JP5537873B2 - Method for producing copper fine particles - Google Patents
Method for producing copper fine particles Download PDFInfo
- Publication number
- JP5537873B2 JP5537873B2 JP2009202945A JP2009202945A JP5537873B2 JP 5537873 B2 JP5537873 B2 JP 5537873B2 JP 2009202945 A JP2009202945 A JP 2009202945A JP 2009202945 A JP2009202945 A JP 2009202945A JP 5537873 B2 JP5537873 B2 JP 5537873B2
- Authority
- JP
- Japan
- Prior art keywords
- gelatin
- fine particles
- metal
- molecular weight
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000010419 fine particle Substances 0.000 title claims description 59
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 229910052802 copper Inorganic materials 0.000 title claims description 13
- 239000010949 copper Substances 0.000 title claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 12
- 229920000159 gelatin Polymers 0.000 claims description 70
- 108010010803 Gelatin Proteins 0.000 claims description 68
- 235000019322 gelatine Nutrition 0.000 claims description 68
- 235000011852 gelatine desserts Nutrition 0.000 claims description 68
- 239000008273 gelatin Substances 0.000 claims description 66
- 230000001603 reducing effect Effects 0.000 claims description 8
- 229930182817 methionine Natural products 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004472 Lysine Chemical group 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Chemical group NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000011859 microparticle Substances 0.000 claims description 2
- 239000005749 Copper compound Substances 0.000 claims 2
- 150000001880 copper compounds Chemical class 0.000 claims 2
- 125000001360 methionine group Chemical group N[C@@H](CCSC)C(=O)* 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 59
- 239000002184 metal Substances 0.000 description 58
- 239000002245 particle Substances 0.000 description 41
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 35
- 238000000034 method Methods 0.000 description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 24
- -1 halogen ions Chemical class 0.000 description 24
- 229910052717 sulfur Inorganic materials 0.000 description 23
- 239000011593 sulfur Substances 0.000 description 23
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 238000011282 treatment Methods 0.000 description 18
- 230000007062 hydrolysis Effects 0.000 description 16
- 238000006460 hydrolysis reaction Methods 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 16
- 102000004190 Enzymes Human genes 0.000 description 15
- 108090000790 Enzymes Proteins 0.000 description 15
- 229940088598 enzyme Drugs 0.000 description 15
- 239000000243 solution Substances 0.000 description 13
- 150000002736 metal compounds Chemical class 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 238000007385 chemical modification Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 239000000084 colloidal system Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 229910001111 Fine metal Inorganic materials 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 239000002923 metal particle Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 8
- 239000008139 complexing agent Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000004365 Protease Substances 0.000 description 7
- 235000001014 amino acid Nutrition 0.000 description 7
- 150000001413 amino acids Chemical class 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 102000035195 Peptidases Human genes 0.000 description 6
- 108091005804 Peptidases Proteins 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 241000251468 Actinopterygii Species 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 4
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 108090000526 Papain Proteins 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-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
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229940055729 papain Drugs 0.000 description 3
- 235000019834 papain Nutrition 0.000 description 3
- 235000019419 proteases Nutrition 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 241000283690 Bos taurus Species 0.000 description 2
- 102000008186 Collagen Human genes 0.000 description 2
- 108010035532 Collagen Proteins 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 102000012479 Serine Proteases Human genes 0.000 description 2
- 108010022999 Serine Proteases Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 101710097834 Thiol protease Proteins 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000000539 amino acid group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229920001436 collagen Polymers 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 2
- 238000002523 gelfiltration Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- SUVIGLJNEAMWEG-UHFFFAOYSA-N propane-1-thiol Chemical compound CCCS SUVIGLJNEAMWEG-UHFFFAOYSA-N 0.000 description 2
- KJRCEJOSASVSRA-UHFFFAOYSA-N propane-2-thiol Chemical compound CC(C)S KJRCEJOSASVSRA-UHFFFAOYSA-N 0.000 description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- 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
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- BGPJLYIFDLICMR-UHFFFAOYSA-N 1,4,2,3-dioxadithiolan-5-one Chemical compound O=C1OSSO1 BGPJLYIFDLICMR-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 description 1
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 1
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004475 Arginine Substances 0.000 description 1
- 108091005658 Basic proteases Proteins 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- 101710155556 Calcium-dependent protease Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000003908 Cathepsin D Human genes 0.000 description 1
- 108090000258 Cathepsin D Proteins 0.000 description 1
- 102000005600 Cathepsins Human genes 0.000 description 1
- 108010084457 Cathepsins Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000251730 Chondrichthyes Species 0.000 description 1
- 108090001069 Chymopapain Proteins 0.000 description 1
- 108090000746 Chymosin Proteins 0.000 description 1
- 108060005980 Collagenase Proteins 0.000 description 1
- 102000029816 Collagenase Human genes 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021593 Copper(I) fluoride Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
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- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- NONOKGVFTBWRLD-UHFFFAOYSA-N thioisocyanate group Chemical group S(N=C=O)N=C=O NONOKGVFTBWRLD-UHFFFAOYSA-N 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- 239000012989 trithiocarbonate Substances 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000003809 water extraction Methods 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 1
Images
Description
本発明は金属微粒子の製造方法に関し、詳しくは、金属イオンを還元して金属微粒子を製造する方法に関する。 The present invention relates to a method for producing metal fine particles, and more particularly to a method for producing metal fine particles by reducing metal ions.
従来、金属微粒子の製造方法としては、バルク金属を粉砕することによって微粒子を調製する物理法と、溶液中の金属イオンを還元することにより微粒子を調製する化学法（湿式法）が知られているが、均一な粒径の微粒子を得るためには化学法の方が一般に優れている。 Conventionally, as a method for producing metal fine particles, a physical method for preparing fine particles by pulverizing bulk metal and a chemical method (wet method) for preparing fine particles by reducing metal ions in a solution are known. However, in order to obtain fine particles having a uniform particle size, the chemical method is generally superior.
このような化学法として、例えば、少なくとも、銅イオン、ハロゲンイオンおよび有機物分散媒が溶解している還元反応溶液において、銅イオンの還元反応により粒子径が１〜５００ｎｍの範囲にある銅微粒子を析出させることを特徴とする銅微粒子の製造方法が知られている（特許文献１参照）。また、保護コロイドと金属微粒子を含有した分散液に保護コロイド除去剤を添加して金属微粒子を凝集させ、次いで、分別することを特徴とする金属微粒子の製造方法が知られている（特許文献２参照）。 As such a chemical method, for example, in a reduction reaction solution in which at least copper ions, halogen ions, and an organic dispersion medium are dissolved, copper fine particles having a particle diameter in the range of 1 to 500 nm are deposited by reduction reaction of copper ions. There is known a method for producing copper fine particles characterized in that it is produced (see Patent Document 1). Further, a method for producing metal fine particles is known, in which a protective colloid remover is added to a dispersion containing protective colloid and metal fine particles to aggregate the metal fine particles, and then fractionate (Patent Document 2). reference).
上記特許文献１の技術は、粒径が小さく、粒度分布が比較的狭く、分散安定性に優れ、かつ、デンドロイト化が抑制された銅微粒子を、簡便かつ大量に生成できる金属微粒子の製造方法であるとされ、上記特許文献２の技術は、一般的な湿式法により得られる保護コロイドと金属微粒子を含有した分散液から保護コロイドを除去することで、金属微粒子を凝集させ、ろ過を容易とするものとされている。 The technique of the above-mentioned Patent Document 1 is a method for producing fine metal particles that can easily and in large quantities produce copper fine particles having a small particle size, a relatively narrow particle size distribution, excellent dispersion stability, and dendrite formation. It is assumed that the technique of Patent Document 2 described above removes protective colloid from a dispersion containing protective colloid and metal fine particles obtained by a general wet method, thereby aggregating metal fine particles and facilitating filtration. It is supposed to be.
