JP2007039718A - Method for producing silver powder - Google Patents
Method for producing silver powder Download PDFInfo
- Publication number
- JP2007039718A JP2007039718A JP2005222855A JP2005222855A JP2007039718A JP 2007039718 A JP2007039718 A JP 2007039718A JP 2005222855 A JP2005222855 A JP 2005222855A JP 2005222855 A JP2005222855 A JP 2005222855A JP 2007039718 A JP2007039718 A JP 2007039718A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- particle powder
- dispersion
- protective agent
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 111
- 229910052709 silver Inorganic materials 0.000 claims abstract description 93
- 239000004332 silver Substances 0.000 claims abstract description 93
- 239000000843 powder Substances 0.000 claims abstract description 53
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 230000009467 reduction Effects 0.000 claims abstract description 31
- 239000003223 protective agent Substances 0.000 claims abstract description 27
- 238000009835 boiling Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229920005862 polyol Polymers 0.000 claims abstract description 10
- 150000003077 polyols Chemical class 0.000 claims abstract description 10
- 150000003141 primary amines Chemical class 0.000 claims abstract description 10
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000006185 dispersion Substances 0.000 claims description 52
- 239000012752 auxiliary agent Substances 0.000 claims description 8
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 7
- 150000003335 secondary amines Chemical class 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000011946 reduction process Methods 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 abstract description 3
- 239000002671 adjuvant Substances 0.000 abstract 2
- 238000000034 method Methods 0.000 description 36
- 238000006722 reduction reaction Methods 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 15
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 14
- -1 silver ions Chemical class 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 239000002609 medium Substances 0.000 description 13
- 239000010944 silver (metal) Substances 0.000 description 13
- 239000002270 dispersing agent Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 239000007791 liquid phase Substances 0.000 description 7
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
- 150000003379 silver compounds Chemical class 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 230000005012 migration Effects 0.000 description 4
- 238000013508 migration Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910001923 silver oxide Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- 150000003573 thiols Chemical class 0.000 description 3
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- ZCUAOSPTDXJIJR-UHFFFAOYSA-N ethanol;2-(2-hydroxyethylamino)ethanol Chemical group CCO.OCCNCCO ZCUAOSPTDXJIJR-UHFFFAOYSA-N 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000009766 low-temperature sintering Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 2
- UMFJAHHVKNCGLG-UHFFFAOYSA-N n-Nitrosodimethylamine Chemical compound CN(C)N=O UMFJAHHVKNCGLG-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003378 silver Chemical class 0.000 description 2
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 2
- 229910001958 silver carbonate Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 1
- LTHNHFOGQMKPOV-UHFFFAOYSA-N 2-ethylhexan-1-amine Chemical compound CCCCC(CC)CN LTHNHFOGQMKPOV-UHFFFAOYSA-N 0.000 description 1
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- DVFGEIYOLIFSRX-UHFFFAOYSA-N 3-(2-ethylhexoxy)propan-1-amine Chemical compound CCCCC(CC)COCCCN DVFGEIYOLIFSRX-UHFFFAOYSA-N 0.000 description 1
- FAXDZWQIWUSWJH-UHFFFAOYSA-N 3-methoxypropan-1-amine Chemical compound COCCCN FAXDZWQIWUSWJH-UHFFFAOYSA-N 0.000 description 1
- DGRGLKZMKWPMOH-UHFFFAOYSA-N 4-methylbenzene-1,2-diamine Chemical compound CC1=CC=C(N)C(N)=C1 DGRGLKZMKWPMOH-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
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- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
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- KXPQJUQBPMZFAT-UHFFFAOYSA-N N(CCO)(CCO)CCO.C(C)O.C(C)O.C(C)O Chemical compound N(CCO)(CCO)CCO.C(C)O.C(C)O.C(C)O KXPQJUQBPMZFAT-UHFFFAOYSA-N 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 239000008346 aqueous phase Substances 0.000 description 1
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- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- LAWOZCWGWDVVSG-UHFFFAOYSA-N dioctylamine Chemical compound CCCCCCCCNCCCCCCCC LAWOZCWGWDVVSG-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000010946 fine silver Substances 0.000 description 1
- 229940083124 ganglion-blocking antiadrenergic secondary and tertiary amines Drugs 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
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Abstract
Description
本発明は微細な（特に粒径がナノメートルオーダーの）銀の粒子粉末の製造法に係り、詳しくは、微細な回路パターンを形成するための配線形成用材料例えばインクジェット法による配線形成用材料等に好適な銀粒子粉末の製造法に関する。 The present invention relates to a method for producing fine silver particle powder (particularly having a particle size on the order of nanometers). The present invention relates to a method for producing a silver particle powder suitable for.
固体物質の大きさがｎｍオーダー（ナノメートルオーダー）になると比表面積が非常に大きくなるために、固体でありながら気体や液体の界面が極端に大きくなる。したがって、その表面の特性が固体物質の性質を大きく左右する。金属粒子粉末の場合は、融点がバルク状態のものに比べ劇的に低下することが知られており、そのためにμｍオーダーの粒子に比べて微細な配線の描画が可能になり、しかも低温焼結できるなどの利点を具備するようになる。金属粒子粉末の中でも銀粒子粉末は、低抵抗でかつ高い耐候性をもち、金属の価格も他の貴金属と比較して安価であることから、微細な配線幅をもつ次世代の配線材料として特に期待されている。 When the size of the solid substance is on the order of nm (on the order of nanometers), the specific surface area becomes very large, so that the interface between the gas and the liquid becomes extremely large while being solid. Therefore, the properties of the surface greatly influence the properties of the solid substance. In the case of metal particle powder, it is known that the melting point is drastically lower than that in the bulk state, which makes it possible to draw fine wiring compared to particles on the order of μm, and low temperature sintering. It has the advantage that it can be done. Among the metal particle powders, the silver particle powder has low resistance and high weather resistance, and the price of the metal is low compared with other noble metals, so it is particularly useful as a next-generation wiring material with a fine wiring width. Expected.
ｎｍオーダーの銀の粒子粉末の製造方法としては大別して気相法と液相法が知られている。気相法ではガス中での蒸着法が普通であり、特許文献１にはヘリウム等の不活性ガス雰囲気でかつ０．５Ｔｏｒｒ程度の低圧中で銀を蒸発させる方法が記載されている。液相法に関しては、特許文献２では、水相で銀イオンをアミンで還元し、得られた銀の析出相を有機溶媒相（高分子量の分散剤）に移動して銀のコロイドを得る方法を開示しており、特許文献３には、溶媒中でハロゲン化銀を還元剤（アルカリ金属水素化ホウ酸塩またはアンモニウム水素化ホウ酸塩）を用いてチオール系の保護剤の存在下で還元する方法が記載されている。
特許文献１の気相法で得られる銀粒子は、粒径が１０ｎｍ以下で溶媒中での分散性が良好である。しかし、この技術は特別な装置が必要である。このため産業用の銀ナノ粒子を大量に合成するには難がある。 Silver particles obtained by the vapor phase method of Patent Document 1 have a particle size of 10 nm or less and good dispersibility in a solvent. However, this technique requires special equipment. For this reason, it is difficult to synthesize industrial silver nanoparticles in large quantities.
これに対して液相法は基本的に大量合成に適した方法であるが、液中ではそのナノ粒子は極めて凝集性が高いので単一粒子に分散したナノ粒子粉末を得難いという問題がある。一般に、ナノ粒子を製造するためには分散剤としてクエン酸を用いる例が多く、また液中の金属イオン濃度も１０ｍｍｏｌ／Ｌ（＝０．０１ｍｏｌ／Ｌ）以下と極めて低いのが通常であり、このため、産業上の応用面でのネックとなっている。 On the other hand, the liquid phase method is basically a method suitable for large-scale synthesis, but there is a problem in that it is difficult to obtain nanoparticle powder dispersed in a single particle because the nanoparticles are extremely cohesive in the liquid. In general, in order to produce nanoparticles, there are many examples using citric acid as a dispersing agent, and the metal ion concentration in the liquid is usually extremely low as 10 mmol / L (= 0.01 mol / L) or less, This is a bottleneck in industrial applications.
