JP6902321B2 - Method for manufacturing copper film and conductor obtained by it - Google Patents
Method for manufacturing copper film and conductor obtained by it Download PDFInfo
- Publication number
- JP6902321B2 JP6902321B2 JP2015023192A JP2015023192A JP6902321B2 JP 6902321 B2 JP6902321 B2 JP 6902321B2 JP 2015023192 A JP2015023192 A JP 2015023192A JP 2015023192 A JP2015023192 A JP 2015023192A JP 6902321 B2 JP6902321 B2 JP 6902321B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- copper film
- alkylamine
- carbon atoms
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 175
- 229910052802 copper Inorganic materials 0.000 title claims description 172
- 239000010949 copper Substances 0.000 title claims description 172
- 238000004519 manufacturing process Methods 0.000 title claims description 37
- 238000000034 method Methods 0.000 title description 75
- 239000004020 conductor Substances 0.000 title description 48
- 239000002245 particle Substances 0.000 claims description 66
- 238000010438 heat treatment Methods 0.000 claims description 55
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 53
- 229930195729 fatty acid Natural products 0.000 claims description 53
- 239000000194 fatty acid Substances 0.000 claims description 53
- 150000004665 fatty acids Chemical class 0.000 claims description 52
- 230000001603 reducing effect Effects 0.000 claims description 51
- 150000003973 alkyl amines Chemical class 0.000 claims description 45
- 239000000203 mixture Substances 0.000 claims description 43
- 125000004432 carbon atom Chemical group C* 0.000 claims description 40
- 150000001875 compounds Chemical class 0.000 claims description 38
- 239000007771 core particle Substances 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 25
- 239000012298 atmosphere Substances 0.000 claims description 20
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 16
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 16
- -1 copper salt compound Chemical class 0.000 claims description 14
- 239000002612 dispersion medium Substances 0.000 claims description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 8
- 235000019253 formic acid Nutrition 0.000 claims description 8
- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 claims description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- BWVZAZPLUTUBKD-UHFFFAOYSA-N 3-(5,6,6-Trimethylbicyclo[2.2.1]hept-1-yl)cyclohexanol Chemical compound CC1(C)C(C)C2CC1CC2C1CCCC(O)C1 BWVZAZPLUTUBKD-UHFFFAOYSA-N 0.000 claims description 5
- HBNHCGDYYBMKJN-UHFFFAOYSA-N 2-(4-methylcyclohexyl)propan-2-yl acetate Chemical compound CC1CCC(C(C)(C)OC(C)=O)CC1 HBNHCGDYYBMKJN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002429 hydrazines Chemical class 0.000 claims description 4
- 150000002443 hydroxylamines Chemical class 0.000 claims description 4
- 239000000126 substance Substances 0.000 description 28
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 17
- 230000008569 process Effects 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000005416 organic matter Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000005751 Copper oxide Substances 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 238000007650 screen-printing Methods 0.000 description 5
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 4
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 4
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 4
- 239000005750 Copper hydroxide Substances 0.000 description 4
- 239000012691 Cu precursor Substances 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 4
- 229910001956 copper hydroxide Inorganic materials 0.000 description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 150000004671 saturated fatty acids Chemical class 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- HZULDDWVCRWYCB-UHFFFAOYSA-L copper;nonanoate Chemical compound [Cu+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O HZULDDWVCRWYCB-UHFFFAOYSA-L 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 235000003441 saturated fatty acids Nutrition 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 238000005979 thermal decomposition reaction Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- DDHUNHGZUHZNKB-UHFFFAOYSA-N 2,2-dimethylpropane-1,3-diamine Chemical compound NCC(C)(C)CN DDHUNHGZUHZNKB-UHFFFAOYSA-N 0.000 description 2
- BPGIOCZAQDIBPI-UHFFFAOYSA-N 2-ethoxyethanamine Chemical compound CCOCCN BPGIOCZAQDIBPI-UHFFFAOYSA-N 0.000 description 2
- JZUHIOJYCPIVLQ-UHFFFAOYSA-N 2-methylpentane-1,5-diamine Chemical compound NCC(C)CCCN JZUHIOJYCPIVLQ-UHFFFAOYSA-N 0.000 description 2
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-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
- CJKRXEBLWJVYJD-UHFFFAOYSA-N N,N'-diethylethylenediamine Chemical compound CCNCCNCC CJKRXEBLWJVYJD-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 239000005700 Putrescine Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000001464 adherent effect Effects 0.000 description 2
- 125000005263 alkylenediamine group Chemical group 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- PWSKHLMYTZNYKO-UHFFFAOYSA-N heptane-1,7-diamine Chemical compound NCCCCCCCN PWSKHLMYTZNYKO-UHFFFAOYSA-N 0.000 description 2
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000012493 hydrazine sulfate Substances 0.000 description 2
- 229910000377 hydrazine sulfate Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- FGKJLKRYENPLQH-UHFFFAOYSA-N isocaproic acid Chemical compound CC(C)CCC(O)=O FGKJLKRYENPLQH-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- MDKQJOKKKZNQDG-UHFFFAOYSA-N n,n'-dimethylhexane-1,6-diamine Chemical compound CNCCCCCCNC MDKQJOKKKZNQDG-UHFFFAOYSA-N 0.000 description 2
- UQUPIHHYKUEXQD-UHFFFAOYSA-N n,n′-dimethyl-1,3-propanediamine Chemical compound CNCCCNC UQUPIHHYKUEXQD-UHFFFAOYSA-N 0.000 description 2
- ICVFPLUSMYSIFO-UHFFFAOYSA-N n-ethylpentan-1-amine Chemical compound CCCCCNCC ICVFPLUSMYSIFO-UHFFFAOYSA-N 0.000 description 2
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229940100684 pentylamine Drugs 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 1
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- XAMBIJWZVIZZOG-UHFFFAOYSA-N (4-methylphenyl)hydrazine Chemical compound CC1=CC=C(NN)C=C1 XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 description 1
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- PWGJDPKCLMLPJW-UHFFFAOYSA-N 1,8-diaminooctane Chemical compound NCCCCCCCCN PWGJDPKCLMLPJW-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- ADMTUGZFHLWYAU-UHFFFAOYSA-N 2,2-dimethylpropylhydrazine Chemical compound CC(C)(C)CNN ADMTUGZFHLWYAU-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- KDWGEPODFRBACT-UHFFFAOYSA-N 2-[hydroxy(2-sulfoethyl)amino]ethanesulfonic acid Chemical compound OS(=O)(=O)CCN(O)CCS(O)(=O)=O KDWGEPODFRBACT-UHFFFAOYSA-N 0.000 description 1
- GBHCABUWWQUMAJ-UHFFFAOYSA-N 2-hydrazinoethanol Chemical compound NNCCO GBHCABUWWQUMAJ-UHFFFAOYSA-N 0.000 description 1
- VJHLHGFTPAGQSG-UHFFFAOYSA-N 2-methylbutan-2-ylhydrazine Chemical compound CCC(C)(C)NN VJHLHGFTPAGQSG-UHFFFAOYSA-N 0.000 description 1
- NGSOWKPBNFOQCR-UHFFFAOYSA-N 2-methylpropylhydrazine Chemical compound CC(C)CNN NGSOWKPBNFOQCR-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- GOKVSLADUAKALT-UHFFFAOYSA-N 3-[2-carboxyethyl(hydroxy)amino]propanoic acid Chemical compound OC(=O)CCN(O)CCC(O)=O GOKVSLADUAKALT-UHFFFAOYSA-N 0.000 description 1
- SOYBEXQHNURCGE-UHFFFAOYSA-N 3-ethoxypropan-1-amine Chemical compound CCOCCCN SOYBEXQHNURCGE-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
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Description
本発明は、銅膜の製造方法及びそれにより得られた導電体に関する。 The present invention relates to a method for producing a copper film and a conductor obtained thereby.
金属パターンの形成方法として、銅等の金属粒子を含むインク、ペースト等の導電材料をインクジェット印刷、スクリーン印刷等により基板上に付与する工程と、導電材料を加熱して金属粒子を焼結させ、導電性を発現させる導体化工程とを含む方法が知られている。 As a method for forming a metal pattern, a step of applying a conductive material such as an ink containing metal particles such as copper or a paste onto a substrate by inkjet printing, screen printing or the like, and a step of heating the conductive material to sinter the metal particles are performed. A method including a conductor-forming step of exhibiting conductivity is known.
導電材料に印刷性を付与する観点から、導電材料にはバインダー樹脂等が一般的に添加される。また、ペースト等の導電材料中での金属粒子の分散性を高める観点から、導電材料に有機分散剤が添加されることがある。更には、金属粒子が銅粒子の場合、銅は酸化しやすい物質であるため保護剤が使用されることがある。バインダー樹脂、有機分散剤、保護剤等の有機物成分は、導体化工程において金属粒子同士の焼結を阻害する要因となる。それゆえ、体積抵抗率の低い導体を得るためには有機物成分を除去する必要があり、導体化工程を酸素雰囲気下において高温で行い、これら有機物成分を燃焼させて除去している。 From the viewpoint of imparting printability to the conductive material, a binder resin or the like is generally added to the conductive material. Further, from the viewpoint of enhancing the dispersibility of metal particles in a conductive material such as a paste, an organic dispersant may be added to the conductive material. Furthermore, when the metal particles are copper particles, a protective agent may be used because copper is a substance that is easily oxidized. Organic components such as binder resins, organic dispersants, and protective agents are factors that hinder the sintering of metal particles in the conductor formation step. Therefore, in order to obtain a conductor having a low volume resistivity, it is necessary to remove the organic matter component, and the conductor formation step is performed at a high temperature in an oxygen atmosphere, and these organic matter components are burned and removed.
他方、生産効率の向上、使用する基板の種類の多様化等の観点から、より低温（例えば、１５０℃以下）での導電材料の導体化を可能にする技術の開発が求められている。また、銅は酸素雰囲気下での加熱により容易に酸化銅となってしまうため、有機物成分を除去した後で還元雰囲気において焼結するという工程の煩雑さがある。 On the other hand, from the viewpoints of improving production efficiency and diversifying the types of substrates used, there is a need for the development of a technique that enables conducting of a conductive material at a lower temperature (for example, 150 ° C. or lower). Further, since copper is easily converted into copper oxide by heating in an oxygen atmosphere, there is a complicated process of sintering in a reducing atmosphere after removing organic components.