このように、従来技術としては、粒径を小さくすることや、金属微粒子の回収方法の改善などに関するものだけであり、粒子径を広範囲で制御するための方法については一切提案されてこなかったのであるが、金属微粒子の粒径は、如何なる用途に用いるかなどによって求められる値が異なるものであり、今後は、目的に応じて粒子径を制御することが必要となってくる。 As described above, the prior art is only related to the reduction of the particle size and the improvement of the method for collecting the metal fine particles, and no method for controlling the particle size over a wide range has been proposed. However, the value of the particle size of the metal fine particles varies depending on the application used, and in the future, it will be necessary to control the particle size according to the purpose.
そこで、本発明が解決しようとする課題は、所望の平均粒子径に制御された金属微粒子を簡便に製造することのできる、金属微粒子の製造方法を提供することにある。 Therefore, the problem to be solved by the present invention is to provide a method for producing metal fine particles, which can easily produce metal fine particles controlled to have a desired average particle diameter.
本発明者は、上記課題を解決するため鋭意検討を行った。その結果、金属化合物が溶解あるいは分散している液中で、ゼラチン等の存在下、前記金属化合物が持つ金属イオンを還元することにより、金属微粒子を得る方法において、前記保護コロイドとして加水分解の有無や程度、および／または、化学修飾の有無や内容が異なるゼラチンを用いたとき、すなわち、種類の異なるゼラチン等を用いたとき、その種類によって、得られる金属微粒子の平均粒子径が相関的に変動することを見出し、その確認を経て、本発明を完成するに至った。 The present inventor has intensively studied to solve the above problems. As a result, in the method of obtaining metal fine particles by reducing metal ions of the metal compound in the presence of gelatin or the like in a solution in which the metal compound is dissolved or dispersed, the presence or absence of hydrolysis as the protective colloid and extent, and / or, when the presence or content of chemical modification using different gelatin, i.e., when using different types of gelatin, depending on the type, the average particle size of the resulting metal microparticles correlatively vary As a result, the present invention has been completed.
すなわち、本発明にかかる金属微粒子の製造方法は、金属化合物が溶解あるいは分散している液中で、ゼラチン等の存在下、前記金属化合物が持つ金属イオンを還元することにより、金属微粒子を得る方法において、前記ゼラチン等の種類を選択することによって前記金属微粒子の粒子径を制御する、ことを特徴とする。 That is, the method for producing metal fine particles according to the present invention is a method for obtaining metal fine particles by reducing metal ions of the metal compound in the presence of gelatin or the like in a solution in which the metal compound is dissolved or dispersed. The particle size of the metal fine particles is controlled by selecting the type of gelatin or the like .
以下において、「ゼラチン等」とは、抽出したままの状態のゼラチンのみでなく、これを加水分解して低分子量化したものや、これらのゼラチン等に対して化学修飾を施したもの、のすべてを含む概念であり、特に断る必要があるときにのみ、「加水分解ゼラチン」とか「修飾ゼラチン」とか言うこととする。また、金属化合物とは、錯体をも含む概念であり、金属化合物が持つ金属イオンとは、錯イオンをも含む概念である。 In the following, “gelatin and the like ” are not limited to gelatin as it is extracted, but are all hydrolyzed to reduce the molecular weight and those obtained by chemically modifying these gelatins and the like . The term “hydrolyzed gelatin” or “modified gelatin” is used only when there is a need to refuse. The metal compound is a concept including a complex, and the metal ion of the metal compound is a concept including a complex ion.
本発明によれば、所望の平均粒子径に制御された金属微粒子を簡便に製造することができる。 According to the present invention, fine metal particles controlled to a desired average particle diameter can be easily produced.
以下、本発明の実施の形態について、詳細に説明する。本発明の範囲はこれらの説明に拘束されることはなく、以下の例示以外についても、本発明の趣旨を損なわない範囲で適宜変更実施し得る。 Hereinafter, embodiments of the present invention will be described in detail. The scope of the present invention is not limited by these descriptions, and modifications other than the following examples can be made as appropriate without departing from the spirit of the present invention.
〔金属化合物〕
本発明にかかる金属微粒子の製造方法は、遷移金属元素、典型金属元素のいずれにも適用でき、例えば、種々の用途に汎用的に用いられている、周期表第ＶＩＩＩ族に属する鉄、コバルト、ニッケル、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金や、周期表第ＩＢ族に属する銅、銀、金などへの適用が好ましい。中でも、導電性に優れる金、銀、白金、パラジウム、銅、ニッケルが好ましく、銅、銀、ニッケルがより好ましく、特に、廉価な銅が好ましい。また、これらは、１種に限らず、２種以上組み合せても良く、合金であっても良い。
[Metal compounds]
The method for producing fine metal particles according to the present invention can be applied to both transition metal elements and typical metal elements. For example, iron, cobalt belonging to Group VIII of the periodic table, which is widely used for various purposes, Application to nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum, copper, silver, gold, etc. belonging to Group IB of the periodic table is preferred. Among these, gold, silver, platinum, palladium, copper, and nickel that are excellent in conductivity are preferable, copper, silver, and nickel are more preferable, and inexpensive copper is particularly preferable. These are not limited to one type, but may be a combination of two or more types, or may be an alloy.
本発明にかかる金属微粒子の製造方法では、金属化合物が持つ金属イオンを還元することにより金属微粒子を得るようにするが、本発明により得ようとする金属微粒子の種類に応じて、例えば、上記金属元素の硫酸塩、硝酸塩、炭酸塩、塩化物、酸化物などの金属化合物を水系溶剤あるいは有機溶剤に溶解あるいは分散させるようにする。 In the method for producing metal fine particles according to the present invention, the metal fine particles are obtained by reducing the metal ions of the metal compound. Depending on the type of the metal fine particles to be obtained according to the present invention, for example, the above metal Metal compounds such as elemental sulfates, nitrates, carbonates, chlorides and oxides are dissolved or dispersed in an aqueous solvent or an organic solvent.
前記溶液に錯化剤を添加しても良く、この場合、前記錯化剤としては、特に限定されないが、例えば、配位子のドナー原子が、金属イオンまたは金属と結合して金属錯体化合物を形成し得る化合物を言い、ドナー原子としては、例えば、窒素、酸素、硫黄などが挙げられる。 A complexing agent may be added to the solution. In this case, the complexing agent is not particularly limited. For example, a ligand donor atom is bonded to a metal ion or a metal to form a metal complex compound. A compound that can be formed, and examples of the donor atom include nitrogen, oxygen, and sulfur.
