JP6996100B2 - Conductors and their manufacturing methods, conductor forming compositions, laminates, and equipment - Google Patents
Conductors and their manufacturing methods, conductor forming compositions, laminates, and equipment Download PDFInfo
- Publication number
- JP6996100B2 JP6996100B2 JP2017068096A JP2017068096A JP6996100B2 JP 6996100 B2 JP6996100 B2 JP 6996100B2 JP 2017068096 A JP2017068096 A JP 2017068096A JP 2017068096 A JP2017068096 A JP 2017068096A JP 6996100 B2 JP6996100 B2 JP 6996100B2
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- Prior art keywords
- copper
- conductor
- resin
- mass
- containing particles
- Prior art date
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- 239000004020 conductor Substances 0.000 title claims description 105
- 239000000203 mixture Substances 0.000 title claims description 72
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 175
- 229910052802 copper Inorganic materials 0.000 claims description 171
- 239000010949 copper Substances 0.000 claims description 171
- 239000002245 particle Substances 0.000 claims description 129
- 229920005989 resin Polymers 0.000 claims description 76
- 239000011347 resin Substances 0.000 claims description 76
- 238000010438 heat treatment Methods 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 34
- 239000012298 atmosphere Substances 0.000 claims description 32
- 239000000126 substance Substances 0.000 claims description 31
- 239000007771 core particle Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000005416 organic matter Substances 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 11
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 43
- 229930195729 fatty acid Natural products 0.000 description 43
- 239000000194 fatty acid Substances 0.000 description 43
- 150000004665 fatty acids Chemical class 0.000 description 42
- 150000003973 alkyl amines Chemical class 0.000 description 41
- 230000001603 reducing effect Effects 0.000 description 34
- 150000001875 compounds Chemical class 0.000 description 33
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 18
- 150000002430 hydrocarbons Chemical group 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000002184 metal Substances 0.000 description 13
- 239000000853 adhesive Substances 0.000 description 12
- 230000001070 adhesive effect Effects 0.000 description 12
- 239000005751 Copper oxide Substances 0.000 description 11
- -1 copper fatty acids Chemical class 0.000 description 11
- 229910000431 copper oxide Inorganic materials 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000002923 metal particle Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 238000010306 acid treatment Methods 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 5
- 239000005750 Copper hydroxide Substances 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 229910001956 copper hydroxide Inorganic materials 0.000 description 5
- 239000002612 dispersion medium Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- HZULDDWVCRWYCB-UHFFFAOYSA-L copper;nonanoate Chemical compound [Cu+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O HZULDDWVCRWYCB-UHFFFAOYSA-L 0.000 description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 150000004671 saturated fatty acids Chemical class 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 3
- 239000012691 Cu precursor Substances 0.000 description 3
- 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
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 150000002429 hydrazines Chemical class 0.000 description 3
- 150000002443 hydroxylamines Chemical class 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000002203 pretreatment Methods 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000011135 tin Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 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
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-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
- 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
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating 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
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003985 ceramic capacitor Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 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
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000976 ink Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000011256 inorganic filler Substances 0.000 description 2
- 229910003475 inorganic filler Inorganic materials 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
- BMFVGAAISNGQNM-UHFFFAOYSA-N isopentylamine Chemical compound CC(C)CCN BMFVGAAISNGQNM-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
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- UODXCYZDMHPIJE-UHFFFAOYSA-N menthanol Chemical compound CC1CCC(C(C)(C)O)CC1 UODXCYZDMHPIJE-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
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- 239000011574 phosphorus Substances 0.000 description 2
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
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- 239000009719 polyimide resin Substances 0.000 description 2
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- 239000000843 powder Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 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
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- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 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
- 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
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- GDVFVEWTCYWKGV-UHFFFAOYSA-N 1-hydroxyheptan-2-one Chemical compound CCCCCC(=O)CO GDVFVEWTCYWKGV-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 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 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
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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Description
本発明は、導体及びその製造方法、導体形成用組成物、積層体、並びに装置に関する。 The present invention relates to a conductor and a method for producing the conductor, a composition for forming a conductor, a laminate, and an apparatus.
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材上に金属を含む層を形成する工程と、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、いわゆるプリンテッドエレクトロニクス法が知られている。導電材料に含まれる金属粒子としては、例えば、金属の酸化を抑制して保存性を高めるために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及び特許文献２参照）。 As a method for forming a metal pattern, a step of forming a layer containing metal on a substrate by inkjet printing, screen printing, or the like of an ink containing metal particles such as copper or a conductive material such as a paste, and a step of heating the conductive material to form a metal. A so-called printed electronics method is known, which includes a step of forming a conductor by sintering particles to develop conductivity. As the metal particles contained in the conductive material, for example, those in which an organic substance as a coating material is attached to the surface in order to suppress the oxidation of the metal and improve the storage stability are known (for example, Patent Document 1 and Patent). See Document 2).
しかし、金属粒子を焼結して形成された導体は、基材の種類によっては充分な接着力が得られずに基材から剥離してしまい、装置に欠陥が生じてしまう場合がある。近年用いられている基材の材質は、樹脂、金属、セラミック、ガラス、無機フィラー含有樹脂等と多様化しつつあり、これらの多様な基材に対する導体の接着力向上が課題となっている。 However, depending on the type of the base material, the conductor formed by sintering the metal particles may not have sufficient adhesive force and may peel off from the base material, resulting in defects in the apparatus. The materials of the base materials used in recent years are diversifying into resins, metals, ceramics, glass, resins containing inorganic fillers, and the like, and improving the adhesive strength of conductors to these various base materials has become an issue.
基材に対する導体の接着力を向上させる方法としては、金属粒子を含むペースト等の導体形成用組成物に樹脂成分を添加する方法が挙げられる。しかし、絶縁性である樹脂成分の添加は、金属粒子の焼結を阻害し十分な導電性の発現を妨げる傾向にある。このため、基材に対する接着性と導体の導電性とを両立することは困難であった。さらに、金属粒子の焼結を低温で行う場合、樹脂成分の添加が少量であっても著しく導電性を損なってしまうおそれがある。 Examples of the method for improving the adhesive force of the conductor to the base material include a method of adding a resin component to a conductor forming composition such as a paste containing metal particles. However, the addition of an insulating resin component tends to inhibit the sintering of metal particles and prevent the development of sufficient conductivity. For this reason, it has been difficult to achieve both adhesiveness to the base material and conductivity of the conductor. Further, when the metal particles are sintered at a low temperature, even a small amount of the resin component added may significantly impair the conductivity.
また、金属粒子は酸化され易い性質を持ち、特に銅粒子は、金粒子又は銀粒子に比べてより酸化され易い性質を持つ。金属粒子が酸化されると、金属酸化物が粒子同士の焼結を阻害して、十分な導電性の発現が妨げられる。このため、金属粒子を焼結させる際には、金属粒子の酸化を抑制するために、酸素を含まない窒素等の不活性雰囲気又は還元性雰囲気下で加熱が行われる。しかし、不活性雰囲気又は還元性雰囲気下で使用できる加熱装置は特殊であるため、酸素を含む大気雰囲気下で焼結した場合にも導電性を確保できることが望ましい。 Further, the metal particles have a property of being easily oxidized, and in particular, copper particles have a property of being more easily oxidized as compared with gold particles or silver particles. When the metal particles are oxidized, the metal oxide inhibits the sintering of the particles, and the development of sufficient conductivity is hindered. Therefore, when the metal particles are sintered, heating is performed in an inert atmosphere such as nitrogen containing no oxygen or a reducing atmosphere in order to suppress the oxidation of the metal particles. However, since the heating device that can be used in an inert atmosphere or a reducing atmosphere is special, it is desirable that conductivity can be ensured even when sintered in an atmospheric atmosphere containing oxygen.
本発明は、基材に対する接着性に優れ、かつ大気雰囲気下で焼結させた場合であっても導電性に優れる導体を得るための導体の製造方法、導体、及び導体形成用組成物を提供することを主な目的とする。 The present invention provides a method for producing a conductor, a conductor, and a composition for forming a conductor in order to obtain a conductor having excellent adhesiveness to a substrate and excellent conductivity even when sintered in an air atmosphere. The main purpose is to do.
上記課題を解決するための手段には、以下の態様が含まれる。
＜１＞ 基材上に設けられた組成物であって、銅含有粒子と、銅含有粒子１００質量部に対して１．０質量部～３０質量部の樹脂とを含有する組成物を加熱した後、酸で処理して、焼結体を得る工程を備える、導体の製造方法。
＜２＞ 加熱は、酸素濃度が１００体積ｐｐｍ以上である雰囲気下で行われる、＜１＞に記載の導体の製造方法。
＜３＞ 焼結体上にめっき層を形成する工程を更に備える、＜１＞又は＜２＞に記載の導体の製造方法。
＜４＞ 銅含有粒子は、銅を含むコア粒子と、コア粒子の表面の少なくとも一部を被覆する有機物とを備える、＜１＞～＜３＞のいずれかに記載の導体の製造方法。
＜５＞ 銅含有粒子と、銅含有粒子１００質量部に対して１．０質量部～３０質量部の樹脂と、を含有する、導体形成用組成物。
＜６＞ 銅含有粒子は、銅を含むコア粒子と、コア粒子の表面の少なくとも一部を被覆する有機物とを備える、＜５＞に記載の導体形成用組成物。
＜７＞ １８０℃以下での加熱により導体化が可能である、＜５＞又は＜６＞に記載の導体形成用組成物。
＜８＞ ＜５＞～＜７＞のいずれかに記載の導体形成用組成物を焼結させてなる焼結体を含む、導体。
＜９＞ 基材と、基材上に設けられた、＜８＞に記載の導体と、を備える積層体。
＜１０＞ ＜９＞に記載の積層体を備える、装置。
The means for solving the above problems include the following aspects.
<1> A composition provided on a substrate and containing 1.0 part by mass to 30 parts by mass of a resin with respect to 100 parts by mass of copper-containing particles was heated. After that, a method for manufacturing a conductor, comprising a step of treating with an acid to obtain a sintered body.
<2> The method for manufacturing a conductor according to <1>, wherein the heating is performed in an atmosphere where the oxygen concentration is 100 volume ppm or more.
<3> The method for manufacturing a conductor according to <1> or <2>, further comprising a step of forming a plating layer on the sintered body.
<4> The method for producing a conductor according to any one of <1> to <3>, wherein the copper-containing particles include core particles containing copper and an organic substance that covers at least a part of the surface of the core particles.
<5> A conductor-forming composition containing copper-containing particles and a resin of 1.0 part by mass to 30 parts by mass with respect to 100 parts by mass of copper-containing particles.
<6> The conductor-forming composition according to <5>, wherein the copper-containing particles include core particles containing copper and an organic substance that covers at least a part of the surface of the core particles.
<7> The composition for forming a conductor according to <5> or <6>, which can be made into a conductor by heating at 180 ° C. or lower.
<8> A conductor comprising a sintered body obtained by sintering the conductor-forming composition according to any one of <5> to <7>.
<9> A laminate comprising a base material and the conductor according to <8> provided on the base material.
<10> An apparatus comprising the laminate according to <9>.