そこで、銅の酸化を抑制して保存性を高めるために、銅粒子の表面に被覆材としての有機物を付着させたものが知られている。例えば、特許文献１には、低温で焼結でき、良好な導電性を発現する被覆銅粒子及びその製造方法が記載されている。特許文献１に記載の銅粒子は、シュウ酸銅等の銅前駆体とヒドラジン等の還元性化合物とを混合して複合化合物を得る工程と、前記複合化合物をアルキルアミンの存在下で加熱する工程とを有する方法によって製造されるものである。特許文献１の実施例では、作製した銅粒子を含むインクをアルゴン雰囲気中、６０℃／分で３００℃まで加熱して３０分保持することで導体化を達成している。 Therefore, in order to suppress the oxidation of copper and improve the storage stability, an organic substance as a coating material is attached to the surface of copper particles. For example, Patent Document 1 describes coated copper particles that can be sintered at a low temperature and exhibit good conductivity, and a method for producing the same. The copper particles described in Patent Document 1 are a step of mixing a copper precursor such as copper oxalate and a reducing compound such as hydrazine to obtain a composite compound, and a step of heating the composite compound in the presence of an alkylamine. It is manufactured by a method having and. In the example of Patent Document 1, the produced ink containing copper particles is heated to 300 ° C. at 60 ° C./min in an argon atmosphere and held for 30 minutes to achieve conductor formation.
特許文献２には、導電性金属粉末、有機ビヒクル等を含む導電性ペースト組成物が記載されている。有機バインダー除去を目的に、通常、２５０〜３３０℃、空気雰囲気、窒素雰囲気等で熱処理を施して有機ビヒクルを燃焼させた後、金属粉末が酸化されないように中性又は還元雰囲気で８５０〜１３００℃で焼結することが記載されている。 Patent Document 2 describes a conductive paste composition containing a conductive metal powder, an organic vehicle, and the like. For the purpose of removing the organic binder, heat treatment is usually performed at 250 to 330 ° C. in an air atmosphere, a nitrogen atmosphere, etc. to burn the organic vehicle, and then the temperature is 850 to 1300 ° C. in a neutral or reducing atmosphere so that the metal powder is not oxidized. It is described that it is sintered with.
近年、生産効率の向上、使用する基板の種類の多様化等の観点から、より低温（例えば、１５０℃以下）での金属粒子の導体化を可能にする技術の開発が求められている。また、導体化工程の簡便さが求められている。従って、特許文献１及び２に記載されている温度よりもさらに低い温度で、しかも簡便に実施できる導体化方法の開発が求められている。 In recent years, from the viewpoints of improving production efficiency, diversifying the types of substrates used, and the like, there has been a demand for the development of a technique capable of forming metal particles into conductors at a lower temperature (for example, 150 ° C. or lower). In addition, the simplicity of the conductor formation process is required. Therefore, there is a demand for the development of a conductor method that can be easily carried out at a temperature lower than the temperatures described in Patent Documents 1 and 2.
本発明は上記課題に鑑み、工程が簡略化され且つより低温での導体化が可能な銅膜の製造方法、及びそれを用いた導電体を提供することを目的とする。 In view of the above problems, it is an object of the present invention to provide a method for producing a copper film capable of simplifying the process and forming a conductor at a lower temperature, and providing a conductor using the same.
上記課題を解決するための手段は、以下のとおりである。
＜１＞ 有機物で表面の少なくとも一部を被覆された銅を含有するコア粒子及び分散媒からなる導電性組成物を、還元性ガス雰囲気下、２５０℃以下の温度で加熱処理する工程を含む銅膜の製造方法。
The means for solving the above problems are as follows.
<1> Copper including a step of heat-treating a conductive composition composed of core particles containing copper whose surface is coated with an organic substance at least a part and a dispersion medium at a temperature of 250 ° C. or lower in a reducing gas atmosphere. Method of manufacturing a membrane.
＜２＞ 前記有機物で表面の少なくとも一部を被覆された銅を含有するコア粒子における有機物の含有率が、０．１〜１０．０質量％である、＜１＞に記載の銅膜の製造方法。 <2> Production of the copper film according to <1>, wherein the content of the organic substance in the core particles containing copper whose surface is coated with at least a part of the organic substance is 0.1 to 10.0% by mass. Method.
＜３＞ 前記有機物が、アルキルアミンである＜１＞又は＜２＞に記載の銅膜の製造方法。
＜４＞ 前記有機物で表面の少なくとも一部を被覆された銅を含有するコア粒子が、脂肪酸と銅の塩化合物（脂肪酸銅）と、還元性化合物及びアルキルアミンの混合物を加熱する工程を有して得られる銅含有粒子である前記＜１＞〜＜３＞のいずれか一項に記載の銅膜の製造方法。
<3> The method for producing a copper film according to <1> or <2>, wherein the organic substance is an alkylamine.
<4> The copper-containing core particles whose surface is coated with at least a part of the organic substance have a step of heating a mixture of a fatty acid and a copper salt compound (fatty acid copper), a reducing compound and an alkylamine. The method for producing a copper film according to any one of <1> to <3>, which is the copper-containing particles obtained.
＜５＞ 前記脂肪酸の炭素数が９以下である＜４＞に記載の銅膜の製造方法。 <5> The method for producing a copper film according to <4>, wherein the fatty acid has 9 or less carbon atoms.
＜６＞ 前記還元性化合物が、ヒドラジン、ヒドラジン誘導体、ヒドロキシルアミン及びヒドロキシルアミン誘導体からなる群より選択される少なくとも１種を含む、＜４＞又は＜５＞に記載の銅膜の製造方法。 <6> The method for producing a copper film according to <4> or <5>, wherein the reducing compound contains at least one selected from the group consisting of hydrazine, hydrazine derivatives, hydroxylamine and hydroxylamine derivatives.
＜７＞ 前記アルキルアミンの炭素数が７以下である＜３＞〜＜６＞のいずれか一項に記載の銅膜の製造方法。
＜８＞ ＜１＞〜＜７＞のいずれか一項に記載の銅膜の製造方法により得られた導電体。
<7> The method for producing a copper film according to any one of <3> to <6>, wherein the alkylamine has 7 or less carbon atoms.
<8> A conductor obtained by the method for producing a copper film according to any one of <1> to <7>.
本発明によれば、工程が簡略化され且つより低温での導体化が可能な銅膜の製造方法、及びその製造方法により得られた導電体を提供することができる。 According to the present invention, it is possible to provide a method for producing a copper film capable of simplifying the process and forming a conductor at a lower temperature, and a conductor obtained by the method for producing the copper film.
本明細書において「〜」を用いて示された数値範囲は、「〜」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。さらに本明細書において組成物中の各成分の含有量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。 The numerical range indicated by using "~" in the present specification indicates a range including the numerical values before and after "~" as the minimum value and the maximum value, respectively. Further, in the present specification, the content of each component in the composition is the total amount of the plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition. Means.
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の目的が達成されれば、本用語に含まれる。 In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended purpose of the process is achieved even if it cannot be clearly distinguished from other processes. ..
本明細書において「膜」との語は、平面図として観察したときに、全面に形成されている形状の構成に加え、一部に形成されている形状の構成も包含される。 In the present specification, the term "membrane" includes not only the configuration of the shape formed on the entire surface but also the configuration of the shape formed in a part when observed as a plan view.
本明細書において「導体化」との語は、金属含有粒子を焼結させて導電性を有する物体に変化させることをいう。「導電体（導体）」とは、導電性を有する物体をいう。導電性とは、体積抵抗率が３００μΩ・ｃｍ以下であることを意味する。 As used herein, the term "conductor" refers to sintering metal-containing particles into a conductive object. "Conductor" means an object having conductivity. Conductivity means that the volume resistivity is 300 μΩ · cm or less.
＜銅膜の製造方法＞
本発明の銅膜の製造方法は、有機物で表面の少なくとも一部を被覆された銅を含有するコア粒子及び分散媒からなる導電性組成物を、還元性ガス雰囲気下、２５０℃以下の温度で加熱処理する工程を含む。本発明の銅膜の製造方法は、必要に応じて、その他の工程を含んでいてもよい。
<Copper film manufacturing method>
In the method for producing a copper film of the present invention, a conductive composition composed of core particles containing copper whose surface is coated with an organic substance at least a part and a dispersion medium is prepared in a reducing gas atmosphere at a temperature of 250 ° C. or lower. Includes a step of heat treatment. The method for producing a copper film of the present invention may include other steps, if necessary.
本発明の銅膜の製造方法は、上記構成を採ることにより、工程が簡略化され、且つより低温での導体化が可能となる。これにより、耐熱性が比較的低い基板上にも銅膜を形成することができる。その理由は以下のように推察される。 By adopting the above structure, the method for producing a copper film of the present invention simplifies the process and enables the formation of a conductor at a lower temperature. As a result, a copper film can be formed even on a substrate having a relatively low heat resistance. The reason can be inferred as follows.
銅は容易に酸化される。しかし、本発明に係る銅含有粒子は、表面の少なくとも一部が有機物で被覆されているため、大気中で保存しても酸化が抑制されるという利点を有する。 Copper is easily oxidized. However, since at least a part of the surface of the copper-containing particles according to the present invention is coated with an organic substance, there is an advantage that oxidation is suppressed even when stored in the atmosphere.
また、熱処理工程を還元性ガス雰囲気下で実施することで、より低い熱処理温度で導体化が実現できる。この理由は定かではないが、還元性ガスにより、酸化物が還元されることに加え、銅含有粒子表面に存在する有機物の脱離及び分解を促進するためであると推測される。尚、特許文献１に記載の実施例では加熱の際の雰囲気中の酸素濃度について具体的な記載がなく、有機物の熱分解を充分なものとするために加熱を最高温度３００℃で実施している。 Further, by carrying out the heat treatment step in a reducing gas atmosphere, conductor formation can be realized at a lower heat treatment temperature. The reason for this is not clear, but it is presumed that the reducing gas reduces the oxide and promotes the elimination and decomposition of organic substances existing on the surface of the copper-containing particles. In the examples described in Patent Document 1, there is no specific description about the oxygen concentration in the atmosphere during heating, and heating is performed at a maximum temperature of 300 ° C. in order to sufficiently thermally decompose organic substances. There is.
