JP5906245B2 - Dispersant and dispersible metal nanoparticle composition - Google Patents
Dispersant and dispersible metal nanoparticle composition Download PDFInfo
- Publication number
- JP5906245B2 JP5906245B2 JP2013531273A JP2013531273A JP5906245B2 JP 5906245 B2 JP5906245 B2 JP 5906245B2 JP 2013531273 A JP2013531273 A JP 2013531273A JP 2013531273 A JP2013531273 A JP 2013531273A JP 5906245 B2 JP5906245 B2 JP 5906245B2
- Authority
- JP
- Japan
- Prior art keywords
- tartaric acid
- nickel
- anisoyl
- toluoyl
- dispersant
- 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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- 239000002082 metal nanoparticle Substances 0.000 title claims description 96
- 239000002270 dispersing agent Substances 0.000 title claims description 63
- 239000000203 mixture Substances 0.000 title claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 177
- 229910052759 nickel Inorganic materials 0.000 claims description 97
- 239000002245 particle Substances 0.000 claims description 75
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 26
- 150000003892 tartrate salts Chemical class 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 229960001270 d- tartaric acid Drugs 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- CMIBUZBMZCBCAT-HZPDHXFCSA-N (2r,3r)-2,3-bis[(4-methylbenzoyl)oxy]butanedioic acid Chemical compound C1=CC(C)=CC=C1C(=O)O[C@@H](C(O)=O)[C@H](C(O)=O)OC(=O)C1=CC=C(C)C=C1 CMIBUZBMZCBCAT-HZPDHXFCSA-N 0.000 claims description 8
- YONLFQNRGZXBBF-ZIAGYGMSSA-N (2r,3r)-2,3-dibenzoyloxybutanedioic acid Chemical compound O([C@@H](C(=O)O)[C@@H](OC(=O)C=1C=CC=CC=1)C(O)=O)C(=O)C1=CC=CC=C1 YONLFQNRGZXBBF-ZIAGYGMSSA-N 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- CMIBUZBMZCBCAT-HOTGVXAUSA-N (2s,3s)-2,3-bis[(4-methylbenzoyl)oxy]butanedioic acid Chemical compound C1=CC(C)=CC=C1C(=O)O[C@H](C(O)=O)[C@@H](C(O)=O)OC(=O)C1=CC=C(C)C=C1 CMIBUZBMZCBCAT-HOTGVXAUSA-N 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- KWWCVCFQHGKOMI-UHFFFAOYSA-N 2,3-bis[(4-methoxybenzoyl)oxy]butanedioic acid Chemical compound C1=CC(OC)=CC=C1C(=O)OC(C(O)=O)C(C(O)=O)OC(=O)C1=CC=C(OC)C=C1 KWWCVCFQHGKOMI-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- CCIUQRKCMXXTOI-WOJBJXKFSA-N (2r,3r)-2,3-dihydroxy-2,3-bis(4-methoxybenzoyl)butanedioic acid Chemical compound C1=CC(OC)=CC=C1C(=O)[C@@](O)(C(O)=O)[C@](O)(C(O)=O)C(=O)C1=CC=C(OC)C=C1 CCIUQRKCMXXTOI-WOJBJXKFSA-N 0.000 claims description 4
- DVFMYDXKJZNVGI-WOJBJXKFSA-N C(C=1C(=CC=CC=1)OC)(=O)[C@@]([C@@](C(=O)O)(O)C(C=1C(=CC=CC=1)OC)=O)(O)C(=O)O Chemical compound C(C=1C(=CC=CC=1)OC)(=O)[C@@]([C@@](C(=O)O)(O)C(C=1C(=CC=CC=1)OC)=O)(O)C(=O)O DVFMYDXKJZNVGI-WOJBJXKFSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- HYQFZIWQHXXBER-WOJBJXKFSA-N C(C1=CC(=CC=C1)OC)(=O)[C@@]([C@@](C(=O)O)(O)C(C1=CC(=CC=C1)OC)=O)(O)C(=O)O Chemical compound C(C1=CC(=CC=C1)OC)(=O)[C@@]([C@@](C(=O)O)(O)C(C1=CC(=CC=C1)OC)=O)(O)C(=O)O HYQFZIWQHXXBER-WOJBJXKFSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 3
- 229960001367 tartaric acid Drugs 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 description 62
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 40
- 239000000243 solution Substances 0.000 description 38
- 239000002002 slurry Substances 0.000 description 34
- -1 phosphate ester compounds Chemical class 0.000 description 33
- 150000003141 primary amines Chemical class 0.000 description 32
- 238000009826 distribution Methods 0.000 description 31
- 238000010438 heat treatment Methods 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 23
- 238000000034 method Methods 0.000 description 23
- 239000003960 organic solvent Substances 0.000 description 23
- 230000000694 effects Effects 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000007791 liquid phase Substances 0.000 description 14
- 230000002776 aggregation Effects 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229910001453 nickel ion Inorganic materials 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000004220 aggregation Methods 0.000 description 12
- 125000004432 carbon atom Chemical group C* 0.000 description 12
- 230000009918 complex formation Effects 0.000 description 12
- 238000005755 formation reaction Methods 0.000 description 11
- 239000003638 chemical reducing agent Substances 0.000 description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 9
- 230000000536 complexating effect Effects 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000003446 ligand Substances 0.000 description 8
- 238000006722 reduction reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 150000001412 amines Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 150000002815 nickel Chemical class 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000009471 action Effects 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000010668 complexation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- HZPNKQREYVVATQ-UHFFFAOYSA-L nickel(2+);diformate Chemical group [Ni+2].[O-]C=O.[O-]C=O HZPNKQREYVVATQ-UHFFFAOYSA-L 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 4
- 150000002148 esters Chemical group 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 241000284156 Clerodendrum quadriloculare Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910001111 Fine metal Inorganic materials 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000012770 industrial material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- SMAMDWMLHWVJQM-UHFFFAOYSA-L nickel(2+);diformate;dihydrate Chemical compound O.O.[Ni+2].[O-]C=O.[O-]C=O SMAMDWMLHWVJQM-UHFFFAOYSA-L 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 2
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical compound CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- PLZVEHJLHYMBBY-UHFFFAOYSA-N Tetradecylamine Chemical compound CCCCCCCCCCCCCCN PLZVEHJLHYMBBY-UHFFFAOYSA-N 0.000 description 2
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 2
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- UFHJEZDFEHUYCR-HTQZYQBOSA-N (2r,3r)-2,3-bis(2,2-dimethylpropanoyloxy)butanedioic acid Chemical compound CC(C)(C)C(=O)O[C@@H](C(O)=O)[C@H](C(O)=O)OC(=O)C(C)(C)C UFHJEZDFEHUYCR-HTQZYQBOSA-N 0.000 description 1
- DNISEZBAYYIQFB-PHDIDXHHSA-N (2r,3r)-2,3-diacetyloxybutanedioic acid Chemical compound CC(=O)O[C@@H](C(O)=O)[C@H](C(O)=O)OC(C)=O DNISEZBAYYIQFB-PHDIDXHHSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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- 239000003054 catalyst Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical group 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- NAVSKFYJNZQECG-UHFFFAOYSA-N nickel;propanoic acid Chemical compound [Ni].CCC(O)=O NAVSKFYJNZQECG-UHFFFAOYSA-N 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- BKLZIAYVINRQEJ-UHFFFAOYSA-K trifluoroalumane;trihydrate Chemical compound O.O.O.F[Al](F)F BKLZIAYVINRQEJ-UHFFFAOYSA-K 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/002—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
- C09K23/34—Higher-molecular-weight carboxylic acid esters
- C09K23/36—Esters of polycarboxylic acids
Description
本発明は、金属ナノ粒子の凝集を抑制する分散剤及び分散性金属ナノ粒子組成物に関する。 The present invention relates to a dispersant for suppressing aggregation of metal nanoparticles and a dispersible metal nanoparticle composition.
金属微粒子は、バルク金属とは異なる物理的・化学的特性を有することから、例えば、導電性ペーストや透明導電膜などの電極材料、高密度記録材料、触媒材料、インクジェット用インク材料等の様々な工業材料に利用されている。近年では、電子機器の小型化や薄型化に伴い、金属微粒子も、数十〜数百ｎｍ程度まで微粒子化が進んでいる。例えば、電子機器の小型化に伴い、積層セラミックコンデンサーの電極は薄膜多層化が進んでおり、これに伴い電極層の材料には、ニッケルナノ粒子などの金属ナノ粒子が使用されている。 Since the metal fine particles have physical and chemical characteristics different from those of bulk metals, various materials such as electrode materials such as conductive pastes and transparent conductive films, high-density recording materials, catalyst materials, and ink-jet ink materials are used. It is used for industrial materials. In recent years, with the downsizing and thinning of electronic devices, fine metal particles have been made finer to about several tens to several hundreds of nanometers. For example, with the miniaturization of electronic devices, multilayer ceramic capacitor electrodes are becoming thinner and more multilayered, and as a material for the electrode layers, metal nanoparticles such as nickel nanoparticles are used.
上記のように、工業材料に使用される金属ナノ粒子は、その粒子径が例えば１５０ｎｍを下回る程度に小さく、粒子径が均一で、かつ分散性に優れることが求められる。しかしながら、微粒子化が進むことで、表面エネルギーの増加により、金属ナノ粒子が凝集し易くなる、という問題が生じている。 As described above, the metal nanoparticles used for industrial materials are required to have a particle diameter as small as, for example, less than 150 nm, a uniform particle diameter, and excellent dispersibility. However, with the progress of micronization, there is a problem that metal nanoparticles tend to aggregate due to an increase in surface energy.
金属ナノ粒子を分散させるために用いる分散剤として、例えば多価カルボン酸を含む脂肪酸や不飽和脂肪酸などを含むアニオン系分散剤（例えば、特許文献１）、高分子系イオン性分散剤（例えば、特許文献２）、りん酸エステル系化合物（例えば、特許文献３）などが知られている。これらの分散剤は、ある程度の分散効果が得られるものの、微粒子化の進行に伴い、数十〜数百ｎｍ程度の金属微粒子に対しては、凝集を抑えることが十分にできていないのが現状である。従って、金属ナノ粒子の微粒子化に対応した高い分散性を示す分散剤が求められている。 As a dispersant used for dispersing metal nanoparticles, for example, an anionic dispersant (for example, Patent Document 1) including a fatty acid containing polyvalent carboxylic acid, an unsaturated fatty acid, or the like, a polymer ionic dispersant (for example, Patent Document 2), phosphate ester compounds (for example, Patent Document 3) and the like are known. Although these dispersants can achieve a certain degree of dispersion effect, with the progress of micronization, it is not possible to sufficiently suppress aggregation of metal fine particles of about several tens to several hundreds of nanometers. It is. Accordingly, there is a demand for a dispersant exhibiting high dispersibility corresponding to the micronization of metal nanoparticles.