本発明者らの検討により、樹脂を含む導体形成用組成物は、加熱後に酸で処理することで、基材に対する接着性と導電性との両方に優れる導体を形成可能であることがわかった。樹脂を含む導体形成用組成物から形成される導体が基材に対する接着性に優れている理由は明らかではないが、例えば、樹脂と基材との間で水素結合を形成するため、あるいは基材表面の凹凸に食い込んで起こるアンカー効果によるものと考えられる。 According to the studies by the present inventors, it has been found that the conductor-forming composition containing a resin can form a conductor having excellent adhesiveness and conductivity to a substrate by treating with an acid after heating. .. It is not clear why a conductor formed from a conductor-forming composition containing a resin has excellent adhesiveness to a substrate, but for example, to form a hydrogen bond between the resin and the substrate, or to form a substrate. It is considered that this is due to the anchor effect that occurs by biting into the unevenness of the surface.
また、銅含有粒子は酸化され易いため、大気雰囲気下での加熱により好適に焼結させることは困難であった。本発明では、導体形成用組成物に含まれる樹脂が粒子を被覆することにより、粒子と酸素との接触及びそれによる酸化を抑制している。加えて、導体内部での粒子間の隙間を樹脂が埋めることで、酸素の侵入も抑制できるため、大気雰囲気で加熱しても、導体内部の銅含有粒子の酸化を抑制することができると考えられる。 Further, since the copper-containing particles are easily oxidized, it is difficult to sinter them appropriately by heating in an atmospheric atmosphere. In the present invention, the resin contained in the conductor-forming composition coats the particles to suppress the contact between the particles and oxygen and the oxidation thereof. In addition, since the resin fills the gaps between the particles inside the conductor, the intrusion of oxygen can be suppressed, so it is thought that the oxidation of the copper-containing particles inside the conductor can be suppressed even when heated in an atmospheric atmosphere. Be done.
さらに、導体表面に存在する酸化した銅含有粒子においては、酸処理によって粒子そのもの又は粒子表面の酸化銅層が溶解し除去される。これによって、導電性の高い酸化されていない銅（純銅）表面が露出し、優れた導電性が発現する。したがって、酸で処理する工程を経ることによって、大気雰囲気下の加熱でも導電性の高い導体が形成されると考えられる。加えて、銅は酸化銅に変化すると体積が約１．７倍に膨張するため、導体表面の銅粒子が酸化されると、粒子の膨張が起こる。これにより、粒子を被覆する樹脂が割れて酸化銅層が露出する。そのため、酸で処理することにより、当初は樹脂で覆われていた酸化銅層を溶解して除去することができると同時に、酸化銅層に付着した樹脂層も一緒に除去される（洗い流される）と考えられる。 Further, in the oxidized copper-containing particles existing on the surface of the conductor, the particles themselves or the copper oxide layer on the surface of the particles are dissolved and removed by the acid treatment. As a result, the surface of highly conductive unoxidized copper (pure copper) is exposed, and excellent conductivity is exhibited. Therefore, it is considered that a highly conductive conductor is formed even by heating in an atmospheric atmosphere through the process of treating with an acid. In addition, when copper is converted to copper oxide, its volume expands about 1.7 times, so that when the copper particles on the conductor surface are oxidized, the particles expand. As a result, the resin covering the particles is cracked and the copper oxide layer is exposed. Therefore, by treating with acid, the copper oxide layer initially covered with the resin can be dissolved and removed, and at the same time, the resin layer adhering to the copper oxide layer is also removed (washed out). it is conceivable that.
本発明によれば、基材に対する接着性に優れ、かつ大気雰囲気下で焼結させた場合であっても導電性に優れる導体を得るための導体の製造方法、導体、及び導体形成用組成物が提供される。また、そのような導体を用いた積層体及び導体が提供される。 According to the present invention, a method for manufacturing a conductor, a conductor, and a composition for forming a conductor for obtaining a conductor having excellent adhesiveness to a substrate and excellent conductivity even when sintered in an air atmosphere. Is provided. Also provided are laminates and conductors using such conductors.
以下、本発明を実施するための形態について詳細に説明する。但し、本発明は以下の実施形態に限定されるものではない。以下の実施形態において、その構成要素（要素ステップ等も含む）は、特に明示した場合を除き、必須ではない。数値及びその範囲についても同様であり、本発明を制限するものではない。 Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention.
本明細書において「工程」との語には、他の工程から独立した工程に加え、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目的が達成されれば、当該工程も含まれる。 本明細書において「～」を用いて示された数値範囲には、「～」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本明細書中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本明細書中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本明細書において組成物中の各成分の含有率又は含有量は、組成物中に各成分に該当する物質が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本明細書において組成物中の各成分の粒子径は、組成物中に各成分に該当する粒子が複数種存在する場合、特に断らない限り、組成物中に存在する当該複数種の粒子の混合物についての値を意味する。
本明細書において「層」又は「膜」との語には、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本明細書において「積層」との語は、層を積み重ねることを示し、二以上の層が結合されていてもよく、二以上の層が着脱可能であってもよい。
In the present specification, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other processes. Is done. In the numerical range indicated by using "-" in the present specification, the numerical values before and after "-" are included as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present specification, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range described stepwise. good. Further, in the numerical range described in the present specification, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present specification, the content or content of each component in the composition refers to the content or content of each component in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. It means the total content or content of substances.
In the present specification, the particle size of each component in the composition is a mixture of the plurality of particles present in the composition when a plurality of particles corresponding to each component are present in the composition, unless otherwise specified. Means a value for.
In the present specification, the term "layer" or "membrane" is used as a part of the region in addition to the case where the layer or the membrane is formed in the entire region when the region is observed. The case where only is formed is also included.
As used herein, the term "laminated" refers to stacking layers, and two or more layers may be bonded or the two or more layers may be removable.
本明細書において「導体化」とは、銅含有粒子を焼結させて導体に変化させることをいう。「導体」とは、導電性を有する物体をいい、より具体的には表面抵抗率が１０００００Ω/□以下である物体をいう。本明細書において導体の表面抵抗率は、４端針面抵抗測定器で測定した値である。銅含有粒子の「個数％」は、個数基準の割合（百分率）を意味する。 As used herein, the term "conductor" means that copper-containing particles are sintered and transformed into a conductor. The "conductor" means an object having conductivity, and more specifically, an object having a surface resistivity of 100,000 Ω / □ or less. In the present specification, the surface resistivity of the conductor is a value measured by a four-ended needle surface resistance measuring instrument. "Percentage" of copper-containing particles means a percentage based on the number of particles.
本明細書において、導体形成用組成物が「焼結」された状態、すなわち「焼結体」には、銅含有粒子が完全に又は部分的に融け合って一体化（融着）している状態、及び銅含有粒子が融合せずに接触しているのみの状態のいずれもが含まれ、また、樹脂が残存している状態及び残存していない状態のいずれもが含まれる。 In the present specification, the copper-containing particles are completely or partially fused and integrated (fused) in the "sintered" state of the conductor-forming composition, that is, in the "sintered body". Both the state and the state in which the copper-containing particles are only in contact without fusion are included, and both the state in which the resin remains and the state in which the resin does not remain are included.
＜導体形成用組成物＞
本実施形態の導体形成用組成物は、銅含有粒子と樹脂とを含有する。樹脂の含有量は、銅含有粒子１００質量部に対して１．０質量部～３０質量部である。導体形成用組成物としては、具体的には、導電塗料、導電ペースト、導電インク等が挙げられる。
<Conductor forming composition>
The conductor-forming composition of the present embodiment contains copper-containing particles and a resin. The content of the resin is 1.0 part by mass to 30 parts by mass with respect to 100 parts by mass of the copper-containing particles. Specific examples of the conductor forming composition include conductive paints, conductive pastes, and conductive inks.
［銅含有粒子］
銅含有粒子は、少なくとも金属銅を含み、必要に応じてその他の物質を含んでもよい。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、有機物、酸化銅、塩化銅などを挙げることができる。導電性により優れる導体を形成する観点から、銅含有粒子中の銅の含有率は、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。
[Copper-containing particles]
The copper-containing particles contain at least metallic copper and may contain other substances as needed. Examples of other substances include metals such as gold, silver, platinum, tin and nickel, compounds containing these metal elements, organic substances, copper oxide, copper chloride and the like. From the viewpoint of forming a conductor having better conductivity, the content of copper in the copper-containing particles is preferably 50% by mass or more, more preferably 60% by mass or more, and more preferably 70% by mass or more. Is more preferable.
銅含有粒子の大きさは、特に制限されないが、低温での焼結性の観点から、長軸の長さが５０ｎｍ以下である銅含有粒子（以下、「小径粒子」ともいう。）の割合が５５個数％以下であることが好ましい。 The size of the copper-containing particles is not particularly limited, but from the viewpoint of sinterability at low temperatures, the proportion of copper-containing particles having a major axis length of 50 nm or less (hereinafter, also referred to as “small diameter particles”) is It is preferably 55% by number or less.
本明細書において、銅含有粒子の長軸の長さは、銅含有粒子に外接し、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。本明細書において、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は、無作為に選択される２００個の銅含有粒子中に占める割合を意味する。例えば、長軸の長さが５０ｎｍ以下である銅含有粒子が２００個中に１１０個である場合は、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は５５個数％である。 As used herein, the length of the major axis of the copper-containing particles means the distance between the two planes circumscribing the copper-containing particles and selected so that the distance between the two planes parallel to each other is maximized. As used herein, the proportion of copper-containing particles having a major axis length of 50 nm or less means the proportion of the 200 randomly selected copper-containing particles. For example, when the number of copper-containing particles having a major axis length of 50 nm or less is 110 out of 200, the proportion of copper-containing particles having a major axis length of 50 nm or less is 55% by number.
低温での焼結性の観点から、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は、５０個数％以下であることが好ましく、３５個数％以下であることがより好ましく、２０個数％以下であることが更に好ましい。 From the viewpoint of sinterability at low temperatures, the proportion of copper-containing particles having a major axis length of 50 nm or less is preferably 50% by number or less, more preferably 35% by number or less, and 20 pieces or less. It is more preferably% or less.
低温での焼結性の観点から、長軸の長さが７０ｎｍ以上である銅含有粒子の割合は、３０個数％以上であることが好ましく、５０個数％以上であることがより好ましく、６０個数％以上であることが更に好ましい。本明細書において、長軸の長さが７０ｎｍ以上である銅含有粒子の割合は、無作為に選択される２００個の銅含有粒子に占める割合を意味する。 From the viewpoint of sinterability at low temperatures, the proportion of copper-containing particles having a major axis length of 70 nm or more is preferably 30% by number or more, more preferably 50% by number or more, and 60 pieces or more. % Or more is more preferable. As used herein, the proportion of copper-containing particles having a major axis length of 70 nm or more means the proportion of the 200 randomly selected copper-containing particles.
低温での焼結性の観点から、銅含有粒子の長軸の長さの平均値は、５５ｎｍ以上であることが好ましく、７０ｎｍ以上であることがより好ましく、９０ｎｍ以上であることが更に好ましい。低温での焼結性の観点から、銅含有粒子の長軸の長さの平均値は、５００ｎｍ以下であることが好ましく、３００ｎｍ以下であることがより好ましく、２００ｎｍ以下であることが更に好ましい。本明細書において、長軸の長さの平均値は、無作為に選択される２００個の銅含有粒子について測定した長軸の長さの算術平均値を意味する。 From the viewpoint of sinterability at low temperatures, the average length of the major axis of the copper-containing particles is preferably 55 nm or more, more preferably 70 nm or more, and further preferably 90 nm or more. From the viewpoint of sinterability at low temperature, the average value of the length of the major axis of the copper-containing particles is preferably 500 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less. As used herein, the mean length of the major axis means the arithmetic mean of the length of the major axis measured for 200 randomly selected copper-containing particles.