また、本発明における銅含有粒子では酸化が抑制されるため、従来の銅含有粒子に比べて銅酸化物の含有率は少なくなり、仮に銅酸化物を少量含有しているとしても、還元性ガス雰囲気下で熱処理されることで、銅酸化物が還元されて金属銅が生成する。したがって、より低抵抗な銅膜（導体）が得られる。しかも、有機物の熱分解と金属銅への還元とが一括して行われるため、工程の簡略化が図られる。 Further, since the copper-containing particles in the present invention suppress oxidation, the content of copper oxide is lower than that of the conventional copper-containing particles, and even if a small amount of copper oxide is contained, the reducing gas By heat treatment in an atmosphere, copper oxide is reduced to produce metallic copper. Therefore, a copper film (conductor) having a lower resistance can be obtained. Moreover, since the thermal decomposition of the organic substance and the reduction to metallic copper are performed collectively, the process can be simplified.
以上により、本発明の銅膜の製造方法によれば、より低温での導体化が実現され、且つ有機物の熱分解の工程後に還元工程を行わずに済み、工程が簡略化される。 As described above, according to the method for producing a copper film of the present invention, conductor formation at a lower temperature is realized, and the reduction step does not have to be performed after the step of thermal decomposition of the organic substance, and the step is simplified.
（基板）
本発明では、導電性組成物を基板に設けて、加熱処理する。基板の材質は特に制限されず、導電性を有していても有していなくてもよい。例えば、Ｃｕ、Ａｕ、Ｐｔ、Ｐｄ、Ａｇ、Ｚｎ、Ｎｉ、Ｃｏ、Ｆｅ、Ａｌ、Ｓｎ等の金属、これら金属の合金、ＩＴＯ、ＺｎＯ、ＳｎＯ、Ｓｉ等の半導体、ガラス、黒鉛、グラファイト等のカーボン材料、樹脂、紙などを挙げることができる。
(substrate)
In the present invention, the conductive composition is provided on the substrate and heat-treated. The material of the substrate is not particularly limited, and may or may not have conductivity. For example, metals such as Cu, Au, Pt, Pd, Ag, Zn, Ni, Co, Fe, Al, Sn, alloys of these metals, semiconductors such as ITO, ZnO, SnO, Si, glass, graphite, graphite and the like. Examples include carbon materials, resins, and paper.
本発明の銅膜の製造方法は、特に、耐熱性が比較的低い材質からなる基板を用いる場合に好適に適用することができる。このような材質としては、熱可塑性樹脂が挙げられる。熱可塑性樹脂としては、ポリエチレン、ポリプロピレン、ポリメチルペンテン等のポリオレフィン樹脂、ポリエチレンテレフタレートやポリエチレンナフタレート等のポリエステル、ポリカーボネート、ポリイミド樹脂等が挙げられる。
基板の形状は特に制限されず、板状、棒状、ロール状、フィルム状等であってよい。
The method for producing a copper film of the present invention can be suitably applied particularly when a substrate made of a material having relatively low heat resistance is used. Examples of such a material include thermoplastic resins. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene and polymethylpentene, polyesters such as polyethylene terephthalate and polyethylene naphthalate, polycarbonate and polyimide resins.
The shape of the substrate is not particularly limited, and may be a plate shape, a rod shape, a roll shape, a film shape, or the like.
（導電性組成物）
本発明の銅膜の製造方法において使用される導電性組成物は、銅を含有するコア粒子と前記コア粒子の表面の少なくとも一部に配置される有機物とを有する銅含有粒子、及び分散媒を含み、必要に応じてその他の成分を含んでいてもよい。
(Conductive composition)
The conductive composition used in the method for producing a copper film of the present invention comprises copper-containing particles having copper-containing core particles and an organic substance arranged on at least a part of the surface of the core particles, and a dispersion medium. It may be included and, if necessary, other components may be included.
−銅含有粒子−
本発明における銅含有粒子は、銅を含有するコア粒子の表面の少なくとも一部に有機物が配置される。コア粒子の表面の少なくとも一部が有機物により被覆されると、銅含有粒子の酸化が抑制され、大気中でも長期保存が可能な銅含有粒子を得ることができる。
-Copper-containing particles-
In the copper-containing particles in the present invention, organic substances are arranged on at least a part of the surface of the copper-containing core particles. When at least a part of the surface of the core particles is coated with an organic substance, oxidation of the copper-containing particles is suppressed, and copper-containing particles that can be stored for a long time even in the atmosphere can be obtained.
銅含有粒子の酸化をより効果的に抑制する観点からは、有機物の含有率は銅含有粒子中、０．１質量％以上であることが好ましく、０．２質量％以上であることがより好ましく、０．３質量％以上であることが更に好ましい。より低温での導体化を図る観点からは、有機物の含有率は銅含有粒子中、１０質量％以下であることが好ましく、５質量％以下であることがより好ましく、３質量％以下であることが更に好ましい。 From the viewpoint of more effectively suppressing the oxidation of the copper-containing particles, the content of the organic substance in the copper-containing particles is preferably 0.1% by mass or more, more preferably 0.2% by mass or more. , 0.3% by mass or more is more preferable. From the viewpoint of forming a conductor at a lower temperature, the content of organic matter in the copper-containing particles is preferably 10% by mass or less, more preferably 5% by mass or less, and 3% by mass or less. Is more preferable.
有機物の含有率は、有機物が熱分解する温度以上の温度で銅含有粒子を加熱し、加熱前後の質量を比較することで得られる。 The organic matter content is obtained by heating the copper-containing particles at a temperature equal to or higher than the temperature at which the organic matter is thermally decomposed and comparing the masses before and after heating.
本発明の好ましい一実施態様では、有機物は、炭素数が７以下のアルキル基を有し、アルキルアミンに由来する物質を含む。アルキルアミンはＲＮＨ２（Ｒは炭化水素基であり、環状又は分岐状であってもよい）で表される１級アミン、Ｒ１Ｒ２ＮＨ（Ｒ１及びＲ２は同じであっても異なっていてもよい炭化水素基であり、環状又は分岐状であってもよい）で表される２級アミン、炭化水素鎖に２つのアミノ基が置換したアルキレンジアミン等を意味する。アルキルアミンは、１つ以上の二重結合を有していてもよく、酸素、ケイ素、窒素、硫黄、リン等の原子を有していてもよい。アルキルアミンは、１種のみであっても２種以上であってもよい。 In one preferred embodiment of the invention, the organic material comprises a substance having an alkyl group having 7 or less carbon atoms and being derived from an alkylamine. Alkyl amines are primary amines represented by RNH 2 (R is a hydrocarbon group and may be cyclic or branched), R 1 R 2 NH (R 1 and R 2 are the same but different. It is a hydrocarbon group which may be present, and may be cyclic or branched), and means a secondary amine, an alkylenediamine in which two amino groups are substituted in a hydrocarbon chain, and the like. The alkylamine may have one or more double bonds and may have atoms such as oxygen, silicon, nitrogen, sulfur and phosphorus. The alkylamine may be only one kind or two or more kinds.
本発明の方法に使用される１級アミンとして具体的には、エチルアミン、２−エトキシエチルアミン、プロピルアミン、ブチルアミン、イソブチルアミン、ペンチルアミン、イソペンチルアミン、ヘキシルアミン、シクロヘキシルアミン、ヘプチルアミン、オクチルアミン、ノニルアミン、デシルアミン、ドデシルアミン、ヘキサデシルアミン、オレイルアミン、３−メトキシプロピルアミン、３−エトキシプロピルアミン等を挙げることができる。 Specifically, as the primary amine used in the method of the present invention, ethylamine, 2-ethoxyethylamine, propylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine. , Nonylamine, decylamine, dodecylamine, hexadecylamine, oleylamine, 3-methoxypropylamine, 3-ethoxypropylamine and the like.
本発明の方法に使用される２級アミンとして具体的には、ジエチルアミン、ジプロピルアミン、ジブチルアミン、エチルプロピルアミン、エチルペンチルアミン、ジブチルアミン、ジペンチルアミン、ジヘキシルアミン等を挙げることができる。 Specific examples of the secondary amine used in the method of the present invention include diethylamine, dipropylamine, dibutylamine, ethylpropylamine, ethylpentylamine, dibutylamine, dipentylamine, dihexylamine and the like.
本発明の方法に使用されるアルキレンジアミンとして具体的には、エチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ´−ジメチルエチレンジアミン、Ｎ，Ｎ−ジエチルエチレンジアミン、Ｎ，Ｎ´−ジエチルエチレンジアミン、１，３−プロパンジアミン、２，２−ジメチル−１，３−プロパンジアミン、Ｎ，Ｎ−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ´−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ−ジエチル−１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノ−２−メチルペンタン、１，６−ジアミノへキサン、Ｎ，Ｎ´−ジメチル−１，６−ジアミノへキサン、１，７−ジアミノヘプタン、１，８−ジアミノオクタン、１，９−ジアミノノナン、１，１２−ジアミノドデカン等を挙げることができる。 Specifically, as the alkylenediamine used in the method of the present invention, ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-diethylethylenediamine, 1, 3-Propane diamine, 2,2-dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N-diethyl -1,3-diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N'-dimethyl-1,6-diaminohexane, 1 , 7-Diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,12-diaminododecane and the like.
アルキルアミンの炭化水素基の炭素数は、７以下であることが好ましい。炭素数が７以下のアルキルアミン（特定アルキルアミン）は、分子量が比較的小さいために、比較的低い温度でも熱分解する傾向がある。より良好な導体化を達成する観点からは、アルキルアミンの炭化水素基の炭素数は６以下であることがより好ましい。また、アルキルアミンの炭化水素基の炭素数は４以上であることが好ましい。 The hydrocarbon group of the alkylamine preferably has 7 or less carbon atoms. Alkylamines having 7 or less carbon atoms (specific alkylamines) have a relatively small molecular weight and therefore tend to be thermally decomposed even at a relatively low temperature. From the viewpoint of achieving better conductor formation, it is more preferable that the hydrocarbon group of the alkylamine has 6 or less carbon atoms. Further, the hydrocarbon group of the alkylamine preferably has 4 or more carbon atoms.
炭素数が７以下である１級アミンとして具体的には、エチルアミン、２−エトキシエチルアミン、プロピルアミン、ブチルアミン、イソブチルアミン、ペンチルアミン、イソペンチルアミン、ヘキシルアミン、シクロヘキシルアミン、ヘプチルアミン等を挙げることができる。 Specific examples of the primary amine having 7 or less carbon atoms include ethylamine, 2-ethoxyethylamine, propylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine, and heptylamine. Can be done.