窒素がドナー原子である錯化剤としては、アミン類（例えば、ブチルアミン、エチルアミン、プロピルアミン、エチレンジアミンなどの１級アミン類、ジブチルアミン、ジエチルアミン、ジプロピルアミン、および、ピペリジン、ピロリジンなどのイミン類などの２級アミン類、トリブチルアミン、トリエチルアミン、トリプロピルアミンなどの３級アミン類、ジエチレントリアミン、トリエチレンテトラミンの１分子内に１〜３級アミンを２種以上有するものなど）、窒素含有複素環式化合物（例えば、イミダゾール、ピリジン、ビピリジンなど）、ニトリル類（例えば、アセトニトリル、ベンゾニトリルなど）およびシアン化合物、アンモニアおよびアンモニウム化合物（例えば、塩化アンモニウム、硫酸アンモニウムなど）、オキシム類などが挙げられる。 Complexing agents in which nitrogen is a donor atom include amines (for example, primary amines such as butylamine, ethylamine, propylamine, and ethylenediamine, dibutylamine, diethylamine, dipropylamine, and imines such as piperidine and pyrrolidine. Secondary amines such as tributylamine, triethylamine, tripropylamine, etc., diethylenetriamine, triethylenetetramine having two or more primary to tertiary amines in one molecule), nitrogen-containing heterocyclic ring Formula compounds (eg, imidazole, pyridine, bipyridine, etc.), nitriles (eg, acetonitrile, benzonitrile, etc.) and cyanide compounds, ammonia and ammonium compounds (eg, ammonium chloride, ammonium sulfate, etc.), oximes And the like.
酸素がドナー原子である錯化剤としては、カルボン酸類（例えば、クエン酸、リンゴ酸、酒石酸、乳酸などのオキシカルボン酸類、酢酸、ギ酸などのモノカルボン酸類、シュウ酸、マロン酸などのジカルボン酸類、安息香酸などの芳香族カルボン酸類など）、ケトン類（例えば、アセトンなどのモノケトン類、アセチルアセトン、ベンゾイルアセトンなどのジケトン類など）、アルデヒド類、アルコール類（１価アルコール類、グリコール類、グリセリン類など）、キノン類、エーテル類、リン酸（正リン酸）およびリン酸系化合物（例えば、ヘキサメタリン酸、ピロリン酸、亜リン酸、次亜リン酸など）、スルホン酸またはスルホン酸系化合物などが挙げられる。 Complexing agents in which oxygen is a donor atom include carboxylic acids (for example, oxycarboxylic acids such as citric acid, malic acid, tartaric acid and lactic acid, monocarboxylic acids such as acetic acid and formic acid, and dicarboxylic acids such as oxalic acid and malonic acid. , Aromatic carboxylic acids such as benzoic acid), ketones (for example, monoketones such as acetone, diketones such as acetylacetone and benzoylacetone), aldehydes, alcohols (monohydric alcohols, glycols, glycerins) Quinones, ethers, phosphoric acid (regular phosphoric acid) and phosphoric acid compounds (eg, hexametaphosphoric acid, pyrophosphoric acid, phosphorous acid, hypophosphorous acid, etc.), sulfonic acid or sulfonic acid compounds, etc. Can be mentioned.
硫黄がドナー原子である錯化剤としては、脂肪族チオール類（例えば、メチルメルカプタン、エチルメルカプタン、プロピルメルカプタン、イソプロピルメルカプタン、ｎ−ブチルメルカプタン、アリルメルカプタン、ジメチルメルカプタンなど）、脂環式チオール類（シクロヘキシルチオールなど）、芳香族チオール類（チオフェノールなど）、チオケトン類、チオエーテル類、ポリチオール類、チオ炭酸類（トリチオ炭酸類）、硫黄含有複素環式化合物（例えば、ジチオール、チオフェン、チオピランなど）、チオシアナート類およびイソチオシアナート類、無機硫黄化合物（例えば、硫化ナトリウム、硫化カリウム、硫化水素など）などが挙げられる。 Complexing agents in which sulfur is a donor atom include aliphatic thiols (eg, methyl mercaptan, ethyl mercaptan, propyl mercaptan, isopropyl mercaptan, n-butyl mercaptan, allyl mercaptan, dimethyl mercaptan, etc.), alicyclic thiols ( Cyclohexylthiol, etc.), aromatic thiols (eg, thiophenol), thioketones, thioethers, polythiols, thiocarbonates (trithiocarbonates), sulfur-containing heterocyclic compounds (eg, dithiol, thiophene, thiopyran), Examples include thiocyanates and isothiocyanates, inorganic sulfur compounds (for example, sodium sulfide, potassium sulfide, hydrogen sulfide, etc.).
２種以上のドナー原子を有する錯化剤としては、アミノ酸類（ドナー原子が窒素および酸素：例えば、グリシン、アラニンなどの中性アミノ酸類、ヒスチジン、アルギニンなどの塩基性アミノ酸類、アスパラギン酸、グルタミン酸などの酸性アミノ酸類）、アミノポリカルボン酸類（ドナー原子が窒素および酸素：例えば、エチレンジアミンテトラ酢酸（ＥＤＴＡ）、ニトリロトリ酢酸（ＮＴＡ）、イミノジ酢酸（ＩＤＡ）、エチレンジアミンジ酢酸（ＥＤＤＡ）、エチレングリコールジエチルエーテルジアミンテトラ酢酸（ＧＥＤＡ）など）、アルカノールアミン類（ドナー原子が窒素および酸素：例えば、エタノールアミン、ジエタノールアミン、トリエタノールアミンなど）、ニトロソ化合物およびニトロシル化合物（ドナー原子が窒素および酸素）、メルカプトカルボン酸類（ドナーが硫黄および酸素：例えば、メルカプトプロピオン酸、メルカプト酢酸、チオジプロピオン酸、メルカプトコハク酸、ジメルカプトコハク酸、チオ酢酸、チオジグリコール酸など）、チオグリコール類（ドナーが硫黄および酸素：例えば、メルカプトエタノール、チオジエチレングリコールなど）、チオン酸類（ドナーが硫黄および酸素）、チオ炭酸類（ドナー原子が硫黄および酸素：例えば、モノチオ炭酸、ジチオ炭酸、チオン炭酸）、アミノチオール類（ドナーが硫黄および窒素：アミノエチルメルカプタン、チオジエチルアミンなど）
、チオアミド類（ドナー原子が硫黄および窒素：例えば、チオホルムアミドなど）、チオ尿素類（ドナー原子が硫黄および窒素）、チアゾール類（ドナー原子が硫黄および窒素：例えばチアゾール、ベンゾチアゾールなど）、含硫黄アミノ酸類（ドナーが硫黄、窒素および酸素：システイン、メチオニンなど）などが挙げられる。
Complexing agents having two or more donor atoms include amino acids (the donor atom is nitrogen and oxygen: neutral amino acids such as glycine and alanine, basic amino acids such as histidine and arginine, aspartic acid and glutamic acid. Acidic amino acids such as, aminopolycarboxylic acids (donor atoms are nitrogen and oxygen: for example, ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), ethylenediaminediacetic acid (EDDA), ethylene glycol diethyl Ether diamine tetraacetic acid (GEDA), alkanolamines (donor atoms are nitrogen and oxygen: for example, ethanolamine, diethanolamine, triethanolamine, etc.), nitroso compounds and nitrosyl compounds (donor atoms are nitrogen And oxygen), mercaptocarboxylic acids (donor is sulfur and oxygen: for example, mercaptopropionic acid, mercaptoacetic acid, thiodipropionic acid, mercaptosuccinic acid, dimercaptosuccinic acid, thioacetic acid, thiodiglycolic acid), thioglycols (Donor is sulfur and oxygen: eg mercaptoethanol, thiodiethylene glycol, etc.), thioic acids (donor is sulfur and oxygen), thiocarbonates (donor atom is sulfur and oxygen: eg monothiocarbonate, dithiocarbonate, thione carbonate), Aminothiols (donor is sulfur and nitrogen: aminoethyl mercaptan, thiodiethylamine, etc.)