金属ナノ粒子は、固相反応や液相反応によって得られることが知られている。ニッケルナノ粒子を例に挙げると、固相反応としては、塩化ニッケルの化学気相蒸着やギ酸ニッケル塩の熱分解等が挙げられる。液相反応としては、塩化ニッケル等のニッケル塩を水素化ホウ素ナトリウム等の強力な還元剤で直接還元する方法、ＮａＯＨ存在下ヒドラジン等の還元剤を添加して前駆体［Ｎｉ（Ｈ2ＮＮＨ2）2］ＳＯ4・２Ｈ2Ｏを形成した後に熱分解する方法、塩化ニッケル等のニッケル塩や有機配位子を含有するニッケル錯体を溶媒とともに圧力容器に入れて水熱合成する方法、ギ酸ニッケル塩や酢酸ニッケル塩を１級アミン等の還元剤を添加して、マイクロ波を照射する方法等が挙げられる。It is known that metal nanoparticles can be obtained by solid phase reaction or liquid phase reaction. Taking nickel nanoparticles as an example, solid phase reactions include chemical vapor deposition of nickel chloride and thermal decomposition of nickel formate. In the liquid phase reaction, a nickel salt such as nickel chloride is directly reduced with a strong reducing agent such as sodium borohydride, a reducing agent such as hydrazine is added in the presence of NaOH, and the precursor [Ni (H 2 NNH 2 2 ] Method of thermal decomposition after forming SO 4 · 2H 2 O, Method of hydrothermal synthesis by putting nickel complex such as nickel chloride and nickel complex containing organic ligand into pressure vessel with solvent, nickel formate Examples thereof include a method of adding a reducing agent such as a primary amine to a salt or nickel acetate salt and irradiating with microwaves.
従来、固相反応で得られたニッケル粒子から積層セラミックコンデンサーなどの内部電極用のペーストを製造する際は、ビヒクル中にニッケル粒子を混練して、所定のタイミングでカチオン系分散剤、ノニオン系分散剤、両性イオン系などの分散剤を添加し、分散させてニッケルペーストを作製していた。しかしながら、この製造方法では凝集したニッケル粒子を含むため、凝集した状態で分散剤による被覆が行われ、十分な分散効果が得られない。また、ジェットミルや高圧ホモジナイザーを用いて、ニッケル粉末の解砕処理を行い、有機溶媒と飽和脂肪酸を加えて有機溶媒中で分散処理する方法も提案されている（特許文献４）。しかし、微粒子化によって生じる凝集を抑えることができていないのが現状である。 Conventionally, when producing pastes for internal electrodes such as multilayer ceramic capacitors from nickel particles obtained by solid phase reaction, nickel particles are kneaded in a vehicle, and cationic dispersants and nonionic dispersions are prepared at a predetermined timing. A nickel paste was prepared by adding and dispersing a dispersing agent such as an agent and a zwitterionic system. However, since this production method includes agglomerated nickel particles, coating with a dispersant is performed in the agglomerated state, and a sufficient dispersion effect cannot be obtained. In addition, a method has also been proposed in which nickel powder is pulverized using a jet mill or a high-pressure homogenizer, and an organic solvent and a saturated fatty acid are added and dispersed in the organic solvent (Patent Document 4). However, the present situation is that aggregation caused by micronization cannot be suppressed.
液相反応の技術に関して、ニッケル前駆物質、有機アミンおよび還元剤を混合した後、加熱することでニッケルナノ粒子を得る技術が開示されている（特許文献５）。この技術によれば、ニッケルナノ粒子の大きさおよび形状の制御が容易であるとされている。その理由は定かではないが、ニッケルナノ粒子が有機アミンにコーティングされることで有機溶剤中での分散性が優れることが挙げられている。しかしながら、この製造方法で、強力な還元剤を用いると、反応を制御することが難しく、分散性が高度に優れたニッケルナノ粒子は必ずしも好適には得られない。一方、還元力の弱い還元剤を用いると、酸化還元電位が負電位であるニッケル金属を還元するには高温に加熱する必要があり、それに伴った反応制御が必要になる。 Regarding the technique of liquid phase reaction, a technique for obtaining nickel nanoparticles by mixing a nickel precursor, an organic amine, and a reducing agent and then heating is disclosed (Patent Document 5). According to this technique, it is said that the control of the size and shape of nickel nanoparticles is easy. Although the reason is not certain, it is mentioned that the dispersibility in an organic solvent is excellent because nickel nanoparticles are coated with an organic amine. However, when a strong reducing agent is used in this production method, it is difficult to control the reaction, and nickel nanoparticles having a high degree of dispersibility are not necessarily obtained suitably. On the other hand, when a reducing agent having a weak reducing power is used, it is necessary to heat to high temperature in order to reduce nickel metal having a negative oxidation-reduction potential, and accordingly, reaction control is required.
また、ポリオール溶液に、還元剤、分散剤、およびニッケル塩を添加して混合溶液を製造する工程と、混合溶液を撹拌および加熱する工程と、混合溶液を反応させてニッケルナノ粒子を生成する工程と、を含むニッケルナノ粒子の製造方法が開示されている（特許文献６）。この場合、還元剤は前記のような強力な還元剤を使用するものではあるが、粒度が均一で、凝集することなく分散性に優れたニッケルナノ粒子を得ることができるとされている。分散剤としては、陽イオン系界面活性剤、陰イオン系界面活性剤、セルロース誘導体等が記載されている。 Also, a step of adding a reducing agent, a dispersant, and a nickel salt to the polyol solution to produce a mixed solution, a step of stirring and heating the mixed solution, and a step of reacting the mixed solution to produce nickel nanoparticles And the manufacturing method of the nickel nanoparticle containing is disclosed (patent document 6). In this case, although the reducing agent uses a strong reducing agent as described above, it is said that nickel nanoparticles having a uniform particle size and excellent dispersibility can be obtained without aggregation. As the dispersant, a cationic surfactant, an anionic surfactant, a cellulose derivative and the like are described.
本発明の目的は、金属ナノ粒子を効果的に分散できる分散剤を提供することである。 An object of the present invention is to provide a dispersant capable of effectively dispersing metal nanoparticles.
本発明の分散剤は、下記の一般式（I）で表される酒石酸誘導体からなるものである。 The dispersant of the present invention comprises a tartaric acid derivative represented by the following general formula (I).
本発明の分散剤は、前記置換されていてもよいフェニル基が、フェニル基、アルキル基で置換されていてもよいフェニル基、又は、アルコキシ基で置換されていてもよいフェニル基であってもよい。この場合、前記置換されていてもよいフェニル基が、フェニル基、トリル基、又は、アニソイル基であることが好ましい。 In the dispersant of the present invention, the optionally substituted phenyl group may be a phenyl group, a phenyl group optionally substituted with an alkyl group, or a phenyl group optionally substituted with an alkoxy group. Good. In this case, the phenyl group which may be substituted is preferably a phenyl group, a tolyl group or an anisoyl group.
本発明の分散剤は、上記一般式（Ｉ）で表される酒石酸誘導体が、ジベンゾイル−Ｄ−酒石酸、ジベンゾイル−Ｌ−酒石酸、ジ−ｐ−トルオイル−Ｌ−酒石酸、ジ−ｐ−トルオイル−Ｄ−酒石酸、ジ−ｏ−４−トルオイル−Ｌ−酒石酸、ジ−ｏ−４−トルオイル−Ｄ−酒石酸、ジ−ｍ−４−トルオイル−Ｌ−酒石酸、ジ−ｍ−４−トルオイル−Ｄ−酒石酸、ジ−ｐ−アニソイル−Ｌ−酒石酸、ジ−ｐ−アニソイル−Ｄ−酒石酸、ジ−ｏ−アニソイル−Ｌ−酒石酸、ジ−ｏ−アニソイル−Ｄ−酒石酸、ジ−ｍ−アニソイル−Ｌ−酒石酸、及びジ−ｍ−アニソイル−Ｄ−酒石酸よりなる群から選択される少なくとも１種であってもよい。 In the dispersant of the present invention, the tartaric acid derivative represented by the above general formula (I) is dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, di-p-toluoyl-L-tartaric acid, di-p-toluoyl-D. -Tartaric acid, di-o-4-toluoyl-L-tartaric acid, di-o-4-toluoyl-D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, di-m-4-toluoyl-D-tartaric acid , Di-p-anisoyl-L-tartaric acid, di-p-anisoyl-D-tartaric acid, di-o-anisoyl-L-tartaric acid, di-o-anisoyl-D-tartaric acid, di-m-anisoyl-L-tartaric acid And at least one selected from the group consisting of di-m-anisoyl-D-tartaric acid.
本発明の分散剤は、金属ナノ粒子の分散に用いられるものであってもよい。 The dispersant of the present invention may be used for dispersing metal nanoparticles.
本発明の分散性金属ナノ粒子組成物は、金属ナノ粒子と、上記いずれかの分散剤と、を含有する。 The dispersible metal nanoparticle composition of the present invention contains metal nanoparticles and any one of the above dispersants.
本発明の分散性金属ナノ粒子組成物は、前記金属ナノ粒子の粒子径が１５０ｎｍ以下であってもよい。 In the dispersible metal nanoparticle composition of the present invention, the metal nanoparticle may have a particle size of 150 nm or less.
本発明の分散性金属ナノ粒子組成物は、前記金属ナノ粒子が、金、銀、白金、銅、ニッケル、チタン及びコバルトよりなる群から選択される少なくとも１種であってもよい。 In the dispersible metal nanoparticle composition of the present invention, the metal nanoparticles may be at least one selected from the group consisting of gold, silver, platinum, copper, nickel, titanium, and cobalt.
本発明の分散性金属ナノ粒子組成物は、さらに溶媒を含有するものであってもよい。この場合、前記溶媒がアルコール系溶媒であってもよい。 The dispersible metal nanoparticle composition of the present invention may further contain a solvent. In this case, the solvent may be an alcohol solvent.
本発明の分散性金属ナノ粒子組成物は、前記金属ナノ粒子が、液相でのマイクロ波照射により得られたニッケルナノ粒子であってもよい。この場合、前記ニッケルナノ粒子は、酸素原子を０．５〜５．０質量％の範囲内で含有し、かつ、炭素原子を０．１〜５．０質量％の範囲内で含有するものであってもよい。 In the dispersible metal nanoparticle composition of the present invention, the metal nanoparticles may be nickel nanoparticles obtained by microwave irradiation in a liquid phase. In this case, the nickel nanoparticles contain oxygen atoms in the range of 0.5 to 5.0 mass% and carbon atoms in the range of 0.1 to 5.0 mass%. There may be.
本発明の分散剤によれば、例えば粒子径が１５０ｎｍ以下の微細な金属ナノ粒子についても、凝集を抑制し、単一粒子が分散した粒子径分布のシャープな金属ナノ粒子の集合体を得ることができる。また、本発明の分散剤は、金属ナノ粒子に対し、強い凝集抑制作用を有することから、少量でも優れた分散効果が期待できる。 According to the dispersant of the present invention, for example, even for fine metal nanoparticles having a particle size of 150 nm or less, aggregation is suppressed and an aggregate of metal nanoparticles having a sharp particle size distribution in which single particles are dispersed is obtained. Can do. Further, since the dispersant of the present invention has a strong aggregation suppressing action on metal nanoparticles, an excellent dispersion effect can be expected even with a small amount.