炭素数が７以下である２級アミンとして具体的には、ジエチルアミン、ジプロピルアミン、ジブチルアミン、エチルプロピルアミン、エチルペンチルアミン等を挙げることができる。 Specific examples of the secondary amine having 7 or less carbon atoms include diethylamine, dipropylamine, dibutylamine, ethylpropylamine, and ethylpentylamine.
炭素数が７以下であるアルキルジアミンとして具体的には、エチレンジアミン、Ｎ，Ｎ−ジメチルエチレンジアミン、Ｎ，Ｎ´−ジメチルエチレンジアミン、Ｎ，Ｎ−ジエチルエチレンジアミン、Ｎ，Ｎ´−ジエチルエチレンジアミン、１，３−プロパンジアミン、２，２−ジメチル−１，３−プロパンジアミン、Ｎ，Ｎ−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ´−ジメチル−１，３−ジアミノプロパン、Ｎ，Ｎ−ジエチル−１，３−ジアミノプロパン、１，４−ジアミノブタン、１，５−ジアミノ−２−メチルペンタン、１，６−ジアミノへキサン、Ｎ，Ｎ´−ジメチル−１，６−ジアミノへキサン、１，７−ジアミノヘプタン等を挙げることができる。 Specifically, as an alkyldiamine having 7 or less carbon atoms, ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N-dimethylethylenediamine, N, N'-diethylethylenediamine, 1,3 -Propane diamine, 2,2-dimethyl-1,3-propanediamine, N, N-dimethyl-1,3-diaminopropane, N, N'-dimethyl-1,3-diaminopropane, N, N-diethyl- 1,3-Diaminopropane, 1,4-diaminobutane, 1,5-diamino-2-methylpentane, 1,6-diaminohexane, N, N'-dimethyl-1,6-diaminohexane, 1, 7-Diaminoheptane and the like can be mentioned.
本発明に係わる銅含有粒子の形状は特に制限されない。例えば、球状、長粒状、扁平状等を挙げることができ、銅含有粒子の用途にあわせて選択できる。印刷用ペーストを調製する観点からは、球状又は長粒状であることが好ましい。 The shape of the copper-containing particles according to the present invention is not particularly limited. For example, spherical, long-granular, flat, etc. can be mentioned, and can be selected according to the use of the copper-containing particles. From the viewpoint of preparing a printing paste, it is preferably spherical or long-granular.
本発明に係わる銅含有粒子は、粒子直径の平均値（無作為に選択される２００個の銅含有粒子の長軸の長さの平均値：平均粒子径）が５〜３００ｎｍの銅含有粒子が少なくとも１つ以上密着した二次構造を有する。また３０〜３００ｎｍの銅含有粒子に、平均粒子径５〜５０ｎｍの銅含有粒子が少なくとも１つ以上密着した二次構造を有する。コアとなる粒子直径の平均値が３０〜３００ｎｍの銅含有粒子（コア粒子）は主に導電性の機能を担い、コア粒子に密着した平均粒子径５〜５０ｎｍの銅含有粒子（密着粒子）は、加熱時に低温で溶融することでコア粒子同士を接着する機能を担う。コア粒子の粒子直径の平均値が３０ｎｍ未満の場合には周囲の密着粒子が溶融しても導電パスを形成することが困難であり、３００ｎｍを超えて大きい場合にもコア粒子同士の距離があることから導電パスを形成することが困難である。また、密着粒子の粒子直径の平均値が５ｎｍ未満の場合には酸化の影響を受け易く、５０ｎｍを超えて大きい場合には低温での溶融が困難であるため、コア粒子同士を接着しにくくなる。 The copper-containing particles according to the present invention include copper-containing particles having an average particle diameter (average length of 200 randomly selected copper-containing particles on the major axis: average particle diameter) of 5 to 300 nm. It has at least one or more closely attached secondary structures. Further, it has a secondary structure in which at least one or more copper-containing particles having an average particle diameter of 5 to 50 nm are in close contact with copper-containing particles having an average particle diameter of 30 to 300 nm. Copper-containing particles (core particles) having an average particle diameter of 30 to 300 nm as the core mainly play a conductive function, and copper-containing particles (adhesive particles) having an average particle diameter of 5 to 50 nm in close contact with the core particles. It has the function of adhering core particles to each other by melting at a low temperature during heating. When the average value of the particle diameters of the core particles is less than 30 nm, it is difficult to form a conductive path even if the surrounding adherent particles are melted, and when the average value exceeds 300 nm, there is a distance between the core particles. Therefore, it is difficult to form a conductive path. Further, when the average value of the particle diameters of the adherent particles is less than 5 nm, it is easily affected by oxidation, and when it is larger than 50 nm, it is difficult to melt at a low temperature, so that it becomes difficult to bond the core particles to each other. ..
本発明において長軸の長さとは、粒子に外接し、互いに平行である二平面の間の距離が最大となるように選ばれる二平面間の距離を意味する。本発明において長軸の長さの中央値とは、２００個の銅含有粒子の長軸の長さの値を小さい順に並べたときに中央に位置する２つの値（１００番目及び１０１番目）の算術平均値を意味する。銅含有粒子の長軸の長さは、電子顕微鏡による観察等の通常の方法によって測定できる。 In the present invention, the length of the major axis means the distance between two planes circumscribing the particle and selected so that the distance between the two planes parallel to each other is maximized. In the present invention, the median length of the major axis is the two values (100th and 101st) located in the center when the major axis length values of 200 copper-containing particles are arranged in ascending order. It means the arithmetic mean value. The length of the long axis of the copper-containing particles can be measured by a usual method such as observation with an electron microscope.
本発明に係わる銅含有粒子は、少なくとも金属銅（銅を含有するコア粒子）及びその表面に有機物を含み、必要に応じてその他の物質を含んでもよい。有機物は、アルキルアミンが好ましい。その他の物質としては、金、銀、白金、錫、ニッケル等の金属又はこれらの金属元素を含む化合物、後述する脂肪酸銅、還元性化合物、銅酸化物、塩化銅等を挙げることができる。導電性に優れる銅パターンを形成する観点からは、銅含有粒子中の金属銅の含有率は５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。 The copper-containing particles according to the present invention contain at least metallic copper (copper-containing core particles) and an organic substance on the surface thereof, and may contain other substances as necessary. The organic substance is preferably an alkylamine. Examples of other substances include metals such as gold, silver, platinum, tin and nickel, compounds containing these metal elements, fatty acid copper, reducing compounds, copper oxides, copper chloride and the like, which will be described later. From the viewpoint of forming a copper pattern having excellent conductivity, the content of metallic copper in the copper-containing particles is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is more preferable to have.
本発明における銅含有粒子は、コア粒子の表面の少なくとも一部にアルキルアミンのようにアミノ基を有する有機物が存在しているために酸化が抑制されており、銅酸化物の含有率が小さい。例えば、ある実施態様では、コア粒子中の銅酸化物の含有率が５質量％以下である。コア粒子中の銅酸化物の含有率は、例えば、Ｘ線回折スペクトル（ＸＲＤ、X-ray diffraction）によって測定することができる。コア粒子中の銅酸化物の含有率は、導体化の前に測定したときの値である。 The copper-containing particles in the present invention are suppressed in oxidation because an organic substance having an amino group such as alkylamine is present on at least a part of the surface of the core particles, and the content of copper oxide is small. For example, in one embodiment, the content of copper oxide in the core particles is 5% by mass or less. The content of copper oxide in the core particles can be measured by, for example, an X-ray diffraction spectrum (XRD, X-ray diffraction). The content of copper oxide in the core particles is the value measured before conductor formation.
−銅含有粒子の製造方法−
本発明に係る銅含有粒子の製造方法は特に制限されない。本発明の好ましい一実施態様では、炭素数が９以下である脂肪酸と銅との金属塩（塩化合物、脂肪酸銅）と、還元性化合物と、炭素数が７以下であるアルキルアミンを含むアルキルアミンと、を含む組成物を加熱する工程を有する方法によって本発明に係る銅含有粒子を製造することができる。
-Manufacturing method of copper-containing particles-
The method for producing copper-containing particles according to the present invention is not particularly limited. In a preferred embodiment of the present invention, an alkylamine containing a metal salt (salt compound, copper fatty acid) of a fatty acid having 9 or less carbon atoms and copper, a reducing compound, and an alkylamine having 7 or less carbon atoms. The copper-containing particles according to the present invention can be produced by a method having a step of heating a composition containing the above.
前記方法は、銅前駆体として、炭素数が９以下である脂肪酸と銅との金属塩を使用するものである。これにより、銅前駆体としてシュウ酸銅等を用いる特許文献１に記載の方法と比較して、より沸点の低い（すなわち、分子量の小さい）アルキルアミンを反応媒として使用することが可能になると考えられる。その結果、得られる銅含有粒子の表面に存在する有機物がより熱分解しやすいものとなり、導体化を低温で実施することが可能になっていると考えられる。 The method uses a metal salt of a fatty acid having 9 or less carbon atoms and copper as a copper precursor. It is considered that this makes it possible to use an alkylamine having a lower boiling point (that is, a smaller molecular weight) as a reaction medium as compared with the method described in Patent Document 1 in which copper oxalate or the like is used as a copper precursor. Be done. As a result, it is considered that the organic matter existing on the surface of the obtained copper-containing particles becomes more easily thermally decomposed, and the conductor formation can be carried out at a low temperature.
−脂肪酸−
前記方法に使用される脂肪酸は、ＲＣＯＯＨで表される１価のカルボン酸（Ｒは鎖状の炭化水素基であり、直鎖状であっても分岐を有していてもよい）である。本発明で使用される脂肪酸は、飽和脂肪酸又は不飽和脂肪酸のいずれであってもよい。コア粒子の良好な被覆を得る観点からは、直鎖状の飽和脂肪酸が好ましい。脂肪酸は１種のみでも、２種以上であってもよい。
-Fatty acid-
The fatty acid used in the method is a monovalent carboxylic acid represented by RCOOH (R is a chain hydrocarbon group, which may be linear or branched). The fatty acid used in the present invention may be either a saturated fatty acid or an unsaturated fatty acid. Linear saturated fatty acids are preferred from the standpoint of obtaining good coverage of the core particles. The fatty acid may be only one kind or two or more kinds.