Thioamides (donor atoms are sulfur and nitrogen: eg thioformamide), thioureas (donor atoms are sulfur and nitrogen), thiazoles (donor atoms are sulfur and nitrogen: eg thiazole, benzothiazole, etc.), sulfur-containing Examples include amino acids (donors are sulfur, nitrogen and oxygen: cysteine, methionine, etc.).
上記の化合物の塩や誘導体としては、例えば、クエン酸トリナトリウム、酒石酸ナトリウム・カリウム、次亜リン酸ナトリウム、エチレンジアミンテトラ酢酸ジナトリウムなどのアルカリ金属塩や、カルボン酸、リン酸、スルホン酸などのエステルなどが挙げられる。 Examples of the salt or derivative of the above compound include alkali metal salts such as trisodium citrate, sodium / potassium tartrate, sodium hypophosphite, disodium ethylenediaminetetraacetate, carboxylic acid, phosphoric acid, sulfonic acid and the like. Examples include esters.
〔ゼラチン等〕
本発明に用いるゼラチン等は、牛や豚などの哺乳動物の骨、皮部分や、サメやティラピアなどの魚類の骨、皮、鱗部分などのコラーゲンを含有する原料から従来公知の方法で得ることができ、具体的には、例えば、熱水抽出、アルカリ処理、酸処理などによって得ることができる。
[Gelatin, etc. ]
Gelatin and the like used in the present invention can be obtained by a conventionally known method from raw materials containing collagen such as bones and skins of mammals such as cattle and pigs, and fish bones, skins and scales such as sharks and tilapia. Specifically, for example, it can be obtained by hot water extraction, alkali treatment, acid treatment and the like.
本発明は、ゼラチン等の種類を選択することによって、得られる金属微粒子の粒子径を制御する点に特徴を有するが、ゼラチン等の種類を選択することには、例えば、ゼラチン等の平均分子量の大小の選択や、ゼラチン等に対する化学修飾の有無の選択か、および／または、化学修飾の内容の選択や、ゼラチン等を得るための原料の種類の選択などが含まれる。 The present invention, by selecting the type of gelatin and the like, has a feature in that to control the particle size of the obtained fine metal particles, to select the type of gelatin and the like, for example, an average molecular weight of gelatin This includes selection of size, selection of whether or not gelatin or the like is chemically modified, and / or selection of the content of chemical modification, selection of the type of raw material for obtaining gelatin or the like .
加水分解ゼラチンは、コラーゲンに抽出処理を行った後に加水分解処理することにより得ることができる。加水分解ゼラチンを得るための加水分解方法としては、従来公知の方法が採用でき、例えば、酵素を用いる方法、酸やアルカリで化学的に処理する方法などによって加水分解を行うことができる。 Hydrolyzed gelatin can be obtained by subjecting collagen to an extraction treatment followed by a hydrolysis treatment. As a hydrolysis method for obtaining hydrolyzed gelatin, a conventionally known method can be employed. For example, hydrolysis can be performed by a method using an enzyme, a chemical treatment with an acid or an alkali, or the like.
前記酵素としては、ゼラチンのペプチド結合を切断する機能を有する酵素であればよい。通常、タンパク質分解酵素あるいはプロアテーゼと呼ばれる酵素である。具体的には、例えば、コラゲナーゼ、チオールプロテアーゼ、セリンプロテアーゼ、酸性プロテアーゼ、アルカリ性プロテアーゼ、メタルプロテアーゼなどが挙げられ、これらを単独あるいは複数種類を組み合わせて使用することができる。 The enzyme may be an enzyme having a function of cleaving gelatin peptide bonds. Usually, it is an enzyme called proteolytic enzyme or pro-thesis. Specific examples include collagenase, thiol protease, serine protease, acidic protease, alkaline protease, metal protease, and the like, and these can be used alone or in combination.
前記チオールプロテアーゼとしては、例えば、植物由来のキモパパイン、パパイン、プロメライン、フィシン、動物由来のカテプシン、カルシウム依存性プロテアーゼなどが挙げられる。前記セリンプロテアーゼとしては、トリプシン、カテプシンＤなどが挙げられる。前記酸性プロテアーゼとしては、ペプシン、キモシンなどが挙げられる。 Examples of the thiol protease include plant-derived chymopapain, papain, promelain, ficin, animal-derived cathepsin, and calcium-dependent protease. Examples of the serine protease include trypsin and cathepsin D. Examples of the acidic protease include pepsin and chymosin.
前記酸としては、例えば、塩酸、硫酸、硝酸などが挙げられる。 Examples of the acid include hydrochloric acid, sulfuric acid, and nitric acid.
前記アルカリとしては、例えば、水酸化ナトリウム、水酸化カルシウムなどが挙げられる。 Examples of the alkali include sodium hydroxide and calcium hydroxide.
酵素を用いる場合、加水分解処理前のゼラチン１００重量部に対して０．０１〜５重量部用いることが好ましく、加水分解の温度条件としては３０〜７０℃、処理時間としては０．５〜２４時間が好ましい。 When using an enzyme, it is preferable to use 0.01-5 weight part with respect to 100 weight part of gelatin before a hydrolysis process, 30-70 degreeC as temperature conditions of hydrolysis, and 0.5-24 as process time. Time is preferred.
酸またはアルカリを用いる場合、ゼラチン溶液をｐＨ３以下またはｐＨ１０以上とすることが好ましく、加水分解の温度条件としては５０〜９０℃、処理時間としては１〜８時間が好ましい。 When acid or alkali is used, the gelatin solution is preferably adjusted to pH 3 or lower or pH 10 or higher, the hydrolysis temperature condition is preferably 50 to 90 ° C., and the treatment time is preferably 1 to 8 hours.
酵素により加水分解した場合には、処理後に酵素失活を行う。酵素失活は加熱により行うことができ、加熱温度としては、例えば、７０〜１００℃である。 When hydrolyzed by an enzyme, the enzyme is deactivated after the treatment. Enzyme deactivation can be performed by heating, and the heating temperature is, for example, 70 to 100 ° C.
酸やアルカリにより加水分解した場合には、中和剤による中和やイオン交換樹脂などによる脱塩を行う。 When hydrolyzed with an acid or alkali, neutralization with a neutralizing agent or desalting with an ion exchange resin or the like is performed.
前記加水分解処理を終えた段階では、加水分解ゼラチンは加水分解処理液中に溶解あるいは分散した状態である。この溶液に、通常採用される各種の精製処理を施すことができる。 At the stage of finishing the hydrolysis treatment, the hydrolyzed gelatin is in a state of being dissolved or dispersed in the hydrolysis treatment solution. This solution can be subjected to various purification processes that are usually employed.
前記精製処理としては、特に限定されないが、例えば、活性炭を添加することにより色調、風味の改良、不純物除去を行ったり、ろ過や遠心分離などの従来公知の固液分離処理を施して不純物除去を行ったりすることができる。 The purification treatment is not particularly limited, but for example, by adding activated carbon to improve color tone, flavor, impurity removal, or by performing a conventionally known solid-liquid separation treatment such as filtration or centrifugation to remove impurities. Can go.
本発明で用いる上記ゼラチン等は、化学修飾がなされたもの、すなわち、ゼラチン等が持つ各アミノ酸残基の側鎖や、末端アミノ基、末端カルボキシル基などが化学的に修飾されたものであっても良い。 The gelatin or the like used in the present invention is chemically modified, that is, the side chain of each amino acid residue, the terminal amino group, the terminal carboxyl group or the like of gelatin or the like is chemically modified. Also good.