低温での焼結性の観点から、長軸の長さが最長である銅含有粒子（以下、「最大径粒子」ともいう）の長軸の長さは、５００ｎｍ以下であることが好ましく、３００ｎｍ以下であることがより好ましく、２５０ｎｍ以下であることが更に好ましい。本明細書において、最大径粒子の長軸の長さは、無作為に選択される２００個の銅含有粒子中で長軸の長さが最長である銅含有粒子の長軸の長さを意味する。 From the viewpoint of sinterability at low temperature, the length of the major axis of the copper-containing particles (hereinafter, also referred to as “maximum diameter particles”) having the longest major axis is preferably 500 nm or less, preferably 300 nm. It is more preferably 25 nm or less, and further preferably 250 nm or less. As used herein, the length of the major axis of the maximum diameter particles means the length of the major axis of the copper-containing particles having the longest major axis length among the 200 randomly selected copper-containing particles. do.
低温での焼結性の観点から、長軸の長さが最短である銅含有粒子（以下、「最小径粒子」ともいう）の長軸の長さは、５ｎｍ以上であることが好ましく、８ｎｍ以上であることがより好ましく、１０ｎｍ以上であることが更に好ましい。本明細書において、最小径粒子の長軸の長さは、無作為に選択される２００個の銅含有粒子中で長軸の長さが最短である銅含有粒子の長軸の長さを意味する。 From the viewpoint of sinterability at low temperature, the length of the major axis of the copper-containing particles (hereinafter, also referred to as “minimum diameter particles”) having the shortest major axis is preferably 5 nm or more, preferably 8 nm. It is more preferably 10 nm or more, and further preferably 10 nm or more. As used herein, the length of the major axis of the smallest diameter particle means the length of the major axis of the copper-containing particle having the shortest major axis length among 200 randomly selected copper-containing particles. do.
銅含有粒子の長軸の長さは、例えば、後述する銅含有粒子の製造方法における原材料の種類、原材料を混合する際の温度、反応時間、反応温度、洗浄工程、洗浄溶媒等の条件を調節することによって調整することができる。 The length of the major axis of the copper-containing particles adjusts the conditions such as the type of raw material in the method for producing copper-containing particles described later, the temperature at which the raw materials are mixed, the reaction time, the reaction temperature, the cleaning process, and the cleaning solvent. It can be adjusted by doing.
銅含有粒子の長軸と短軸との比（長軸／短軸）であるアスペクト比の平均値は、１．０～８．０であることが好ましく、１．１～６．０であることがより好ましく、１．２～３．０であることが更に好ましい。本明細書において、アスペクト比の平均値は、無作為に選択される２００個の銅含有粒子の長軸の算術平均値と短軸の算術平均値をそれぞれ求め、得られた長軸の算術平均値を短軸の算術平均値で除して得られる値を意味する。銅含有粒子の短軸の長さとは、銅含有粒子に外接し、互いに平行である二平面の間の距離が最小となるように選ばれる二平面間の距離を意味する。 The average value of the aspect ratio, which is the ratio of the major axis to the minor axis (major axis / minor axis) of the copper-containing particles, is preferably 1.0 to 8.0, preferably 1.1 to 6.0. More preferably, it is more preferably 1.2 to 3.0. In the present specification, the mean value of the aspect ratio is obtained by obtaining the long-axis arithmetic mean value and the short-axis arithmetic mean value of 200 randomly selected copper-containing particles, respectively, and obtaining the long-axis arithmetic mean value. It means the value obtained by dividing the value by the arithmetic mean value on the short axis. The length of the minor axis of the copper-containing particles means the distance between the two planes circumscribing the copper-containing particles and selected so that the distance between the two planes parallel to each other is minimized.
銅含有粒子のアスペクト比の調節は、例えば、後述する銅含有粒子の製造方法において使用される脂肪酸の炭素数等の条件を調節することによって行うことができる。 The aspect ratio of the copper-containing particles can be adjusted, for example, by adjusting conditions such as the number of carbon atoms of the fatty acid used in the method for producing copper-containing particles described later.
銅含有粒子の長軸及び短軸の長さは、電子顕微鏡による観察等の公知の方法により、測定することができる。電子顕微鏡で観察する場合の倍率は、特に制限されないが、例えば、２０倍～５００００倍とすることができる。なお、電子顕微鏡像から無作為に銅含有粒子を選択する際には、粒子径が３ｎｍ未満である銅含有粒子は測定対象から除外する。 The lengths of the major axis and the minor axis of the copper-containing particles can be measured by a known method such as observation with an electron microscope. The magnification when observing with an electron microscope is not particularly limited, but can be, for example, 20 times to 50,000 times. When randomly selecting copper-containing particles from the electron microscope image, copper-containing particles having a particle diameter of less than 3 nm are excluded from the measurement target.
低温での焼結を促進する観点から、銅含有粒子は表面に凹凸を有する銅含有粒子を含むことが好ましい。より具体的には、円形度の平均値が０．７０～０．９９であることがより好ましい。円形度は、４π×Ｓ／Ｌ２で表される値であり、Ｓ及びＬは、それぞれ測定対象粒子の電子顕微鏡（二次元像）における当該粒子の面積及び周囲（外周）の長さである。円形度は、画像処理ソフトを用いて電子顕微鏡像を解析することにより求めることができ、円形度の平均値は、任意に選択した２００個の銅含有粒子について測定した円形度の平均値とする。 From the viewpoint of promoting sintering at a low temperature, the copper-containing particles preferably contain copper-containing particles having irregularities on the surface. More specifically, it is more preferable that the average value of the circularity is 0.70 to 0.99. The circularity is a value represented by 4π × S / L 2 , and S and L are the area and the length of the periphery (outer circumference) of the particle to be measured in an electron microscope (two-dimensional image), respectively. .. The circularity can be obtained by analyzing an electron microscope image using image processing software, and the average value of the circularity is the average value of the circularity measured for 200 arbitrarily selected copper-containing particles. ..
銅含有粒子が表面に凹凸を有する銅含有粒子を含むことで低温での焼結が促進される理由は明らかではないが、銅含有粒子の表面に凹凸が存在することによりいわゆるナノサイズ効果による融点低下が生じ、低温での焼結性が促進されると推測される。 It is not clear why the copper-containing particles contain copper-containing particles having irregularities on the surface, which promotes sintering at low temperature, but the presence of irregularities on the surface of the copper-containing particles causes the melting point due to the so-called nanosize effect. It is presumed that the decrease will occur and the sinterability at low temperature will be promoted.
銅含有粒子の形状は、特に制限されずに、球状、長粒状、扁平状、繊維状等の形状から導体形成用組成物の用途にあわせて選択できる。導体形成用組成物を印刷法に適用する場合は、銅含有粒子の形状は球状又は長粒状である（具体的には、例えば、アスペクト比の平均値が１．５～８．０である）と、混合物の粘度の調整が容易であるために好ましい。 The shape of the copper-containing particles is not particularly limited and can be selected from spherical, long-granular, flat, fibrous and the like according to the use of the conductor-forming composition. When the composition for forming a conductor is applied to a printing method, the shape of the copper-containing particles is spherical or long-granular (specifically, for example, the average value of the aspect ratio is 1.5 to 8.0). It is preferable because the viscosity of the mixture can be easily adjusted.
保存性の観点から、銅含有粒子は、銅を含むコア粒子と、コア粒子の表面の少なくとも一部を被覆する有機物と、を備えることが好ましい。このような銅含有粒子は、有機物が保護材としての役割を果たし、コア粒子の酸化が抑制される傾向にある。このため、大気中で長期保存した後も低温での良好な焼結性が維持される傾向にある。なお、有機物は銅含有粒子を焼結させる際の加熱により、熱分解又は揮発して、完全に又は部分的に消失する。 From the viewpoint of storage stability, the copper-containing particles preferably include core particles containing copper and an organic substance that covers at least a part of the surface of the core particles. In such copper-containing particles, the organic substance plays a role as a protective material, and the oxidation of the core particles tends to be suppressed. Therefore, even after long-term storage in the atmosphere, good sinterability at low temperatures tends to be maintained. The organic matter is thermally decomposed or volatilized by heating when the copper-containing particles are sintered, and completely or partially disappears.
コア粒子の表面の少なくとも一部を被覆する有機物は、アルキルアミンに由来する有機物を含むことが好ましい。コア粒子が有機物又はアルキルアミンで被覆されていることは、窒素雰囲気下で有機物又はアルキルアミンが熱分解又は揮発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によって確認することができる。アルキルアミンとしては、後述する銅含有粒子の製造方法に用いられるアルキルアミンが挙げられる。 The organic substance that covers at least a part of the surface of the core particles preferably contains an organic substance derived from an alkylamine. The fact that the core particles are coated with an organic substance or an alkylamine is obtained by heating the copper-containing particles at a temperature higher than the temperature at which the organic substance or the alkylamine is thermally decomposed or volatilized in a nitrogen atmosphere and comparing the mass before and after heating. You can check. Examples of the alkylamine include alkylamines used in the method for producing copper-containing particles described later.
コア粒子の表面の少なくとも一部を被覆する有機物は、アルキルアミンに由来する有機物を含むことが好ましい。コア粒子が有機物又はアルキルアミンで被覆されていることは、窒素雰囲気下で有機物又はアルキルアミンが熱分解又は揮発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によって確認することができる。 The organic substance that covers at least a part of the surface of the core particles preferably contains an organic substance derived from an alkylamine. The fact that the core particles are coated with an organic substance or an alkylamine is obtained by heating the copper-containing particles at a temperature higher than the temperature at which the organic substance or the alkylamine is thermally decomposed or volatilized in a nitrogen atmosphere and comparing the mass before and after heating. You can check.
コア粒子の表面の少なくとも一部を被覆する有機物は、その割合がコア粒子及び有機物の合計に対して０．１質量％～２０質量％であることが好ましい。有機物の割合が０．１質量％以上であると、充分な耐酸化性が得られる傾向にある。有機物の割合が２０質量％以下であると、低温での焼結性が良好となる傾向にある。コア粒子及び有機物の合計に対する有機物の割合は０．３質量％～１０質量％であることがより好ましく、０．５質量％～５質量％であることが更に好ましい。 The proportion of the organic matter covering at least a part of the surface of the core particles is preferably 0.1% by mass to 20% by mass with respect to the total of the core particles and the organic matter. When the proportion of organic matter is 0.1% by mass or more, sufficient oxidation resistance tends to be obtained. When the proportion of organic matter is 20% by mass or less, the sinterability at low temperature tends to be good. The ratio of the organic matter to the total of the core particles and the organic matter is more preferably 0.3% by mass to 10% by mass, further preferably 0.5% by mass to 5% by mass.