低温で良好な焼結を得る観点からは、前記脂肪酸の炭素数が９以下であることが好ましい。炭素数が９以下である飽和脂肪酸としては、酢酸（炭素数２）、プロピオン酸（炭素数３）、酪酸及びイソ酪酸（炭素数４）、吉草酸及びイソ吉草酸（炭素数５）、カプロン酸（炭素数６）、エナント酸及びイソエナント酸（炭素数７）、カプリル酸、イソカプリル酸及びイソカプロン酸（炭素数８）、ノナン酸及びイソノナン酸（炭素数９）等を挙げることができる。炭素数が９以下である不飽和脂肪酸としては、上記の飽和脂肪酸の炭化水素基中に１つ以上の二重結合を有するものを挙げることができる。 From the viewpoint of obtaining good sintering at low temperature, the fatty acid preferably has 9 or less carbon atoms. Saturated fatty acids having 9 or less carbon atoms include acetic acid (2 carbon atoms), propionic acid (3 carbon atoms), butyric acid and isobutyric acid (4 carbon atoms), valeric acid and isovaleric acid (5 carbon atoms), and caproic acid. Acids (6 carbon atoms), enanthic acid and isoenanthic acid (7 carbon atoms), capric acid, isocaprilic acid and isocaproic acid (8 carbon atoms), nonanoic acid and isononanoic acid (9 carbon atoms) and the like can be mentioned. Examples of unsaturated fatty acids having 9 or less carbon atoms include those having one or more double bonds in the hydrocarbon groups of the above-mentioned saturated fatty acids.
本発明における銅含有粒子の製造に使用される脂肪酸の種類は、得られる銅含有粒子の分散媒（溶媒）への分散性、焼結性等の性質に影響しうる。このため、銅含有粒子の用途に応じて脂肪酸の種類を選択することが好ましい。分散媒への分散性と低温での導体化性を両立する観点からは、炭素数が５以上、９以下である脂肪酸と、炭素数が４以下である脂肪酸とを併用することが好ましい。例えば、炭素数が９であるノナン酸と、炭素数が２である酢酸とを併用することが好ましい。 The type of fatty acid used for producing the copper-containing particles in the present invention may affect properties such as dispersibility of the obtained copper-containing particles in a dispersion medium (solvent) and sinterability. Therefore, it is preferable to select the type of fatty acid according to the use of the copper-containing particles. From the viewpoint of achieving both dispersibility in a dispersion medium and conductivity at low temperature, it is preferable to use a fatty acid having 5 or more and 9 or less carbon atoms and a fatty acid having 4 or less carbon atoms in combination. For example, it is preferable to use nonanoic acid having 9 carbon atoms and acetic acid having 2 carbon atoms in combination.
炭素数が５以上、９以下である脂肪酸と炭素数が４以下である脂肪酸とを併用する場合の比率は、特に制限されない。尚、炭素数が９以下である脂肪酸中の炭素数が４以下である脂肪酸の割合を４０モル％未満とすると、一方の方向に長く延びる長粒の形状の銅含有粒子を安定して製造することができる。一方、炭素数が４以下である脂肪酸の割合を４０モル％以上とすると、球形の形状に制御される傾向にある。 The ratio when a fatty acid having 5 or more and 9 or less carbon atoms and a fatty acid having 4 or less carbon atoms are used in combination is not particularly limited. When the proportion of fatty acids having 4 or less carbon atoms in the fatty acids having 9 or less carbon atoms is less than 40 mol%, long-grained copper-containing particles extending in one direction are stably produced. be able to. On the other hand, when the proportion of fatty acids having 4 or less carbon atoms is 40 mol% or more, the shape tends to be controlled into a spherical shape.
炭素数が９以下である脂肪酸と銅との塩化合物（脂肪酸銅）を得る方法は特に制限されない。例えば、水酸化銅と脂肪酸とを溶媒中で混合することで得てもよく、市販されている脂肪酸銅を用いてもよい。あるいは、水酸化銅、脂肪酸及び還元性化合物を溶媒中で混合することで、脂肪酸銅の生成と、脂肪酸銅と還元性化合物との間で形成される錯体の生成とを一括して行ってもよい。 The method for obtaining a salt compound (fatty acid copper) of a fatty acid having 9 or less carbon atoms and copper is not particularly limited. For example, it may be obtained by mixing copper hydroxide and a fatty acid in a solvent, or commercially available fatty acid copper may be used. Alternatively, by mixing copper hydroxide, a fatty acid and a reducing compound in a solvent, the production of the fatty acid copper and the formation of the complex formed between the fatty acid copper and the reducing compound may be carried out collectively. Good.
−還元性化合物−
前記方法に使用される還元性化合物は、脂肪酸銅と混合した際に両化合物間で錯体等の複合化合物を形成すると考えられる。これにより、還元性化合物が脂肪酸銅中の銅イオンに対する電子のドナーとなり銅イオンの還元が生じやすくなり、錯体を形成していない状態の脂肪酸銅よりも自発的な熱分解による銅原子の遊離が生じやすくなると考えられる。還元性化合物は１種を単独で用いても、２種以上を併用してもよい。
-Reducing compound-
It is considered that the reducing compound used in the above method forms a complex compound such as a complex between the two compounds when mixed with the fatty acid copper. As a result, the reducing compound becomes an electron donor to the copper ions in the fatty acid copper, and the copper ions are more likely to be reduced, and the copper atoms are released by spontaneous thermal decomposition as compared with the fatty acid copper in the state where the complex is not formed. It is thought that it is likely to occur. One type of reducing compound may be used alone, or two or more types may be used in combination.
還元性化合物として具体的には、ヒドラジン、ヒドラジン誘導体、塩酸ヒドラジン、硫酸ヒドラジン、抱水ヒドラジン等のヒドラジン化合物、ヒドロキシルアミン、ヒドロキシルアミン誘導体等のヒドロキシルアミン化合物、水素化ホウ素ナトリウム、亜硫酸ナトリウム、亜硫酸水素ナトリウム、チオ硫酸ナトリウム、次亜リン酸ナトリウム等のナトリウム化合物などを挙げることができる。 Specific examples of the reducing compound include hydrazine, hydrazine derivative, hydrazine hydrochloride, hydrazine sulfate, hydrazine sulfate such as hydrazine hydrate, hydroxylamine compound such as hydroxylamine and hydroxylamine derivative, sodium boron hydride, sodium sulfite, and hydrogen sulfite. Examples thereof include sodium compounds such as sodium, sodium thiosulfate, and sodium hypophosphate.
脂肪酸銅中の銅原子に対して配位結合を形成しやすい、脂肪酸銅の構造を維持した状態で錯体を形成しやすい等の観点からは、アミノ基を有する還元性化合物が好ましい。アミノ基を有する還元性化合物としては、ヒドラジン及びその誘導体、ヒドロキシルアミン及びその誘導体等を挙げることができる。 A reducing compound having an amino group is preferable from the viewpoints of easily forming a coordination bond with respect to a copper atom in the fatty acid copper and easily forming a complex while maintaining the structure of the fatty acid copper. Examples of the reducing compound having an amino group include hydrazine and its derivative, hydroxylamine and its derivative, and the like.
前記方法において脂肪酸銅、還元性化合物及びアルキルアミンを含む組成物を加熱する工程（以下では加熱工程ともいう）における加熱温度を低くする（例えば、１５０℃以下）観点からは、アルキルアミンの蒸発又は分解を生じない温度範囲において銅原子の還元及び遊離を生じる錯体を形成可能な還元性化合物を選択することが好ましい。このような還元性化合物としては、ヒドラジン及びその誘導体、ヒドロキシルアミン及びその誘導体等を挙げることができる。これらの還元性化合物は、骨格を成す窒素原子が銅原子との配位結合を形成して錯体を形成可能である。また、これらの還元性化合物は一般にアルキルアミンと比較して還元力が強いため、生成した錯体が比較的穏和な条件で自発的な分解を生じ、銅原子の還元及び遊離が生じる傾向にある。 From the viewpoint of lowering the heating temperature (for example, 150 ° C. or lower) in the step of heating the composition containing the fatty acid copper, the reducing compound and the alkylamine in the above method (hereinafter, also referred to as a heating step), evaporation of the alkylamine or It is preferable to select a reducing compound capable of forming a complex that causes reduction and liberation of copper atoms in a temperature range that does not cause decomposition. Examples of such reducing compounds include hydrazine and its derivatives, hydroxylamine and its derivatives, and the like. In these reducing compounds, the nitrogen atom forming the skeleton can form a coordination bond with the copper atom to form a complex. In addition, since these reducing compounds generally have a stronger reducing power than alkylamines, the formed complex tends to spontaneously decompose under relatively mild conditions, resulting in reduction and liberation of copper atoms.
ヒドラジン又はヒドロキシルアミンの代わりにこれらの誘導体から好適なものを選択することで、脂肪酸銅との反応性を調節することができ、所望の条件で自発分解を生じる錯体を生成することができる。ヒドラジン誘導体としては、メチルヒドラジン、エチルヒドラジン、ｎ−プロピルヒドラジン、イソプロピルヒドラジン、ｎ−ブチルヒドラジン、イソブチルヒドラジン、ｓｅｃ−ブチルヒドラジン、ｔ−ブチルヒドラジン、ｎ−ペンチルヒドラジン、イソペンチルヒドラジン、ｎｅｏ−ペンチルヒドラジン、ｔ−ペンチルヒドラジン、ｎ−ヘキシルヒドラジン、イソヘキシルヒドラジン、ｎ−ヘプチルヒドラジン、ｎ−オクチルヒドラジン、ｎ−ノニルヒドラジン、ｎ−デシルヒドラジン、ｎ−ウンデシルヒドラジン、ｎ−ドデシルヒドラジン、シクロヘキシルヒドラジン、フェニルヒドラジン、４−メチルフェニルヒドラジン、ベンジルヒドラジン、２−フェニルエチルヒドラジン、２−ヒドラジノエタノール、アセトヒドラジン等を挙げることができる。ヒドロキシルアミンの誘導体としては、Ｎ，Ｎ−ジ（スルホエチル）ヒドロキシルアミン、モノメチルヒドロキシルアミン、ジメチルヒドロキシルアミン、モノエチルヒドロキシルアミン、ジエチルヒドロキシルアミン、Ｎ，Ｎ−ジ（カルボキシエチル）ヒドロキシルアミン等を挙げることができる。 By selecting a suitable derivative from these derivatives instead of hydrazine or hydroxylamine, the reactivity with the fatty acid copper can be adjusted, and a complex that causes spontaneous decomposition can be produced under desired conditions. Examples of hydrazine derivatives include methyl hydrazine, ethyl hydrazine, n-propyl hydrazine, isopropyl hydrazine, n-butyl hydrazine, isobutyl hydrazine, sec-butyl hydrazine, t-butyl hydrazine, n-pentyl hydrazine, isopentyl hydrazine, neo-pentyl hydrazine. , T-pentyl hydrazine, n-hexyl hydrazine, isohexyl hydrazine, n-heptyl hydrazine, n-octyl hydrazine, n-nonyl hydrazine, n-decyl hydrazine, n-undecyl hydrazine, n-dodecyl hydrazine, cyclohexyl hydrazine, phenyl Examples thereof include hydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazinoethanol, acetohydrazine and the like. Examples of the hydroxylamine derivative include N, N-di (sulfoethyl) hydroxylamine, monomethylhydroxylamine, dimethylhydroxylamine, monoethylhydroxylamine, diethylhydroxylamine, N, N-di (carboxyethyl) hydroxylamine and the like. Can be done.