本発明者の検討によって、ゼラチン等に対する化学修飾の有無や内容に基づく金属微粒子の粒子径制御に関し、窒素元素や硫黄元素、特に硫黄元素の存在が重要な役割を果たすということ、具体的には、これらの元素、特に硫黄元素が多く存在するゼラチン等ほど粒子径の大きな金属微粒子が得られるということが今回初めて判明した。この知見によれば、窒素元素や硫黄元素を有する化合物、特に硫黄元素を有する化合物による化学修飾が、平均粒子径の制御に有効である。このような化合物によってゼラチン等が持つアミノ酸残基の側鎖を化学修飾し、例えば、アミノ基、イミノ基、シアノ基、アゾ基、アジ基、ニトリル基、イソニトリル基、ジイミド基、シアノ基、イソシアネート基、ニトロ基などの窒素元素を含む官能基、チオール基、スルホン基、スルフィド基、ジスルフィド基などの硫黄元素を含む官能基、チオイソシアネート基、チオアミド基などの窒素元素と硫黄元素の両方を含む官能基を導入することで、その官能基の種類や量により、得られる金属微粒子の平均粒子径を様々に制御できる。 According to the study of the present inventors, regarding the particle size control of the metal fine particles based on the presence or absence of chemical modification to gelatin and the like , the presence of nitrogen element and sulfur element, particularly sulfur element plays an important role, specifically these elements, in particular that large metal fine particle size as gelatin that there are many elemental sulfur obtained was found for the first time. According to this knowledge, chemical modification with a compound containing nitrogen element or sulfur element, particularly a compound containing sulfur element, is effective in controlling the average particle diameter. The side chain of the amino acid residue of gelatin or the like is chemically modified with such a compound, for example, amino group, imino group, cyano group, azo group, azide group, nitrile group, isonitrile group, diimide group, cyano group, isocyanate Group, functional group containing nitrogen element such as nitro group, functional group containing sulfur element such as thiol group, sulfone group, sulfide group and disulfide group, and both nitrogen element and sulfur element such as thioisocyanate group and thioamide group By introducing a functional group, the average particle size of the obtained metal fine particles can be variously controlled depending on the type and amount of the functional group.
一般的な化学修飾の手法として、例えば、ゼラチン等の水溶液に水溶性カルボジイミドを添加して、ゼラチン等が持つカルボキシル基を活性化し、そこに任意のアミノ化合物を反応させてアミド化する方法が採用できる。この方法によって、例えば、メチオニンなどの硫黄元素を含有するアミノ酸やリジンなどの窒素元素を含有するアミノ酸を簡易に導入することができる。前記水溶性カルボジイミドとしては、例えば、１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド（ＥＤＣ）、１−シクロヘキシル−３−（２−モルホリニル−４−エチル）カルボジイミド・ｐ−トルエンスルホン酸塩（ＣＭＣ）、Ｎ，Ｎ’−ジシクロヘキシルカルボジイミド（ＤＣＣ）などが挙げられる。 As a general chemical modification method, for example, a method in which water-soluble carbodiimide is added to an aqueous solution of gelatin, etc., the carboxyl group of gelatin, etc. is activated, and an arbitrary amino compound is reacted therewith to be amidated is adopted. it can. By this method, for example, an amino acid containing a sulfur element such as methionine or an amino acid containing a nitrogen element such as lysine can be easily introduced. Examples of the water-soluble carbodiimide include 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDC), 1-cyclohexyl-3- (2-morpholinyl-4-ethyl) carbodiimide / p-toluenesulfonate. (CMC), N, N′-dicyclohexylcarbodiimide (DCC) and the like.
本発明に適用できるゼラチン等としては、加水分解処理がなされ、かつ、化学修飾がなされたものであってもよいが、この場合、加水分解した後に化学修飾したものであってもよいし、化学修飾した後に加水分解したものであっても良い。 Gelatin or the like applicable to the present invention may be hydrolyzed and chemically modified, but in this case, it may be chemically modified after hydrolysis, It may be hydrolyzed after modification.
本発明では、ゼラチン等の平均分子量の大小を選択することにより金属微粒子の平均粒子径を制御することができるが、平均分子量の大小は、重量平均分子量や数平均分子量などの測定方法によらず、いずれを基準にしても良い。具体的には、例えば、用いるゼラチン等の重量平均分子量は２０００〜２０００００であることが好ましい。また、ゼラチン等の数平均分子量は２００〜６００００であることが好ましい。平均分子量が小さすぎると保護コロイドとしての機能が充分に果たせないおそれがあり、平均分子量が大きすぎると平均粒子径の制御が困難となるおそれや、また、保護コロイドの示す有機含有量が多くなりすぎるおそれがある。ゼラチン等の重量平均分子量は、より好ましくは１５００００以下であり、さらに好ましくは１０００００以下であり、特に好ましくは５０００〜２００００である。また、ゼラチン等の数平均分子量は、より好ましくは５００００以下であり、さらに好ましくは３００００以下であり、特に好ましくは５００〜２００００である。このように、加水分解により低分子量化された加水分解ゼラチンが好ましい理由は、このようなゼラチンを用いれば、得られる金属微粒子の粒子径分布のばらつきが小さいものとなるからである。なお、本発明における「平均分子量」は、実施例において後述する「パギイ法」によって測定される値である。 In the present invention, the average particle size of the metal fine particles can be controlled by selecting the average molecular weight such as gelatin, but the average molecular weight is independent of the measurement method such as the weight average molecular weight or the number average molecular weight. Any of these may be used as a reference. Specifically, for example, the weight average molecular weight of gelatin or the like to be used is preferably 2000 to 200000. Moreover, it is preferable that the number average molecular weights of gelatin etc. are 200-60000. If the average molecular weight is too small, the function as a protective colloid may not be sufficiently achieved. If the average molecular weight is too large, it may be difficult to control the average particle size, and the organic content of the protective colloid increases. It may be too much. The weight average molecular weight of gelatin or the like is more preferably 150,000 or less, still more preferably 100,000 or less, and particularly preferably 5,000 to 20,000. Further, the number average molecular weight of gelatin or the like is more preferably 50000 or less, further preferably 30000 or less, and particularly preferably 500 to 20000. Thus, the reason why hydrolyzed gelatin reduced in molecular weight by hydrolysis is preferable is that, when such gelatin is used, the dispersion of the particle size distribution of the obtained metal fine particles becomes small. The “average molecular weight” in the present invention is a value measured by the “Pagii method” described later in Examples.
本発明では、ゼラチン等の量をも選択することによって、よりきめ細やかな粒子径制御が可能である。特に限定されないが、例えば、その添加量を、金属化合物１００重量部に対し５〜６０重量部の範囲とすることができる。 In the present invention, finer particle size control is possible by selecting the amount of gelatin or the like . Although it does not specifically limit, For example, the addition amount can be made into the range of 5-60 weight part with respect to 100 weight part of metal compounds.
〔還元処理〕
本発明にかかる金属微粒子の製造方法における還元処理としては、特に限定されず、例えば、還元剤を添加することによって行っても良いし、還元剤を用いない電解還元などによる還元処理であっても良い。
[Reduction treatment]
The reduction treatment in the method for producing fine metal particles according to the present invention is not particularly limited. For example, the reduction treatment may be performed by adding a reducing agent, or may be a reduction treatment by electrolytic reduction without using a reducing agent. good.
