JP2022069342A - Method for surrounding fine crystal of metallic compound precipitating metal or metallic oxide by thermal decomposition with liquid organic compound, surrounding nanoparticle of metal or metallic oxide with liquid organic compound so as to be precipitated, and precipitating nanoparticle of metal or metallic oxide without flocculation - Google Patents
Method for surrounding fine crystal of metallic compound precipitating metal or metallic oxide by thermal decomposition with liquid organic compound, surrounding nanoparticle of metal or metallic oxide with liquid organic compound so as to be precipitated, and precipitating nanoparticle of metal or metallic oxide without flocculation Download PDFInfo
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- JP2022069342A JP2022069342A JP2020178481A JP2020178481A JP2022069342A JP 2022069342 A JP2022069342 A JP 2022069342A JP 2020178481 A JP2020178481 A JP 2020178481A JP 2020178481 A JP2020178481 A JP 2020178481A JP 2022069342 A JP2022069342 A JP 2022069342A
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- Prior art keywords
- metal
- compound
- suspension
- organic compound
- liquid organic
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- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 203
- 239000002184 metal Substances 0.000 title claims abstract description 196
- 238000005979 thermal decomposition reaction Methods 0.000 title claims abstract description 186
- 239000013078 crystal Substances 0.000 title claims abstract description 177
- 239000007788 liquid Substances 0.000 title claims abstract description 153
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 132
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 89
- 230000001376 precipitating effect Effects 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims description 56
- 229910000765 intermetallic Inorganic materials 0.000 title abstract 4
- 230000016615 flocculation Effects 0.000 title 1
- 238000005189 flocculation Methods 0.000 title 1
- 229910052751 metal Inorganic materials 0.000 claims abstract description 193
- 239000000725 suspension Substances 0.000 claims abstract description 183
- 238000004519 manufacturing process Methods 0.000 claims abstract description 37
- 238000011282 treatment Methods 0.000 claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 240
- 150000002736 metal compounds Chemical class 0.000 claims description 228
- -1 metal complex ion Chemical class 0.000 claims description 226
- 238000009835 boiling Methods 0.000 claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 82
- 150000004706 metal oxides Chemical class 0.000 claims description 80
- 239000002244 precipitate Substances 0.000 claims description 72
- 239000000126 substance Substances 0.000 claims description 59
- 238000010521 absorption reaction Methods 0.000 claims description 49
- 239000010419 fine particle Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 150000004671 saturated fatty acids Chemical class 0.000 claims description 34
- 230000008018 melting Effects 0.000 claims description 33
- 238000002844 melting Methods 0.000 claims description 33
- 239000003446 ligand Substances 0.000 claims description 31
- 229910021645 metal ion Inorganic materials 0.000 claims description 31
- 150000002500 ions Chemical class 0.000 claims description 29
- 230000008569 process Effects 0.000 claims description 29
- 239000012298 atmosphere Substances 0.000 claims description 28
- 230000001133 acceleration Effects 0.000 claims description 22
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 20
- 239000006185 dispersion Substances 0.000 claims description 19
- 235000003441 saturated fatty acids Nutrition 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 230000035939 shock Effects 0.000 claims description 10
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 10
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 7
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 22
- 239000012535 impurity Substances 0.000 abstract description 6
- 239000010949 copper Substances 0.000 description 61
- 229910052802 copper Inorganic materials 0.000 description 50
- 230000001965 increasing effect Effects 0.000 description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 35
- 229910052709 silver Inorganic materials 0.000 description 34
- 239000004332 silver Substances 0.000 description 34
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 31
- 238000001704 evaporation Methods 0.000 description 30
- 230000008020 evaporation Effects 0.000 description 30
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 28
- 230000008859 change Effects 0.000 description 27
- 239000002082 metal nanoparticle Substances 0.000 description 26