特許文献２は、液相法により０．２〜０．６ｍｏｌ／Ｌの高い金属イオン濃度と、高い原料仕込み濃度で安定して分散した銀ナノ粒子を合成しているが、凝集を抑制するために数平均分子量が数万の高分子量の分散剤を用いている。高分子量の分散剤を用いたものでは、これを色剤として用いる場合は問題ないが、回路形成用途に用いる場合には高分子分散剤が燃焼し難いために焼成時に残存しやすいこと、さらには焼成後も配線にポアが発生しやすいこと等から抵抗が高くなったり断線が生じたりするので、低温焼成により微細な配線を形成するには問題がある。また高分子量の分散剤を使用している関係上、微粒子銀の分散液の粘度が高くなることも問題となる。 Patent Document 2 synthesizes silver nanoparticles stably dispersed at a high metal ion concentration of 0.2 to 0.6 mol / L and a high raw material feed concentration by a liquid phase method, but to suppress aggregation. In addition, a high molecular weight dispersant having a number average molecular weight of tens of thousands is used. In the case of using a high molecular weight dispersant, there is no problem when this is used as a colorant, but when used for circuit formation, the high molecular weight dispersant is difficult to burn, so it is likely to remain during firing. There is a problem in forming fine wiring by low-temperature firing because resistance increases or disconnection occurs because the pores are easily generated after firing. In addition, since a high molecular weight dispersant is used, the viscosity of the fine particle silver dispersion is also problematic.
特許文献３は、液相法により、仕込み濃度も０．１ｍｏｌ／Ｌ以上の比較的高い濃度で反応させ、得られた１０ｎｍ以下の銀粒子を有機分散媒に分散させているが、特許文献３では分散剤としてチオール系の分散剤が提案されている。チオール系の分散剤は分子量が２００程度と低いことから、配線形成時に低温焼成で容易に除去させることができるが、硫黄（Ｓ）が含まれており、この硫黄分は、配線やその他電子部品を腐食させる原因となるために配線形成用途には好ましくはない。 In Patent Document 3, reaction is performed at a relatively high concentration of 0.1 mol / L or more by a liquid phase method, and the obtained silver particles of 10 nm or less are dispersed in an organic dispersion medium. Proposed a thiol-based dispersant as a dispersant. Since the thiol-based dispersant has a low molecular weight of about 200, it can be easily removed by low-temperature firing at the time of wiring formation, but it contains sulfur (S), and this sulfur content is used for wiring and other electronic components. This is not preferable for wiring formation applications.
したがって本発明はこのような問題を解決し、微細な配線形成用途に適し、かつ低温焼結性が良好な高分散性球状銀粒子の分散液を安価かつ大量に高い収率で得ることを課題としたものである。 Therefore, the present invention solves such problems, and it is an object to obtain a dispersion of highly dispersible spherical silver particles that is suitable for fine wiring formation applications and has good low-temperature sinterability at low cost and in large yield. It is what.
本発明によれば、沸点８０℃〜２００℃のアルコール中または沸点１５０〜３００℃のポリオール中で、銀塩を、有機保護剤および還元補助剤の共存下で且つ温度８０℃〜２００℃の範囲で還元処理する、極性の低い液状有機媒体への分散性に優れた銀粒子粉末の製造法を提供する。ここで、有機保護剤としては分子量１００〜１０００で構造内に不飽和結合をもつ１級アミンを使用し、還元補助剤としては２級アミンおよび／または３級アミンを使用する。この還元処理は、
Ａｇイオン濃度：０．０５〜５．０モル／Ｌ、
有機保護剤／Ａｇのモル比：０．０５〜５．０、
還元補助剤／Ａｇのモル比：０．１〜２０、
アルコールまたはポリオール／Ａｇのモル比：０．５〜５０
の量比で行うのがよい。還元処理で得られる銀粒子粉末は平均粒径ＤTEMが好ましくは５０ｎｍ以下であり、粒子表面には前記の有機保護剤が被着している。このため、ナノ粒子であっても極性の低い液状有機媒体への分散性が良好である。
According to the present invention, in an alcohol having a boiling point of 80 ° C. to 200 ° C. or in a polyol having a boiling point of 150 to 300 ° C., the silver salt is in the range of a temperature of 80 ° C. to 200 ° C. in the presence of an organic protective agent and a reducing aid. A method for producing a silver particle powder excellent in dispersibility in a liquid organic medium having a low polarity, which is reduced by 1 is provided. Here, a primary amine having a molecular weight of 100 to 1000 and having an unsaturated bond in the structure is used as the organic protective agent, and a secondary amine and / or a tertiary amine is used as the reducing auxiliary agent. This reduction process
Ag ion concentration: 0.05 to 5.0 mol / L,
Organic protective agent / Ag molar ratio: 0.05 to 5.0,
Reduction auxiliary agent / Ag molar ratio: 0.1-20,
Alcohol or polyol / Ag molar ratio: 0.5-50
It is good to carry out by the quantity ratio. The silver particle powder obtained by the reduction treatment preferably has an average particle diameter DTEM of 50 nm or less, and the organic protective agent is deposited on the particle surface. For this reason, even if it is a nanoparticle, the dispersibility to the liquid organic medium with low polarity is favorable.
本発明はまた１級アミン中で、銀塩を、２級アミンまたは３級アミンの一方または両方の共存下で且つ温度８０〜２００℃の範囲で還元処理する、極性の低い液状有機媒体への分散性の優れた銀粒子粉末の製造法を提供する。 The present invention also provides a low-polarity liquid organic medium in which a silver salt is reduced in a primary amine in the presence of one or both of a secondary amine and a tertiary amine and at a temperature in the range of 80 to 200 ° C. A method for producing a silver particle powder having excellent dispersibility is provided.
本発明の製造法で得られた銀粒子粉末を、極性の低い液状有機媒体に分散させてなる銀粒子粉末の分散液は、
ｐＨ：６．５以上
分散液中の銀濃度：５〜９０wt％、
粘度：５０ｍＰａ・ｓ以下、
表面張力：８０ｍＮ／ｍ以下
のニュートン流体としての性質を有することができる。また、この分散液は、液中の銀粒子粉末の平均粒径＋２０ｎｍの孔径を有するメンブランフィルターを通過するほどの良好な分散性を具備できる。
A dispersion of silver particle powder obtained by dispersing the silver particle powder obtained by the production method of the present invention in a liquid organic medium having low polarity,
pH: 6.5 or more Silver concentration in the dispersion: 5-90 wt%,
Viscosity: 50 mPa · s or less,
Surface tension: It can have properties as a Newtonian fluid of 80 mN / m or less. Moreover, this dispersion liquid can have the dispersibility so favorable that it passes the membrane filter which has the average particle diameter of the silver particle powder in a liquid + the hole diameter of 20 nm.
本発明法で得られた銀粒子粉末はナノ粒子でありながら極性の低い液状有機媒体に良好に分散させることができるので、低温での焼結性が良好な銀粒子粉末の分散液が得られる。この分散液は粒子個々が単分散している単分散率が高いので特にインクジェット法による配線形成や塗布による薄膜形成に適している。 Since the silver particle powder obtained by the method of the present invention is a nanoparticle, it can be well dispersed in a liquid organic medium having low polarity, so that a dispersion of silver particle powder having good sinterability at low temperatures can be obtained. . Since this dispersion liquid has a high monodispersion ratio in which particles are monodispersed, it is particularly suitable for forming a wiring by an ink jet method or forming a thin film by coating.