前記還元剤としては、特に限定されず、例えば、ヒドラジンや、塩酸ヒドラジン、硫酸ヒドラジン、抱水ヒドラジンなどのヒドラジン系還元剤や、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、亜硝酸ナトリウム、次亜硝酸ナトリウム、亜リン酸、亜リン酸ナトリウム、次亜リン酸、次亜リン酸ナトリウム、アルデヒド類、アルコール類、アミン類、糖類などが挙げられ、これらを１種または２種以上を用いても良い。還元剤の還元作用を促すために、必要に応じて、温度やｐＨを調整するようにしても良い。例えば、還元温度は１０〜５０℃が好ましく、ｐＨは１１．５〜１２．５が好ましい。また、還元剤の使用量は、金属イオンを還元するのに適した量であれば、特に限定されず、例えば、金属化合物に含まれる金属元素１モルに対し０．２〜５モルの範囲とすることができる。 The reducing agent is not particularly limited, and examples thereof include hydrazine-based reducing agents such as hydrazine, hydrazine hydrochloride, hydrazine sulfate, hydrazine hydrate, sodium borohydride, sodium sulfite, sodium bisulfite, sodium thiosulfate, Examples include sodium nitrate, sodium hyponitrite, phosphorous acid, sodium phosphite, hypophosphorous acid, sodium hypophosphite, aldehydes, alcohols, amines, saccharides, etc., one or two of these The above may be used. In order to promote the reducing action of the reducing agent, the temperature and pH may be adjusted as necessary. For example, the reduction temperature is preferably 10 to 50 ° C., and the pH is preferably 11.5 to 12.5. The amount of the reducing agent used is not particularly limited as long as it is an amount suitable for reducing metal ions. For example, the reducing agent is used in a range of 0.2 to 5 mol with respect to 1 mol of metal element contained in the metal compound. can do.
電解還元を行う場合、陰極材料としては、白金、カーボンなどの棒状、板状電極、ドット電極のようなナノ構造電極が例示でき、陽極としては、銅、カーボン、白金などの棒状・板状・網状の形状電極が例示できる。なお、陰極表面付近に析出した粒子を脱離、回収するために陰極に超音波振動などの揺動を与えることが可能な構造とすることもできる。電流密度は好ましくは０．０１〜１００ｋＡ／ｄｍ２、より好ましくは０．１〜５０ｋＡ／ｄｍ２程度であり、直流のほかパルス電流とすることもできる。還元温度は、１０〜７０℃が好ましく、１０〜４０℃がより好ましい。還元温度は、高温になるほど還元反応速度は速くなり、低温になるほど析出する粒子の粒径は小さくなる傾向がある。 When performing electrolytic reduction, examples of the cathode material include rods such as platinum and carbon, plate-like electrodes, and nanostructure electrodes such as dot electrodes. As the anode, rods and plates such as copper, carbon, and platinum are used. A net-shaped electrode can be exemplified. In addition, in order to desorb and collect particles deposited in the vicinity of the cathode surface, it is possible to adopt a structure capable of imparting oscillation such as ultrasonic vibration to the cathode. The current density is preferably 0.01 to 100 kA / dm 2 , more preferably about 0.1 to 50 kA / dm 2 , and can be a pulse current in addition to direct current. 10-70 degreeC is preferable and, as for reduction temperature, 10-40 degreeC is more preferable. As the reduction temperature increases, the reduction reaction rate increases, and as the temperature decreases, the particle size of the precipitated particles tends to decrease.
具体的には、例えば、上記した電極を有する浴中に、金属イオン、保護コロイド、錯化剤などを含む溶液を調製し、上記した条件で電解還元反応を行い、還元反応終了後、カソード表面付近に析出した金属微粒子を回収する。 Specifically, for example, a solution containing a metal ion, a protective colloid, a complexing agent, etc. is prepared in a bath having the above-described electrode, and an electrolytic reduction reaction is performed under the above-described conditions. Collect fine metal particles deposited in the vicinity.
いずれの還元処理を採用する場合においても、ハロゲンイオン存在下で行うことにより、デンドロイト状の凝集を抑制し、粒子径分布の狭い金属微粒子が得られやすいので、これにより、金属微粒子の粒子径分布を制御することができる。ハロゲンイオンは、フッ素イオン、塩素イオン、臭素イオンおよび沃素イオンから選択される１種または２種以上であり、イオン性ハロゲン化物が該ハロゲンイオンの供給源となることができ、その具体例としては、塩化水素、塩化カリウム、塩化ナトリウム、塩化第一銅、塩化第二銅、臭化水素、臭化カリウム、臭化ナトリウム、臭化第一銅、臭化第二銅、沃化水素、沃化カリウム、沃化ナトリウム、沃化第一銅、沃化第二銅、フッ化水素、フッ化カリウム、フッ化ナトリウム、フッ化第一銅、フッ化第二銅、塩化カルシウム、塩化バリウム、塩化アンモニウム、臭化カルシウム、臭化バリウム、臭化アンモニウム、沃化カルシウム、沃化バリウム、沃化アンモニウム、弗化アンモニウムなどが挙げられる。これらは２種以上であってもよい。上記ハロゲンイオンのうち特に好ましいのは、塩素イオンである。ハロゲンイオンの濃度は、溶液中において０．００２〜１．０モル／リットル（Ｌ）が好ましい。ハロゲンイオンの濃度が前記０．００２モル／Ｌ未満では一価ないし二価の銅イオン性化合物の混入という不都合を生じ、１．０モル／Ｌを超えるとハロゲンイオンの除去に不都合を生じる場合がある。より好ましいハロゲンイオンの濃度は、０．００５〜０．２モル／Ｌである。 In any of the reduction treatments, dendrite-like aggregation can be suppressed and metal fine particles with a narrow particle size distribution can be easily obtained by performing in the presence of halogen ions. Can be controlled. The halogen ion is one or more selected from fluorine ion, chlorine ion, bromine ion and iodine ion, and an ionic halide can serve as a source of the halogen ion. , Hydrogen chloride, potassium chloride, sodium chloride, cuprous chloride, cupric chloride, hydrogen bromide, potassium bromide, sodium bromide, cuprous bromide, cupric bromide, hydrogen iodide, iodide Potassium, sodium iodide, cuprous iodide, cupric iodide, hydrogen fluoride, potassium fluoride, sodium fluoride, cuprous fluoride, cupric fluoride, calcium chloride, barium chloride, ammonium chloride Calcium bromide, barium bromide, ammonium bromide, calcium iodide, barium iodide, ammonium iodide, ammonium fluoride and the like. Two or more of these may be used. Of the halogen ions, particularly preferred are chlorine ions. The concentration of the halogen ion is preferably 0.002 to 1.0 mol / liter (L) in the solution. When the halogen ion concentration is less than 0.002 mol / L, there is a problem that a monovalent or divalent copper ionic compound is mixed. is there. A more preferable halogen ion concentration is 0.005 to 0.2 mol / L.
また、いずれの還元処理を採用した場合においても、金属微粒子を析出させた後は、ろ過や遠心分離などによる金属微粒子の回収、洗浄、乾燥などの通常の処理を行うことができる。 In any of the reduction treatments, after the metal fine particles are deposited, normal treatments such as collection, washing, and drying of the metal fine particles by filtration or centrifugation can be performed.