脂肪酸銅に含まれる銅と還元性化合物の比率は、所望の錯体が形成される条件であれば特に制限されない。例えば、前記比率（銅：還元性化合物）はモル基準で１：１〜１：４の範囲とすることができ、１：１〜１：３の範囲とすることが好ましく、１：１〜１：２の範囲とすることがより好ましい。 The ratio of copper to the reducing compound contained in the fatty acid copper is not particularly limited as long as the desired complex is formed. For example, the ratio (copper: reducing compound) can be in the range of 1: 1 to 1: 4 on a molar basis, preferably in the range of 1: 1 to 1: 3, and 1: 1 to 1. : It is more preferable to set it in the range of 2.
−アルキルアミン−
前記方法に使用されるアルキルアミンは、脂肪酸銅と還元性化合物とから形成される錯体の分解反応の反応媒として機能すると考えられる。さらに、還元性化合物の還元作用によって生じるプロトンを捕捉し、反応溶液が酸性に傾いて銅原子が酸化されることを抑制すると考えられる。
-Alkylamine-
The alkylamine used in the method is considered to function as a reaction medium for the decomposition reaction of the complex formed from the fatty acid copper and the reducing compound. Furthermore, it is considered that the protons generated by the reducing action of the reducing compound are captured, and the reaction solution is inclined to be acidic to suppress the oxidation of copper atoms.
アルキルアミンは、本発明の銅含有粒子の表面に存在する有機物に関連して述べたものと同様である。アルキルアミンが特定アルキルアミン（炭素数が７以下であるアルキルアミン）以外のアルキルアミンを含む場合、アルキルアミン全体に占める特定アルキルアミンの割合は５０質量％以上であることが好ましく、６０質量％以上であることがより好ましく、７０質量％以上であることが更に好ましい。 Alkylamines are similar to those described in relation to the organic matter present on the surface of the copper-containing particles of the present invention. When the alkylamine contains an alkylamine other than the specific alkylamine (alkylamine having 7 or less carbon atoms), the ratio of the specific alkylamine to the total alkylamine is preferably 50% by mass or more, preferably 60% by mass or more. Is more preferable, and 70% by mass or more is further preferable.
脂肪酸銅に含まれる銅とアルキルアミンの比率は、所望の銅含有粒子が得られる条件であれば特に制限されない。例えば、前記比率（銅：アルキルアミン）はモル基準で１：１〜１：８の範囲とすることができ、１：１〜１：６の範囲とすることが好ましく、１：１〜１：４の範囲とすることがより好ましい。 The ratio of copper to alkylamine contained in the fatty acid copper is not particularly limited as long as the desired copper-containing particles can be obtained. For example, the ratio (copper: alkylamine) can be in the range of 1: 1 to 1: 8 on a molar basis, preferably in the range of 1: 1 to 1: 6, and 1: 1 to 1: 1. The range of 4 is more preferable.
−加熱工程−
前記方法において、脂肪酸銅、還元性化合物及びアルキルアミンを含む組成物を加熱する工程を実施するための方法は特に制限されない。例えば、脂肪酸銅と還元性化合物とを混合した後にアルキルアミンを添加して得た組成物を加熱する方法、脂肪酸銅とアルキルアミンとを混合した後に還元性化合物を添加して得た組成物を加熱する方法、脂肪酸銅の出発物質である水酸化銅、脂肪酸、還元性化合物及びアルキルアミンを混合して得た組成物を加熱する方法等を挙げることができる。
-Heating process-
In the above method, the method for carrying out the step of heating the composition containing the fatty acid copper, the reducing compound and the alkylamine is not particularly limited. For example, a method of heating a composition obtained by adding an alkylamine after mixing a fatty acid copper and a reducing compound, and a composition obtained by adding a reducing compound after mixing a fatty acid copper and an alkylamine. Examples thereof include a method of heating, a method of heating a composition obtained by mixing copper hydroxide, which is a starting material of fatty acid copper, a fatty acid, a reducing compound and an alkylamine.
脂肪酸銅、還元性化合物及びアルキルアミンを含む組成物の加熱は、脂肪酸銅と還元性化合物とから形成される錯体が分解する温度で行われる。例えば、前記加熱は１５０℃以下で行うことが好ましく、１３０℃以下で行うことがより好ましく、１００℃以下で行うことが更に好ましい。前記方法では、銅前駆体として特定の脂肪酸銅を用いることにより、加熱工程を比較的低温で行うことができる。 The composition containing the fatty acid copper, the reducing compound and the alkylamine is heated at a temperature at which the complex formed from the fatty acid copper and the reducing compound decomposes. For example, the heating is preferably performed at 150 ° C. or lower, more preferably 130 ° C. or lower, and even more preferably 100 ° C. or lower. In the above method, the heating step can be performed at a relatively low temperature by using a specific fatty acid copper as the copper precursor.
脂肪酸銅、還元性化合物及びアルキルアミンを含む組成物は、さらに溶媒を含んでもよい。脂肪酸銅と還元性化合物による錯体の形成を促進する観点からは、極性溶媒を含むことが好ましい。ここで極性溶媒とは、２５℃で水に対する溶解度を有するものであることが好ましく、アルコール溶媒であることがより好ましい。溶媒としてアルコールを用いることで錯体の形成が促進される理由は明らかではないが、固体である脂肪酸銅を溶解させながら水溶性である還元性化合物との接触が促進されるためと考えられる。溶媒は１種を単独で用いても、２種以上を併用してもよい。 The composition containing the fatty acid copper, the reducing compound and the alkylamine may further contain a solvent. From the viewpoint of promoting the formation of a complex of the fatty acid copper and the reducing compound, it is preferable to contain a polar solvent. Here, the polar solvent is preferably one having solubility in water at 25 ° C., and more preferably an alcohol solvent. The reason why the formation of the complex is promoted by using alcohol as the solvent is not clear, but it is considered that the contact with the water-soluble reducing compound is promoted while dissolving the solid fatty acid copper. One type of solvent may be used alone, or two or more types may be used in combination.
２５℃で水に対する溶解度を示すアルコールとしては、炭素数が１〜８であり、分子中に水酸基を１つ有するアルコールを挙げることができる。このようなアルコールとしては、直鎖状のアルキルアルコール、フェノール、分子内にエーテル結合を有する炭化水素の水素原子を水酸基で置換したもの等を挙げることができる。より強い極性を発現する観点からは、分子中に水酸基を２個以上含むアルコールも好ましく用いられる。また、製造される銅含有粒子の用途に応じて硫黄原子、リン原子、ケイ素原子等を含むアルコールを用いてもよい。 Examples of the alcohol showing solubility in water at 25 ° C. include alcohols having 1 to 8 carbon atoms and having one hydroxyl group in the molecule. Examples of such alcohols include linear alkyl alcohols, phenols, and those in which the hydrogen atom of a hydrocarbon having an ether bond in the molecule is replaced with a hydroxyl group. From the viewpoint of exhibiting stronger polarity, an alcohol containing two or more hydroxyl groups in the molecule is also preferably used. Further, alcohol containing a sulfur atom, a phosphorus atom, a silicon atom and the like may be used depending on the use of the produced copper-containing particles.
溶媒として用いるアルコールとして具体的には、メタノール、エタノール、１−プロパノール、２−プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、アリルアルコール、ベンジルアルコール、ピナコール、プロピレングリコール、メントール、カテコール、ヒドロキノン、サリチルアルコール、グリセリン、ペンタエリスリトール、スクロース、グルコース、キシリトール、メトキシエタノール、トリエチレングリコールモノメチルエーテル、エチレングリコール、トリエチレングリコール、テトラエチレングリコール、ペンタエチレングリコール等を挙げることができる。 Specific examples of alcohols used as solvents include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptanol, octanol, allyl alcohol, benzyl alcohol, pinacol, propylene glycol, menthol, catechol, hydroquinone, and so on. Examples thereof include salicyl alcohol, glycerin, pentaerythritol, sucrose, glucose, xylitol, methoxyethanol, triethylene glycol monomethyl ether, ethylene glycol, triethylene glycol, tetraethylene glycol and pentaethylene glycol.
前記アルコールのうち、水に対する溶解度が極めて大きいメタノール、エタノール、１−プロパノール及び２−プロパノールが好ましく、１−プロパノール及び２−プロパノールがより好ましく、１−プロパノールが更に好ましい。 Among the alcohols, methanol, ethanol, 1-propanol and 2-propanol having extremely high solubility in water are preferable, 1-propanol and 2-propanol are more preferable, and 1-propanol is further preferable.
（分散媒）
本発明に係る導電性組成物に使用される分散媒（溶媒）は特に制限されず、導電性インク、導電性ペースト等の作製に一般に用いられる有機溶剤から用途に応じて選択できる。例えば、粘度コントロールの観点からは、テルピネオール、イソボルニルシクロヘキサノール、ジヒドロターピネオール、ジヒドロターピネオールアセテート等が好ましい。
(Dispersion medium)
The dispersion medium (solvent) used in the conductive composition according to the present invention is not particularly limited, and can be selected from organic solvents generally used for producing conductive inks, conductive pastes and the like, depending on the intended use. For example, from the viewpoint of viscosity control, terpineol, isobornylcyclohexanol, dihydroterpineol, dihydroterpineol acetate and the like are preferable.