本発明者は液相法で銀の粒子粉末を製造する試験を重ねてきたが、沸点が８５〜１５０℃のアルコール中で、硝酸銀を、８５〜１５０℃の温度で（蒸発したアルコールを液相に還流させながら）、例えば分子量１００〜４００のアミン化合物からなる保護剤の共存下で還元処理すると、粒径の揃った球状の銀のナノ粒子粉末が得られることを知見し、特願２００５−２６８０５号明細書および図面に記載した。また、沸点が８５℃以上のアルコールまたはポリオール中で、銀化合物（代表的には炭酸銀または酸化銀）を、８５℃以上の温度で、例えば分子量１００〜４００の脂肪酸からなる保護剤の共存下で還元処理すると、腐食性化合物の少ない粒径の揃った球状の銀の粒子粉末が得ることを知見し、特願２００５−２６８６６号明細書および図面に記載した。さらに、沸点が８５〜１５０℃のアルコール中で硝酸銀を、８５℃以上の温度で有機保護剤（分子量１００〜１０００の脂肪酸またはアミン化合物）の存在下で還元処理する際、極性抑制剤として沸点８５℃以上の炭化水素類を入れておくと、高度に分散可能な銀粒子粉末が高い収率で得られることを知見し、この発明を特願２００５−５６０３５号明細書および図面に記載した。 The present inventor has repeatedly conducted tests for producing silver particle powder by a liquid phase method. In an alcohol having a boiling point of 85 to 150 ° C., silver nitrate is heated at a temperature of 85 to 150 ° C. (evaporated alcohol is liquid phase). For example, when a reduction treatment is performed in the presence of a protective agent composed of an amine compound having a molecular weight of 100 to 400, a spherical silver nanoparticle powder having a uniform particle size can be obtained. This is described in the specification of No. 26805 and the drawings. Further, in an alcohol or polyol having a boiling point of 85 ° C. or higher, a silver compound (typically silver carbonate or silver oxide) is mixed with a protective agent comprising a fatty acid having a molecular weight of 100 to 400, for example, at a temperature of 85 ° C. or higher. It was found that when the reduction treatment was performed, spherical silver particle powder having a uniform particle size with few corrosive compounds was obtained and described in Japanese Patent Application No. 2005-26866 and drawings. Furthermore, when reducing the silver nitrate in alcohol having a boiling point of 85 to 150 ° C. in the presence of an organic protective agent (fatty acid or amine compound having a molecular weight of 100 to 1000) at a temperature of 85 ° C. or higher, a boiling point of 85 as a polar inhibitor. It has been found that high-dispersible silver particle powder can be obtained in a high yield when hydrocarbons at ℃ or higher are added, and this invention is described in Japanese Patent Application No. 2005-56035 and drawings.
いずれの場合にも、その銀粒子粉末を非極性もしくは極性の小さな液状有機媒体に分散させることによって銀粒子の分散液を得ることができ、この分散液から遠心分離等で粗粒子を除くと粒径のバラツキの少ない（ＣＶ値＝標準偏差σ／個数平均粒子の百分率が４０％未満の）銀粒子が単分散した分散液を得ることができる。 In either case, a dispersion of silver particles can be obtained by dispersing the silver particle powder in a non-polar or small polar liquid organic medium. When coarse particles are removed from the dispersion by centrifugation or the like, A dispersion in which silver particles having a small variation in diameter (CV value = standard deviation σ / percentage of number average particles is less than 40%) are monodispersed can be obtained.
しかし、これら方法では、反応温度を高くすると、液中の銀イオンが効率よく還元されるが、粒子の焼結が起こって粗粒子化し、目的とする５０ｎｍ以下の銀粒子粉末が得られ難くなり、反面、反応温度を低くすれば焼結は抑制できるが、液中の銀イオンの還元効率が低下してしまって収率が下がる等のことから、効率よく目的とする５０ｎｍ以下の銀粒子粉末の作製を行うにはさらなる改善を必要とした。この問題に対し、有機保護剤として用いるアミン化合物量を増やすと、単分散率は向上するが還元率が低下し、結果的に収率が低下するという問題が起きた。単分散率が低いことは、焼結した粒子や強固に凝集した銀粒子が多いことを意味するので、更なる単分散率向上のための改善を必要とした。 However, in these methods, when the reaction temperature is increased, silver ions in the liquid are efficiently reduced, but the particles are sintered and coarsened, making it difficult to obtain the desired silver particle powder of 50 nm or less. On the other hand, if the reaction temperature is lowered, sintering can be suppressed, but the reduction efficiency of silver ions in the liquid is reduced, resulting in a decrease in yield. Further improvements were required to make the. In contrast to this problem, when the amount of the amine compound used as the organic protective agent is increased, the monodispersion rate is improved, but the reduction rate is lowered, and as a result, the yield is lowered. Since the low monodispersion rate means that there are many sintered particles and strongly agglomerated silver particles, further improvement for improving the monodispersion rate was required.
この課題に対し、鋭意研究を進めた結果、前記の還元反応において還元補助剤として２級アミンおよび／または３級アミンを共存させると高い還元率を維持した反応を実現でき且つ極性の低い液状有機媒体に高い単分散率で分散する銀粒子粉末が得られることを知見した。特に、この還元補助剤は還元反応の終了近くで添加するのがよく、還元補助剤の添加量は対Ａｇのモル比で０．１〜２０の範囲であるのがよい。 As a result of diligent research on this problem, a liquid organic compound having a low polarity and capable of realizing a reaction maintaining a high reduction rate when a secondary amine and / or a tertiary amine coexist as a reduction auxiliary agent in the above reduction reaction. It was found that a silver particle powder dispersed in a medium at a high monodispersity can be obtained. In particular, this reduction aid is preferably added near the end of the reduction reaction, and the addition amount of the reduction aid is preferably in the range of 0.1 to 20 in terms of the molar ratio of Ag to Ag.
以下に本発明法の詳細を述べる。 Details of the method of the present invention will be described below.
本発明法は、沸点が８０℃〜１５０℃のアルコールまたは沸点が１５０〜３００℃のポリオール中で、銀化合物（各種の銀塩や銀酸化物等）を、有機保護剤の共存下で８５℃〜１５０℃の温度で還元処理することによって銀粒子粉末を製造する際に、還元補助剤をＡｇモル比で０．１〜２０の範囲で添加して製造する点に特徴がある。 In the method of the present invention, a silver compound (various silver salts, silver oxides, etc.) is added at 85 ° C. in the presence of an organic protective agent in an alcohol having a boiling point of 80 ° C. to 150 ° C. or a polyol having a boiling point of 150 to 300 ° C. When the silver particle powder is produced by reduction treatment at a temperature of ˜150 ° C., it is characterized in that it is produced by adding a reducing aid in the range of 0.1 to 20 in terms of Ag molar ratio.
沸点が８０℃〜１５０℃のアルコールまたは１５０〜３００℃のポリオールは銀化合物の還元剤としてまた反応媒体として機能するものである。反応媒体兼還元剤であるアルコールとしては、イソブタノール、１−ブタノール、２−プロパノール、１−ヘキサノール、エタノールなどが挙げられる。還元反応は加熱下でこの反応媒体兼還元剤の蒸発と凝縮を繰り返す還流条件下で行なわせるのがよい。使用する銀イオン原料（各種銀塩、銀化合物）としては、塩化銀、硝酸銀、酸化銀、炭酸銀などがあるが、工業的観点から硝酸銀が好ましいが、硝酸銀に限定するものではない。本発明法では反応時の液中のＡｇイオン濃度は５０ｍｍｏｌ／Ｌ以上、好ましくは０．０５〜５．０モル／Ｌで行うことができる。有機保護剤／Ａｇのモル比については０．０５〜５．０の範囲、還元補助剤／Ａｇのモル比については０．１〜２０の範囲、アルコールまたはポリオール／Ａｇのモル比については０．５〜５０の範囲であるのがよい。 An alcohol having a boiling point of 80 ° C. to 150 ° C. or a polyol having a boiling point of 150 to 300 ° C. functions as a reducing agent for the silver compound and as a reaction medium. Examples of the alcohol that is the reaction medium and reducing agent include isobutanol, 1-butanol, 2-propanol, 1-hexanol, ethanol, and the like. The reduction reaction is preferably performed under reflux conditions in which the reaction medium / reducing agent is repeatedly evaporated and condensed under heating. Silver ion raw materials (various silver salts and silver compounds) to be used include silver chloride, silver nitrate, silver oxide, and silver carbonate. Silver nitrate is preferred from an industrial viewpoint, but is not limited to silver nitrate. In the method of the present invention, the Ag ion concentration in the solution during the reaction can be 50 mmol / L or more, preferably 0.05 to 5.0 mol / L. The organic protective agent / Ag molar ratio is in the range of 0.05 to 5.0, the reducing auxiliary agent / Ag molar ratio is in the range of 0.1-20, and the alcohol or polyol / Ag molar ratio is 0.00. It is good to be in the range of 5-50.