コア粒子は、少なくとも金属銅を含み、必要に応じてその他の物質を含んでもよい。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、還元性化合物又はアルキルアミンに由来する有機物であってコア粒子の内部に入り込んでいる有機物、酸化銅、塩化銅などを挙げることができる。導電性により優れる導体を形成する観点から、コア粒子中の銅の含有率は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 core particles contain at least metallic copper and may contain other substances as needed. Other substances include metals such as gold, silver, platinum, tin, and nickel, or compounds containing these metal elements, copper fatty acids described later, reducing compounds, or organic substances derived from alkylamines, which are contained inside the core particles. Examples include organic substances that have entered, copper oxide, copper chloride, and the like. From the viewpoint of forming a conductor having better conductivity, the content of copper in the core particles is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. preferable.
銅含有粒子は、コア粒子の表面の少なくとも一部が有機物によって被覆されているために、大気中で保存しても銅の酸化が抑制されており、酸化物の含有率が小さい傾向にある。例えば、銅含有粒子中の酸化物の含有率が５質量％以下であってもよい。銅含有粒子中の酸化物の含有率は、例えばＸＲＤ（Ｘ－ｒａｙ ｄｉｆｆｒａｃｔｉｏｎ、Ｘ線回折）によって測定することができる。 Since at least a part of the surface of the core particles of the copper-containing particles is covered with an organic substance, the oxidation of copper is suppressed even when stored in the atmosphere, and the oxide content tends to be small. For example, the content of the oxide in the copper-containing particles may be 5% by mass or less. The content of oxides in the copper-containing particles can be measured, for example, by XRD (X-ray diffraction, X-ray diffraction).
（銅含有粒子の製造方法）
銅含有粒子の製造方法は特に制限されない。例えば、銅含有粒子は脂肪酸と銅との金属塩と、還元性化合物と、アルキルアミンと、を含む組成物を加熱撹拌する工程を有する方法によって製造される。前記方法は、必要に応じて加熱撹拌工程後の遠心分離工程、洗浄工程等の工程を有していてもよい。
(Manufacturing method of copper-containing particles)
The method for producing the copper-containing particles is not particularly limited. For example, copper-containing particles are produced by a method comprising a step of heating and stirring a composition comprising a fatty acid, a metal salt of copper, a reducing compound, and an alkylamine. The method may include steps such as a centrifugation step and a washing step after the heating and stirring step, if necessary.
上記方法は、銅前駆体として、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銀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においてコア粒子の表面に存在する有機物がより熱分解又は揮発し易いものとなり、銅含有粒子を焼結（融着）させて導体に変化させることを低温で実施することがより容易になると考えられる。 The above method uses a metal salt of fatty acid 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 silver oxalate or the like is used as a copper precursor. Be done. As a result, in the obtained copper-containing particles, the organic matter existing on the surface of the core particles becomes more easily pyrolyzed or volatilized, and the copper-containing particles are sintered (fused) and changed into a conductor at a low temperature. Will be easier.
（脂肪酸）
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。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。コア粒子を効率的に被覆して酸化を抑制する観点から、直鎖状の飽和脂肪酸が好ましい。脂肪酸は１種を単独で用いても、２種以上を併用してもよい。
(fatty acid)
The fatty acid is a monovalent carboxylic acid represented by RCOOH (R is a chain hydrocarbon group and may be linear or branched). The fatty acid may be either a saturated fatty acid or an unsaturated fatty acid. Linear saturated fatty acids are preferred from the viewpoint of efficiently coating core particles and suppressing oxidation. One type of fatty acid may be used alone, or two or more types may be used in combination.
脂肪酸の炭素数は、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、例えば、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。 The number of carbon atoms of the fatty acid is preferably 9 or less. 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. Examples thereof include acids (6 carbon atoms), enanthic acid and isoenantic acid (7 carbon atoms), capric acid, isocaprilic acid and isocaproic acid (8 carbon atoms), nonanoic acid and isononanoic acid (9 carbon atoms). Examples of the unsaturated fatty acid having 9 or less carbon atoms include those having one or more double bonds in the hydrocarbon group of the saturated fatty acid.
脂肪酸の種類は、銅含有粒子の分散媒への分散性、融着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。粒子形状の均一化の観点から、炭素数が５～９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。炭素数が５～９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。 The type of fatty acid can affect properties such as dispersibility of copper-containing particles in a dispersion medium and fusion property. Therefore, it is preferable to select the type of fatty acid according to the use of the copper-containing particles. From the viewpoint of homogenizing the particle shape, it is preferable to use a fatty acid having 5 to 9 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. The ratio when the fatty acid having 5 to 9 carbon atoms and the fatty acid having 4 or less carbon atoms are used in combination is not particularly limited.
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同じ工程中で行ってもよい。 The method for obtaining a salt compound of fatty acid and copper (fatty acid 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 formation of the fatty acid copper and the formation of the complex formed between the fatty acid copper and the reducing compound are carried out in the same step. May be good.
（還元性化合物）
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易いなり、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易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 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 ion in the fatty acid copper, and the reduction of the copper ion is likely to occur, and the copper atom is liberated by spontaneous thermal decomposition as compared with the fatty acid copper in the state where the complex is not formed. 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 derivatives, hydrazine hydrochloride, hydrazine sulfate, hydrazine compounds such as hydrazine hydrate, hydroxylamine compounds such as hydroxylamine and hydroxylamine derivatives, sodium boron hydride, sodium sulfite, and hydrogen sulfite. Examples thereof include sodium compounds such as sodium, sodium thiosulfate, and sodium hypophosphite.
脂肪酸銅中の銅原子に対して配位結合を形成し易い、脂肪酸銅の構造を維持した状態で錯体を形成し易い等の観点から、還元性化合物は、アミノ基を有することが好ましい。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。 The reducing compound preferably has an amino group from the viewpoints of easily forming a coordinate bond with respect to the 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.
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における加熱温度を低くする（例えば、１５０℃以下）観点から、還元性化合物は、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、銅イオンを還元し易く、銅原子から遊離し易いもの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窒素原子を有するため、窒素原子が銅原子との配位結合を形成して錯体を形成することができる。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、銅イオンの還元及び銅原子からの遊離が生じ易い傾向にある。 From the viewpoint of lowering the heating temperature in the step of heating the composition containing the fatty acid copper, the reducing compound and the alkylamine (for example, 150 ° C. or lower), the reducing compound is in a temperature range in which the alkylamine does not evaporate or decompose. , It is preferable to select a compound that easily reduces copper ions and is easily liberated from copper atoms. Examples of such reducing compounds include hydrazine and its derivatives, hydroxylamine and its derivatives, and the like. Since these reducing compounds have a nitrogen atom, the nitrogen atom can form a coordinate bond with a copper atom to form a complex. In addition, since these reducing compounds generally have stronger reducing power than alkylamines, the generated complex spontaneously decomposes under relatively mild conditions, resulting in reduction of copper ions and liberation from copper atoms. It tends to be easy.
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 the hydrazine derivative include methylhydrazine, ethylhydrazine, n-propylhydrazine, isopropylhydrazine, n-butylhydrazine, isobutylhydrazine, sec-butylhydrazine, t-butylhydrazine, n-pentylhydrazine, isopentylhydrazine, neo-pentylhydrazine. , T-pentylhydrazine, n-hexylhydrazine, isohexylhydrazine, n-heptylhydrazine, n-octylhydrazine, n-nonylhydrazine, n-decylhydrazine, n-undecylhydrazine, n-dodecylhydrazine, cyclohexylhydrazine, phenyl Examples thereof include hydrazine, 4-methylphenylhydrazine, benzylhydrazine, 2-phenylethylhydrazine, 2-hydrazineoethanol, 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との比率は、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 contained in the fatty acid copper to the reducing compound 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）
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)
Alkylamine 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、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であってもよい。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、イオウ、リン等の原子を有していてもよい。アルキルアミンは、１種を単独で用いてもよく、２種以上を併用してもよい。 The alkylamine is a primary amine 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. It is also a hydrocarbon group which may be different, and may be a secondary amine represented by cyclic or branched), an alkylenediamine in which two amino groups are substituted in a hydrocarbon chain, or the like. .. The alkylamine may have one or more double bonds and may have atoms such as oxygen, silicon, nitrogen, sulfur and phosphorus. As the alkylamine, one type may be used alone, or two or more types may be used in combination.
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。アルキルアミンの炭化水素基の炭素数が７以下であると、銅含有粒子を融着させて導体を形成するための加熱の際に、アルキルアミンが熱分解し易く、良好に銅含有粒子を焼結（融着）させることができる傾向にある。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く、３以上であることが更に好ましい。 The hydrocarbon group of the alkylamine preferably has 7 or less carbon atoms. When the hydrocarbon group of the alkylamine has 7 or less carbon atoms, the alkylamine is easily thermally decomposed during heating for fusing the copper-containing particles to form a conductor, and the copper-containing particles are sintered satisfactorily. It tends to be able to be bound (fused). The hydrocarbon group of the alkylamine preferably has 6 or less carbon atoms, and more preferably 3 or more carbon atoms.
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 primary amines, ethylamine, 2-ethoxyethylamine, propylamine, butylamine, isobutylamine, pentylamine, isopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, Hexadecylamine, oleylamine, 3-methoxypropylamine, 3-ethoxypropylamine and the like can be mentioned.
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 include diethylamine, dipropylamine, dibutylamine, ethylpropylamine, ethylpentylamine, dibutylamine, dipentylamine, dihexylamine and the like.
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。 Specific examples of the alkylenediamine include ethylenediamine, N, N-dimethylethylenediamine, N, N'-dimethylethylenediamine, N, N-diethylethylenediamine, N, N'-diethylethylenediamine, 1,3-propanediamine, 2,2. -Diamine-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, Examples thereof include 8-diaminooctane, 1,9-diaminononane, and 1,12-diaminododecane.
アルキルアミンは、炭化水素基の炭素数が７以下であるアルキルアミンの少なくとも１種を含むことが好ましい。これにより、低温での焼結性（融着性）により優れる銅含有粒子を製造することができる。アルキルアミンは１種を単独で用いても、２種以上を併用してよい。アルキルアミンは、炭化水素基の炭素数が７以下であるアルキルアミンと、炭化水素基の炭素数が８以上のアルキルアミンと、を含んでもよい。炭化水素基の炭素数が７以下であるアルキルアミンと炭化水素基の炭素数が８以上のアルキルアミンとを併用する場合、アルキルアミン全体に占める炭化水素基の炭素数が７以下である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。 The alkylamine preferably contains at least one of the alkylamines having 7 or less carbon atoms in the hydrocarbon group. This makes it possible to produce copper-containing particles having excellent sinterability (fusing property) at low temperatures. One type of alkylamine may be used alone, or two or more types may be used in combination. The alkylamine may contain an alkylamine having a hydrocarbon group having 7 or less carbon atoms and an alkylamine having a hydrocarbon group having 8 or more carbon atoms. When an alkylamine having 7 or less carbon atoms in a hydrocarbon group and an alkylamine having 8 or more carbon atoms in a hydrocarbon group are used in combination, the alkylamine having 7 or less carbon atoms in the hydrocarbon group occupies the entire alkylamine. Is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more.
脂肪酸銅に含まれる銅とアルキルアミンとの比率は、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 the 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.