［分散剤］
分散剤は、上記一般式（I）で表される酒石酸誘導体からなる。一般式（Ｉ）中、置換されていてもよいフェニル基としては、例えば、フェニル基、アルキル基で置換されていてもよいフェニル基、アルコキシ基で置換されていてもよいフェニル基等を挙げることができる。ここで、アルキル基としては、例えば炭素数１〜４の低級アルキル基が優れた分散効果を有するので好ましく、メチル基がより好ましい。また、アルコキシ基としては、炭素数１〜４の低級アルコキシ基が優れた分散効果を有するので好ましく、メトキシ基がより好ましい。従って、置換されていてもよいフェニル基の具体例としては、フェニル基、ｏ−、ｍ−もしくはｐ−トリル基、又は、ｏ−、ｍ−もしくはｐ−アニソイル基が好ましく、これらの中でもｏ−、ｍ−もしくはｐ−トリル基が最も好ましい。[Dispersant]
The dispersant is composed of a tartaric acid derivative represented by the above general formula (I). Examples of the phenyl group which may be substituted in the general formula (I) include a phenyl group, a phenyl group which may be substituted with an alkyl group, and a phenyl group which may be substituted with an alkoxy group. Can do. Here, as the alkyl group, for example, a lower alkyl group having 1 to 4 carbon atoms is preferable because it has an excellent dispersion effect, and a methyl group is more preferable. Moreover, as an alkoxy group, since a C1-C4 lower alkoxy group has the outstanding dispersion | distribution effect, a methoxy group is more preferable. Accordingly, specific examples of the optionally substituted phenyl group include a phenyl group, o-, m- or p-tolyl group, or o-, m- or p-anisoyl group. Among these, o- Most preferred are m, or p-tolyl groups.
上記一般式（I）で表される酒石酸誘導体の好ましい具体例としては、ジベンゾイル−Ｄ−酒石酸、ジベンゾイル−Ｌ−酒石酸、ジ−ｐ−トルオイル−Ｌ−酒石酸、ジ−ｐ−トルオイル−Ｄ−酒石酸、ジ−ｏ−４−トルオイル−Ｌ−酒石酸、ジ−ｏ−４−トルオイル−Ｄ−酒石酸、ジ−ｍ−４−トルオイル−Ｌ−酒石酸、ジ−ｍ−４−トルオイル−Ｄ−酒石酸、ジ−ｐ−アニソイル−Ｌ−酒石酸、ジ−ｐ−アニソイル−Ｄ−酒石酸、ジ−ｏ−アニソイル−Ｌ−酒石酸、ジ−ｏ−アニソイル−Ｄ−酒石酸、ジ−ｍ−アニソイル−Ｌ−酒石酸、ジ−ｍ−アニソイル−Ｄ−酒石酸などを挙げることができる。これらの中でも、優れた分散効果を有するジ−ｐ−トルオイル−Ｌ−酒石酸、ジ−ｐ−トルオイル−Ｄ−酒石酸、ジ−ｏ−４−トルオイル−Ｌ−酒石酸、ジ−ｏ−４−トルオイル−Ｄ−酒石酸、ジ−ｍ−４−トルオイル−Ｌ−酒石酸、ジ−ｍ−４−トルオイル−Ｄ−酒石酸が最も好ましい。 Preferred examples of the tartaric acid derivative represented by the general formula (I) include dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, di-p-toluoyl-L-tartaric acid, and di-p-toluoyl-D-tartaric acid. Di-o-4-toluoyl-L-tartaric acid, di-o-4-toluoyl-D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, di-m-4-toluoyl-D-tartaric acid, di- -P-anisoyl-L-tartaric acid, di-p-anisoyl-D-tartaric acid, di-o-anisoyl-L-tartaric acid, di-o-anisoyl-D-tartaric acid, di-m-anisoyl-L-tartaric acid, di- -M-anisoyl-D-tartaric acid and the like can be mentioned. Among these, di-p-toluoyl-L-tartaric acid, di-p-toluoyl-D-tartaric acid, di-o-4-toluoyl-L-tartaric acid, and di-o-4-toluoyl- having excellent dispersing effect Most preferred are D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, and di-m-4-toluoyl-D-tartaric acid.
上記一般式（Ｉ）で表される酒石酸誘導体は、２種以上を組み合わせて使用することもできる。また、発明の効果を損なわない範囲で、他の化合物からなる分散剤と組み合わせて使用することもできる。 The tartaric acid derivative represented by the general formula (I) can be used in combination of two or more. Moreover, it can also be used in combination with the dispersing agent which consists of another compound in the range which does not impair the effect of invention.
［金属ナノ粒子］
本実施の形態の分散剤により分散させる対象である金属ナノ粒子としては、例えば、卑金属又は貴金属のナノ粒子を挙げることができる。卑金属としては、例えば、ニッケル、チタン、コバルト、銅、クロム、マンガン、鉄、ジルコニウム、スズ、タングステン、モリブデン、バナジウム等を挙げることができる。貴金属としては、例えば、金、銀、白金、パラジウム、イリジウム、オスミウム、ルテニウム、ロジウム、レニウム等を挙げることができる。上記卑金属又は貴金属のナノ粒子の中でも、例えば、ニッケル、チタン、コバルト、銅、金、銀、白金等のナノ粒子が好ましい。また、これらの中でも特に、後述する液相でのマイクロ波照射により製造することができるナノ粒子が特に好ましく、例えば、ニッケル、コバルト、銅、金、銀、白金等のナノ粒子が挙げられる。なお、金属ナノ粒子は上記の金属元素を、単独で又は２種以上含有していてもよく、また水素、炭素、窒素、硫黄等の金属元素以外の元素を含有していてもよいし、これらの合金であってもよい。さらに、単一の金属ナノ粒子で構成されていてもよく、２種以上の金属ナノ粒子を混合したものであってもよい。[Metal nanoparticles]
As a metal nanoparticle which is the object disperse | distributed with the dispersing agent of this Embodiment, the nanoparticle of a base metal or a noble metal can be mentioned, for example. Examples of the base metal include nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, vanadium, and the like. Examples of the noble metal include gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium and the like. Among the above base metal or noble metal nanoparticles, for example, nanoparticles of nickel, titanium, cobalt, copper, gold, silver, platinum and the like are preferable. Among these, nanoparticles that can be produced by microwave irradiation in a liquid phase, which will be described later, are particularly preferable, and examples thereof include nanoparticles such as nickel, cobalt, copper, gold, silver, and platinum. The metal nanoparticles may contain the above metal elements alone or in combination of two or more, and may contain elements other than metal elements such as hydrogen, carbon, nitrogen and sulfur. An alloy of Furthermore, it may be composed of a single metal nanoparticle or a mixture of two or more metal nanoparticles.
金属ナノ粒子の粒子径は、特に制限はなく、その使用目的に応じて、例えば１〜２００ｎｍの範囲内から選択される。本実施の形態の分散剤は、公知の分散剤では分散効果が期待できない小さな粒子径、例えば１５０ｎｍ以下、特に１００ｎｍ以下の粒子径の金属ナノ粒子に対しても、優れた分散効果が得られる。換言すれば、本実施の形態の分散剤の適用対象は、例えば粒子径が１５０ｎｍ以下の金属ナノ粒子が好ましく、１００ｎｍ以下の金属ナノ粒子がより好ましい。別の観点から、金属ナノ粒子の平均粒子径は、好ましくは１０〜１５０ｎｍの範囲内、より好ましくは２０〜１２０ｎｍの範囲内がよい。 There is no restriction | limiting in particular in the particle diameter of a metal nanoparticle, According to the use purpose, it selects from the range of 1-200 nm, for example. The dispersing agent of the present embodiment can provide an excellent dispersing effect even for metal nanoparticles having a small particle diameter, for example, 150 nm or less, particularly 100 nm or less, which cannot be expected with a known dispersing agent. In other words, for example, metal nanoparticles having a particle diameter of 150 nm or less are preferable, and metal nanoparticles having a particle diameter of 100 nm or less are more preferable. From another viewpoint, the average particle diameter of the metal nanoparticles is preferably in the range of 10 to 150 nm, more preferably in the range of 20 to 120 nm.
［金属ナノ粒子への適用方法］
分散剤の適用方法は、特に制限はなく、例えば、ａ）金属ナノ粒子に対して所定量の分散剤を混合し、混練分散させる方法、ｂ）金属ナノ粒子を液相法で合成した後で液相中に分散剤を所定量添加する方法、ｃ）高圧ホモジナイザーなどの分散機を用いて金属ナノ粒子を機械的に解砕し、その解砕の前又は後に、分散剤を所定量添加し分散させる方法など、様々な方法が挙げられる。一般式（Ｉ）で表される酒石酸誘導体は、常温で固体（粉末）であるため、そのまま金属ナノ粒子に混合してもよいし、任意の溶媒に溶解した状態で金属ナノ粒子に混合してもよい。[Application method to metal nanoparticles]
The application method of the dispersant is not particularly limited. For example, a) a method in which a predetermined amount of the dispersant is mixed and kneaded and dispersed in the metal nanoparticles, and b) after the metal nanoparticles are synthesized by the liquid phase method. A method of adding a predetermined amount of a dispersant in the liquid phase, c) mechanically crushing the metal nanoparticles using a dispersing machine such as a high-pressure homogenizer, and adding a predetermined amount of the dispersant before or after the crushing. There are various methods such as a method of dispersing. Since the tartaric acid derivative represented by the general formula (I) is solid (powder) at room temperature, it may be mixed with the metal nanoparticles as it is, or mixed with the metal nanoparticles in a state of being dissolved in an arbitrary solvent. Also good.
本実施の形態の分散剤は、強い凝集抑制作用を有することから、少量でも優れた分散効果が期待できる。本実施の形態の分散剤の使用量は、金属ナノ粒子１００質量部に対して０．１質量部以上４０質量部以下の範囲内とすることが好ましく、１質量部以上３０質量部以下の範囲内がより好ましい。金属ナノ粒子１００質量部に対する分散剤の使用量が０．１質量部未満では分散効果が十分に得られない傾向があり、４０質量部を超えると、分散剤の残渣による凝集体が発生する傾向がある。また、上記の上限を超えて分散剤を過剰に使用すると、金属ナノ粒子中に残留した分散剤によって製品に影響を与える場合がある。例えば、本実施の形態の分散剤を用いて分散させた金属ナノ粒子を、積層セラミックコンデンサーの製造に使用する場合、分散剤の使用量が過剰であると、製造工程おける焼成時の体積変化が大きくなり、剥離や膜切れの原因となる場合がある。 Since the dispersant of the present embodiment has a strong aggregation suppressing action, an excellent dispersion effect can be expected even in a small amount. The amount of the dispersant used in the present embodiment is preferably in the range of 0.1 to 40 parts by mass with respect to 100 parts by mass of the metal nanoparticles, and preferably in the range of 1 to 30 parts by mass. The inside is more preferable. If the amount of the dispersant used relative to 100 parts by mass of the metal nanoparticles is less than 0.1 parts by mass, the dispersion effect tends to be insufficient, and if it exceeds 40 parts by mass, aggregates due to the residue of the dispersant tend to be generated. There is. Further, if the dispersant is used excessively beyond the above upper limit, the product may be affected by the dispersant remaining in the metal nanoparticles. For example, when the metal nanoparticles dispersed using the dispersant of the present embodiment are used for the production of a multilayer ceramic capacitor, if the amount of the dispersant used is excessive, the volume change during firing in the production process will occur. It may become large and cause peeling or film breakage.