有機保護剤としては、分子量１００〜１０００の脂肪酸またはアミン化合物を使用することができる。脂肪酸では、プロピオン酸、カプリル酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、ベヘン酸、アクリル酸、オレイン酸、リノール酸、アラキドン酸などが挙げられる。アミノ化合物では、エチルアミン、アリルアミン、イソプロピルアミン、プロピルアミン、エチレンジアミン、２−アミノエタノール、２−ブタンアミン、ｎ−ブチルアミン、ｔ−ブチルアミン、３−ヒドロキシプロピルアミン、３−（メチルアミノ）プロピルアミン、３−メトキシプロピルアミン、シクロヘキシルアミン、ヘキシルアミン、３−（ジメチルアミノ）プロピルアミン、ヘキサノールアミン、ピペラジン、ベンジルアミン、ｍ−フェニレンジアミン、ｏ−フェニレンジアミン、ｐ−フェニレンジアミン、１、６−ヘキサジアミン、ヘキサメチレンジアミン、２−メチル−１、３−フェニレンジアミン、トリレン−３、４−ジアミン、アニシジン、２−エチルヘキシルアミン、Ｍ−キシレン−α α’ジアミン、キシリレンジアミン、トルイジン、３−（２−エチルヘキシルオキシ）プロピルアミン、オレイルアミンなどが挙げられる。 As the organic protective agent, a fatty acid having a molecular weight of 100 to 1000 or an amine compound can be used. Examples of fatty acids include propionic acid, caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, acrylic acid, oleic acid, linoleic acid, arachidonic acid and the like. As amino compounds, ethylamine, allylamine, isopropylamine, propylamine, ethylenediamine, 2-aminoethanol, 2-butaneamine, n-butylamine, t-butylamine, 3-hydroxypropylamine, 3- (methylamino) propylamine, 3- Methoxypropylamine, cyclohexylamine, hexylamine, 3- (dimethylamino) propylamine, hexanolamine, piperazine, benzylamine, m-phenylenediamine, o-phenylenediamine, p-phenylenediamine, 1,6-hexadiamine, hexa Methylenediamine, 2-methyl-1,3-phenylenediamine, tolylene-3,4-diamine, anisidine, 2-ethylhexylamine, M-xylene-αα'diamine, xylylenediamine , Toluidine, 3- (2-ethylhexyl oxy) propylamine, etc. oleylamine and the like.
有機保護剤としてのこれらは単独で使用しても良く、２種以上を併用しても良い。特に銀に配位性の金属配位性化合物であるのが良い。銀に配位性がないか又は低い化合物を使用した場合、銀ナノ粒子を作成するのに大量の保護剤が必要となり実用的でない。アミン化合物の中でも第１級アミンが好ましい。アミン化合物は、分子量が１００〜１０００のものであるのがよく、分子量が１００未満のものでは粒子の凝集抑制効果が低く、分子量が１０００を超えるものでは凝集抑制力は高くても銀粉末の分散液を塗布して焼成するときに粒子間の焼結を阻害して配線の抵抗が高くなってしまい、場合によっては、導電性をもたなくなることもある。第１級アミンがより好ましく、さらに好ましくは１分子中に１個以上の不飽和結合を有するアミノ化合物が好ましい。これらの中でも特にオレイルアミンが好ましい。 These as an organic protective agent may be used independently and may use 2 or more types together. In particular, a metal coordinating compound coordinated with silver is preferable. When a compound having no or low coordination property is used for silver, a large amount of protective agent is required to produce silver nanoparticles, which is not practical. Of the amine compounds, primary amines are preferred. The amine compound should have a molecular weight of 100 to 1000. If the molecular weight is less than 100, the effect of suppressing aggregation of particles is low. If the molecular weight exceeds 1000, the dispersion of silver powder is high even if the aggregation suppression power is high. When the liquid is applied and fired, sintering between the particles is hindered and the resistance of the wiring is increased, and in some cases, the electric conductivity may be lost. Primary amines are more preferable, and amino compounds having one or more unsaturated bonds in one molecule are more preferable. Among these, oleylamine is particularly preferable.
還元補助剤としては、分子量１００〜１０００のアミン化合物を使用することができ、例えばジイソプロピルアミン、ジエチレントリアミン、Ｎ−（２−アミノエチル）エタノールアミン、ジエタノールアミン、ビス（２−シアノエチル）アミン、イミノビス（プロピルアミン）、Ｎ−ｎブチルアニリン、ジフェニルアミン、ジ−２−エチルヘキシルアミン、ジオクチルアミン、トリメチルアミン、ジメチルエチルアミン、ジメチルエチルアミン、Ｎ−ニトロソジメチルアミン、２−ジメチルアミノエタノール、ジメチルアミノエタノール、トリエチルアミン、テトラメチルエチレンジアミン、ジエチルエタノールアミン、メチルジエタノールアミン、トリアリルアミン、Ｎ−メチル−３、３’−イミノビス（プロピルアミン）、トリエタノールアミン、Ｎ、Ｎ−ジブチルエタノールアミン、３−（ジブチルアミノ）プロピルアミン、Ｎ−ニトロソジフェニルアミン、トリフェニルアミン、トリ−ｎ−オクチルアミンなどが挙げられる。 As the reduction aid, an amine compound having a molecular weight of 100 to 1000 can be used. For example, diisopropylamine, diethylenetriamine, N- (2-aminoethyl) ethanolamine, diethanolamine, bis (2-cyanoethyl) amine, iminobis (propyl). Amine), Nnbutylaniline, diphenylamine, di-2-ethylhexylamine, dioctylamine, trimethylamine, dimethylethylamine, dimethylethylamine, N-nitrosodimethylamine, 2-dimethylaminoethanol, dimethylaminoethanol, triethylamine, tetramethylethylenediamine , Diethylethanolamine, methyldiethanolamine, triallylamine, N-methyl-3,3′-iminobis (propylamine), triethanol Triethanolamine, N, N- dibutyl ethanolamine, 3- (dibutylamino) propylamine, N- nitrosodiphenylamine, triphenylamine, tri -n- octyl amine.
還元補助剤としてのこれらのアミン化合物は単独で使用しても良く、２種以上を併用しても良い。還元補助剤についても有機保護剤と同様、分子量が１００未満のものでは粒子の凝集抑制効果が低く、分子量が１０００を超えるものでは凝集抑制力は高くても銀粉末の分散液を塗布して焼成するときに粒子間の焼結を阻害して配線の抵抗が高くなってしまい、場合によっては、導電性をもたなくなることもあるので、分子量１００〜１０００のアミン化合物を使用するのがよい。アミン化合物の中でも還元力の強い第２級、第３級アミンが良く、これらのうちジエタノールアミン、トリエタノールアミンを用いるのが特に好ましい。 These amine compounds as a reducing aid may be used alone or in combination of two or more. Similarly to the organic protective agent, the reduction auxiliary agent has a low particle aggregation inhibiting effect when the molecular weight is less than 100, and when the molecular weight exceeds 1000, the silver powder dispersion is applied and baked even if the aggregation inhibiting force is high. In this case, the sintering of the particles is hindered to increase the resistance of the wiring, and in some cases, the conductivity may be lost. Therefore, an amine compound having a molecular weight of 100 to 1000 is preferably used. Among amine compounds, secondary and tertiary amines having strong reducing power are good, and among these, diethanolamine and triethanolamine are particularly preferable.
別法として、１級アミン中で、銀塩を、２級アミンまたは３級アミンの一方または両方の共存下で且つ温度８０〜２００℃の範囲で還元処理することによって、極性の低い液状有機媒体への分散性の優れた銀粒子粉末を製造することもできる。この場合には、沸点が前記方法の８０℃〜１５０℃のアルコールまたは沸点が１５０〜３００℃のポリオールに代えて、１級アミンを銀イオンの反応媒体兼還元剤として使用するものであり、使用する１級アミン、２級アミン、３級アミンは、前掲のものを使用することができる。 Alternatively, a liquid organic medium having a low polarity can be obtained by reducing the silver salt in a primary amine in the presence of one or both of a secondary amine and a tertiary amine and at a temperature in the range of 80 to 200 ° C. It is also possible to produce a silver particle powder having excellent dispersibility. In this case, instead of the alcohol having a boiling point of 80 ° C. to 150 ° C. or a polyol having a boiling point of 150 to 300 ° C., a primary amine is used as a silver ion reaction medium and reducing agent. As the primary amine, secondary amine, and tertiary amine to be used, those described above can be used.