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撹拌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溶媒に混合した後にアルキルアミンを添加して加熱する方法、脂肪酸銅とアルキルアミンとを溶媒と混合した後に還元性化合物を添加して加熱する方法、脂肪酸銅の出発物質である水酸化銅と脂肪酸、還元性化合物及びアルキルアミンを溶媒に混合して加熱する方法、脂肪酸銅の出発物質である水酸化銅と脂肪酸、及びアルキルアミンを溶媒に混合した後に還元性化合物を添加して加熱する方法等を挙げることができる。 The method for carrying out the step of heating and stirring the composition containing the fatty acid copper, the reducing compound and the alkylamine is not particularly limited. For example, a method of mixing fatty acid copper and a reducing compound in a solvent and then adding an alkylamine and heating, a method of mixing fatty acid copper and an alkylamine with a solvent and then adding a reducing compound and heating, a method of adding and heating fatty acid copper. Method of mixing copper hydroxide and fatty acid, reducing compound and alkylamine, which are the starting materials of the above, in a solvent and heating, copper hydroxide and fatty acid, which are the starting materials of fatty acid copper, and alkylamine are mixed in the solvent and then reduced. Examples thereof include a method of adding a sex compound and heating.
加熱撹拌工程は、銅前駆体として炭素数が９以下である脂肪酸銅を用いることにより、比較的低温で行うことができる。例えば、１５０℃以下で行うことができ、１３０℃以下で行うことが好ましく、１００℃以下で行うことがより好ましい。 The heating and stirring step can be performed at a relatively low temperature by using fatty acid copper having 9 or less carbon atoms as the copper precursor. For example, it can be carried out at 150 ° C. or lower, preferably at 130 ° C. or lower, and more preferably at 100 ° C. or lower.
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、溶媒を更に含んでもよい。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、極性溶媒を含むことが好ましい。ここで極性溶媒とは、２５℃で水に溶解する溶媒を意味する。極性溶媒を用いることで、錯体の形成が促進される傾向にある。その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 means a solvent that dissolves in water at 25 ° C. The use of polar solvents tends to promote the formation of complexes. The reason 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.
極性溶媒としては、２５℃で水に溶解するアルコールが挙げられる。２５℃で水に溶解する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個以上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、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イオウ原子、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 polar solvent include alcohols that dissolve in water at 25 ° C. Examples of the alcohol that dissolves in water at 25 ° C. include alcohols having 1 to 8 carbon atoms and having one or more hydroxyl groups 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 copper-containing particles to be produced.
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 include methanol, ethanol, 1-propanol, 2-propanol, butanol, pentanol, hexanol, heptonol, octanol, allyl alcohol, benzyl alcohol, pinacol, propylene glycol, menthol, catechol, hydroquinone, and salicyl alcohol. Examples thereof include glycerin, pentaerythritol, sucrose, glucose, xylitol, methoxyethanol, triethylene glycol monomethyl ether, ethylene glycol, triethylene glycol, tetraethylene glycol, pentaethylene glycol and the like.
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。 Of the alcohols, methanol, ethanol, 1-propanol and 2-propanol, which have extremely high solubility in water, are preferable, 1-propanol and 2-propanol are more preferable, and 1-propanol is further preferable.
［樹脂］
樹脂の分子構造及び分子量は、特に制限されず、導体形成用組成物の用途、基材の種類等に応じて選択できる。樹脂は、熱可塑性樹脂及び熱硬化性樹脂のどちらであってもよいが、導体の強度及び基材に対する接着性の観点から、好ましくは熱硬化性樹脂である。樹脂は、１種を単独で用いても、分子構造、分子量等が異なる２種以上を併用してもよい。
[resin]
The molecular structure and molecular weight of the resin are not particularly limited and can be selected according to the use of the conductor forming composition, the type of the base material, and the like. The resin may be either a thermoplastic resin or a thermosetting resin, but is preferably a thermosetting resin from the viewpoint of the strength of the conductor and the adhesiveness to the substrate. As the resin, one type may be used alone, or two or more types having different molecular structures, molecular weights, etc. may be used in combination.
樹脂としては、具体的には（メタ）アクリル樹脂、ビスマレイミド樹脂、ポリイミド樹脂、ポリエステル樹脂、ウレタン樹脂、ポリフェニレンエーテル樹脂、シリコーン樹脂、エポキシ樹脂、フェノール樹脂、ポリエチレン樹脂、ポリ塩化ビニル樹脂、ポリエチレンテレフタラート樹脂、ナイロン樹脂、ポリフッ化ビニリデン樹脂、ポリビニルクロライド、ポリサルフォン樹脂、ポリエーテルサルフォン樹脂、ニトリルブタジエン樹脂、ＡＢＳ樹脂、メラミン樹脂、ウレア樹脂、ポリカーボネート樹脂、ポリアセタール樹脂、シリコーン樹脂、ポリエーテルイミド樹脂、フェノキシ樹脂、変性ポリフェニレンエーテル樹脂、ポリアミド樹脂、ポリアラミド樹脂、ポリビニルブチラール樹脂、シアネートエステル樹脂、アルキド樹脂、不飽和ポリエステル樹脂、レゾルシノールホルムアルデヒド樹脂、キシレン樹脂、フラン樹脂、ケトン樹脂、トリアリルシアヌレート樹脂、ポリイソシアネート樹脂、フッ素樹脂、各種変性樹脂等が挙げられる。これらの中でも、導体の強度及び基材に対する接着性の観点から、（メタ）アクリル樹脂、ビスマレイミド樹脂、ポリイミド樹脂、ポリエステル樹脂、ウレタン樹脂、エポキシ樹脂又はフェノール樹脂が好ましい。 Specific examples of the resin include (meth) acrylic resin, bismaleimide resin, polyimide resin, polyester resin, urethane resin, polyphenylene ether resin, silicone resin, epoxy resin, phenol resin, polyethylene resin, polyvinyl chloride resin, and polyethylene tereph. Talat resin, nylon resin, polyvinylidene fluoride resin, polyvinyl chloride, polysulfone resin, polyether sulfone resin, nitrile butadiene resin, ABS resin, melamine resin, urea resin, polycarbonate resin, polyacetal resin, silicone resin, polyetherimide resin, Phenoxy resin, modified polyphenylene ether resin, polyamide resin, polyaramid resin, polyvinyl butyral resin, cyanate ester resin, alkyd resin, unsaturated polyester resin, resorcinol formaldehyde resin, xylene resin, furan resin, ketone resin, triallyl cyanurate resin, poly Examples thereof include isocyanate resin, fluororesin, and various modified resins. Among these, (meth) acrylic resin, bismaleimide resin, polyimide resin, polyester resin, urethane resin, epoxy resin or phenol resin are preferable from the viewpoint of the strength of the conductor and the adhesiveness to the base material.
導体形成用組成物が樹脂を含むか否かは、例えばゲル浸透クロマトグラフィー測定によって確認することができる。具体的には、導体形成用組成物から溶解している有機物成分をろ過などで取り出し、ゲル浸透クロマトグラフィー測定で分子量が１０００以上の成分を検出することによって観測できる。液状の硬化性樹脂等の分子量は、１０００以下である場合がある。このような樹脂は、反応後に硬化樹脂を形成するための官能基（例えば、エポキシ基、アミノ基、ヒドロキシ基、メルカプト基、ビニル基、アルキニル基、アクリロイル基、イソシアナート基等）を有している。したがって、分子量が１０００以下である樹脂が含まれるか否かは、例えば１Ｈ－ＮＭＲ測定、赤外吸収スペクトル測定、マススペクトル測定等により、上記の官能基が含まれるか否かに基づき確認することができる。 Whether or not the conductor-forming composition contains a resin can be confirmed, for example, by gel permeation chromatography measurement. Specifically, it can be observed by taking out the dissolved organic component from the conductor forming composition by filtration or the like and detecting the component having a molecular weight of 1000 or more by gel permeation chromatography measurement. The molecular weight of the liquid curable resin or the like may be 1000 or less. Such a resin has a functional group (for example, an epoxy group, an amino group, a hydroxy group, a mercapto group, a vinyl group, an alkynyl group, an acryloyl group, an isocyanato group, etc.) for forming a cured resin after the reaction. There is. Therefore, whether or not a resin having a molecular weight of 1000 or less is contained is confirmed based on whether or not the above functional groups are contained, for example, by 1 H-NMR measurement, infrared absorption spectrum measurement, mass spectrum measurement, or the like. be able to.
樹脂の含有量が多いほど、導体の強度及び基材に対する接着性は向上する傾向にある。一方、銅含有粒子の抑制し、導電性を更に向上させる観点からは、樹脂の含有量は、銅含有粒子１００質量部に対して５.０質量部以上であることが好ましい。また、樹脂自体の絶縁性を確保しつつ、樹脂によって銅含有粒子の焼結が阻害されることを抑制し、導電性を更に向上させる観点からは、樹脂の含有量は、２５質量部以下であることが好ましい。そのため、導電性及び接着性の両方を向上せ褪せる観点から、樹脂の含有量は、銅含有粒子１００質量部に対して、１.０質量部～３０質量部であり、５.０質量部～２５質量部であることが好ましく、８.０質量部～２０質量部であることがより好ましい。 The higher the resin content, the stronger the conductor and the adhesiveness to the substrate tend to be. On the other hand, from the viewpoint of suppressing the copper-containing particles and further improving the conductivity, the resin content is preferably 5.0 parts by mass or more with respect to 100 parts by mass of the copper-containing particles. Further, from the viewpoint of suppressing the inhibition of sintering of copper-containing particles by the resin and further improving the conductivity while ensuring the insulating property of the resin itself, the content of the resin is 25 parts by mass or less. It is preferable to have. Therefore, from the viewpoint of improving both conductivity and adhesiveness and fading, the content of the resin is 1.0 part by mass to 30 parts by mass with respect to 100 parts by mass of the copper-containing particles, and 5.0 parts by mass to It is preferably 25 parts by mass, more preferably 8.0 parts by mass to 20 parts by mass.
［分散媒］
導体形成用組成物は、分散媒を含有していてもよい。分散媒の種類は特に制限されず、導体形成用組成物の用途に応じて一般に用いられる有機溶媒から選択でき、１種を単独で用いても、２種以上を併用してもよい。導体形成用組成物を印刷法に適用する場合は、導体形成用組成物の粘度コントロールの観点から、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及びジヒドロターピネオールアセテートからなる群より選択される少なくとも１種を含むことが好ましい。
[Dispersion medium]
The conductor-forming composition may contain a dispersion medium. The type of the dispersion medium is not particularly limited, and can be selected from commonly used organic solvents depending on the use of the conductor-forming composition, and one type may be used alone or two or more types may be used in combination. When the conductor-forming composition is applied to a printing method, at least one selected from the group consisting of terpineol, isobornylcyclohexanol, dihydro-terpineol and dihydro-terpineol acetate from the viewpoint of viscosity control of the conductor-forming composition. It is preferable to include.