金属ナノ粒子に分散剤を適用した後、余剰の分散剤を洗浄して除去することが好ましい。洗浄は、例えばイソプロパノールなどのアルコール系溶媒を用いて行うことができる。 After applying the dispersant to the metal nanoparticles, it is preferable to remove the excess dispersant by washing. The washing can be performed using, for example, an alcohol solvent such as isopropanol.
一般式（Ｉ）で表される酒石酸誘導体が、金属ナノ粒子に対して優れた分散作用を有する理由は未だ明らかではないが、金属ナノ粒子と一般式（Ｉ）で表される酒石酸誘導体との間に、何らかの相互作用が生じているものと推測される。例えば、一般式（Ｉ）で表される酒石酸誘導体は、分子内にカルボン酸から誘導された２つのエステル構造と、これらのエステル構造の形成にそれぞれ関与する２つの嵩高い又は疎水性の芳香環を有している。これらのエステル構造−芳香環が分散作用に関与している可能性がある。すなわち、２つのエステル構造−芳香環によって金属ナノ粒子との間に相互作用が生じ、金属ナノ粒子の周囲に前記酒石酸誘導体が近接した状態で存在することによって、金属ナノ粒子の表面の電気的性質を変化させ、あるいは立体的な障害によって、金属ナノ粒子同士の凝集を抑制し、更には溶媒との親和性によって分散性を付与しているものと考えられる。ここで、一般式（Ｉ）で表される酒石酸誘導体と金属ナノ粒子との相互作用としては、例えばイオン性結合、共有結合、静電結合、配位結合、水素結合等が考えられる。 The reason why the tartaric acid derivative represented by the general formula (I) has an excellent dispersing action on the metal nanoparticles is not yet clear, but the metal nanoparticles and the tartaric acid derivative represented by the general formula (I) It is presumed that some kind of interaction has occurred between them. For example, the tartaric acid derivative represented by the general formula (I) has two ester structures derived from a carboxylic acid in the molecule and two bulky or hydrophobic aromatic rings respectively involved in the formation of these ester structures. have. These ester structures-aromatic rings may be involved in the dispersing action. That is, the interaction between the metal structure and the two ester structures-aromatic ring occurs, and the presence of the tartaric acid derivative in the vicinity of the metal nanoparticle results in the electrical properties of the surface of the metal nanoparticle. It is considered that the agglomeration between the metal nanoparticles is suppressed by steric hindrance or the dispersibility is imparted by affinity with the solvent. Here, as the interaction between the tartaric acid derivative represented by the general formula (I) and the metal nanoparticles, for example, an ionic bond, a covalent bond, an electrostatic bond, a coordinate bond, a hydrogen bond, and the like can be considered.
本実施の形態に係る分散剤を用いることによって、粒子径が１５０ｎｍ以下の微細な金属ナノ粒子についても、凝集を抑制し、単一粒子が分散した粒子径分布のシャープな金属ナノ粒子の集合体を得ることができる。また、本実施の形態に係る分散剤は、強い凝集抑制作用を有することから、少量でも優れた分散効果が期待できる。さらに、余剰の分散剤を除去することで、焼成工程などで発生する揮発分を低減できる効果も得られる。このように、凝集粒子が少なく、シャープな粒子径分布を持つ金属ナノ粒子は、例えば積層セラミックコンデンサーの内部電極材料等の工業材料として好適に用いることができる。 By using the dispersant according to this embodiment, aggregation of fine metal nanoparticles having a particle size of 150 nm or less is suppressed, and aggregation of metal nanoparticles having a sharp particle size distribution in which single particles are dispersed. Can be obtained. Further, since the dispersant according to the present embodiment has a strong aggregation suppressing action, an excellent dispersion effect can be expected even in a small amount. Furthermore, by removing the excess dispersant, an effect of reducing the volatile matter generated in the baking process or the like can be obtained. As described above, the metal nanoparticles having few aggregated particles and having a sharp particle size distribution can be suitably used as an industrial material such as an internal electrode material of a multilayer ceramic capacitor.
［分散性金属ナノ粒子組成物］
本発明の分散性金属ナノ粒子組成物は、分散剤と、金属ナノ粒子と、を含有する。ここで、分散剤及び金属ナノ粒子としては、上記のものが用いられる。[Dispersible metal nanoparticle composition]
The dispersible metal nanoparticle composition of the present invention contains a dispersant and metal nanoparticles. Here, as the dispersant and the metal nanoparticles, those described above are used.
また、本発明の分散性金属ナノ粒子組成物は、任意成分として、溶媒を含有していてもよい。溶媒としては、金属ナノ粒子の表面に存在する酸化物又は水酸化物の被膜の状態を変化させにくいという観点から、有機溶媒が好ましく、例えば炭素数４〜３０のエーテル系有機溶媒、炭素数７〜３０の飽和又は不飽和の炭化水素系有機溶媒、炭素数３〜１８のアルコール系溶媒等を使用することができる。更に、本発明の分散性金属ナノ粒子組成物中に存在する分散剤は、溶媒に溶解した状態にすることによって、その効果を発揮しやすくなるので、分散剤を溶解させやすい有機溶媒がより好ましく、その具体例としては、イソプロパノール、テトラエチレングリコール、ｎ−オクチルエーテル等が挙げられる。また、後述するように、金属ナノ粒子の液相合成に使用した１級アミンをそのまま溶媒として用いることもできる。 Moreover, the dispersible metal nanoparticle composition of the present invention may contain a solvent as an optional component. The solvent is preferably an organic solvent from the viewpoint that it is difficult to change the state of the oxide or hydroxide film present on the surface of the metal nanoparticles, and for example, an ether-based organic solvent having 4 to 30 carbon atoms, 7 carbon atoms. -30 saturated or unsaturated hydrocarbon organic solvents, C3-C18 alcohol solvents, and the like can be used. Furthermore, the dispersant present in the dispersible metal nanoparticle composition of the present invention is more preferably an organic solvent in which the dispersant can be easily dissolved because it can easily exert its effect by being dissolved in the solvent. Specific examples thereof include isopropanol, tetraethylene glycol, n-octyl ether and the like. Moreover, as will be described later, the primary amine used for the liquid phase synthesis of the metal nanoparticles can be used as a solvent as it is.
分散性金属ナノ粒子組成物において、分散剤と金属ナノ粒子とは、複合体を形成していてもよい。ここで複合体とは、一般式（Ｉ）で表される酒石酸誘導体が有する官能基と、金属ナノ粒子の表面又は該表面に存在する官能基（例えば水酸基）との相互作用により、金属ナノ粒子の周囲に前記酒石酸誘導体が付着したり、配位したりしている状態を意味する。 In the dispersible metal nanoparticle composition, the dispersant and the metal nanoparticles may form a composite. Here, the composite is a metal nanoparticle due to the interaction between the functional group of the tartaric acid derivative represented by the general formula (I) and the surface of the metal nanoparticle or a functional group (for example, hydroxyl group) present on the surface. Means that the tartaric acid derivative is attached or coordinated around
本実施の形態において、分散性金属ナノ粒子組成物の調製は、特に制限はなく、分散剤と、金属ナノ粒子とを混合し、必要により、混練、攪拌等を行えばよい。この場合、金属ナノ粒子への分散剤の適用は、例えば上記ａ）〜ｃ）に準じて実施できる。 In the present embodiment, the preparation of the dispersible metal nanoparticle composition is not particularly limited, and the dispersant and the metal nanoparticles may be mixed, and if necessary, kneading, stirring, or the like may be performed. In this case, the application of the dispersant to the metal nanoparticles can be performed according to, for example, the above a) to c).
本実施の形態の分散性金属ナノ粒子組成物における分散剤の含有量は、金属ナノ粒子１００質量部に対して０．１質量部以上４０質量部以下の範囲内とすることが好ましく、１質量部以上３０質量部以下の範囲内がより好ましい。金属ナノ粒子１００質量部に対する分散剤の含有量が０．１質量部未満では分散性が低下する傾向があり、４０質量部を超えると、凝集が生じ易くなる傾向がある。 The content of the dispersant in the dispersible metal nanoparticle composition of the present embodiment is preferably in the range of 0.1 parts by mass or more and 40 parts by mass or less with respect to 100 parts by mass of the metal nanoparticles. More preferably within the range of not less than 30 parts and not more than 30 parts by mass. When the content of the dispersing agent with respect to 100 parts by mass of the metal nanoparticles is less than 0.1 parts by mass, the dispersibility tends to decrease, and when it exceeds 40 parts by mass, aggregation tends to occur.
［金属ナノ粒子の製造方法］
本発明の分散剤の適用対象である金属ナノ粒子、又は本発明の分散性金属ナノ粒子組成物に含有される金属ナノ粒子は、上記例示の金属種のナノ粒子であれば特に制限はないが、分散剤の効果を十分に発揮させるために、粒子径が１５０ｎｍ以下で粒子径分布が狭い［例えば、粒子径の変動係数（ＣＶ値；標準偏差／平均粒子径）が０．２以下の］金属ナノ粒子であることが好ましい。このような粒子径分布の金属ナノ粒子を製造することは一般に困難を伴うが、液相でのマイクロ波照射により製造することができる。そこで、ニッケルナノ粒子を例に挙げて、液相でのマイクロ波照射による製造方法を説明する。また、分散剤の効果を十分に発揮させるために、金属ナノ粒子の表面に、例えば水酸基などの官能基が存在することが好ましいが、このような金属ナノ粒子を得やすいという点でも、以下に述べる液相でのマイクロ波照射による製造方法が適している。[Production method of metal nanoparticles]
The metal nanoparticles to which the dispersant of the present invention is applied or the metal nanoparticles contained in the dispersible metal nanoparticle composition of the present invention are not particularly limited as long as they are nanoparticles of the above-described metal species. In order to fully exhibit the effect of the dispersant, the particle size distribution is narrow with a particle size of 150 nm or less [for example, the coefficient of variation of particle size (CV value; standard deviation / average particle size) is 0.2 or less] Metal nanoparticles are preferred. Although it is generally difficult to produce metal nanoparticles having such a particle size distribution, they can be produced by microwave irradiation in a liquid phase. Therefore, taking a nickel nanoparticle as an example, a manufacturing method by microwave irradiation in a liquid phase will be described. Further, in order to sufficiently exert the effect of the dispersant, it is preferable that a functional group such as a hydroxyl group is present on the surface of the metal nanoparticle, but the following is also easy to obtain such a metal nanoparticle. The production method by microwave irradiation in the liquid phase described is suitable.