いずれにしても、本発明法で得られる銀粒子粉末は好ましくは平均粒径ＤTEMが５０ｎｍ以下であることができ、結晶粒子径ＤXは５０ｎｍ以下、単結晶化度（（ＤTEM）／（ＤX５０））は好ましくは２．０以下である。 In any case, the silver particle powder obtained by the method of the present invention can preferably have an average particle diameter D TEM of 50 nm or less, a crystal particle diameter D X of 50 nm or less, and a single crystallinity ((D TEM ) / (D X 50)) is preferably 2.0 or less.
また、本発明法によると前記の有機保護剤で覆われたナノ銀粒子粉末が得られ、この有機保護剤で覆われたナノ銀粒子粉末は極性の低い液状有機媒体に対して非常に分散性が優れる。ここで、極性の低い液状有機媒体とは、沸点が６０〜３００℃の非極性もしくは極性の小さい液状有機媒体を意味し、「非極性もしくは極性の小さい」というのは２５℃での比誘電率が１５以下であることを指す。より好ましく５以下のものを指す。比誘電率が１５を超える場合、銀粒子の分散性が悪化し沈降することがあり、好ましくない。分散液の用途に応じて各種の液状有機媒体が使用できるが、炭化水素系が好適に使用でき、とくに、イソオクタン、ｎ−デカン、イソドデカン、イソヘキサン、ｎ−ウンデカン、ｎ−テトラデカン、ｎ−ドデカン、トリデカン、ヘキサン、ヘプタン等の脂肪族炭化水素、ベンゼン、トルエン、キシレン、エチルベンゼン、デカリン、テトラリン等の芳香族炭化水素等が使用できる。これらの液状有機媒体は１種類または２種類以上を使用することができ、ケロシンのような混合物であっても良い。更に、極性を調整するために、混合後の液状有機媒体の２５℃での比誘電率が１５以下となる範囲でアルコール系、ケトン系、エーテル系、エステル系等の極性有機媒体を添加しても良い。 In addition, according to the method of the present invention, nano silver particle powder covered with the organic protective agent is obtained, and the nano silver particle powder covered with the organic protective agent is very dispersible in a liquid organic medium having low polarity. Is excellent. Here, the low-polarity liquid organic medium means a non-polar or low-polarity liquid organic medium having a boiling point of 60 to 300 ° C., and “non-polar or low-polarity” means a relative dielectric constant at 25 ° C. Is 15 or less. More preferably 5 or less. When the relative dielectric constant exceeds 15, the dispersibility of silver particles may deteriorate and settle, which is not preferable. Various liquid organic media can be used depending on the use of the dispersion, but hydrocarbons can be preferably used, in particular, isooctane, n-decane, isododecane, isohexane, n-undecane, n-tetradecane, n-dodecane, Aliphatic hydrocarbons such as tridecane, hexane and heptane, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, decalin and tetralin can be used. These liquid organic media may be used alone or in combination of two or more, and may be a mixture such as kerosene. Further, in order to adjust the polarity, polar organic media such as alcohols, ketones, ethers, esters, etc. are added within a range where the relative permittivity at 25 ° C. of the mixed liquid organic media is 15 or less. Also good.
このような液状有機媒体に本発明の銀粒子粉末を分散させてなる分散液は、高沸点のバインダー等を含んでおらず、強熱減量（３００℃熱処理時の減量−１０００℃熱処理時の減量）が分散液の５％以内である銀粒子粉末分散液となり得る。
この分散液は、
ｐＨ：６．５以上
分散液中の銀濃度：５〜９０wt％、
粘度：５０ｍＰａ・ｓ以下、
表面張力：８０ｍＮ／ｍ以下
のニュートン流体としての性質を有することができる。また、この分散液は、液中の銀粒子粉末の平均粒径＋２０ｎｍの孔径を有するメンブランフィルターを通過するほどの良好な分散性を具備できる。
The dispersion obtained by dispersing the silver particle powder of the present invention in such a liquid organic medium does not contain a high-boiling binder or the like, and is reduced in ignition (reduction in heat treatment at 300 ° C.−reduction in heat treatment at 1000 ° C. ) Can be a silver particle powder dispersion with 5% or less of the dispersion.
This dispersion is
pH: 6.5 or more Silver concentration in the dispersion: 5-90 wt%,
Viscosity: 50 mPa · s or less,
Surface tension: It can have properties as a Newtonian fluid of 80 mN / m or less. Moreover, this dispersion liquid can have the dispersibility so favorable that it passes the membrane filter which has the average particle diameter of the silver particle powder in a liquid + the hole diameter of 20 nm.
以下に本発明で用いている用語を説明する。
〔還元率〕
還元率とは、反応開始時に仕込んだ銀の重量（ａ）に対する還元反応終了時に銀ナノ粒子として生成した銀の重量（ｂ）を次式によって表したものである。
還元率（％）＝（ｂ／ａ）×１００
The terms used in the present invention will be described below.
[Reduction rate]
The reduction ratio is the weight (b) of silver produced as silver nanoparticles at the end of the reduction reaction with respect to the weight (a) of silver charged at the start of the reaction, expressed by the following formula.
Reduction rate (%) = (b / a) × 100
〔単分散率〕
単分散率とは、還元反応によって得られた銀ナノ粒子の銀量（ｂ）に対する分散液中の銀ナノ粒子の重量（ｃ）を次式によって表したものである。
単分散率（％）＝（ｃ／ｂ）×１００
[Monodispersion]
The monodispersion rate represents the weight (c) of the silver nanoparticles in the dispersion with respect to the silver amount (b) of the silver nanoparticles obtained by the reduction reaction, by the following formula.
Monodispersion rate (%) = (c / b) × 100
〔収率〕
収率とは、還元率と単分散率を積算したもので、反応開始時に仕込んだ銀の重量（ａ）に対する分散液中の銀ナノ粒子の重量（ｃ）を意味し、次式で表される。
収率（％）＝還元率（％）×単分散率（％）×１００
＝（ｂ／ａ）×（ｃ／ｂ）×１００
＝（ｃ／ａ）×１００
〔yield〕
The yield is the sum of the reduction rate and the monodispersion rate, and means the weight (c) of silver nanoparticles in the dispersion relative to the weight of silver (a) charged at the start of the reaction. The
Yield (%) = reduction rate (%) × monodispersion rate (%) × 100
= (B / a) x (c / b) x 100
= (C / a) x 100
還元反応終了時に銀粒子として生成した銀の重量（ｂ）および単分散液中の銀ナノ粒子の重量（ｃ）については、次の洗浄、分散および分級工程を経て、下記の手順によって算出する。 The weight (b) of silver produced as silver particles at the end of the reduction reaction and the weight (c) of silver nanoparticles in the monodispersed liquid are calculated by the following procedure through the following washing, dispersion, and classification steps.
洗浄工程：
(1) 反応後のスラリー４０ｍＬを日立工機（株）製の遠心分離器ＣＦ７Ｄ２を用い、３０００ｒｐｍで３０分固液分離を実施し、上澄みを廃棄する。
(2) 沈殿物にメタノール４０ｍＬを加えて超音波分散機で分散させる。
(3) 前記の(1) →（2) を３回繰り返す。
(4) 前記の(1) を実施して上澄み廃棄し沈殿物を得る。
Cleaning process:
(1) Using a centrifuge CF7D2 manufactured by Hitachi Koki Co., Ltd., 40 mL of the slurry after the reaction is subjected to solid-liquid separation at 3000 rpm for 30 minutes, and the supernatant is discarded.
(2) Add 40 mL of methanol to the precipitate and disperse with an ultrasonic disperser.
(3) Repeat (1) → (2) above three times.
(4) Carry out the above (1) and discard the supernatant to obtain a precipitate.
分散工程：
(1) 前記の洗浄工程を得た沈殿物にケロシン（沸点１８０〜２７０℃）を４０ｍＬ添加する。
(2) 次いで超音波分散機にかける。
Dispersion process:
(1) 40 mL of kerosene (boiling point 180-270 ° C.) is added to the precipitate obtained from the washing step.
(2) Then apply to an ultrasonic disperser.
