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group. )
Or
-[N + R 1 R 2 R 3 ] X 1 - group
(However, R 1 , R 2 and R 3 are each independently
C1-C8 alkyl group, C1-C8 hydroxyalkyl group, C2-C8 alkoxyalkyl group, C7-C10 substituted or unsubstituted phenylalkyl group, C6-C8 substituted or unsubstituted phenyl group, C12- A group selected from the group consisting of a C16 substituted or unsubstituted naphthyl group and a C3 to C8 linear or branched alkenyl group,
X 1 - is a halide ion, CH 3 SO 4 - is a monovalent anion selected from the group consisting of))
Conductive metal powder paste which is a nitrogen-containing organic substance represented by
を含む、導電性焼成体の製造方法。 A step of firing the conductive metal powder paste according to any one of claims 1 to 4 to obtain a fired body,
A method for producing a conductive fired body, comprising:
得られた塗膜を焼成して、焼成体を得る工程、
を含む、導電性焼成体の製造方法。 A step of applying the conductive metal powder paste according to any one of claims 1 to 4 to obtain a coated film,
Baking the obtained coating film to obtain a fired body,
A method for producing a conductive fired body, comprising:
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