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 23
- 238000013459 approach Methods 0.000 description 23
- 229910001431 copper ion Inorganic materials 0.000 description 22
- 239000010936 titanium Substances 0.000 description 22
- 239000005749 Copper compound Substances 0.000 description 21
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- 230000008016 vaporization Effects 0.000 description 20
- 150000001880 copper compounds Chemical class 0.000 description 19
- 238000009834 vaporization Methods 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 18
- NDKYEUQMPZIGFN-UHFFFAOYSA-N Butyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCC NDKYEUQMPZIGFN-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 15
- 229910052719 titanium Inorganic materials 0.000 description 15
- GXROCGVLAIXUAF-UHFFFAOYSA-N copper octan-1-ol Chemical compound [Cu].CCCCCCCCO GXROCGVLAIXUAF-UHFFFAOYSA-N 0.000 description 14
- YYZUSRORWSJGET-UHFFFAOYSA-N ethyl octanoate Chemical compound CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 14
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 14
- CMBYOWLFQAFZCP-UHFFFAOYSA-N Hexyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCCCCCC CMBYOWLFQAFZCP-UHFFFAOYSA-N 0.000 description 13
- 229940100463 hexyl laurate Drugs 0.000 description 13
- WYKQDEPZMVTTSJ-UHFFFAOYSA-J titanium(4+);tetrabenzoate Chemical compound [Ti+4].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 WYKQDEPZMVTTSJ-UHFFFAOYSA-J 0.000 description 12
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 150000003609 titanium compounds Chemical class 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- 239000002253 acid Substances 0.000 description 10
- YRHYCMZPEVDGFQ-UHFFFAOYSA-N methyl decanoate Chemical compound CCCCCCCCCC(=O)OC YRHYCMZPEVDGFQ-UHFFFAOYSA-N 0.000 description 10
- JGHZJRVDZXSNKQ-UHFFFAOYSA-N methyl octanoate Chemical compound CCCCCCCC(=O)OC JGHZJRVDZXSNKQ-UHFFFAOYSA-N 0.000 description 10
- 229940100890 silver compound Drugs 0.000 description 10
- 150000003379 silver compounds Chemical class 0.000 description 10
- LWLRMRFJCCMNML-UHFFFAOYSA-N 2-ethylhexyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OCC(CC)CCCC LWLRMRFJCCMNML-UHFFFAOYSA-N 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 9
- YWWVWXASSLXJHU-AATRIKPKSA-N Myristoleic acid Natural products CCCC\C=C\CCCCCCCC(O)=O YWWVWXASSLXJHU-AATRIKPKSA-N 0.000 description 9
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical group [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- WCGIIHOFOFCKSM-UHFFFAOYSA-N Isopropyl octanoate Chemical compound CCCCCCCC(=O)OC(C)C WCGIIHOFOFCKSM-UHFFFAOYSA-N 0.000 description 8
- DJNTZVRUYMHBTD-UHFFFAOYSA-N Octyl octanoate Chemical compound CCCCCCCCOC(=O)CCCCCCC DJNTZVRUYMHBTD-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 8
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 8
- RGXWDWUGBIJHDO-UHFFFAOYSA-N ethyl decanoate Chemical compound CCCCCCCCCC(=O)OCC RGXWDWUGBIJHDO-UHFFFAOYSA-N 0.000 description 8
- MMKRHZKQPFCLLS-UHFFFAOYSA-N ethyl myristate Chemical compound CCCCCCCCCCCCCC(=O)OCC MMKRHZKQPFCLLS-UHFFFAOYSA-N 0.000 description 8
- BYEVBITUADOIGY-UHFFFAOYSA-N ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCC BYEVBITUADOIGY-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- IJXHLVMUNBOGRR-UHFFFAOYSA-N methyl nonanoate Chemical compound CCCCCCCCC(=O)OC IJXHLVMUNBOGRR-UHFFFAOYSA-N 0.000 description 8
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 8
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 8
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 7
- 239000003317 industrial substance Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 150000007524 organic acids Chemical class 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 6
- 150000001242 acetic acid derivatives Chemical class 0.000 description 6
- 150000004699 copper complex Chemical class 0.000 description 6
- 229960004643 cupric oxide Drugs 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 150000002344 gold compounds Chemical class 0.000 description 6
- 229960002446 octanoic acid Drugs 0.000 description 6
- YWWVWXASSLXJHU-UHFFFAOYSA-N 9E-tetradecenoic acid Natural products CCCCC=CCCCCCCCC(O)=O YWWVWXASSLXJHU-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 5
- 239000005640 Methyl decanoate Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 235000020778 linoleic acid Nutrition 0.000 description 5
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000005968 1-Decanol Substances 0.000 description 4
- HIQIXEFWDLTDED-UHFFFAOYSA-N 4-hydroxy-1-piperidin-4-ylpyrrolidin-2-one Chemical compound O=C1CC(O)CN1C1CCNCC1 HIQIXEFWDLTDED-UHFFFAOYSA-N 0.000 description 4