分級工程：
(1) 分散工程を経た銀粒子とケロシンの混濁液４０ｍＬを前記と同様の遠心分離器を用い、３０００ｒｐｍで３０分間固液分離を実施する。
(2) 上澄み液を回収する。この上澄み液が最終的な銀粒子粉末分散液となる。この重量をｄとする。
Classification process:
(1) Using a centrifuge similar to the above, 40 mL of a turbid solution of silver particles and kerosene that has undergone the dispersion step is subjected to solid-liquid separation at 3000 rpm for 30 minutes.
(2) Collect the supernatant. This supernatant becomes the final silver particle powder dispersion. Let this weight be d.
還元反応終了時に銀ナノ粒子として生成した銀の重量の算出法：
(1) 反応終了時、得られた全スラリー重量（ｅ）、および前記洗浄工程で分取したスラリー４０ｍｌの重量（ｆ）を測定する。
(2) 前記の洗浄工程で得られた沈殿物を重量既知の容器に入れ、ｙａｍａｔｏ科学（株）製の角型真空乾燥機ＡＤＰ−２００を用いて２００℃で１２時間真空乾燥する。
(3) 室温まで冷却した後に真空乾燥機より取り出して重量を測定する。
(4) 前記(3) の重量から容器重量を減じて、反応後のスラリー４０ｍＬに含まれる銀ナノ粒子として生成した銀の重量（ｇ）が得られる。
(5) 還元反応終了時に銀ナノ粒子として生成した銀の質量（ｂ）は、以下の式によって算出することができる。
ｂ＝（ｇ／ｆ）×ｅ
Method for calculating the weight of silver produced as silver nanoparticles at the end of the reduction reaction:
(1) At the end of the reaction, the total slurry weight (e) obtained and the weight (f) of 40 ml of the slurry fractionated in the washing step are measured.
(2) The precipitate obtained in the above washing step is put in a container of known weight and vacuum dried at 200 ° C. for 12 hours using a square vacuum dryer ADP-200 manufactured by Yamato Scientific Co., Ltd.
(3) After cooling to room temperature, remove from the vacuum dryer and measure the weight.
(4) By subtracting the container weight from the weight of (3), the weight (g) of silver produced as silver nanoparticles contained in 40 mL of the slurry after the reaction can be obtained.
(5) The mass (b) of silver produced as silver nanoparticles at the end of the reduction reaction can be calculated by the following equation.
b = (g / f) × e
銀粒子粉末分散液中の銀粒子粉末濃度の算出法：
(1) 前記の分級工程で得られた銀粒子粉末分散液を、重量既知の容器に移す。
(2) 真空乾燥機に該容器をセットして突沸しないように十分注意しながら真空度と温度を上げて濃縮・乾燥を行い、液体が観察されなくなってから、真空状態２４０℃で１２時間乾燥を行う。
(3) 室温まで冷却した後に真空乾燥機より取り出して重量を測定する。
(4) 前記(3) の重量から容器重量を減じて銀粒子粉末分散液中の銀粒子の重量（ｈ）を求める。
(5)分散液中の銀粒子濃度を次式から求める。
ｈ／ｄ×１００
また、単分散率ｃ／ｂ×１００は、以下の式で置き換えられる。
ｃ／ｂ×１００＝ｈ／ｇ×１００
よって、分散液中の銀ナノ粒子の重量（ｃ）は次式で求められる。
ｃ＝ｂ×ｈ／ｇ
Calculation method of silver particle powder concentration in silver particle powder dispersion:
(1) Transfer the silver particle powder dispersion obtained in the classification step to a container of known weight.
(2) Set up the container in a vacuum dryer and increase the degree of vacuum and temperature while paying careful attention to prevent bumping. Concentrate and dry, and after the liquid is no longer observed, dry at 240 ° C in vacuum for 12 hours I do.
(3) After cooling to room temperature, remove from the vacuum dryer and measure the weight.
(4) The container weight is subtracted from the weight of (3) to determine the weight (h) of silver particles in the silver particle powder dispersion.
(5) The silver particle concentration in the dispersion is determined from the following equation.
h / d × 100
The monodispersion rate c / b × 100 is replaced by the following formula.
c / b × 100 = h / g × 100
Therefore, the weight (c) of the silver nanoparticles in the dispersion is obtained by the following formula.
c = b × h / g
〔平均粒径ＤTEM〕
本発明で得られる銀粒子粉末は、ＴＥＭ（透過電子顕微鏡）観察により測定される平均粒径（ＤTEMと記す）が２００ｎｍ以下、好ましくは１００ｎｍ以下、さらに好ましくは５０ｎｍ以下、さらに好ましくは３０ｎｍ以下、場合によっては２０ｎｍ以下である。このため、本発明の銀粒子粉末分散液は微細な配線を形成するのに適する。ＴＥＭ観察では６０万倍に拡大した画像から重なっていない独立した粒子３００個の径を測定して平均値を求める。
[Average particle diameter D TEM ]
Silver particle powder obtained in the present invention, TEM (referred to as D TEM) average particle size measured by (transmission electron microscope) observation 200nm or less, preferably 100nm or less, more preferably 50nm or less, more preferably 30nm or less In some cases, it is 20 nm or less. For this reason, the silver particle powder dispersion of the present invention is suitable for forming fine wiring. In TEM observation, the average value is obtained by measuring the diameter of 300 independent particles that are not overlapped from an image magnified 600,000 times.
〔Ｘ線結晶粒径ＤX〕
本発明の銀粒子粉末は、結晶粒子径（ＤXと記す）が５０ｎｍ以下である。銀粒子粉末のＸ線結晶粒径はＸ線回折結果から Scherrer の式を用いて求めることができる。その求め方は、次のとおりである。
Scherrer の式は、次の一般式で表現される。
ＤX＝Ｋ・λ／β COSθ
式中、Ｋ：Scherrer定数、ＤX：結晶粒子径、λ：測定Ｘ線波長、β：Ｘ線回折で得られたピークの半価幅、θ：回折線のブラッグ角をそれぞれ表す。Ｋは０．９４の値を採用し、Ｘ線の管球はＣｕを用いると、前式は下式のように書き換えられる。
ＤX＝0.94×1.5405／β COSθ
[X-ray crystal grain size D X ]
The silver particle powder of the present invention has a crystal particle diameter (denoted as D X ) of 50 nm or less. The X-ray crystal grain size of the silver particle powder can be determined from the X-ray diffraction result using the Scherrer equation. How to find it is as follows.
Scherrer's formula is expressed by the following general formula.
D X = K · λ / β COSθ
In the formula, K: Scherrer constant, D X : crystal particle diameter, λ: measured X-ray wavelength, β: half width of peak obtained by X-ray diffraction, θ: Bragg angle of diffraction line. If K adopts a value of 0.94 and the X-ray tube uses Cu, the previous equation can be rewritten as the following equation.
D X = 0.94 × 1.5405 / β COSθ
〔単結晶化度〕
本発明の銀粒子粉末は単結晶化度（ＤTEM/ ＤX）が２．０以下である。このため、緻密な配線を形成でき、耐マイグレーション性も優れている。単結晶化度が２．０より大きくなると、多結晶化度が高くなって多結晶粒子間に不純物を含み易くなり、焼成時にポアが生じ易くなり、緻密な配線を形成できなくなるので、好ましくない。また、多結晶粒子間の不純物のために耐マイグレーション性も低下する
[Single crystallinity]
The silver particle powder of the present invention has a single crystallinity (D TEM / D X ) of 2.0 or less. For this reason, dense wiring can be formed, and migration resistance is also excellent. If the single crystallinity is larger than 2.0, the degree of polycrystallinity is high, and impurities are easily contained between the polycrystalline particles, and pores are easily generated during firing, so that it is impossible to form a dense wiring. . Also, migration resistance decreases due to impurities between polycrystalline grains
〔粘度〕
本発明に従う銀粒子粉末を液状有機媒体に分散させた分散液はニュートン流体であり、温度２５℃における粘度が５０ｍＰａ・ｓ以下である。このため、本発明の銀粒子分散液はインクジェット法による配線形成用材料として好適である。インクジェット法で配線形成を行う場合には、配線の平坦性を維持するために基板上に着弾する液滴の量的な均一性が求められるが、本発明の銀粒子分散液はニュートン流体で且つ粘度が５０ｍＰａ・ｓ以下であるために、ノズル詰まりなく円滑な液滴の吐出ができるので、この要求を満たすことができる。粘度測定は、東機産業株式会社製のＲ５５０形粘度計ＲＥ５５０Ｌにコーンロータ０．８°のものを取り付け、２５℃の恒温にて行うことができる。
〔viscosity〕
A dispersion obtained by dispersing silver particle powder according to the present invention in a liquid organic medium is a Newtonian fluid, and has a viscosity of 50 mPa · s or less at a temperature of 25 ° C. For this reason, the silver particle dispersion liquid of the present invention is suitable as a wiring forming material by an ink jet method. When wiring is formed by the ink jet method, the uniformity of the amount of droplets that land on the substrate is required to maintain the flatness of the wiring, but the silver particle dispersion of the present invention is a Newtonian fluid and Since the viscosity is 50 mPa · s or less, the liquid droplets can be smoothly discharged without clogging the nozzle, so that this requirement can be satisfied. Viscosity can be measured at a constant temperature of 25 ° C. with a cone rotor of 0.8 ° attached to an R550 viscometer RE550L manufactured by Toki Sangyo Co., Ltd.