ニッケルナノ粒子は、次の工程Ａ及びＢ；
Ａ）カルボン酸ニッケル及び１級アミンを含む混合物を、１００℃〜１６５℃の範囲内の温度に加熱して錯化反応液を得る錯化反応液生成工程、
及び、
Ｂ）該錯化反応液を、マイクロ波照射によって１７０℃以上の温度に加熱して該錯化反応液中のニッケルイオンを還元し、金属ニッケルナノ粒子のスラリーを得る金属ニッケルナノ粒子スラリー生成工程、
を含むマイクロ波照射による液相法により調製することができる。このように製造されたニッケルナノ粒子に対して、本実施の形態の分散剤は、後記実施例に示すように、非常に優れた分散効果を示す。液相でのマイクロ波照射により製造されたニッケルナノ粒子は、例えば酸素原子を０．５〜５．０質量％の範囲内で含有し、炭素原子を０．１〜５．０質量％の範囲内で含有することが好ましい。これらの酸素原子及び炭素原子は、液相反応によるニッケルナノ粒子の合成過程で、ニッケルナノ粒子の表面に、水酸化物又は有機物として付着したものである。なお、「ニッケルナノ粒子」とは、ニッケル元素を５０重量％以上含有すればよく、ニッケル以外の金属を含むニッケル合金のナノ粒子であってもよい。この場合、ニッケル以外の金属として、例えば、銅、コバルト等を挙げることができる。Nickel nanoparticles are produced in the following steps A and B;
A) Complexation reaction liquid production | generation process which heats the mixture containing nickel carboxylate and primary amine to the temperature within the range of 100 to 165 degreeC, and obtains a complexation reaction liquid,
as well as,
B) Metal nickel nanoparticle slurry generation step of heating the complexing reaction liquid to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexing reaction liquid to obtain a metal nickel nanoparticle slurry. ,
It can prepare by the liquid phase method by microwave irradiation containing. With respect to the nickel nanoparticles thus manufactured, the dispersant of the present embodiment exhibits a very excellent dispersion effect as shown in the examples described later. The nickel nanoparticles produced by microwave irradiation in the liquid phase contain, for example, oxygen atoms in the range of 0.5 to 5.0% by mass and carbon atoms in the range of 0.1 to 5.0% by mass. It is preferable to contain within. These oxygen atoms and carbon atoms are attached to the surface of the nickel nanoparticles as hydroxides or organic substances in the process of synthesizing the nickel nanoparticles by a liquid phase reaction. The “nickel nanoparticle” may contain nickel element in an amount of 50% by weight or more, and may be a nickel alloy nanoparticle containing a metal other than nickel. In this case, examples of metals other than nickel include copper and cobalt.
＜工程Ａ；錯化反応液生成工程＞
（カルボン酸ニッケル）
カルボン酸ニッケル（カルボン酸のニッケル塩）は、カルボン酸の種類を限定するものではなく、例えば、カルボキシル基が１つのモノカルボン酸であってもよく、また、カルボキシル基が２つ以上のカルボン酸であってもよい。また、非環式カルボン酸であってもよく、環式カルボン酸であってもよい。このようなカルボン酸ニッケルとして、非環式モノカルボン酸ニッケルを好適に用いることができ、非環式モノカルボン酸ニッケルのなかでも、ギ酸ニッケル、酢酸ニッケル、プロピオン酸ニッケル、シュウ酸ニッケル、安息香酸ニッケル等を用いることがより好ましい。これらの非環式モノカルボン酸ニッケルを用いることによって、得られるニッケルナノ粒子は、その形状のばらつきが抑制され、均一な形状として形成されやすくなる。カルボン酸ニッケルは、無水物であってもよく、また水和物であってもよい。<Step A: Complexation reaction solution generation step>
(Nickel carboxylate)
The nickel carboxylate (nickel salt of carboxylic acid) is not limited to the type of carboxylic acid. For example, the carboxyl group may be a monocarboxylic acid having one carboxyl group, or a carboxylic acid having two or more carboxyl groups. It may be. Moreover, acyclic carboxylic acid may be sufficient and cyclic carboxylic acid may be sufficient. As such nickel carboxylate, nickel acyclic monocarboxylate can be preferably used, and among nickel acyclic monocarboxylate, nickel formate, nickel acetate, nickel propionate, nickel oxalate, benzoic acid It is more preferable to use nickel or the like. By using these nickel acyclic monocarboxylates, the resulting nickel nanoparticles are less likely to have a variation in shape and are easily formed as a uniform shape. The nickel carboxylate may be an anhydride or a hydrate.
（１級アミン）
１級アミンは、ニッケルイオンとの錯体を形成することができ、ニッケル錯体（又はニッケルイオン）に対する還元能を効果的に発揮するので好ましい。２級アミンは、１級アミンと比較して、立体障害が大きく、還元能が低いため、ニッケル錯体の良好な形成を阻害するおそれがある。また、３級アミンはニッケルイオンの還元能を有しないため、還元剤を新たに追加する必要がある。なお、１級アミンを使用する上で、生成するニッケルナノ粒子の形状に支障を与えない範囲でこれらを併用することは差し支えない。１級アミンは、ニッケルイオンとの錯体を形成できるものであれば、特に限定するものではなく、常温で固体又は液体のものが使用できる。ここで、常温とは、２０℃±１５℃をいう。常温で液体の１級アミンは、ニッケル錯体を形成する際の有機溶媒としても機能する。なお、常温で固体の１級アミンであっても、１００℃以上の加熱によって液体であるか、又は有機溶媒を用いて溶解するものであれば、特に問題はない。(Primary amine)
The primary amine is preferable because it can form a complex with nickel ions and effectively exhibits a reducing ability for nickel complexes (or nickel ions). A secondary amine has a larger steric hindrance and a lower reducing ability than a primary amine, and thus may hinder good formation of a nickel complex. Further, since the tertiary amine does not have the ability to reduce nickel ions, it is necessary to newly add a reducing agent. In addition, when using a primary amine, these may be used together in the range which does not have trouble in the shape of the nickel nanoparticle to produce | generate. The primary amine is not particularly limited as long as it can form a complex with nickel ions, and can be a solid or liquid at room temperature. Here, room temperature means 20 ° C. ± 15 ° C. The primary amine that is liquid at room temperature also functions as an organic solvent for forming the nickel complex. In addition, even if it is a primary amine solid at normal temperature, there is no particular problem as long as it is liquid by heating at 100 ° C. or higher, or can be dissolved using an organic solvent.
１級アミンは、芳香族１級アミンであってもよいが、反応液におけるニッケル錯体形成の容易性の観点からは脂肪族１級アミンが好適である。脂肪族１級アミンは、例えばその炭素鎖の長さを調整することによって生成するナノ粒子の粒子径を制御することができ、特に平均粒子径が２０ｎｍ〜１００ｎｍの範囲内にあるナノ粒子を製造する場合において有利である。ナノ粒子の粒子径を制御する観点から、脂肪族１級アミンは、その炭素数が６〜２０程度のものから選択して用いることが好適である。炭素数が多いほど得られるナノ粒子の粒子径が小さくなる。このようなアミンとして、例えばオクチルアミン、ヘキサデシルアミン、ドデシルアミン、テトラデシルアミン、ステアリルアミン、オレイルアミン、ミリスチルアミン、ラウリルアミン等を挙げることができる。例えばオレイルアミンは、ナノ粒子生成過程に於ける温度条件下において液体状態として存在するため均一溶液で反応を効率的に進行できる。 The primary amine may be an aromatic primary amine, but an aliphatic primary amine is preferred from the viewpoint of easy nickel complex formation in the reaction solution. Aliphatic primary amines can control the particle size of the produced nanoparticles, for example, by adjusting the length of their carbon chains, and in particular produce nanoparticles with an average particle size in the range of 20 nm to 100 nm. This is advantageous. From the viewpoint of controlling the particle diameter of the nanoparticles, the aliphatic primary amine is preferably selected from those having about 6 to 20 carbon atoms. The larger the carbon number, the smaller the particle size of the resulting nanoparticles. Examples of such amines include octylamine, hexadecylamine, dodecylamine, tetradecylamine, stearylamine, oleylamine, myristylamine, laurylamine and the like. For example, oleylamine exists in a liquid state under the temperature conditions in the nanoparticle production process, so that the reaction can proceed efficiently in a homogeneous solution.
１級アミンは、ナノ粒子の生成時に表面修飾剤として機能するため、１級アミンの除去後においても二次凝集を抑制できる。また、１級アミンは、還元反応後に、生成したナノ粒子の固体成分と溶剤または未反応の１級アミン等を分離する洗浄工程における処理操作の容易性の観点からは室温で液体のものが好ましい。更に、１級アミンは、ニッケル錯体を還元して金属ニッケルナノ粒子を得るときの反応制御の容易性の観点からは還元温度より沸点が高いものが好ましい。すなわち、脂肪族１級アミンにおいては沸点が１８０℃以上のものが好ましく、２００℃以上のものがより好ましく、また、炭素数が９以上のものが好ましい。ここで、例えば炭素数が９である脂肪族アミン［Ｃ９Ｈ２１Ｎ(ノニルアミン)］の沸点は２０１℃である。１級アミンの量は、ニッケル１ｍｏｌに対して２ｍｏｌ以上用いることが好ましく、２．２ｍｏｌ以上用いることがより好ましく、４ｍｏｌ以上用いることが望ましい。Since the primary amine functions as a surface modifier during the production of the nanoparticles, secondary aggregation can be suppressed even after removal of the primary amine. The primary amine is preferably a liquid at room temperature from the viewpoint of ease of processing operation in the washing step for separating the solid component of the produced nanoparticles from the solvent or the unreacted primary amine after the reduction reaction. . Further, the primary amine preferably has a boiling point higher than the reduction temperature from the viewpoint of ease of reaction control when the nickel complex is reduced to obtain metallic nickel nanoparticles. That is, the aliphatic primary amine preferably has a boiling point of 180 ° C. or higher, more preferably 200 ° C. or higher, and preferably has 9 or more carbon atoms. Here, for example, the boiling point of aliphatic amine [C 9 H 21 N (nonylamine)] having 9 carbon atoms is 201 ° C. The amount of primary amine is preferably 2 mol or more, more preferably 2.2 mol or more, and more preferably 4 mol or more with respect to 1 mol of nickel.