- YPQSPODHFDGVAC-UHFFFAOYSA-N Butyl heptanoate Chemical compound CCCCCCC(=O)OCCCC YPQSPODHFDGVAC-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000005639 Lauric acid Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000004696 coordination complex Chemical class 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 229910001410 inorganic ion Inorganic materials 0.000 description 4
- 229940094933 n-dodecane Drugs 0.000 description 4
- 150000002886 octanoic acid esters Chemical class 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910001111 Fine metal Inorganic materials 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 229940112669 cuprous oxide Drugs 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 229940070765 laurate Drugs 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000003378 silver Chemical group 0.000 description 3
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- 239000005641 Methyl octanoate Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000002027 dodecanoic acid esters Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000003951 lactams Chemical class 0.000 description 2
- HLQKKXPTQUDRCG-UHFFFAOYSA-J octanoate titanium(4+) Chemical compound [Ti+4].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O HLQKKXPTQUDRCG-UHFFFAOYSA-J 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- DUXYWXYOBMKGIN-UHFFFAOYSA-N trimyristin Chemical compound CCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCC DUXYWXYOBMKGIN-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- SZZYLYUVTJLJQM-UHFFFAOYSA-J Cl[Cu](Cl)(Cl)Cl Chemical compound Cl[Cu](Cl)(Cl)Cl SZZYLYUVTJLJQM-UHFFFAOYSA-J 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical group N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910018331 Mn(C7H15COO)2 Inorganic materials 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000012327 Ruthenium complex Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- VPONMBLTGNYMND-UHFFFAOYSA-N azane copper(1+) Chemical compound N.N.N.N.[Cu+] VPONMBLTGNYMND-UHFFFAOYSA-N 0.000 description 1
- WIEZTXFTOIBIOC-UHFFFAOYSA-L azane;dichloropalladium Chemical group N.N.Cl[Pd]Cl WIEZTXFTOIBIOC-UHFFFAOYSA-L 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- QKSIFUGZHOUETI-UHFFFAOYSA-N copper;azane Chemical compound N.N.N.N.[Cu+2] QKSIFUGZHOUETI-UHFFFAOYSA-N 0.000 description 1
- JDPSPYBMORZJOD-UHFFFAOYSA-L copper;dodecanoate Chemical compound [Cu+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O JDPSPYBMORZJOD-UHFFFAOYSA-L 0.000 description 1
- 150000001954 decanoic acid esters Chemical class 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- VAROLYSFQDGFMV-UHFFFAOYSA-K di(octanoyloxy)alumanyl octanoate Chemical compound [Al+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VAROLYSFQDGFMV-UHFFFAOYSA-K 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical class CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- SGLXWMAOOWXVAM-UHFFFAOYSA-L manganese(2+);octanoate Chemical compound [Mn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O SGLXWMAOOWXVAM-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002842 nonanoic acids Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
Images
Abstract
Description
本発明は、熱分解で金属ないしは金属酸化物を析出する金属化合物の結晶を、２０ｎｍ前後の大きさの微細結晶に粉砕し、該微細結晶を、液体の有機化合物で取り囲み、該液体の有機化合物中に分散した懸濁液を製造する。さらに、金属ないしは金属酸化物からなる１０ｎｍ前後の大きさのナノ粒子を、前記液体の有機化合物に取り囲んで析出させる。この後、前記液体の有機化合物を気化し、金属ないしは金属酸化物のナノ粒子が、凝集せずに個々のナノ粒子に分離した該ナノ粒子の集まりとして得られる。
本発明に先行して、本発明者は、飽和カルボン酸からなるエステル類に属する固体の有機化合物で覆われた金属ないしは金属酸化物からなるナノ粒子の集まりを製造する方法に係る発明を、特願２０２０－０９０８９２（令和２年５月１５日出願）として出願した。本発明は、熱分解で金属ないしは金属酸化物を析出する金属化合物の結晶を、２０ｎｍ前後の大きさの微細結晶に粉砕し、該微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した第一の懸濁液を作成する。さらに、第一の懸濁液を昇温し、前記金属化合物を熱分解すると、金属ないしは金属酸化物からなる１０ｎｍ前後の大きさのナノ粒子が、前記液体の有機化合物に囲まれて析出し、該液体の有機化合物中に分散した第二の懸濁液が得られる。本発明は、金属化合物の結晶を２０ｎｍ前後の大きさに粉砕したため、前記した先行出願に比べ、金属化合物の結晶の大きさが１／５程度に縮小する。これによって、金属化合物の微細結晶を熱分解すると、金属ないしは金属酸化物からなる１０ｎｍ前後の大きさのナノ粒子が、液体の有機化合物に囲まれて析出し、先行出願に比べ、ナノ粒子の大きさが１／５程度に縮小する。さらに、本発明では、ナノ粒子を液体の有機化合物で囲み、該液体の有機化合物中に分散させるため、固体の有機化合物でナノ粒子を囲む先行出願より、ナノ粒子の保存とナノ粒子を取り出すことが容易になる。
In the present invention, a crystal of a metal compound that precipitates a metal or a metal oxide by thermal decomposition is pulverized into fine crystals having a size of about 20 nm, and the fine crystals are surrounded by a liquid organic compound, and the liquid organic compound is used. Produce a suspension dispersed therein. Further, nanoparticles having a size of about 10 nm, which are made of a metal or a metal oxide, are surrounded by the liquid organic compound and precipitated. After that, the liquid organic compound is vaporized, and the nanoparticles of the metal or the metal oxide are obtained as a collection of the nanoparticles separated into individual nanoparticles without agglomeration.