〔金属微粒子の用途〕
本発明にかかる金属微粒子の製造方法により得られる金属微粒子は、所望の平均粒子径を有するものであり、金属微粒子が使用される一般的な用途、例えば、塗料、インキ、金属微粒子ペーストなどとして好適に利用できる。より具体的には、平均粒子径が１０〜５０ｎｍのものであれば塗料などに好適に利用でき、平均粒子径が３０〜５００ｎｍのものであれば金属微粒子ペーストなどに好適に利用できる。なお、ここにいう平均粒子径の値は、後述の実施例記載の方法で測定される値を基準としている。
[Use of metal fine particles]
The metal fine particles obtained by the method for producing metal fine particles according to the present invention have a desired average particle diameter, and are suitable for general uses in which the metal fine particles are used, for example, paints, inks, metal fine particle pastes and the like. Available to: More specifically, if it has an average particle diameter of 10 to 50 nm, it can be suitably used for paints, and if it has an average particle diameter of 30 to 500 nm, it can be suitably used for metal fine particle pastes. In addition, the value of an average particle diameter here is based on the value measured by the method of the below-mentioned Example description.
以下に、実施例によって本発明をより具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.
下記実施例において、ゼラチン等の平均分子量、金属微粒子の平均粒子径は、以下の測定方法により算出した値である。 In the following examples, the average molecular weight of gelatin and the like and the average particle diameter of the metal fine particles are values calculated by the following measuring method.
＜ゼラチン等の平均分子量＞
ゼラチンやその加水分解物の重量平均分子量や数平均分子量は、パギイ法により測定した。ここで「パギイ法」とは、高速液体クロマトグラフィーを用いたゲル濾過法によって、試料溶液のクロマトグラムを求め、分子量分布を推定する方法である。具体的には、以下の方法により測定した。
<Average molecular weight of gelatin, etc. >
The weight average molecular weight and number average molecular weight of gelatin and its hydrolyzate were measured by the Paguii method. Here, the “Pagii method” is a method for estimating a molecular weight distribution by obtaining a chromatogram of a sample solution by gel filtration using high performance liquid chromatography. Specifically, it measured by the following method.
試料２．０ｇを１００ｍＬ容メスフラスコに取り、０．１Ｍリン酸二水素カリウムと０．１Ｍリン酸水素二ナトリウムの等量混合液からなる溶離液を加えて１時間膨張させた後、４０℃で６０分間加熱して溶かし、室温に冷却後、溶離液を正確に１０倍に希釈して、得られた溶液を検液とした。 A sample (2.0 g) was placed in a 100 mL volumetric flask, and an eluent composed of an equal volume of 0.1 M potassium dihydrogen phosphate and 0.1 M disodium hydrogen phosphate was added and expanded for 1 hour. The solution was heated for 60 minutes to dissolve, cooled to room temperature, the eluent was diluted exactly 10 times, and the resulting solution was used as a test solution.
前記検液のクロマトグラムを以下のゲル濾過法により求めた。 The chromatogram of the test solution was determined by the following gel filtration method.
カラム：Ｓｈｏｄｅｘ Ａｓａｈｉｐａｋ ＧＳ ６２０ ７Ｇを２本直列に装着したものを用いた。 Column: A column equipped with two Shodex Asahipak GS 620 7G in series was used.
流速：１．０ｍＬ／分
カラム温度：５０℃
測定波長：２３０ｎｍ
分子量既知のプルラン（Ｐ−８２、昭和電工社製）で溶出時間を求めて検量線を作成した。その後、ゼラチン等を分析し、検体の重量平均分子量と数平均分子量を下式から求めた。下式において、Ｓｉは各ポイントでの吸光度、Ｍｉは溶出時間Ｔｉでの分子量である。
Flow rate: 1.0 mL / min Column temperature: 50 ° C
Measurement wavelength: 230 nm
A calibration curve was prepared by obtaining elution time with pullulan having a known molecular weight (P-82, manufactured by Showa Denko KK). Thereafter, gelatin and the like were analyzed, and the weight average molecular weight and number average molecular weight of the specimen were obtained from the following formulas. In the following formula, Si is the absorbance at each point, and Mi is the molecular weight at the elution time Ti.
重量平均分子量＝（ΣＳｉ×Ｍｉ）／ΣＳｉ
数平均分子量＝ΣＳｉ／（ΣＳｉ／Ｍｉ）
＜金属微粒子の平均粒子径＞
ＳＥＭ写真観察により視野から無作為に粒子を選択して平均粒子径を求めた。
Weight average molecular weight = (ΣSi × Mi) / ΣSi
Number average molecular weight = ΣSi / (ΣSi / Mi)
<Average particle diameter of metal fine particles>
Particles were randomly selected from the field of view by SEM photograph observation, and the average particle size was determined.
〔製造例１〕
「Ｇ−０７４９Ｋ」（魚由来のゼラチン、重量平均分子量１１００００、数平均分子量２４０００、新田ゼラチン社製）２００ｇを５０℃の温水１８００ｇに溶解し、ＷＳＣ（水溶性カルボジイミド、同仁化学社製）４６ｇを添加し、さらにメチオニン４８ｇを添加して、５０℃、ｐＨ７．０の条件で２時間反応させた。つぎに、化学修飾後のゼラチン９０ｇを６０℃の温水２１０ｇに溶解した。前記ゼラチンゾルにパパイン（タンパク質分解酵素、メルク社製）９ｍｇを添加し、前記酵素の加水分解最適条件下となるように温度６０℃、ｐＨ７．０に調整して、９０分間加水分解処理を行った後、ゾルを７５℃に加熱することにより、酵素を失活させた。
[Production Example 1]
200 g of “G-0749K” (fish-derived gelatin, weight average molecular weight 110000, number average molecular weight 24000, Nitta Gelatin Co., Ltd.) was dissolved in 1800 g of warm water at 50 ° C., and 46 g of WSC (water-soluble carbodiimide, manufactured by Dojin Chemical Co., Ltd.) Was added, and 48 g of methionine was further added, and the mixture was reacted at 50 ° C. and pH 7.0 for 2 hours. Next, 90 g of gelatin after chemical modification was dissolved in 210 g of warm water at 60 ° C. 9 mg of papain (proteolytic enzyme, manufactured by Merck & Co., Inc.) was added to the gelatin sol, adjusted to a temperature of 60 ° C. and pH 7.0 so as to be under the optimum hydrolysis conditions of the enzyme, and hydrolyzed for 90 minutes. Subsequently, the enzyme was inactivated by heating the sol to 75 ° C.
酵素を失活後、乾燥・粉末化し、化学修飾および加水分解がなされたゼラチンを得た。 After deactivation of the enzyme, it was dried and powdered to obtain gelatin that was chemically modified and hydrolyzed.
得られたゼラチンの重量平均分子量は９６００、数平均分子量は２１００であった。 The obtained gelatin had a weight average molecular weight of 9,600 and a number average molecular weight of 2,100.
〔製造例２〕
製造例１において、メチオニン４８ｇに代えて、リジン４４ｇを用いた以外は同様にして、化学修飾および加水分解がなされたゼラチンを得た。このゼラチンの重量平均分子量は９１００、数平均分子量は２２００であった。
[Production Example 2]
Gelatin subjected to chemical modification and hydrolysis was obtained in the same manner as in Production Example 1 except that 44 g of lysine was used instead of 48 g of methionine. This gelatin had a weight average molecular weight of 9,100 and a number average molecular weight of 2,200.