〔表面張力〕
本発明の銀粒子分散液は２５℃での表面張力が８０ｍＮ／ｍ以下である。このためインクジェット法による配線形成用材料として好適である。表面張力の大きい分散液ではノズル先端でのメニスカスの形状が安定しないので吐出量や吐出タイミングの制御が困難になり、基板上に着弾した液滴の濡れが悪く、配線の平坦性が劣る結果となるが、本発明の銀粒子分散液は表面張力が８０ｍＮ／ｍ以下であるから、このようなことがなく、品質のよい配線ができる。表面張力の測定は、協和界面科学株式会社製のCBVP-Zを使用し、２５℃の恒温にて測定できる。
〔surface tension〕
The silver particle dispersion of the present invention has a surface tension at 25 ° C. of 80 mN / m or less. For this reason, it is suitable as a wiring forming material by the ink jet method. In the dispersion liquid with large surface tension, the shape of the meniscus at the nozzle tip is not stable, so it becomes difficult to control the discharge amount and discharge timing, the wetted droplets landing on the substrate are poor, and the flatness of the wiring is poor. However, since the silver particle dispersion of the present invention has a surface tension of 80 mN / m or less, such a situation does not occur and a high-quality wiring can be obtained. The surface tension can be measured at a constant temperature of 25 ° C. using CBVP-Z manufactured by Kyowa Interface Science Co., Ltd.
〔メンブランフィルターの通過径〕
本発明の銀粒子の分散液は銀粒子粉末の平均粒径（ＤTEM）＋２０ｎｍの孔径を有するメンブランフィルターを通過する。銀粒子の平均粒径ＤTEMより２０ｎｍだけ大きい孔径を通過するのであるから、その分散液中の銀粒子は凝集することなく、個々の粒子ごとに液中に流動できる状態にあること、すなわちほぼ完全に単分散していることを意味する。このことも、本発明の銀粒子の分散液はインクジェット法による配線形成用材料として極めて好適である。粒子が凝集した部分があると、ノズル詰まりが起きやすいばかりでなく、形成される配線の充填性が悪くなって焼成時にポアが発生して高抵抗化や断線の原因となるが、このようなことが本発明の分散液では回避できる。メンブランフィルター通過試験において、最も孔径が小さいフィルターとして、Ｗｈａｔｍａｎ社製アノトッププラス２５シリンジフィルタ（孔径２０ｎｍ）を使用できる。
[Passing diameter of membrane filter]
The dispersion of silver particles of the present invention passes through a membrane filter having a mean particle diameter (D TEM ) of silver particle powder + 20 nm. Since the average particle diameter D of the silver particles passes through a pore size that is 20 nm larger than the TEM , the silver particles in the dispersion are in a state of being able to flow into the liquid for each individual particle without agglomeration. It means completely monodispersed. Again, the silver particle dispersion of the present invention is extremely suitable as a wiring forming material by the ink jet method. If there is a part where the particles are aggregated, not only nozzle clogging is likely to occur, but the filling property of the formed wiring deteriorates and pores are generated during firing, leading to high resistance and disconnection. This can be avoided with the dispersion of the invention. In the membrane filter passage test, Whatman Anotop Plus 25 syringe filter (pore diameter 20 nm) can be used as the filter having the smallest pore diameter.
〔ｐＨ〕
本発明の銀粒子分散液はｐＨ（水素イオン濃度）が６．５以上である。このため、配線形成用材料としたときに回路基板上の銅箔を腐食させることがなく、また配線間でのマイグレーションが起こり難いという特徴がある。当該分散液のｐＨの測定は、ＨＯＲＩＢＡ株式会社製ｐＨメーターＤ−５５Ｔと、低導電性水・非水溶媒用ｐＨ電極６３７７−１０Ｄを用いて行うことができる。この方法で測定した分散液のｐＨが６．５未満の場合には、酸成分による回路基板上の銅箔腐食を起こし、また配線間でのマイグレーションが起こり易くなり、回路の信頼性が低下する。
[PH]
The silver particle dispersion of the present invention has a pH (hydrogen ion concentration) of 6.5 or more. For this reason, when used as a wiring forming material, the copper foil on the circuit board is not corroded and migration between wirings hardly occurs. The pH of the dispersion can be measured using a pH meter D-55T manufactured by HORIBA Ltd. and a pH electrode 6377-10D for low conductivity water / non-aqueous solvent. When the pH of the dispersion measured by this method is less than 6.5, corrosion of the copper foil on the circuit board due to the acid component occurs, and migration between the wirings easily occurs, and the reliability of the circuit decreases. .
〔強熱減量〕
銀粒子分散液の強熱減量（％）は次の式で示される値をいう。
強熱減量（％）＝１００×〔（Ｗ50−Ｗ300）／Ｗ50−（Ｗ50−Ｗ1000）／Ｗ50〕
ここで、Ｗ50、Ｗ300およびＷ1000は、温度が５０℃、３００℃および１０００℃における分散液の重量を表す。
本発明の銀粒子分散液の強熱減量は５％未満である。強熱減量が５％未満であるから、配線を焼成する際に有機保護剤が短時間で燃焼して、焼結を抑制することがなく、良好な導電性を有する配線が得られる。強熱減量が５％以上であると、焼成時に有機保護剤が焼結抑制剤として働き、配線の抵抗が高くなってしまい、場合によっては導電性を阻害するので好ましくない。
[Loss on ignition]
The ignition loss (%) of the silver particle dispersion is a value represented by the following formula.
Loss on ignition (%) = 100 × [(W 50 −W 300 ) / W 50 − (W 50 −W 1000 ) / W 50 ]
Here, W 50 , W 300 and W 1000 represent the weight of the dispersion at temperatures of 50 ° C., 300 ° C. and 1000 ° C.
The loss on ignition of the silver particle dispersion of the present invention is less than 5%. Since the loss on ignition is less than 5%, the organic protective agent burns in a short time when the wiring is fired, and the wiring having good conductivity is obtained without suppressing the sintering. When the ignition loss is 5% or more, the organic protective agent acts as a sintering inhibitor during firing, and the resistance of the wiring becomes high.
強熱減量はマックサイエンス／ブルカーエイエックス社製ＴＧ−ＤＴＡ２０００型測定器により、以下の測定条件で測定できる。
試料重量２０±１ｍｇ、
昇温速度１０℃／ｍｉｎ、
雰囲気：大気（通気なし）、
標準試料：アルミナ２０．０ｍｇ、
測定皿：株式会社理学製アルミナ測定皿、
温度範囲：５０℃〜１０００℃。
The ignition loss can be measured with a TG-DTA2000 type measuring instrument manufactured by Mac Science / Bruker Ax Co. under the following measurement conditions.
Sample weight 20 ± 1 mg,
Temperature rising rate 10 ° C / min,
Atmosphere: air (no ventilation),
Standard sample: 20.0 mg of alumina,
Measuring dish: Alumina measuring dish manufactured by Rigaku Corporation
Temperature range: 50 ° C to 1000 ° C.