導体形成用組成物の粘度は特に制限されず、導体形成用組成物の使用方法に応じて選択できる。例えば、導体形成用組成物をスクリーン印刷法に適用する場合は、粘度が０．１Ｐａ・ｓ～３０Ｐａ・ｓであることが好ましく、１Ｐａ・ｓ～３０Ｐａ・ｓであることがより好ましい。導体形成用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、粘度が０．１ｍＰａ・ｓ～３０ｍＰａ・ｓであることが好ましく、５ｍＰａ・ｓ～２０ｍＰａ・ｓであることがより好ましい。導体形成用組成物の粘度はＥ型粘度計（東機産業株式会社製、製品名：ＶＩＳＣＯＭＥＴＥＲ－ＴＶ２２、適用コーンプレート型ロータ：３°×Ｒ１７．６５）を用いて測定される２５℃における粘度を意味する。 The viscosity of the conductor-forming composition is not particularly limited and can be selected according to the method of using the conductor-forming composition. For example, when the conductor forming composition is applied to a screen printing method, the viscosity is preferably 0.1 Pa · s to 30 Pa · s, and more preferably 1 Pa · s to 30 Pa · s. When the conductor forming composition is applied to the inkjet printing method, the viscosity is preferably 0.1 mPa · s to 30 mPa · s, and 5 mPa · s to 20 mPa · s, although it depends on the standard of the inkjet head used. Is more preferable. The viscosity of the conductor forming composition is the viscosity at 25 ° C. measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., product name: VISCOMETER-TV22, applicable cone plate type rotor: 3 ° × R17.65). Means.
［その他の成分］
導体形成用組成物は、必要に応じて銅含有粒子、ウレタン結合を有する樹脂、シランカップリング剤及び分散媒以外のその他の成分を含んでもよい。このような成分としては、ウレタン結合を有する樹脂以外の樹脂、ラジカル開始剤、還元剤等が挙げられる。
[Other ingredients]
The conductor-forming composition may contain copper-containing particles, a resin having a urethane bond, a silane coupling agent, and other components other than the dispersion medium, if necessary. Examples of such a component include resins other than resins having a urethane bond, radical initiators, reducing agents and the like.
以上説明した導体形成用組成物は、低温での導体化が可能である。具体的には、導体形成用組成物は、例えば２００℃以下、好ましくは１８０℃以下の温度での加熱により、導体化が可能である。 The conductor-forming composition described above can be made into a conductor at a low temperature. Specifically, the conductor-forming composition can be made into a conductor by heating at a temperature of, for example, 200 ° C. or lower, preferably 180 ° C. or lower.
＜導体の製造方法＞
本実施形態の導体の製造方法は、基材上に設けられた導体形成用組成物を加熱することにより処理前焼結体を得て、その後、処理前焼結体を酸で処理して処理後焼結体（本明細書では、単に「焼結体」ともいう）を得る工程を備えている。
<Conductor manufacturing method>
In the method for producing a conductor of the present embodiment, a conductor-forming composition provided on a substrate is heated to obtain a pre-treated sintered body, and then the pre-treated sintered body is treated with an acid for treatment. It comprises a step of obtaining a post-sintered body (also simply referred to as “sintered body” in the present specification).
基材の材質は、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。基材の材質としては、具体的には、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、セラミック、黒鉛、グラファイト等のカーボン材料、樹脂、紙、これらの組み合わせなどを挙げることができる。基材の形状は、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 material of the base material is not particularly limited and may or may not have conductivity. Specific examples of the material of the base material include metals such as Cu, Au, Pt, Pd, Ag, Zn, Ni, Co, Fe, Al, and Sn, alloys of these metals, ITO, ZnO, SnO, Si, and the like. Examples include semiconductors, glass, ceramics, carbon materials such as graphite and graphite, resins, papers, and combinations thereof. The shape of the base material is not particularly limited and may be plate-shaped, rod-shaped, roll-shaped, film-shaped or the like.
本実施形態の導体は低温での加熱で得られるため、耐熱性が比較的低い材質からなる基材を用いる場合であっても好適に適用することができる。耐熱性が比較的低い材質としては、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、ポリカーボネート樹脂などが挙げられる。また、基材には、耐熱性が低く、高温での加熱ができないような材料が付与されていてもよい。 Since the conductor of this embodiment is obtained by heating at a low temperature, it can be suitably applied even when a base material made of a material having relatively low heat resistance is used. Examples of materials having relatively low heat resistance include thermoplastic resins. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene and polymethylpentene, and polycarbonate resins. Further, the base material may be provided with a material having low heat resistance and which cannot be heated at a high temperature.
本実施形態の導体形成用組成物（導体）は、所定量の樹脂成分を含有するため、樹脂等の有機材料を含む基材に対して優れた接着性を示す。加えて、本実施形態の導体形成用組成物（導体）では、樹脂の種類に制限がないため、無機基材に適した樹脂を選択することができ、その結果、セラミック、ガラス、無機フィラー含有樹脂等の無機材料を含む基材に対しても優れた接着性を示す。 Since the conductor-forming composition (conductor) of the present embodiment contains a predetermined amount of a resin component, it exhibits excellent adhesiveness to a base material containing an organic material such as a resin. In addition, in the conductor forming composition (conductor) of the present embodiment, since the type of resin is not limited, a resin suitable for the inorganic base material can be selected, and as a result, ceramic, glass, and an inorganic filler are contained. It also exhibits excellent adhesiveness to substrates containing inorganic materials such as resins.
基材上に設けられた導体形成用組成物を加熱する工程（加熱工程）では、導体形成用組成物に含まれる銅含有粒子の表面の有機物を完全に又は部分的に熱分解又は揮発させ、かつ、銅含有粒子同士を焼結させることにより、処理前焼結体を得る。 In the step of heating the conductor-forming composition provided on the substrate (heating step), the organic matter on the surface of the copper-containing particles contained in the conductor-forming composition is completely or partially thermally decomposed or volatilized. Moreover, the pre-treated sintered body is obtained by sintering the copper-containing particles with each other.
加熱工程が実施される雰囲気は、通常の導体の製造工程で用いられる窒素、アルゴン等の不活性雰囲気、又は、水素、ギ酸等の還元性物質を窒素等に飽和させた還元性雰囲気であってよい。加熱工程が実施される雰囲気における酸素濃度は、１００体積ｐｐｍ以上であることが好ましく、１０００体積ｐｐｍ以上であることがより好ましく、１００００体積ｐｐｍ以上であることが更に好ましい。加熱工程が実施される雰囲気は、組成管理の容易さ、及び汎用の加熱装置を使用可能な点から、酸素濃度が２０％以上の大気雰囲気であることが好ましい。加熱工程は、一種の雰囲気下で実施される１工程からなっていてもよく、雰囲気を変えながら実施される２工程以上からなっていてもよい。 The atmosphere in which the heating step is carried out is an inert atmosphere such as nitrogen or argon used in a normal conductor manufacturing process, or a reducing atmosphere in which a reducing substance such as hydrogen or formic acid is saturated with nitrogen or the like. good. The oxygen concentration in the atmosphere in which the heating step is carried out is preferably 100 volume ppm or more, more preferably 1000 volume ppm or more, and further preferably 10,000 volume ppm or more. The atmosphere in which the heating step is carried out is preferably an atmosphere having an oxygen concentration of 20% or more from the viewpoint of easy composition control and the ability to use a general-purpose heating device. The heating step may consist of one step carried out in a kind of atmosphere, or may consist of two or more steps carried out while changing the atmosphere.
加熱工程における圧力は、特に制限されない。加熱工程は、一定の温度で行われても、温度を変えながら行われてもよい。加熱工程で温度を上昇させながら加熱する場合は、一定の昇温速度で加熱しても、昇温速度を変えながら加熱してもよい。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。加熱方法としては、特に制限されず、熱板による加熱、赤外ヒータによる加熱、パルスレーザによる加熱等を挙げることができる。 The pressure in the heating step is not particularly limited. The heating step may be performed at a constant temperature or may be performed while changing the temperature. When heating while raising the temperature in the heating step, heating may be performed at a constant heating rate or heating may be performed while changing the heating rate. 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 examples thereof include heating with a hot plate, heating with an infrared heater, and heating with a pulse laser.
続いて、加熱工程で得られた処理前焼結体を酸で処理する（酸処理工程）。酸処理工程では、処理前焼結体を酸に接触させる（酸で洗浄する）。これにより、銅含有粒子の表面に形成された酸化銅被膜を溶解させて除去し、銅含有粒子内部の酸化されていない銅（純銅）を露出させることができ、その結果、焼結体の導電性を向上させることができる。 Subsequently, the pretreatment sintered body obtained in the heating step is treated with an acid (acid treatment step). In the acid treatment step, the pre-treatment sintered body is brought into contact with an acid (washed with an acid). This makes it possible to dissolve and remove the copper oxide film formed on the surface of the copper-containing particles and expose the unoxidized copper (pure copper) inside the copper-containing particles, resulting in the conductivity of the sintered body. It is possible to improve the sex.
処理液は、酸化銅被膜を溶解させ、純銅を露出させることが可能な液であればよく、特に制限されない。より具体的には、処理液は、銅を酸化させずに、酸化銅（Ｉ）又は酸化銅（ＩＩ）を溶解させることができる酸性の処理液であれば、特に制限されない。処理液は、濃度１～９０質量％の希硫酸水溶液、濃度１～３５質量％の塩酸等であってよく、好ましくは濃度１～９０質量％の希硫酸水溶液である。希硫酸水溶液の濃度は、酸化銅被膜を溶解させる一方で純銅を溶解させないように、好ましくは１～５０質量％である。 The treatment liquid is not particularly limited as long as it is a liquid capable of dissolving the copper oxide film and exposing pure copper. More specifically, the treatment liquid is not particularly limited as long as it is an acidic treatment liquid capable of dissolving copper (I) oxide or copper (II) oxide without oxidizing copper. The treatment liquid may be a dilute sulfuric acid aqueous solution having a concentration of 1 to 90% by mass, hydrochloric acid having a concentration of 1 to 35% by mass, or the like, and is preferably a dilute sulfuric acid aqueous solution having a concentration of 1 to 90% by mass. The concentration of the dilute sulfuric acid aqueous solution is preferably 1 to 50% by mass so as to dissolve the copper oxide film but not pure copper.
酸処理工程の時間は、特に制限されず、処理温度、処理液濃度、加熱温度、加熱時間等を考慮して選択できる。処理方法は、特に制限されず、処理前焼結体を処理液に浸漬させる方法、スプレー、シャワー等により処理前焼結体に処理液を接触させる方法等であってよい。 The time of the acid treatment step is not particularly limited and can be selected in consideration of the treatment temperature, the treatment liquid concentration, the heating temperature, the heating time and the like. The treatment method is not particularly limited, and may be a method of immersing the pre-treatment sintered body in the treatment liquid, a method of bringing the treatment liquid into contact with the pre-treatment sintered body by spraying, showering or the like.
以上の製造方法により得られた焼結体は、めっきシード層として好適に用いることができる。したがって、導体の製造方法は、焼結体上にめっき層を形成する工程（めっき層形成工程）を更に備えていてもよい。めっき層形成工程においてめっき層を形成する方法は、特に制限されず、電解めっき又は無電解めっきのいずれであってもよい。めっき層の形成に用いる金属の種類は、特に制限されず、銅、ニッケル、金、クロム等であってよい。 The sintered body obtained by the above manufacturing method can be suitably used as a plating seed layer. Therefore, the conductor manufacturing method may further include a step of forming a plating layer on the sintered body (plating layer forming step). The method for forming the plating layer in the plating layer forming step is not particularly limited, and may be either electrolytic plating or electroless plating. The type of metal used for forming the plating layer is not particularly limited, and may be copper, nickel, gold, chromium, or the like.