（有機溶媒）
工程Ａでは、均一溶液での反応をより効率的に進行させるために、１級アミンとは別の有機溶媒を新たに添加してもよい。有機溶媒を用いる場合、有機溶媒をカルボン酸ニッケル及び１級アミンと同時に混合してもよいが、カルボン酸ニッケル及び１級アミンを先ず混合し錯形成した後に有機溶媒を加えると、１級アミンが効率的にニッケル原子に配位するので、より好ましい。使用できる有機溶媒としては、１級アミンとニッケルイオンとの錯形成を阻害しないものであれば、特に限定するものではなく、例えば炭素数４〜３０のエーテル系有機溶媒、炭素数７〜３０の飽和又は不飽和の炭化水素系有機溶媒、炭素数８〜１８のアルコール系有機溶媒等を使用することができる。また、マイクロ波照射による加熱条件下でも使用を可能とする観点から、使用する有機溶媒は、沸点が１７０℃以上のものを選択することが好ましく、より好ましくは２００〜３００℃の範囲内にあるものを選択することがよい。このような有機溶媒の具体例としては、例えばテトラエチレングリコール、ｎ−オクチルエーテル等が挙げられる。(Organic solvent)
In step A, an organic solvent different from the primary amine may be newly added in order to allow the reaction in the homogeneous solution to proceed more efficiently. When an organic solvent is used, the organic solvent may be mixed simultaneously with the nickel carboxylate and the primary amine. However, when the organic solvent is added after first mixing the nickel carboxylate and the primary amine to form a complex, It is more preferable because it efficiently coordinates to a nickel atom. The organic solvent that can be used is not particularly limited as long as it does not inhibit the complex formation between the primary amine and the nickel ion. For example, the organic solvent having 4 to 30 carbon atoms, 7 to 30 carbon atoms, and the like. A saturated or unsaturated hydrocarbon organic solvent, an alcohol organic solvent having 8 to 18 carbon atoms, or the like can be used. Moreover, from the viewpoint of enabling use even under heating conditions by microwave irradiation, it is preferable to select an organic solvent having a boiling point of 170 ° C. or higher, more preferably in the range of 200 to 300 ° C. It is better to choose one. Specific examples of such an organic solvent include tetraethylene glycol and n-octyl ether.
２価のニッケルイオンは配位子置換活性種として知られており、形成する錯体の配位子は温度、濃度によって容易に配位子交換により錯形成が変化する可能性がある。例えばカルボン酸ニッケルおよび１級アミンの混合物を熱処理して反応液を得る工程において、用いるアミンの炭素鎖長等の立体障害を考慮すると、例えば、図１に示すように、カルボン酸イオン（Ｒ１ＣＯＯ−、Ｒ２ＣＯＯ−）が二座配位(ａ)または単座配位(ｂ)いずれかで配位する可能性があり、さらにアミンの濃度が大過剰の場合は外圏にカルボン酸イオンが存在する(ｃ)の少なくとも３種の可能性がある。目的とする反応温度（還元温度）に於いて均一溶液とするには、図１(ａ)〜(ｃ)において、少なくともＡ、Ｂ、Ｃ、Ｄ、Ｅ、Ｆの配位子のうち少なくとも一箇所は１級アミンが配位している必要がある。A divalent nickel ion is known as a ligand-substituted active species, and the ligand of the complex to be formed may easily change in complex formation by ligand exchange depending on temperature and concentration. For example, in step of heat treating the mixture of nickel carboxylate and primary amine to obtain a reaction solution, considering the steric hindrance of the carbon chain length of the amine or the like used, for example, as shown in FIG. 1, a carboxylate ion (R 1 COO − , R 2 COO − ) may be coordinated by either bidentate coordination (a) or monodentate coordination (b), and when the amine concentration is in large excess, carboxylate ions in the outer sphere There are at least three possibilities of (c). In order to obtain a homogeneous solution at the target reaction temperature (reduction temperature), at least one of the ligands of at least A, B, C, D, E, and F in FIGS. The location needs to be coordinated by a primary amine.
この錯形成反応は室温に於いても進行することができるが、十分且つ、より効率の良い錯形成反応を行うために、１００℃〜１６５℃の範囲内の温度に加熱して反応を行う。この加熱は、カルボン酸ニッケルとして、例えばギ酸ニッケル２水和物や酢酸ニッケル４水和物のようなカルボン酸ニッケルの水和物を用いた場合に特に有利である。加熱温度は、好ましくは１００℃を超える温度とし、より好ましくは１０５℃以上の温度とすることで、カルボン酸ニッケルに配位した配位水と１級アミンとの配位子置換反応が効率よく行われ、錯体配位子としての水分子を解離させることができ、さらにその水を系外に出すことができるので効率よくアミンとの錯体を形成させることができる。例えば、ギ酸ニッケル２水和物は、室温では２個の配位水と２座配位子である２個のギ酸イオンが存在した錯体構造をとっているため、この２つの配位水と１級アミンの配位子置換により効率よく錯形成させるには、１００℃より高い温度で加熱することでこの錯体配位子としての水分子を解離させることが好ましい。また、カルボン酸ニッケルと１級アミンとの錯形成反応における熱処理は、後に続くニッケル錯体（又はニッケルイオン）のマイクロ波照射による加熱還元の過程と確実に分離し、前記の錯形成反応を完結させるという観点から、上記の上限温度以下とし、好ましくは１６０℃以下、より好ましくは１５０℃以下とすることがよい。 Although this complex formation reaction can proceed even at room temperature, the reaction is carried out by heating to a temperature in the range of 100 ° C. to 165 ° C. in order to perform a sufficient and more efficient complex formation reaction. This heating is particularly advantageous when nickel carboxylate hydrate such as nickel formate dihydrate or nickel acetate tetrahydrate is used as nickel carboxylate. The heating temperature is preferably a temperature exceeding 100 ° C., more preferably a temperature of 105 ° C. or more, so that the ligand substitution reaction between the coordinating water coordinated with nickel carboxylate and the primary amine is efficient. The water molecule as the complex ligand can be dissociated, and the water can be discharged out of the system, so that the complex with the amine can be efficiently formed. For example, nickel formate dihydrate has a complex structure in which two coordination waters and two formate ions as bidentate ligands exist at room temperature. In order to efficiently form a complex by substituting a ligand for a primary amine, it is preferable to dissociate the water molecule as the complex ligand by heating at a temperature higher than 100 ° C. In addition, the heat treatment in the complex formation reaction between nickel carboxylate and primary amine is surely separated from the subsequent heat reduction process by microwave irradiation of the nickel complex (or nickel ion) to complete the complex formation reaction. In view of the above, the temperature is set to the upper limit temperature or lower, preferably 160 ° C. or lower, more preferably 150 ° C. or lower.
加熱時間は、加熱温度や、各原料の含有量に応じて適宜決定することができるが、錯形成反応を完結させるという観点から、１０分以上とすることが好ましい。加熱時間の上限は特にないが、長時間熱処理することはエネルギー消費及び工程時間を節約する観点から無駄である。なお、この加熱の方法は、特に制限されず、例えばオイルバスなどの熱媒体による加熱であっても、マイクロ波照射による加熱であってもよい。 The heating time can be appropriately determined according to the heating temperature and the content of each raw material, but is preferably 10 minutes or more from the viewpoint of completing the complex formation reaction. There is no upper limit on the heating time, but heat treatment for a long time is useless from the viewpoint of saving energy consumption and process time. The heating method is not particularly limited, and may be heating by a heat medium such as an oil bath or heating by microwave irradiation.
カルボン酸ニッケルと１級アミンとの錯形成反応は、カルボン酸ニッケルと１級アミンとを有機溶媒中で混合して得られる溶液を加熱したときに、溶液の色の変化によって確認することができる。また、この錯形成反応は、例えば紫外・可視吸収スペクトル測定装置を用いて、３００ｎｍ〜７５０ｎｍの波長領域において観測される吸収スペクトルの吸収極大の波長を測定し、原料の極大吸収波長（例えばギ酸ニッケル２水和物ではその極大吸収波長は７１０ｎｍであり、酢酸ニッケル４水和物ではその極大吸収波長は７１０ｎｍである。）に対する錯化反応液のシフト（極大吸収波長が６００ｎｍにシフト）を観測することによって確認することができる。 The complex formation reaction between nickel carboxylate and primary amine can be confirmed by a change in the color of the solution when a solution obtained by mixing nickel carboxylate and primary amine in an organic solvent is heated. . In addition, this complex formation reaction is carried out by measuring the absorption maximum wavelength of the absorption spectrum observed in the wavelength region of 300 nm to 750 nm using, for example, an ultraviolet / visible absorption spectrum measuring apparatus, and measuring the maximum absorption wavelength of the raw material (for example, nickel formate). In dihydrate, the maximum absorption wavelength is 710 nm, and in nickel acetate tetrahydrate, the maximum absorption wavelength is 710 nm.) The shift of the complexing reaction solution (the maximum absorption wavelength shifts to 600 nm) is observed. Can be confirmed.
カルボン酸ニッケルと１級アミンとの錯形成が行われた後、得られる反応液を、次に説明するように、マイクロ波照射によって加熱することにより、ニッケル錯体のニッケルイオンが還元され、ニッケルイオンに配位しているカルボン酸イオンが同時に分解し、最終的に酸化数が０価のニッケルを含有する金属ニッケルナノ粒子が生成する。一般にカルボン酸ニッケルは水を溶媒とする以外の条件では難溶性であり、マイクロ波照射による加熱還元反応の前段階として、カルボン酸ニッケルを含む溶液は均一反応溶液とする必要がある。これに対して、本実施の形態で使用される１級アミンは、使用温度条件で液体であり、かつそれがニッケルイオンに配位することで液化し、均一反応溶液を形成すると考えられる。 After the complex formation between nickel carboxylate and primary amine is performed, the resulting reaction solution is heated by microwave irradiation to reduce the nickel ions of the nickel complex as described below. At the same time, the carboxylate ions coordinated to the metal are decomposed, and finally metal nickel nanoparticles containing nickel having an oxidation number of 0 are generated. In general, nickel carboxylate is hardly soluble under conditions other than using water as a solvent, and a solution containing nickel carboxylate needs to be a homogeneous reaction solution as a pre-stage of the heat reduction reaction by microwave irradiation. On the other hand, the primary amine used in the present embodiment is liquid under the operating temperature conditions, and is considered to be liquefied by coordination with nickel ions to form a homogeneous reaction solution.
＜工程Ｂ；ナノ粒子スラリー生成工程＞
本工程では、カルボン酸ニッケルと１級アミンとの錯形成反応によって得られた錯化反応液を、マイクロ波照射によって１７０℃以上の温度に加熱し、錯化反応液中のニッケルイオンを還元して金属ニッケルナノ粒子スラリーを得る。マイクロ波照射によって加熱する温度は、得られるナノ粒子の形状のばらつきを抑制するという観点から、好ましくは１８０℃以上、より好ましくは２００℃以上とすることがよい。加熱温度の上限は特にないが、処理を能率的に行う観点からは例えば２７０℃以下とすることが好適である。なお、マイクロ波の使用波長は、特に限定するものではなく、例えば２．４５ＧＨｚである。加熱温度は、例えばカルボン酸ニッケルの種類や金属ニッケルナノ粒子の核発生を促進させる添加剤の使用などによって、適宜調整することができる。<Process B; Nanoparticle slurry production process>
In this step, the complexing reaction solution obtained by the complexation reaction between nickel carboxylate and primary amine is heated to a temperature of 170 ° C. or higher by microwave irradiation to reduce nickel ions in the complexing reaction solution. To obtain a metal nickel nanoparticle slurry. The temperature for heating by microwave irradiation is preferably 180 ° C. or higher, more preferably 200 ° C. or higher, from the viewpoint of suppressing variation in the shape of the obtained nanoparticles. The upper limit of the heating temperature is not particularly limited, but is preferably set to 270 ° C. or less, for example, from the viewpoint of efficiently performing the treatment. In addition, the use wavelength of a microwave is not specifically limited, For example, it is 2.45 GHz. The heating temperature can be appropriately adjusted depending on, for example, the type of nickel carboxylate or the use of an additive that promotes the nucleation of metallic nickel nanoparticles.