本発明で得られる銀粒子粉末は、ＬＳＩ基板の配線やＦＰＤ（フラットパネルディスプレイ）の電極、配線用途、さらには微細なトレンチ、ビアホール、コンタクトホールの埋め込みなど等の配線形成材料としても好適である。車の塗装などの色材としても適用でき、医療・診断・バイオテクノロジー分野において生化学物質等を吸着させるキャリヤーにも適用できる。 The silver particle powder obtained by the present invention is also suitable as a wiring forming material for LSI substrate wiring, FPD (flat panel display) electrodes, wiring applications, and for embedding fine trenches, via holes, contact holes, and the like. . It can also be used as a coloring material for car paints, and can also be applied to carriers that adsorb biochemicals in the medical, diagnostic, and biotechnology fields.
また、本発明で得られる銀粒子粉末は、低温焼成が可能なため、フレキシブルなフィルム上への電極形成材料として、エレクトロニクス実装に於いては接合材として用いることも出来る。また、導電性皮膜として電磁波シールド膜、透明導電膜などの用途として、光学特性を利用して赤外線反射シールドなどとして好適である。さらに、低温焼結性と導電性を利用して、ガラス基板上へ印刷・焼成し、自動車ウインドウの防曇用熱線などにも好適である。一方、分散液としては、液体（分散媒）とほぼ同様の挙動を示すため、上に挙げたインクジェット法に限らず、スピンコート、ディッピング、ブレードコート、ディスペンサーなど各種塗布方法、およびスクリーン印刷などにも容易に適用可能である。 Further, since the silver particle powder obtained in the present invention can be fired at a low temperature, it can also be used as an electrode forming material on a flexible film and as a bonding material in electronic packaging. Moreover, it is suitable as an electromagnetic wave shielding film, a transparent conductive film, etc. as a conductive film, and as an infrared reflection shield using optical characteristics. Furthermore, using low-temperature sintering and conductivity, it is suitable for printing on a glass substrate and firing, and for anti-fogging heat rays for automobile windows. On the other hand, since the dispersion exhibits almost the same behavior as the liquid (dispersion medium), it is not limited to the above-described ink jet methods, but various coating methods such as spin coating, dipping, blade coating, and dispenser, and screen printing. Is also easily applicable.
〔実施例１〕
反応媒体兼還元剤としてイソブタノール（和光純薬株式会社製の特級）１４０ｍＬに、有機保護剤としてオレイルアミン（和光純薬株式会社 Ｍｗ＝２６７）１８５．８３ｍＬと、銀化合物としての硝酸銀結晶（関東化学株式会社製）１９．２１８ｇとを添加し、マグネットスターラーにて攪拌して硝酸銀を溶解させる。
[Example 1]
140 mL of isobutanol (special grade manufactured by Wako Pure Chemical Industries, Ltd.) as a reaction medium and reducing agent, 185.83 mL of oleylamine (Mw = 267) as an organic protective agent, and silver nitrate crystals as a silver compound (Kanto Chemical) (Made by Co., Ltd.) 19.218 g is added and stirred with a magnetic stirrer to dissolve the silver nitrate.
この溶液を還流器のついた容器に移してオイルバスに載せ、容器内に不活性ガスとして窒素ガスを４００ｍＬ／ｍｉｎの流量で吹込みながら、該溶液をマグネットスターラーにより１００ｒｐｍの回転速度で撹拌しつつ加熱した。１００℃に至るまでの昇温速度は２℃／ｍｉｎとした。 The solution was transferred to a container equipped with a refluxer and placed on an oil bath. The nitrogen gas was blown into the container as an inert gas at a flow rate of 400 mL / min, and the solution was stirred with a magnetic stirrer at a rotation speed of 100 rpm. While heating. The heating rate up to 100 ° C. was 2 ° C./min.
１００℃の温度で５時間の還流を行なった後、還元補助剤として２級アミンのジエタノールアミン（和光純薬株式会社 Ｍｗ＝１０５．６４）１２．０１ｇ（対Ａｇモル比１．０）を添加した。その後、１時間保持した後、反応を終了した。 After refluxing at a temperature of 100 ° C. for 5 hours, 12.01 g (second molar ratio of Ag to 1.0) of secondary ethanol diethanolamine (Wako Pure Chemical Industries, Ltd. Mw = 105.64) was added as a reducing auxiliary agent. . Thereafter, after holding for 1 hour, the reaction was terminated.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級を実施し、本文に記載した方法で還元率、単分散率および収率を算出した。その結果、還元率１００％、単分散率８９．８％、収率８９．８％であった。 The slurry after the reaction was washed, dispersed and classified as described in the text, and the reduction rate, monodispersed rate and yield were calculated by the method described in the text. As a result, the reduction rate was 100%, the monodispersion rate was 89.8%, and the yield was 89.8%.
〔実施例２〕
還元補助剤として、２級アミンのジエタノールアミンに代えて、３級アミンのトリエタノールアミン（和光純薬株式会社 Ｍｗ＝１４９．２）を１７．０５ｇ（対Ａｇモル比１．０）添加した以外は、実施例１を繰り返した。
[Example 2]
As a reducing aid, in place of secondary ethanol diethanolamine, tertiary amine triethanolamine (Wako Pure Chemical Industries, Ltd. Mw = 149.2) was added except 17.05 g (1.0 mole ratio to Ag). Example 1 was repeated.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級を実施し、本文に記載した方法で還元率、単分散率および収率を算出した。その結果、還元率９７．４％、単分散率９４．７％、収率９２．２％であった。 The slurry after the reaction was washed, dispersed and classified as described in the text, and the reduction rate, monodispersed rate and yield were calculated by the method described in the text. As a result, the reduction rate was 97.4%, the monodispersion rate was 94.7%, and the yield was 92.2%.
〔比較例１〕
還元補助剤を添加しなかった以外は、実施例１を繰り返した。ただし、還元補助剤の添加は行なわないので、１００℃で５時間の還流を持って反応終了とした。
[Comparative Example 1]
Example 1 was repeated except that no reducing aid was added. However, since the addition of the reducing aid was not performed, the reaction was completed after refluxing at 100 ° C. for 5 hours.
反応終了後のスラリーについて本文に記載した洗浄、分散および分級を実施し、本文に記載した方法で還元率、単分散率および収率を算出した。その結果、還元率７０．１％、単分散率８３．５％、収率５８．５％であった。実施例１、２に比べると還元率が低く、単分散率も若干低くなって結果的に低い収率となった。 The slurry after the reaction was washed, dispersed and classified as described in the text, and the reduction rate, monodispersed rate and yield were calculated by the method described in the text. As a result, the reduction rate was 70.1%, the monodispersion rate was 83.5%, and the yield was 58.5%. Compared to Examples 1 and 2, the reduction rate was low, and the monodispersion rate was slightly lower, resulting in a lower yield.
Claims (8)
Ａｇイオン濃度：０．０５〜５．０モル／Ｌ、
有機保護剤／Ａｇのモル比：０．０５〜５．０、
還元補助剤／Ａｇのモル比：０．１〜２０、
アルコールまたはポリオール／Ａｇのモル比：０．５〜５０
の量比で行う請求項１、２または３に記載の銀粒子粉末の製造法。 The reduction process
Ag ion concentration: 0.05 to 5.0 mol / L,
Organic protective agent / Ag molar ratio: 0.05 to 5.0,
Reduction auxiliary agent / Ag molar ratio: 0.1-20,
Alcohol or polyol / Ag molar ratio: 0.5-50
The manufacturing method of the silver particle powder of Claim 1, 2 or 3 performed by the quantity ratio of these.
ｐＨ：６．５以上
分散液中の銀濃度：５〜９０wt％、
粘度：５０ｍＰａ・ｓ以下、
表面張力：８０ｍＮ／ｍ以下
のニュートン流体としての性質を具備する銀粒子の分散液。 A dispersion of silver particles in which silver particle powder having an average particle diameter D TEM of 50 nm or less is dispersed in a liquid organic medium having low polarity,
pH: 6.5 or more Silver concentration in the dispersion: 5-90 wt%,
Viscosity: 50 mPa · s or less,
Surface tension: A dispersion of silver particles having properties as a Newtonian fluid of 80 mN / m or less.
に記載の分散液。 8. A membrane filter having an average particle size of silver particle powder in the liquid + a pore size of 20 nm.
The dispersion liquid described in 1.
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Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| LAPS | Cancellation because of no payment of annual fees |