導体の製造方法は、必要に応じてその他の工程を更に備えていてもよい。その他の工程としては、導体形成用組成物を基材上に設ける工程、当該工程の前に、接着成分を基材に付与する工程、加熱工程前に導体形成用組成物中の揮発成分の少なくとも一部を乾燥等により除去する工程、加熱工程後に還元雰囲気中で加熱により生成した酸化銅を還元する工程、加熱工程後に光焼成を行って残存成分を除去する工程、加熱工程後に得られた導体に対して荷重をかける工程、酸処理工程後に純水で不要な成分を除去する工程などを挙げることができる。 The method for manufacturing the conductor may further include other steps, if necessary. Other steps include a step of providing the conductor forming composition on the substrate, a step of applying the adhesive component to the substrate before the step, and at least the volatile components in the conductor forming composition before the heating step. A step of removing a part by drying, a step of reducing copper oxide generated by heating in a reducing atmosphere after the heating step, a step of performing photo-baking after the heating step to remove residual components, and a conductor obtained after the heating step. Examples thereof include a step of applying a load to the surface, a step of removing unnecessary components with pure water after the acid treatment step, and the like.
＜導体＞
本実施形態の導体は、上述した導体の製造方法により得られるものであり、上記実施形態の導体形成用組成物を焼結してなる焼結体を含む。導体の形状は特に制限されず、薄膜状、パターン状等を挙げることができる。本実施形態の導体は、種々の電子部品の配線、被膜等の形成に使用できる。特に、本実施形態の導体は、低温で製造できるため、樹脂等の耐熱性の低い基材上に金属箔、配線パターン等を形成する用途に好適に用いられる。また、通電を目的としない装飾、印字等の用途にも好適に用いられる。
<Conductor>
The conductor of the present embodiment is obtained by the above-mentioned method for manufacturing a conductor, and includes a sintered body obtained by sintering the conductor-forming composition of the above-described embodiment. The shape of the conductor is not particularly limited, and examples thereof include a thin film shape and a pattern shape. The conductor of this embodiment can be used for forming wirings, coatings, etc. of various electronic components. In particular, since the conductor of the present embodiment can be manufactured at a low temperature, it is suitably used for forming a metal foil, a wiring pattern, or the like on a base material having low heat resistance such as a resin. Further, it is suitably used for applications such as decoration and printing that are not intended to be energized.
導体の表面抵抗率は、５００００Ω／□以下であることが好ましく、５０００Ω／□以下であることがより好ましく、１００Ω／□以下であることが更に好ましく、１０Ω／□以下であることが特に好ましい。 The surface resistivity of the conductor is preferably 50,000 Ω / □ or less, more preferably 5000 Ω / □ or less, further preferably 100 Ω / □ or less, and particularly preferably 10 Ω / □ or less.
導体の基材に対する接着力は、０．０５Ｎ／ｍ以上であることが好ましく、０．５Ｎ／ｍ以上であることがより好ましく、５．０Ｎ／ｍ以上であることが更に好ましく、５０Ｎ／ｍ以上であることが特に好ましい。本明細書において、導体の基材に対する接着力は、卓上ピール試験機を用いて幅１０ｍｍの導体をピール角度９０°、ピール速度３０ｍｍ／秒で基材から剥離したときの、基材に対する導体の接着力（Ｎ／ｍ）を意味する。 The adhesive force of the conductor to the substrate is preferably 0.05 N / m or more, more preferably 0.5 N / m or more, further preferably 5.0 N / m or more, and 50 N / m. The above is particularly preferable. In the present specification, the adhesive force of the conductor to the substrate is the adhesive force of the conductor to the substrate when the conductor having a width of 10 mm is peeled from the substrate at a peel angle of 90 ° and a peel speed of 30 mm / sec using a desktop peel tester. It means adhesive strength (N / m).
本実施形態の導体は、種々の用途に用いることができる。具体的には、導体は、積層板、太陽電池パネル、ディスプレイ、タッチパネル、トランジスタ、半導体パッケージ、積層セラミックコンデンサ等の電子部品に使用される、電気配線、放熱膜、表面被覆膜等の部材として利用することができる。特に、本実施形態の導体は、樹脂等の基材上に形成できるため、フレキシブルな積層板、太陽電池パネル、ディスプレイ等の製造に好適である。 The conductor of this embodiment can be used for various purposes. Specifically, the conductor is used as a member of an electric wiring, a heat dissipation film, a surface covering film, etc. used for electronic parts such as a laminated board, a solar cell panel, a display, a touch panel, a transistor, a semiconductor package, and a laminated ceramic capacitor. It can be used. In particular, since the conductor of the present embodiment can be formed on a base material such as resin, it is suitable for manufacturing flexible laminated plates, solar cell panels, displays and the like.
＜積層体＞
本実施形態の積層体は、基材と、基材上に設けられた導体と、を備えている。基材の種類は、特に制限されず、上述した基材と同様であってよい。基材上に配置される導体は、基材の全面に設けられていても、基材の一部にのみ設けられていてもよい。
<Laminated body>
The laminate of the present embodiment includes a base material and a conductor provided on the base material. The type of the base material is not particularly limited and may be the same as the above-mentioned base material. The conductor arranged on the base material may be provided on the entire surface of the base material or may be provided only on a part of the base material.
＜装置＞
本実施形態の装置は、上述した実施形態の導体又は積層体を備えている。装置の種類は、特に制限されず、例えば、上述した実施形態の導体からなる配線、被膜等を有する太陽電池パネル、ディスプレイ、タッチパネル、電子部品（トランジスタ、セラミックコンデンサ、半導体パッケージ等）などであってよい。また、これらの装置を内蔵する電子機器、家電、産業用機械、輸送用機械等も本実施形態の装置に含まれる。
<Device>
The apparatus of this embodiment includes the conductor or laminate of the above-described embodiment. The type of the device is not particularly limited, and is, for example, a solar cell panel having a wiring made of a conductor of the above-described embodiment, a coating film, a display, a touch panel, an electronic component (transistor, ceramic capacitor, semiconductor package, etc.) and the like. good. Further, electronic devices, home appliances, industrial machines, transportation machines and the like incorporating these devices are also included in the devices of the present embodiment.
以下、本実施形態について実施例をもとに説明するが、本実施形態はこれらの実施例に何ら限定されるものではない。 Hereinafter, the present embodiment will be described based on examples, but the present embodiment is not limited to these examples.
［１．１］ノナン酸銅の合成
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、９０％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。
[1.1] Synthesis of copper nonanoate To 91.5 g (0.94 mol) of copper hydroxide (Kanto Chemical Co., Inc., special grade), 150 mL of 1-propanol (Kanto Chemical Co., Inc., special grade) was added and stirred. 370.9 g (2.34 mol) of nonanoic acid (Kanto Chemical Co., Inc., 90% or more) was added. 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 generated 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］銅含有粒子の合成
上記で得られたノナン酸銅（ＩＩ）１５．０１ｇ（０．０４０ｍｏｌ）と酢酸銅（ＩＩ）無水物（関東化学株式会社、特級）７．２１ｇ（０．０４０ｍｏｌ）とをセパラブルフラスコに入れ、１－プロパノール２２ｍＬとヘキシルアミン（東京化成工業株式会社、純度９９％）３２．１ｇ（０．３２ｍｏｌ）とを添加し、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であった。次いで、オイルバス中で１０分間、９０℃で加熱撹拌した。その際、発泡を伴う還元反応が進み、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９０００ｒｐｍ（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、銅光沢を有する銅含有粒子の粉体を含む銅ケークを得た。
[1.2] Synthesis of Copper-Containing Particles 15.01 g (0.040 mol) of copper (II) nonanoate and 7.21 g (0) of copper (II) acetate anhydride (Kanto Chemical Co., Ltd., special grade) obtained above. .040 mol) is placed in a separable flask, 22 mL of 1-propanol and 32.1 g (0.32 mol) of hexylamine (Tokyo Kasei Kogyo Co., Ltd., purity 99%) are added, and the mixture is placed in an oil bath at 80 ° C. It was dissolved by heating and stirring. After transferring to an ice bath and cooling to an internal temperature of 5 ° C., 7.72 mL (0.16 mol) of hydrazine monohydrate (Kanto Chemical Co., Inc., special grade) was stirred in the ice bath. The molar ratio of copper: hexylamine was 1: 4. Then, it was heated and stirred at 90 ° C. for 10 minutes in an oil bath. At that time, the reduction reaction accompanied by effervescence proceeded, the inner wall of the separable flask exhibited a copper luster, and the solution turned dark red. Centrifugation was performed at 9000 rpm (rotation / min) for 1 minute to obtain 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 a powder of copper-containing particles having a copper luster.
上記で合成した銅ケークに含まれる銅含有粒子を透過型電子顕微鏡（商品名：ＪＥＭ－２１００Ｆ、日本電子株式会社）で観察したところ、無作為に選択した２００個の銅含有粒子の長軸の長さの平均値は１０４ｎｍであり、長軸の長さが５０ｎｍ以下である銅含有粒子の割合は１８個数％であり、長軸の長さが７０ｎｍ以上である銅含有粒子の割合は６７個数％であり、最大径粒子の長軸の長さは２００ｎｍであり、アスペクト比の平均値は１．２であった。また、表面に凹凸を有する銅含有粒子が観察され、円形度の平均値は０．８１であった。銅含有粒子の透過型電子顕微鏡像を図１に示す。 When the copper-containing particles contained in the copper cake synthesized above were observed with a transmission electron microscope (trade name: JEM-2100F, Nippon Denshi Co., Ltd.), the long axis of 200 randomly selected copper-containing particles was observed. The average length is 104 nm, the proportion of copper-containing particles having a major axis length of 50 nm or less is 18%, and the proportion of copper-containing particles having a major axis length of 70 nm or more is 67. %, The length of the major axis of the maximum diameter particles was 200 nm, and the average value of the aspect ratio was 1.2. Further, copper-containing particles having irregularities on the surface were observed, and the average value of the circularity was 0.81. A transmission electron microscope image of copper-containing particles is shown in FIG.
銅ケーク（５０質量部）、テルピネオール（２５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）（２５質量部）を混合して、ペースト状混合物を調製した。 Copper cake (50 parts by mass), terpineol (25 parts by mass), and isobornylcyclohexanol (trade name: Telsolv MTPH, Nippon Terpen Chemical Co., Ltd.) (25 parts by mass) were mixed to prepare a paste-like mixture. ..
メトキシシリル基を有するエポキシ樹脂（１００質量部）（商品名：Ｅ２０３、荒川化学工業株式会社）及びイミダゾール系エポキシ硬化剤（商品名：キュアゾールＣ１１Ｚ－ＣＮ、四国化成工業株式会社）（５質量部）を混合して、エポキシ樹脂溶液を調製した。 Epoxy resin having a methoxysilyl group (100 parts by mass) (trade name: E203, Arakawa Chemical Industry Co., Ltd.) and imidazole-based epoxy curing agent (trade name: Curesol C11Z-CN, Shikoku Chemicals Corporation) (5 parts by mass) Was mixed to prepare an epoxy resin solution.
［実施例１－１～１－１１、比較例１－１～１－２］
上記ペースト状混合物及びエポキシ樹脂溶液を混合して、導体形成用組成物を調製した。このときの銅ケーク１００質量部に対するエポキシ樹脂の不揮発分としての含有量（質量部）を表１に示す。
[Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-2]
The paste-like mixture and the epoxy resin solution were mixed to prepare a conductor-forming composition. Table 1 shows the content (parts by mass) of the epoxy resin as a non-volatile component with respect to 100 parts by mass of the copper cake at this time.