本工程では、マイクロ波が反応液内に浸透するため、均一加熱が行われ、かつ、エネルギーを媒体に直接与えることができるため、急速加熱を行うことができる。これにより、反応液全体を所望の温度に均一にすることができ、ニッケル錯体（又はニッケルイオン）の還元、核生成、核成長各々の過程を溶液全体において同時に生じさせ、結果として粒子径分布の狭い単分散な粒子を短時間で容易に製造することができる。 In this step, since microwaves penetrate into the reaction solution, uniform heating is performed, and energy can be directly applied to the medium, so that rapid heating can be performed. As a result, the entire reaction solution can be made uniform at a desired temperature, and the processes of reduction, nucleation, and nucleation of the nickel complex (or nickel ions) occur simultaneously in the entire solution. Narrow monodisperse particles can be easily produced in a short time.
均一な粒子径を有するナノ粒子を生成させるには、工程Ａの錯化反応液生成工程（ニッケル錯体の生成が行われる工程）でニッケル錯体を均一にかつ十分に生成させることと、本工程Ｂのマイクロ波照射によって加熱する工程で、ニッケル錯体（又はニッケルイオン）の還元により生成するニッケル(０価)の核の同時発生・成長を行う必要がある。すなわち、錯化反応液生成工程の加熱温度を上記の特定の範囲内で調整し、ナノ粒子スラリー生成工程におけるマイクロ波による加熱温度よりも確実に低くしておくことで、粒子径・形状の整った粒子が生成し易い。例えば、錯化反応液生成工程で加熱温度が高すぎるとニッケル錯体の生成とニッケル(０価)への還元反応が同時に進行することで、ナノ粒子スラリー生成工程での粒子形状の整った粒子の生成が困難となるおそれがある。また、ナノ粒子スラリー生成工程の加熱温度が低すぎるとニッケル(０価)への還元反応速度が遅くなり核の発生が少なくなるため粒子が大きくなるだけでなく、ナノ粒子の収率の点からも好ましくはない。 In order to produce nanoparticles having a uniform particle size, a nickel complex is uniformly and sufficiently produced in the complexation reaction liquid production step (step in which nickel complex is produced) of step A, and this step B In the step of heating by microwave irradiation, it is necessary to simultaneously generate and grow nickel (zero-valent) nuclei generated by reduction of the nickel complex (or nickel ion). In other words, by adjusting the heating temperature in the complexing reaction liquid generation step within the above specific range and ensuring that it is lower than the heating temperature by the microwave in the nanoparticle slurry generation step, the particle size and shape are adjusted. Particles are easily generated. For example, if the heating temperature is too high in the complexing reaction liquid production process, the formation of nickel complex and the reduction reaction to nickel (zero valence) proceed simultaneously, so that the particles with a uniform particle shape in the nanoparticle slurry production process Generation may be difficult. In addition, if the heating temperature in the nanoparticle slurry generation step is too low, the reduction reaction rate to nickel (zero valence) is slowed and the generation of nuclei is reduced, so that not only the particles are enlarged, but also from the viewpoint of the yield of nanoparticles. Is also not preferred.
マイクロ波照射によって加熱して得られる金属ニッケルナノ粒子スラリーを、例えば、静置分離し、上澄み液を取り除いた後、適当な溶媒を用いて洗浄し、乾燥することで、ニッケルナノ粒子が得られる。ナノ粒子スラリー生成工程においては、必要に応じ、前述した有機溶媒を加えてもよい。なお、前記したように、錯形成反応に使用する１級アミンを有機溶媒としてそのまま用いることが好ましい。 The nickel metal nanoparticles slurry obtained by heating by microwave irradiation is, for example, statically separated, and after removing the supernatant, washed with an appropriate solvent and dried to obtain nickel nanoparticles. . In the nanoparticle slurry generation step, the organic solvent described above may be added as necessary. As described above, the primary amine used for the complex formation reaction is preferably used as it is as the organic solvent.
以上のようにして、表面に水酸基を有する平均粒子径１５０ｎｍ以下のニッケルナノ粒子を調製することができる。なお、ニッケルナノ粒子に限らず、他の金属ナノ粒子を製造する場合も、上記方法に準じて行うことができる。 As described above, nickel nanoparticles having a hydroxyl group on the surface and an average particle diameter of 150 nm or less can be prepared. Note that not only nickel nanoparticles but also other metal nanoparticles can be produced according to the above method.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例によって何ら限定されるものではない。なお、以下の実施例において、特にことわりのない限り各種測定、評価は下記によるものである。 EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the following examples, various measurements and evaluations are as follows unless otherwise specified.
［平均粒子径の測定］
平均粒子径の測定は、ＳＥＭ（走査電子顕微鏡）により試料の写真を撮影して、その中から無作為に２００個を抽出してそれぞれの粒子径を求め、平均粒子径を算出した。[Measurement of average particle size]
The average particle size was measured by taking a photograph of the sample with an SEM (scanning electron microscope), randomly extracting 200 samples from the sample, obtaining each particle size, and calculating the average particle size.
［分散性の評価］
分散性の評価は、レーザ回折／散乱式粒子径分布測定装置（株式会社堀場製作所製、商品名；ＬＡ−９５０Ｖ２）を用いて行った。金属ナノ粒子をイソプロパノールに分散させたスラリー溶液（固形分濃度１０ｗｔ％）を所定の濃度に希釈して、前記粒子径分布測定装置内にて超音波で５分間分散させ、体積分布の測定を行い、粒度分布の結果にて分散性の比較評価を行った。[Evaluation of dispersibility]
Evaluation of dispersibility was performed using a laser diffraction / scattering particle size distribution measuring apparatus (manufactured by Horiba, Ltd., trade name: LA-950V2). A slurry solution (
（合成例１）
１２５．９ｇのラウリルアミンに１８．５ｇのギ酸ニッケル二水和物を加え、窒素フロー下、１２０℃で１０分間加熱することによって、ギ酸ニッケルを溶解させて錯化反応液を得た。次いで、その錯化反応液に、さらに８３．９ｇのラウリルアミンを加え、マイクロ波を用いて１８０℃で１０分間加熱することによって、ニッケルナノ粒子スラリーを得た。(Synthesis Example 1)
18.5 g of nickel formate dihydrate was added to 125.9 g of laurylamine and heated at 120 ° C. for 10 minutes under a nitrogen flow to dissolve nickel formate to obtain a complexing reaction solution. Next, 83.9 g of laurylamine was further added to the complexing reaction solution, and the mixture was heated at 180 ° C. for 10 minutes using a microwave to obtain a nickel nanoparticle slurry.
ニッケルナノ粒子スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いて洗浄し、更にイソプロパノールを用いて洗浄した後、６０℃に維持される真空乾燥機で６時間乾燥することによって、ニッケルナノ粒子を得た。このようにして得られたニッケルナノ粒子の平均粒子径は１００ｎｍであった。このニッケルナノ粒子は、元素分析の結果、Ｃ；０．９、Ｎ；＜０．１、Ｏ；１．４（単位は質量％）であった。 By separating the nickel nanoparticle slurry by static separation, removing the supernatant, washing with toluene, further washing with isopropanol, and drying in a vacuum dryer maintained at 60 ° C. for 6 hours, Nickel nanoparticles were obtained. The average particle diameter of the nickel nanoparticles thus obtained was 100 nm. As a result of elemental analysis, the nickel nanoparticles were C; 0.9, N; <0.1, O; 1.4 (unit: mass%).
（参考例１）
合成例１で得られたニッケルナノ粒子スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いて洗浄し、更にイソプロパノールを用いて洗浄した後、高圧ホモジナイザー（株式会社スギノマシン製、商品名；スターバースト）を用いて、圧力２００ＭＰａの条件にてニッケルナノ粒子を分散させたスラリー溶液１（固形分濃度１０ｗｔ％）を調製した。このスラリー溶液１の粒度分布の測定を行った。結果を表１に示す。(Reference Example 1)
The nickel nanoparticle slurry obtained in Synthesis Example 1 was allowed to stand and separated, the supernatant was removed, washed with toluene, further washed with isopropanol, and then a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., product) Name: Starburst) was used to prepare slurry solution 1 (
（実施例１−１）
参考例１で調製したスラリー溶液１の１０ｇを分取し、これにジ−ｐ−トルオイル−Ｌ−酒石酸の０．２ｇを加え、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表１に示す。(Example 1-1)
10 g of the slurry solution 1 prepared in Reference Example 1 was collected, 0.2 g of di-p-toluoyl-L-tartaric acid was added thereto, and the mixture was stirred for 15 minutes, then washed with isopropanol, and the particle size distribution was measured. went. The results are shown in Table 1.
（実施例１−２）
参考例１で調製したスラリー溶液１の１０ｇを分取し、これにジベンゾイル−Ｄ−酒石酸の０．２ｇを添加し、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表１に示す。(Example 1-2)
10 g of the slurry solution 1 prepared in Reference Example 1 was collected, 0.2 g of dibenzoyl-D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. The results are shown in Table 1.
（実施例１−３）
参考例１で調製したスラリー溶液１の１０ｇを分取し、これにジ−ｐ−アニソイル−Ｄ−酒石酸の０．２ｇを添加し、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表１に示す。(Example 1-3)
10 g of the slurry solution 1 prepared in Reference Example 1 was collected, 0.2 g of di-p-anisoyl-D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and particle size distribution measurement Went. The results are shown in Table 1.
（比較例１−１）
参考例１で調製したスラリー溶液１の１０ｇを分取し、これにＤ−酒石酸の０．２ｇを添加し、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表１に示す。(Comparative Example 1-1)
10 g of the slurry solution 1 prepared in Reference Example 1 was collected, 0.2 g of D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. The results are shown in Table 1.
（比較例１−２）
参考例１で調製したスラリー溶液１の１０ｇを分取し、これにジアセチル−Ｌ−酒石酸の０．２ｇを添加し、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表１に示す。(Comparative Example 1-2)
10 g of the slurry solution 1 prepared in Reference Example 1 was fractionated, 0.2 g of diacetyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. The results are shown in Table 1.
以上の結果をまとめて表１に示す。 The above results are summarized in Table 1.