〔製造例３〕
「Ｇ−０７４９Ｋ」（魚由来のゼラチン、重量平均分子量１１００００、数平均分子量２４０００、新田ゼラチン社製）９０ｇを６０℃の温水２１０ｇに溶解した。前記ゼラチンゾルにパパイン（タンパク質分解酵素、メルク社製）９ｍｇを添加し、前記酵素の加水分解最適条件下となるように温度６０℃、ｐＨ７．０に調整して、９０分間加水分解処理を行った後、ゾルを７５℃に加熱することにより、酵素を失活させた。
[Production Example 3]
90 g of “G-0749K” (gelatin derived from fish, weight average molecular weight 110000, number average molecular weight 24000, Nitta Gelatin Co., Ltd.) was dissolved in 210 g of hot water at 60 ° C. 9 mg of papain (proteolytic enzyme, manufactured by Merck & Co., Inc.) was added to the gelatin sol, adjusted to a temperature of 60 ° C. and pH 7.0 so as to be under the optimum hydrolysis conditions of the enzyme, and hydrolyzed for 90 minutes. Subsequently, the enzyme was inactivated by heating the sol to 75 ° C.
酵素を失活後、乾燥・粉末化し、加水分解ゼラチンを得た。 After deactivating the enzyme, it was dried and powdered to obtain hydrolyzed gelatin.
得られたゼラチンの重量平均分子量は１２５００、数平均分子量２７００であった。 The obtained gelatin had a weight average molecular weight of 12,500 and a number average molecular weight of 2,700.
〔製造例４〕
製造例３において、酵素量を２７ｍｇ、加水分解処理時間を１００分間に変更したこと以外は同様にして、重量平均分子量５９００、数平均分量７００の加水分解ゼラチンを得た。
[Production Example 4]
A hydrolyzed gelatin having a weight average molecular weight of 5900 and a number average amount of 700 was obtained in the same manner as in Production Example 3, except that the amount of enzyme was changed to 27 mg and the hydrolysis treatment time was changed to 100 minutes.
〔実施例１〜４〕
上記製造例１〜４のゼラチン等を保護コロイドとして用いて、以下の操作により、各金属微粒子を製造した。
[Examples 1 to 4]
Using the gelatins and the like of Production Examples 1 to 4 as protective colloids, metal fine particles were produced by the following operation.
保護コロイド３．２ｇを水１００ｍＬに完全に溶解させたのち、金属化合物としての亜酸化銅７．１７ｇ、錯化剤としての２−アミノエタノール１８３ｍｇを添加し、次いで、２５重量％アンモニア水でｐＨ１１に調整した。この溶液を６０℃で３０分加熱撹拌し、さらに、還元剤としてのヒドラジン一水化物１１．７ｍＬを添加したのち２時間加熱撹拌を続けた。 After completely dissolving 3.2 g of the protective colloid in 100 mL of water, 7.17 g of cuprous oxide as a metal compound and 183 mg of 2-aminoethanol as a complexing agent were added, and then pH 11 was added with 25 wt% aqueous ammonia. Adjusted. This solution was heated and stirred at 60 ° C. for 30 minutes, and 11.7 mL of hydrazine monohydrate as a reducing agent was further added, and then the heating and stirring was continued for 2 hours.
〔実施例５〕
「Ｇ−０７４９Ｋ」（魚由来のゼラチン、重量平均分子量１１００００、数平均分子量２４０００、新田ゼラチン社製）を用いたこと以外は、実施例１〜４と同様にして、金属微粒子を製造した。
Example 5
Fine metal particles were produced in the same manner as in Examples 1 to 4, except that “G-0749K” (fish-derived gelatin, weight average molecular weight 110000, number average molecular weight 24000, manufactured by Nitta Gelatin Inc.) was used.
〔実施例６〕
「Ｇ−０７５０」（魚由来のゼラチン、重量平均分子量１７００００、数平均分子量３９０００、新田ゼラチン社製）を用いたこと以外は、実施例１〜４と同様にして、金属微粒子を製造した。
Example 6
Fine metal particles were produced in the same manner as in Examples 1 to 4 except that “G-0750” (gelatin derived from fish, weight average molecular weight 170000, number average molecular weight 39000, manufactured by Nitta Gelatin Inc.) was used.
〔実施例７〕
「Ｇ−０７４６Ｋ」（牛由来のゼラチン、重量平均分子量１９００００、数平均分子量５００００、新田ゼラチン社製）を用いたこと以外は、実施例１〜４と同様にして、金属微粒子を製造した。
Example 7
Fine metal particles were produced in the same manner as in Examples 1 to 4, except that “G-0746K” (bovine-derived gelatin, weight average molecular weight 190000, number average molecular weight 50000, manufactured by Nitta Gelatin Inc.) was used.
〔結果〕
各実施例１〜７で得られた金属微粒子の平均粒子径を表１に示すとともに、各実施例１〜７で得られた各金属微粒子について、各ＳＥＭ写真を図１〜７に示す。
〔result〕
The average particle diameter of the metal fine particles obtained in Examples 1 to 7 is shown in Table 1, and SEM photographs of the metal fine particles obtained in Examples 1 to 7 are shown in FIGS.
上記表１および図１〜７から明らかなように、化学修飾、平均分子量の影響により、得られる金属微粒子の平均粒子径に差が生じることが分かる。 As apparent from Table 1 and FIGS. 1 to 7, it can be seen that there is a difference in the average particle diameter of the obtained metal fine particles due to the influence of chemical modification and average molecular weight.
具体的には、実施例１，２は、化学修飾を施した後に、平均分子量をほぼ同程度に調整して、化学修飾の内容の選択が金属微粒子の平均粒子径に与える影響を見たものであるが、硫黄元素を含む化合物により化学修飾した実施例１のほうが相対的に粒子径が大きく、窒素元素を含む化合物により化学修飾した実施例２のほうが相対的に粒子径が小さくなっていることが分かる。したがって、これらの結果からは、これら硫黄元素や窒素元素の割合によって、得られる金属微粒子の平均粒子径を制御することができ、特に硫黄元素の割合の影響が大であることが理解できる。 Specifically, in Examples 1 and 2, after the chemical modification, the average molecular weight was adjusted to approximately the same level, and the effect of selection of the content of the chemical modification on the average particle diameter of the metal fine particles was observed. However, Example 1 chemically modified with a compound containing sulfur element has a relatively large particle size, and Example 2 chemically modified with a compound containing nitrogen element has a relatively small particle size. I understand that. Therefore, from these results, it can be understood that the average particle diameter of the obtained metal fine particles can be controlled by the ratio of these sulfur elements and nitrogen elements, and in particular, the influence of the ratio of sulfur elements is large.
また、実施例３〜７に見るように、平均分子量の小さい実施例ほど、相対的に平均分子量の大きい実施例よりも、得られる金属微粒子の平均粒子径が小さくなっていることが分かる。 Moreover, as seen in Examples 3 to 7, it can be seen that the smaller the average molecular weight, the smaller the average particle diameter of the metal fine particles obtained than the relatively large average molecular weight.
図１〜７に見るように、未処理のゼラチン、特に平均分子量の大きなゼラチンを用いた実施例よりも、加水分解により低分子量化したり、化学修飾を行った実施例のほうが、粒子径のばらつきが小さく、粒子径分布も制御できていることが分かる。 As shown in FIGS. 1 to 7, the particle diameter variation is more in the examples in which the molecular weight is reduced by hydrolysis or the chemical modification is performed than in the examples using untreated gelatin, particularly gelatin having a large average molecular weight. It can be seen that the particle size distribution can be controlled.
本発明は、金属微粒子が適用される種々の分野、例えば、低融点金属はんだ、金属微粒子ペーストなどに好適に利用することができる。 The present invention can be suitably used in various fields to which metal fine particles are applied, for example, low melting point metal solder, metal fine particle paste and the like.
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| JP5814320B2 (en) * | 2013-01-31 | 2015-11-17 | ニホンハンダ株式会社 | Method for producing solder alloy fine particles, solder alloy fine particles, solder paste, and electronic device |
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