上記で得られた導体形成用組成物を、基材としてのガラス板上に塗布した後、大気雰囲気で加熱して銅を含む薄膜を形成した。加熱は、１気圧の大気雰囲気中、４℃／秒の昇温速度で１４０℃まで加熱し、３０分間保持することによって行った。続いて、得られた薄膜を放冷し、１０質量％希硫酸水溶液中に６０秒浸漬させた。薄膜を取り出し純水で洗い流し、焼結体を得た。 The conductor-forming composition obtained above was applied onto a glass plate as a base material, and then heated in an atmospheric atmosphere to form a thin film containing copper. The heating was carried out by heating to 140 ° C. at a heating rate of 4 ° C./sec in an atmospheric atmosphere of 1 atm and holding for 30 minutes. Subsequently, the obtained thin film was allowed to cool and immersed in a 10 mass% dilute sulfuric acid aqueous solution for 60 seconds. The thin film was taken out and rinsed with pure water to obtain a sintered body.
［実施例２－１～２－１１、比較例２－１～２－２］
エポキシ樹脂に代えて、メトキシシリル基を有するウレタン樹脂（商品名：Ｕ２０１、荒川化学工業株式会社）を用いた以外は、実施例１－１と同様にして導体形成用組成物を調製し、焼結体を得た。このときの銅ケーク１００質量部に対するウレタン樹脂の不揮発分としての含有量（質量部）を表１に示す。
[Examples 2-1 to 2-11, Comparative Examples 2-1 to 2-2]
A conductor forming composition was prepared and baked in the same manner as in Example 1-1 except that a urethane resin having a methoxysilyl group (trade name: U201, Arakawa Chemical Industry Co., Ltd.) was used instead of the epoxy resin. I got a bond. Table 1 shows the content (parts by mass) of the urethane resin as a non-volatile component with respect to 100 parts by mass of the copper cake at this time.
［実施例３－１～３－２］
導体形成用組成物を加熱する雰囲気を、大気雰囲気から酸素含有窒素雰囲気に変更した以外は、実施例２－８と同様にして焼結体を得た。なお、酸素含有窒素雰囲気中の酸素濃度は、実施例３－１では１００体積ｐｐｍ、実施例３－２では１００００体積ｐｐｍとした。
[Examples 3-1 to 3-2]
A sintered body was obtained in the same manner as in Example 2-8, except that the atmosphere for heating the conductor-forming composition was changed from the atmosphere to the oxygen-containing nitrogen atmosphere. The oxygen concentration in the oxygen-containing nitrogen atmosphere was 100% by volume ppm in Example 3-1 and 10000% by volume in Example 3-2.
［比較例４］
ウレタン樹脂を混合しなかった以外は実施例２－１と同様にして導体形成用組成物を調製し、焼結体を得た。
[Comparative Example 4]
A conductor-forming composition was prepared in the same manner as in Example 2-1 except that the urethane resin was not mixed, and a sintered body was obtained.
（導電性の評価）
各実施例及び比較例において、希硫酸で処理する前の銅を含む薄膜、及び希硫酸で処理した後の焼結体の表面抵抗率を、４端針面抵抗測定器で測定した。結果を表１に示す。
(Evaluation of conductivity)
In each Example and Comparative Example, the surface resistivity of the thin film containing copper before being treated with dilute sulfuric acid and the sintered body after being treated with dilute sulfuric acid were measured with a four-ended needle surface resistance measuring instrument. The results are shown in Table 1.
（基材に対する接着力の評価）
各実施例及び比較例において、得られた焼結体を陰極、含リン銅板を陽極として、硫酸銅、硫酸及び塩酸を含む水溶液中において、２Ａ／１ｄｍ２で２０分間の電解銅めっきを行った。次いで、卓上ピール試験機（商品名：小型卓上試験機ＥＺ－Ｓ、株式会社島津製作所）を用いて、電解銅めっきにより厚膜化した導体（焼結体＋めっき膜）を、導体ピール幅１０ｍｍ、ピール角度９０°、ピール速度３０ｍｍ／秒の条件で基材から剥離し、基材に対する導体の接着力（Ｎ／ｍ）を測定した。結果を表１に示す。なお、表１中の「接着力」の欄において、「測定不可」は、得られた焼結体の表面抵抗率が高すぎて電解めっきができず、ピール試験を実施できなかったことを意味し、「≦」は、測定値がその右側の数値と同じであるか、それより小さいことを意味する。「表面抵抗率」の欄における「≧」は、測定値がその右側の数値と同じであるか、それより大きいことを意味する。
(Evaluation of adhesive strength to the base material)
In each Example and Comparative Example, electrolytic copper plating was performed at 2 A / 1 dm 2 for 20 minutes in an aqueous solution containing copper sulfate, sulfuric acid and hydrochloric acid using the obtained sintered body as a cathode and a phosphorus-containing copper plate as an anode. .. Next, using a desktop peel tester (trade name: small desktop tester EZ-S, Shimadzu Corporation), a conductor (sintered body + plating film) thickened by electrolytic copper plating was subjected to a conductor peel width of 10 mm. The conductor was peeled off from the base material under the conditions of a peel angle of 90 ° and a peel speed of 30 mm / sec, and the adhesive force (N / m) of the conductor to the base material was measured. The results are shown in Table 1. In the column of "adhesive strength" in Table 1, "unmeasurable" means that the surface resistivity of the obtained sintered body was too high to perform electrolytic plating, and the peel test could not be performed. However, "≦" means that the measured value is the same as or smaller than the value on the right side. “≧” in the “Surface resistivity” column means that the measured value is the same as or larger than the value on the right side.
実施例１－１～１－１１及び２－１～２－１１より、導体形成用組成物を大気雰囲気で加熱する工程だけでは、得られた処理前焼結体は導通しなかった。一方、酸処理工程を更に経ることで、良好な導電性が得られた。これに対し、比較例１－１、比較例２－１、比較例４では、大気雰囲気で加熱し、かつ酸処理工程を経ても、良好な導電性は得られなかった。これらの比較例では、上述したように、銅の酸化を防ぐ樹脂が少なく、あるいは含んでおらず、銅内部まで酸化が進行したためであると考えられる。このように、所定量の樹脂を含む導体形成用組成物は、樹脂の種類によらず、大気雰囲気での加熱によって、優れた導電性を有する導体を形成可能であることが分かった。また、樹脂の含有量の増加に伴って接着性が向上すること、及び、比較例４との対比から、導体形成用組成物が樹脂を含有することにより、基材に対する接着力が向上することが分かった。 From Examples 1-1 to 1-11 and 2-1 to 2-11, the obtained pre-treated sintered body did not conduct only by the step of heating the conductor-forming composition in the atmospheric atmosphere. On the other hand, good conductivity was obtained by further passing through the acid treatment step. On the other hand, in Comparative Example 1-1, Comparative Example 2-1 and Comparative Example 4, good conductivity was not obtained even after heating in an atmospheric atmosphere and undergoing an acid treatment step. In these comparative examples, as described above, it is considered that the resin that prevents the oxidation of copper is small or not contained, and the oxidation has proceeded to the inside of the copper. As described above, it was found that the conductor-forming composition containing a predetermined amount of resin can form a conductor having excellent conductivity by heating in an atmospheric atmosphere regardless of the type of resin. Further, the adhesiveness is improved as the content of the resin is increased, and in comparison with Comparative Example 4, the conductor-forming composition contains the resin, so that the adhesive strength to the substrate is improved. I understood.
Claims (9)
前記加熱は、酸素濃度が１００体積ｐｐｍ以上である雰囲気下で行われる、導体の製造方法。 A composition provided on a substrate and containing copper-containing particles and a resin containing 1.0 part by mass to 30 parts by mass with respect to 100 parts by mass of the copper-containing particles at 200 ° C. or lower. After heating, it is treated with acid to obtain a sintered body.
The method for manufacturing a conductor, wherein the heating is performed in an atmosphere having an oxygen concentration of 100% by volume or more.
前記有機物は、ＲＮＨ ２ （Ｒは炭素数が７以下の炭化水素基）で表される１級アミン、及びＲ １ Ｒ ２ ＮＨ（Ｒ １ 及びＲ ２ は同じであっても異なっていてもよい炭素数が７以下の炭化水素基）で表される２級アミンからなる群より選ばれる少なくとも１種に由来する有機物を含む、請求項１～３のいずれか一項に記載の導体の製造方法。 The copper-containing particles include core particles containing copper and an organic substance that covers at least a part of the surface of the core particles .
The organic matter is a primary amine represented by RNH 2 (R is a hydrocarbon group having 7 or less carbon atoms), and R 1 R 2 NH (R 1 and R 2 may be the same or different). The method for producing a conductor according to any one of claims 1 to 3 , which comprises an organic substance derived from at least one selected from the group consisting of a secondary amine represented by a hydrocarbon group having 7 or less carbon atoms. ..
前記銅含有粒子は、銅を含むコア粒子と、前記コア粒子の表面の少なくとも一部を被覆する有機物とを備え、
前記有機物は、ＲＮＨ ２ （Ｒは炭素数が７以下の炭化水素基）で表される１級アミン、及びＲ １ Ｒ ２ ＮＨ（Ｒ １ 及びＲ ２ は同じであっても異なっていてもよい炭素数が７以下の炭化水素基）で表される２級アミンからなる群より選ばれる少なくとも１種に由来する有機物を含む、導体形成用組成物。 It contains 1.0 part by mass to 30 parts by mass of the copper-containing particles and 1.0 part by mass to 30 parts by mass of the resin with respect to 100 parts by mass of the copper-containing particles.
The copper-containing particles include core particles containing copper and an organic substance that covers at least a part of the surface of the core particles.
The organic matter is a primary amine represented by RNH 2 (R is a hydrocarbon group having 7 or less carbon atoms), and R 1 R 2 NH (R 1 and R 2 may be the same or different). A composition for forming a conductor, which comprises an organic substance derived from at least one selected from the group consisting of a secondary amine represented by a hydrocarbon group having 7 or less carbon atoms .
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| JP2002084051A (en) | 2000-09-07 | 2002-03-22 | Murata Mfg Co Ltd | Metallized copper composition, low-temperature sintered ceramic wiring board, and method of manufacturing the same |
| JP2008226771A (en) | 2007-03-15 | 2008-09-25 | Mitsuboshi Belting Ltd | Copper conductive paste, conductor circuit board, and electronic component |
| JP2015115147A (en) | 2013-12-10 | 2015-06-22 | 旭硝子株式会社 | Metal particle, paste for forming conductive film, and article |
| JP2015133182A (en) | 2014-01-09 | 2015-07-23 | 旭硝子株式会社 | Conductive paste and substrate having conductive film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002084051A (en) | 2000-09-07 | 2002-03-22 | Murata Mfg Co Ltd | Metallized copper composition, low-temperature sintered ceramic wiring board, and method of manufacturing the same |
| JP2008226771A (en) | 2007-03-15 | 2008-09-25 | Mitsuboshi Belting Ltd | Copper conductive paste, conductor circuit board, and electronic component |
| JP2015115147A (en) | 2013-12-10 | 2015-06-22 | 旭硝子株式会社 | Metal particle, paste for forming conductive film, and article |
| JP2015133182A (en) | 2014-01-09 | 2015-07-23 | 旭硝子株式会社 | Conductive paste and substrate having conductive film |
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