（参考例２）
合成例１で得られたニッケルナノ粒子スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いて洗浄し、更にイソプロパノールを用いて洗浄した後、高圧ホモジナイザー（株式会社スギノマシン製、商品名；スターバースト）を用いて、圧力１００ＭＰａの条件にてニッケルナノ粒子を分散させたスラリー溶液２（固形分濃度１０ｗｔ％）を調製した。このスラリー溶液２の粒度分布の測定を行った。結果を表２に示す。(Reference Example 2)
The nickel nanoparticle slurry obtained in Synthesis Example 1 was allowed to stand and separated, the supernatant was removed, washed with toluene, further washed with isopropanol, and then a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., product) Name: Starburst) was used to prepare slurry solution 2 (solid content concentration: 10 wt%) in which nickel nanoparticles were dispersed under a pressure of 100 MPa. The particle size distribution of the slurry solution 2 was measured. The results are shown in Table 2.
（実施例２−１）
参考例２で調製したスラリー溶液２の１０ｇを分取し、これにジ−ｐ−トルオイル−Ｌ−酒石酸の０．２ｇを加え、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表２に示す。(Example 2-1)
10 g of the slurry solution 2 prepared in Reference Example 2 was collected, 0.2 g of di-p-toluoyl-L-tartaric acid was added thereto, and the mixture was stirred for 15 minutes, then washed with isopropanol, and the particle size distribution was measured. went. The results are shown in Table 2.
（実施例２−２）
参考例２で調製したスラリー溶液２の１０ｇを分取し、これにジ−ｐ−トルオイル−Ｄ−酒石酸の０．２ｇを加え、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表２に示す。(Example 2-2)
10 g of the slurry solution 2 prepared in Reference Example 2 was collected, 0.2 g of di-p-toluoyl-D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. went. The results are shown in Table 2.
（実施例２−３）
参考例２で調製したスラリー溶液２の１０ｇを分取し、これにジベンゾイル−Ｌ−酒石酸の０．２ｇを加え、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表２に示す。(Example 2-3)
10 g of the slurry solution 2 prepared in Reference Example 2 was collected, 0.2 g of dibenzoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. The results are shown in Table 2.
（実施例２−４）
参考例２で調製したスラリー溶液２の１０ｇを分取し、これにジ−ｐ−アニソイル−Ｌ−酒石酸の０．２ｇを加え、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表２に示す。(Example 2-4)
10 g of the slurry solution 2 prepared in Reference Example 2 was collected, 0.2 g of di-p-anisoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. went. The results are shown in Table 2.
以上の結果をまとめて表２に示す。 The above results are summarized in Table 2.
（参考例３）
合成例１で得られたニッケルナノ粒子スラリーを静置分離し、上澄み液を取り除いた後、トルエンを用いて洗浄し、更にイソプロパノールを用いて洗浄した後、高圧ホモジナイザー（株式会社スギノマシン製、商品名；スターバースト）を用いて、圧力１５０ＭＰａの条件にてニッケルナノ粒子を分散させたスラリー溶液３（固形分濃度１０ｗｔ％）を調製した。このスラリー溶液３の粒度分布の測定を行った。結果を表３に示す。(Reference Example 3)
The nickel nanoparticle slurry obtained in Synthesis Example 1 was allowed to stand and separated, the supernatant was removed, washed with toluene, further washed with isopropanol, and then a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., product) Name: Starburst) was used to prepare slurry solution 3 (solid content concentration: 10 wt%) in which nickel nanoparticles were dispersed under a pressure of 150 MPa. The particle size distribution of the slurry solution 3 was measured. The results are shown in Table 3.
（実施例３−１）
参考例３で調製したスラリー溶液３の１０ｇを分取し、これにジ−ｐ−トルオイル−Ｌ−酒石酸の０．２ｇを加え、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表３に示す。(Example 3-1)
10 g of the slurry solution 3 prepared in Reference Example 3 was taken, 0.2 g of di-p-toluoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. went. The results are shown in Table 3.
（実施例３−２）
参考例３で調製したスラリー溶液３の１０ｇを分取し、これにジ−ｐ−トルオイル−Ｄ−酒石酸の０．２ｇを添加し、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表３に示す。(Example 3-2)
10 g of the slurry solution 3 prepared in Reference Example 3 was collected, 0.2 g of di-p-toluoyl-D-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and particle size distribution measurement Went. The results are shown in Table 3.
（実施例３−３）
参考例３で調製したスラリー溶液３の１０ｇを分取し、これにジ−ｏ−トルオイル−Ｌ−酒石酸の０．２ｇを添加し、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表３に示す。(Example 3-3)
10 g of the slurry solution 3 prepared in Reference Example 3 was collected, 0.2 g of di-o-toluoyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and measurement of particle size distribution Went. The results are shown in Table 3.
（比較例３−１）
参考例３で調製したスラリー溶液３の１０ｇを分取し、これにジピバロイル−Ｌ−酒石酸の０．２ｇを添加し、１５分間撹拌した後、イソプロパノールで洗浄し、粒度分布の測定を行った。結果を表３に示す。(Comparative Example 3-1)
10 g of the slurry solution 3 prepared in Reference Example 3 was fractionated, 0.2 g of dipivaloyl-L-tartaric acid was added thereto, stirred for 15 minutes, washed with isopropanol, and the particle size distribution was measured. The results are shown in Table 3.
以上の結果をまとめて表３に示す。 The above results are summarized in Table 3.
平均粒子径１００ｎｍのニッケルナノ粒子を用いて評価した結果、表１〜３に示したように、実施例１−１〜１−３、２−１〜２−４、３−１〜３−３では、体積分布Ｄ５０［メジアン径；小粒子径側からの積算粒度分布（体積基準）が５０％となる粒子径］が十分に小さいのに対し、比較例ではＤ５０が大きく、凝集体が多く存在し、分散性が低いことが判明した。また、粗大凝集粒子の目安となる体積分布Ｄ９０［小粒子径側からの積算粒度分布（体積基準）が９０％となる粒子径］、Ｄ９９［同９９％となる粒子径］についても、実施例は比較例に比べて格段に小さく、凝集粒子が少なく、粒子径分布がシャープで、分散性が良好なことが確認された。 As a result of evaluating using nickel nanoparticles having an average particle diameter of 100 nm, as shown in Tables 1 to 3, Examples 1-1 to 1-3, 2-1 to 2-4, and 3-1 to 3-3 were used. The volume distribution D50 [median diameter; the particle diameter at which the cumulative particle size distribution (volume basis) from the small particle diameter side becomes 50%] is sufficiently small, whereas in the comparative example, D50 is large and there are many aggregates. It was found that the dispersibility was low. Further, examples of the volume distribution D90 [particle diameter at which the cumulative particle size distribution (volume basis) from the small particle diameter side becomes 90%] and D99 [particle diameter at 99% from the small particle diameter side], which are rough coarse aggregated particles, are given as examples As compared with the comparative example, it was confirmed that the particle size was extremely small, the aggregated particles were few, the particle size distribution was sharp, and the dispersibility was good.
以上、本発明の実施の形態を例示の目的で詳細に説明したが、本発明は上記実施の形態に制約されることはない。
As mentioned above, although embodiment of this invention was described in detail for the purpose of illustration, this invention is not restrict | limited to the said embodiment.
Claims (11)
で表される酒石酸誘導体からなり、金属ナノ粒子の分散に用いられるものである分散剤。 The following general formula (I):
In Ri Do tartrate derivative represented, dispersing agent and is used in the dispersion of the metal nanoparticles.
下記の一般式（Ｉ）：
で表される酒石酸誘導体からなる分散剤と、
を含有し、
前記置換されていてもよいフェニル基が、フェニル基、アルキル基で置換されていてもよいフェニル基、又は、アルコキシ基で置換されていてもよいフェニル基である分散性金属ナノ粒子組成物。 Metal nanoparticles,
The following general formula (I):
A dispersant comprising a tartaric acid derivative represented by:
Containing
The dispersible metal nanoparticle composition, wherein the phenyl group which may be substituted is a phenyl group which may be substituted with a phenyl group, an alkyl group, or a phenyl group which may be substituted with an alkoxy group.
下記の一般式（Ｉ）：
で表される酒石酸誘導体からなる分散剤と、
を含有し、
前記置換されていてもよいフェニル基が、フェニル基、トリル基、又は、アニソイル基である分散性金属ナノ粒子組成物。 Metal nanoparticles,
The following general formula (I):
A dispersant comprising a tartaric acid derivative represented by:
Containing
The dispersible metal nanoparticle composition, wherein the optionally substituted phenyl group is a phenyl group, a tolyl group, or an anisoyl group.
下記の一般式（Ｉ）：
で表される酒石酸誘導体からなる分散剤と、
を含有し、
上記一般式（Ｉ）で表される酒石酸誘導体が、ジベンゾイル−Ｄ−酒石酸、ジベンゾイル−Ｌ−酒石酸、ジ−ｐ−トルオイル−Ｌ−酒石酸、ジ−ｐ−トルオイル−Ｄ−酒石酸、ジ−ｏ−４−トルオイル−Ｌ−酒石酸、ジ−ｏ−４−トルオイル−Ｄ−酒石酸、ジ−ｍ−４−トルオイル−Ｌ−酒石酸、ジ−ｍ−４−トルオイル−Ｄ−酒石酸、ジ−ｐ−アニソイル−Ｌ−酒石酸、ジ−ｐ−アニソイル−Ｄ−酒石酸、ジ−ｏ−アニソイル−Ｌ−酒石酸、ジ−ｏ−アニソイル−Ｄ−酒石酸、ジ−ｍ−アニソイル−Ｌ−酒石酸、及びジ−ｍ−アニソイル−Ｄ−酒石酸よりなる群から選択される少なくとも１種である分散性金属ナノ粒子組成物。 Metal nanoparticles,
The following general formula (I):
A dispersant comprising a tartaric acid derivative represented by:
Containing
The tartaric acid derivative represented by the above general formula (I) is dibenzoyl-D-tartaric acid, dibenzoyl-L-tartaric acid, di-p-toluoyl-L-tartaric acid, di-p-toluoyl-D-tartaric acid, di-o- 4-toluoyl-L-tartaric acid, di-o-4-toluoyl-D-tartaric acid, di-m-4-toluoyl-L-tartaric acid, di-m-4-toluoyl-D-tartaric acid, di-p-anisoyl- L-tartaric acid, di-p-anisoyl-D-tartaric acid, di-o-anisoyl-L-tartaric acid, di-o-anisoyl-D-tartaric acid, di-m-anisoyl-L-tartaric acid, and di-m-anisoyl A dispersible metal nanoparticle composition that is at least one selected from the group consisting of -D-tartaric acid.
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| JP2011184836 | 2011-08-26 | ||
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| PCT/JP2012/071395 WO2013031670A1 (en) | 2011-08-26 | 2012-08-24 | Dispersant, and dispersible metal nanoparticle composition |
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| JP6126426B2 (en) * | 2013-03-28 | 2017-05-10 | 新日鉄住金化学株式会社 | Joining method |
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| FR2850301B1 (en) * | 2003-01-23 | 2007-10-19 | Commissariat Energie Atomique | ORGANIC-INORGANIC HYBRID MATERIAL COMPRISING A MESOPOROUS MINERAL PHASE AND AN ORGANIC PHASE, MEMBRANE AND FUEL CELL |
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