（その他の成分）
本発明における導電性組成物は、上述した成分に加え、必要に応じて、当該技術分野で通常用いられるその他の成分を更に含むことができる。その他の成分としては、例えば、チクソ剤、可塑剤、分散剤、界面活性剤、無機結合剤、金属酸化物、セラミック及び有機金属化合物を挙げることができる。
(Other ingredients)
In addition to the above-mentioned components, the conductive composition in the present invention may further contain other components usually used in the art, if necessary. Examples of other components include tincture agents, plasticizers, dispersants, surfactants, inorganic binders, metal oxides, ceramics and organometallic compounds.
（導電性組成物の製造方法）
本発明における導電性組成物の製造方法は特に限定されず、当該技術分野で通常用いられる方法を用いることができる。
例えば、本発明における銅含有粒子及び必要に応じて含まれるその他の成分を分散媒中に分散処理することで調製することができる。分散処理は、石川式攪拌器、自転公転式撹拌機、超薄膜高速回転式分散機、ロールミル、超音波分散機、ビーズミル等のメディア分散機、ホモミキサー、シルバーソン攪拌機等のキャビテーション攪拌装置、アルテマイザー等の対向衝突法を用いることができる。また、これらの手法を適宜組み合わせて用いてもよい。
(Manufacturing method of conductive composition)
The method for producing the conductive composition in the present invention is not particularly limited, and a method usually used in the art can be used.
For example, it can be prepared by dispersing the copper-containing particles and other components contained in the present invention in a dispersion medium. Dispersion processing includes Ishikawa stirrer, rotating and revolving stirrer, ultra-thin high-speed rotary disperser, roll mill, ultrasonic disperser, media disperser such as bead mill, cavitation stirrer such as homomixer and silverson stirrer, Artema An opposed collision method such as Iser can be used. Moreover, you may use these methods in combination as appropriate.
本発明の導電性組成物の状態は特に制限されず、用途に応じて選択できる。例えば、導電性組成物をスクリーン印刷法に適用する場合は、使用する温度で粘度が０．１〜３０Ｐａ・ｓの導電性ペーストであることが好ましく、１〜３０Ｐａ・ｓであることがより好ましい。導電性組成物をインクジェット印刷法に適用する場合は、使用するインクジェットヘッドの規格にもよるが、使用する温度で粘度が０．１〜３０ｍＰａ・ｓの導電性インクであることが好ましく、５〜２０ｍＰａ・ｓであることがより好ましい。 The state of the conductive composition of the present invention is not particularly limited and can be selected according to the intended use. For example, when the conductive composition is applied to the screen printing method, it is preferably a conductive paste having a viscosity of 0.1 to 30 Pa · s at the temperature of use, and more preferably 1 to 30 Pa · s. .. When the conductive composition is applied to the inkjet printing method, it is preferably a conductive ink having a viscosity of 0.1 to 30 mPa · s at the temperature at which it is used, although it depends on the specifications of the inkjet head used. It is more preferably 20 mPa · s.
（導電性組成物の付与方法）
導電性組成物を基板上に付与して導電性組成物の含有層を形成する方法は、導電性組成物を基板上の任意の場所に任意の形状で形成可能な手法であれば特に制限はない。このような手法として、インクジェット法、スーパーインクジェット法、スクリーン印刷法、転写印刷法、オフセット印刷法、ジェットプリンティング法、ディスペンサ法、ジェットディスペンサ法、ニードルディスペンサ法、カンマコート法、スリットコート法、ダイコート法、グラビアコート法、凸版印刷法、凹版印刷法、グラビア印刷法、ソフトリソグラフ法、ディップペンリソグラフ法、粒子堆積法、スプレーコート法、スピンコート法、ディップコート法、電着塗装法等を挙げることができる。中でも、インクジェット法、スーパーインクジェット法、スクリーン印刷法、オフセット印刷法、ジェットプリンティング法、ディスペンサ法、ニードルディスペンサ法、カンマコート法、スリットコート法、ダイコート法及びグラビアコート法からなる群より選択される少なくとも１種の方法であることが好ましい。例えば、ペースト状の導電性組成物をスクリーン印刷法により基板上に付与してもよく、インク状の導電性組成物をインクジェット印刷法により基板上に付与してもよい。
(Method of applying the conductive composition)
The method of applying the conductive composition on the substrate to form the containing layer of the conductive composition is particularly limited as long as it is a method in which the conductive composition can be formed at an arbitrary place on the substrate in an arbitrary shape. Absent. Such methods include an inkjet method, a super inkjet method, a screen printing method, a transfer printing method, an offset printing method, a jet printing method, a dispenser method, a jet dispenser method, a needle dispenser method, a comma coating method, a slit coating method, and a die coating method. , Gravure coating method, letterpress printing method, concave printing method, gravure printing method, soft lithograph method, dip pen lithograph method, particle deposition method, spray coating method, spin coating method, dip coating method, electrodeposition coating method, etc. Can be done. Among them, at least selected from the group consisting of an inkjet method, a super inkjet method, a screen printing method, an offset printing method, a jet printing method, a dispenser method, a needle dispenser method, a comma coating method, a slit coating method, a die coating method and a gravure coating method. One method is preferable. For example, the paste-like conductive composition may be applied onto the substrate by a screen printing method, or the ink-like conductive composition may be applied onto the substrate by an inkjet printing method.
（銅膜の特性）
基板上に形成される銅膜の形状は特に制限されず、目的に応じて適宜選択することができる。
また、銅膜の厚みは特に制限されず、目的に応じて適宜選択することができる。例えば０．２〜５０μｍとすることができ、導電性及び接続信頼性の観点から０．５〜２０μｍであることが好ましい。
(Characteristics of copper film)
The shape of the copper film formed on the substrate is not particularly limited, and can be appropriately selected depending on the intended purpose.
Further, the thickness of the copper film is not particularly limited and can be appropriately selected depending on the intended purpose. For example, it can be 0.2 to 50 μm, and is preferably 0.5 to 20 μm from the viewpoint of conductivity and connection reliability.
＜加熱処理工程＞
加熱処理工程では、還元性ガス雰囲気下で、導電性組成物を２５０℃以下の温度域、好ましくは２００℃以下、更に好ましくは１５０℃以下で加熱処理して銅膜を形成する。
<Heat treatment process>
In the heat treatment step, the conductive composition is heat-treated in a temperature range of 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower in a reducing gas atmosphere to form a copper film.
加熱処理工程における還元性ガスとして導入可能な物質としては、ギ酸や水素等が挙げられるが、特に制限はない。 Examples of the substance that can be introduced as the reducing gas in the heat treatment step include formic acid and hydrogen, but there is no particular limitation.
加熱処理工程における雰囲気において、不活性ガスを用いることができる。不活性ガスとしては、窒素ガス、アルゴンガス、ヘリウムガス等が挙げられる。 An inert gas can be used in the atmosphere of the heat treatment step. Examples of the inert gas include nitrogen gas, argon gas, helium gas and the like.
本発明に係る導電性組成物は上述のように、比較的低い温度で導体化することが可能である。具体的には例えば、２５０℃以下で導体化することができる。従って、例えば、樹脂等の耐熱性の低い基板上に銅配線を形成する場合等にも好適に用いることができる。加熱処理工程は一定の昇温速度で行っても、不規則に変化させてもよい。加熱処理時間は特に限定されず、加熱処理温度、加熱処理雰囲気、銅含有粒子の量等を考慮して選択できる。加熱処理時間は、工程管理の観点から、１０〜１２０分であることが好ましい。 As described above, the conductive composition according to the present invention can be made into a conductor at a relatively low temperature. Specifically, for example, it can be made into a conductor at 250 ° C. or lower. Therefore, for example, it can be suitably used when copper wiring is formed on a substrate having low heat resistance such as resin. The heat treatment step may be performed at a constant heating rate or may be changed irregularly. The heat treatment time is not particularly limited, and can be selected in consideration of the heat treatment temperature, the heat treatment atmosphere, the amount of copper-containing particles, and the like. The heat treatment time is preferably 10 to 120 minutes from the viewpoint of process control.
＜その他の工程＞
本発明の銅膜の製造方法は、必要に応じてその他の工程を含んでもよい。その他の工程としては、加熱処理工程後に酸化銅を還元する工程、加熱処理工程後に光焼成等により残存成分を除去する工程、加熱処理工程後に荷重をかける工程などを挙げることができる。
<Other processes>
The method for producing a copper film of the present invention may include other steps, if necessary. Examples of other steps include a step of reducing copper oxide after the heat treatment step, a step of removing residual components by light firing after the heat treatment step, a step of applying a load after the heat treatment step, and the like.
本発明の銅膜の製造方法により得られる銅層（導電体）付き基板は、従来よりも低温の加熱処理により製造することができるため、基板の損傷が少ない。従って、例えば、樹脂等の耐熱性の低い基板上に銅配線を形成する場合等にも好適に用いることができる。 The substrate with a copper layer (conductor) obtained by the method for producing a copper film of the present invention can be produced by heat treatment at a lower temperature than before, so that the substrate is less damaged. Therefore, for example, it can be suitably used when copper wiring is formed on a substrate having low heat resistance such as resin.
本発明の導電性組成物を導体化する方法において、加熱工程は一定の昇温速度で行っても、不規則に変化させてもよい。加熱工程の時間は特に制限されず、加熱温度、加熱雰囲気、銅含有粒子の量等を考慮して選択できる。加熱方法は特に制限されず、所定の温度まで上昇させられれば熱板による加熱や赤外ヒータなどの加熱、パルスレーザによる加熱などから選択できる。 In the method of forming the conductive composition of the present invention into a conductor, the heating step may be performed at a constant heating rate or may be changed irregularly. The time of the heating step is not particularly limited, and can be selected in consideration of the heating temperature, the heating atmosphere, the amount of copper-containing particles, and the like. The heating method is not particularly limited, and if the temperature is raised to a predetermined temperature, it can be selected from heating with a hot plate, heating with an infrared heater, heating with a pulse laser, and the like.
また、本発明における導電体（銅層）は、基板上に付与された導電材料の焼結物であるため、めっき法等により形成される導体と比較して、添加物として使用されるパラジウム等の不純物の量が少なく、体積抵抗率を低くすることができる傾向にある。 Further, since the conductor (copper layer) in the present invention is a sintered body of the conductive material applied on the substrate, palladium or the like used as an additive is compared with a conductor formed by a plating method or the like. The amount of impurities is small, and the volume resistivity tends to be low.
本発明により形成した銅膜（導電体）は、例えば積層板、太陽電池パネル、ディスプレイ、トランジスタなどの電気配線、放熱膜、表面被覆膜、半導体パッケージなどに利用することができる。 The copper film (conductor) formed by the present invention can be used, for example, for electrical wiring of laminated plates, solar cell panels, displays, transistors, etc., heat dissipation films, surface coating films, semiconductor packages, and the like.
以下、本発明について実施例を示して説明するが、本発明はこれらの実施例に何ら限定されない。 Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
＜実施例１＞
［１．１］ノナン酸銅の合成
脂肪酸と銅の塩化合物（脂肪酸銅）を合成するため水酸化銅（関東化学株式会社、特級）９１．５ｇ（０．９４ｍｏｌ）に１−プロパノール（関東化学株式会社、特級）１５０ｍＬを加えて撹拌し、これにノナン酸（関東化学株式会社、純度９０質量％以上）３７０．９ｇ（２．３４ｍｏｌ）を加えた。得られた混合物を、セパラブルフラスコ中で９０℃、３０分間加熱撹拌した。得られた溶液を加熱したままろ過して未溶解物を除去した。その後放冷し、生成したノナン酸銅を吸引ろ過し、洗浄液が透明になるまでヘキサンで洗浄した。得られた粉体を５０℃の防爆オーブンで３時間乾燥してノナン酸銅（ＩＩ）を得た。収量は３４０ｇ（収率９６質量％）であった。
<Example 1>
[1.1] Synthesis of copper nonanoate 1-propanol (Kanto Chemical Co., Ltd.) in 91.5 g (0.94 mol) of copper hydroxide (Kanto Chemical Co., Inc., special grade) for synthesizing a salt compound (fatty acid copper) of fatty acid and copper. (Co., Ltd., special grade) 150 mL was added and stirred, and 370.9 g (2.34 mol) of nonanoic acid (Kanto Chemical Co., Inc., purity 90% by mass or more) was added thereto. The resulting mixture was heated and stirred in a separable flask at 90 ° C. for 30 minutes. The obtained solution was filtered while being heated to remove undissolved substances. After that, the mixture was allowed to cool, and the produced copper nonanoate was suction-filtered and washed with hexane until the washing liquid became transparent. The obtained powder was dried in an explosion-proof oven at 50 ° C. for 3 hours to obtain copper (II) nonanoate. The yield was 340 g (yield 96% by mass).
［１．２］銅を含有するコア粒子の合成
上記で得られたノナン酸銅（ＩＩ）２１．０１ｇ（０．０５６ｍｏｌ）と酢酸銅（ＩＩ）無水物（関東化学株式会社、特級）４．３３ｇ（０．０２４ｍｏｌ）をセパラブルフラスコに入れ、１−プロパノール１０ｍＬと、アルキルアミンとしてヘキシルアミン（東京化成工業株式会社、純度９９質量％）３２．１ｇ（０．３２ｍｏｌ）を添加し、オイルバス中で、８０℃で加熱撹拌して溶解させた。氷浴に移し、内温が５℃になるまで冷却した後、ヒドラジン一水和物（関東化学株式会社、特級）７．７２ｍＬ（０．１６ｍｏｌ）を１−プロパノール１２ｍＬに溶解させた溶液を脂肪酸銅の溶液に加え、氷浴中で撹拌した。なお、銅：ヘキシルアミンのモル比は１：４である。次いで、オイルバス中で、９０℃で加熱撹拌した。その際、発泡を伴う還元反応が進み、１０分以内で反応が終了した。セパラブルフラスコの内壁が銅光沢を呈し、溶液が暗赤色に変化した。遠心分離を４０００（回転／分）で１分間実施して固体物を得た。固形物を更にヘキサン１５ｍＬで洗浄する工程を３回繰り返し、酸残渣を除去して、銅光沢を有する銅粒子を含む銅ケークを得た。
[1.2] Synthesis of core particles containing copper 21.01 g (0.056 mol) of copper (II) nonanoate and copper (II) anhydride obtained above (Kanto Chemical Co., Inc., special grade) 4. 33 g (0.024 mol) was placed in a separable flask, 10 mL of 1-propanol and 32.1 g (0.32 mol) of hexylamine (Tokyo Kasei Kogyo Co., Ltd., purity 99% by mass) were added as alkylamine, and an oil bath was added. Inside, it was dissolved by heating and stirring at 80 ° C. Transfer to an ice bath, cool to an internal temperature of 5 ° C, and then dissolve 7.72 mL (0.16 mol) of hydrazine monohydrate (Kanto Chemical Co., Inc., special grade) in 12 mL of 1-propanol to make a fatty acid. It was added to the copper solution and stirred in an ice bath. The molar ratio of copper: hexylamine is 1: 4. Then, it was heated and stirred at 90 ° C. in an oil bath. At that time, the reduction reaction accompanied by foaming proceeded, and the reaction was completed within 10 minutes. The inner wall of the separable flask had a copper luster and the solution turned dark red. Centrifugation was performed at 4000 (rotation / min) for 1 minute to give a solid. The step of further washing the solid material with 15 mL of hexane was repeated three times to remove the acid residue to obtain a copper cake containing copper particles having a copper luster.
［１．３］導電性組成物の調製
得られた銅ケーク（銅を含有するコア粒子、６０質量部）、分散媒としてテルピネオール（２０質量部）、及びイソボルニルシクロヘキサノール（商品名：テルソルブＭＴＰＨ、日本テルペン化学株式会社）（２０質量部）を混合して導電性組成物を作製した。
[1.3] Preparation of Conductive Composition The obtained copper cake (copper-containing core particles, 60 parts by mass), terpineol (20 parts by mass) as a dispersion medium, and isobornylcyclohexanol (trade name: Telsolve). MTPH, Nippon Terpineol Chemical Co., Ltd.) (20 parts by mass) was mixed to prepare a conductive composition.
［１．４］導体化
上記の導電性組成物をポリエチレンナフタレート（ＰＥＮ）フィルム上に塗布し、還元性ガス雰囲気として窒素中のギ酸の濃度を５体積％とした雰囲気中、昇温速度１５℃／分で１２０℃まで加熱し、６０分間保持して銅膜を形成した。
[1.4] Conductionization The above conductive composition is applied onto a polyethylene naphthalate (PEN) film, and the temperature rise rate is 15 in an atmosphere in which the concentration of formic acid in nitrogen is 5% by volume as a reducing gas atmosphere. It was heated to 120 ° C. at ° C./min and held for 60 minutes to form a copper film.
［低温導体化の評価］
得られた銅膜の表面抵抗値と膜厚から体積抵抗率を算出した。銅膜の膜厚は、非接触表面・層断面形状計測システム（ＶｅｒｔＳｃａｎ、株式会社菱化システム）で測定した。
上記の結果で体積抵抗率が３００μΩ・ｃｍ以下であると低温導体化が「良好」であり、３００μΩ・ｃｍを超えると低温導体化が「不良」であると評価した。
[Evaluation of low temperature conductor]
The volume resistivity was calculated from the surface resistance value and the film thickness of the obtained copper film. The film thickness of the copper film was measured by a non-contact surface / layer cross-sectional shape measurement system (VertScan, Ryoka System Co., Ltd.).
Based on the above results, it was evaluated that when the volume resistivity was 300 μΩ · cm or less, the low temperature conductor formation was “good”, and when it exceeded 300 μΩ · cm, the low temperature conductor formation was “poor”.
上記により体積抵抗率を測定・算出した結果は、５０μΩ・ｃｍであり、体積抵抗率が充分に低い導電体（導体）が形成されていた。以上より、本発明の銅含有粒子は低温の１２０℃で導体化できることが分かった。 The result of measuring and calculating the volume resistivity as described above was 50 μΩ · cm, and a conductor having a sufficiently low volume resistivity was formed. From the above, it was found that the copper-containing particles of the present invention can be made into a conductor at a low temperature of 120 ° C.
［銅含有粒子中のアミノ基を有する有機物の含有率の測定］
銅ケークを乾燥し、銅ケーク中のヘキサンを除去した後、有機物が熱分解する温度以上の温度で加熱し、加熱前後の質量を比較することで、銅含有粒子中のアミノ基を有する有機物の含有率を測定したところ、３．５質量％であった。
[Measurement of content of organic substances having amino groups in copper-containing particles]
After the copper cake is dried and the hexane in the copper cake is removed, the organic matter is heated at a temperature higher than the temperature at which the organic matter is thermally decomposed, and the masses before and after the heating are compared. When the content was measured, it was 3.5% by mass.
＜実施例２＞
２５０℃で処理したこと以外は実施例１と同様にして導体化を行った。体積抵抗率を測定・算出した結果は３０μΩ・ｃｍであり、体積抵抗率が充分に低い銅膜である導電体が形成されていた。以上より、本発明の銅含有粒子は低温で導体化できることが分かった。
<Example 2>
Conduction was carried out in the same manner as in Example 1 except that the treatment was carried out at 250 ° C. The result of measuring and calculating the volume resistivity was 30 μΩ · cm, and a conductor which was a copper film having a sufficiently low volume resistivity was formed. From the above, it was found that the copper-containing particles of the present invention can be made into a conductor at a low temperature.
＜比較例１＞
ギ酸を導入せず、窒素中１２０℃で処理したこと以外は実施例１と同様にして導体化を行った。体積抵抗率を測定・算出した結果は導通が得られなかった。ギ酸を導入しない場合には１２０℃での加熱では有機物が除去しきれず、体積抵抗率が充分に低い導体が形成されなかった。
<Comparative example 1>
Conductorization was carried out in the same manner as in Example 1 except that formic acid was not introduced and the treatment was carried out in nitrogen at 120 ° C. As a result of measuring and calculating the volume resistivity, no continuity was obtained. When formic acid was not introduced, the organic matter could not be completely removed by heating at 120 ° C., and a conductor having a sufficiently low volume resistivity could not be formed.
＜比較例２＞
ギ酸を導入せず、窒素中２５０℃で処理したこと以外は実施例１と同様にして導体化を行った。体積抵抗率を測定・算出した結果は６０μΩ・ｃｍであり、体積抵抗率が低い銅膜である導電体が形成されていたが、ギ酸を導入した場合よりも抵抗率は高い値を示した。
<Comparative example 2>
Conductorization was carried out in the same manner as in Example 1 except that formic acid was not introduced and the treatment was carried out in nitrogen at 250 ° C. The result of measuring and calculating the volume resistivity was 60 μΩ · cm, and a conductor which was a copper film having a low volume resistivity was formed, but the resistivity was higher than that when formic acid was introduced.
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