Prior to the present invention, the present inventor particular of the present invention relates to a method for producing a collection of nanoparticles made of a metal or a metal oxide covered with a solid organic compound belonging to esters of saturated carboxylic acids. The application was filed as Application 2020-090892 (filed on May 15, 2nd year of Ester). In the present invention, a crystal of a metal compound that precipitates a metal or a metal oxide by thermal decomposition is pulverized into fine crystals having a size of about 20 nm, and the fine crystals are surrounded by a liquid organic compound, and the liquid organic Create a first suspension dispersed in the compound. Further, when the temperature of the first suspension is raised and the metal compound is thermally decomposed, nanoparticles having a size of about 10 nm made of a metal or a metal oxide are precipitated by being surrounded by the liquid organic compound. A second suspension dispersed in the liquid organic compound is obtained. In the present invention, since the crystal of the metal compound is pulverized to a size of about 20 nm, the size of the crystal of the metal compound is reduced to about 1/5 as compared with the above-mentioned prior application. As a result, when the fine crystals of the metal compound are thermally decomposed, nanoparticles having a size of about 10 nm made of a metal or a metal oxide are precipitated surrounded by the liquid organic compound, and the nanoparticles are larger than those in the previous application. Reduces to about 1/5. Further, in the present invention, in order to surround the nanoparticles with a liquid organic compound and disperse the nanoparticles in the liquid organic compound, the nanoparticles are preserved and the nanoparticles are taken out from the prior application in which the nanoparticles are surrounded by the solid organic compound. Will be easier.
ナノレベルの大きさからなる金属ナノ粒子の性質が、バルクからなる金属とは異なる性質を持つため、様々な製法によって様々な金属ナノ粒子が製造されている。
例えば、特許文献１には、銅イオン、及び炭素原子数４－１２のラクタム系化合物が溶解している還元反応水溶液において、銅イオンの電解還元反応により、ラクタム系有機化合物で被覆された銅ナノ粒子を析出させる技術が開示されている。これによって、析出する銅ナノ粒子がデンドライト状に凝集するのが抑制されるとの記載がある。しかし、還元反応水溶液における全ての異物を完全に排除することは困難であるため、本技術によって析出する銅ナノ粒子の純度は低い。さらに、製造できるナノ粒子が銅に限定される。また特殊な薬品に依る還元反応を利用するため、安価なナノ粒子が製造できない。
Since the properties of metal nanoparticles having a nano-level size are different from those of bulk metals, various metal nanoparticles are produced by various manufacturing methods.
For example, Patent Document 1 describes copper nanos coated with a lactam-based organic compound by an electrolytic reduction reaction of copper ions in a reduction reaction aqueous solution in which copper ions and a lactam-based compound having 4-12 carbon atoms are dissolved. A technique for precipitating particles is disclosed. There is a description that this suppresses the precipitation of copper nanoparticles in a dendrite-like manner. However, since it is difficult to completely eliminate all foreign substances in the reduction reaction aqueous solution, the purity of the copper nanoparticles precipitated by this technique is low. Furthermore, the nanoparticles that can be produced are limited to copper. In addition, since the reduction reaction by a special chemical is used, inexpensive nanoparticles cannot be produced.
また、特許文献２には、銅化合物が溶解あるいは分散している液中で、化学的に修飾したゼラチンの存在下で、銅イオンを還元して、銅ナノ粒子を得る技術が開示されている。しかしながら、前記した特許文献１と同様に、化学的に修飾したゼラチンの加水分解において、全ての異物を完全に排除することは困難であり、本技術によって得られる銅ナノ粒子の純度は低い。また、特許文献１と同様に、製造できる金属ナノ粒子が銅に限定される。また特殊な薬品に依る還元反応を利用するため、安価なナノ粒子が製造できない。 Further, Patent Document 2 discloses a technique for obtaining copper nanoparticles by reducing copper ions in the presence of chemically modified gelatin in a liquid in which a copper compound is dissolved or dispersed. .. However, as in Patent Document 1 described above, it is difficult to completely eliminate all foreign substances in the hydrolysis of chemically modified gelatin, and the purity of the copper nanoparticles obtained by this technique is low. Further, as in Patent Document 1, the metal nanoparticles that can be produced are limited to copper. In addition, since the reduction reaction by a special chemical is used, inexpensive nanoparticles cannot be produced.
さらに、特許文献３には、金属酸化物または金属水酸化物と、酸性物質または塩基性物質と、有機修飾剤を含有する有機溶媒からなる反応媒体をマイクロ波で加熱することにより金属ナノ粒子を製造する技術が開示されている。しかしながら、反応媒質に均一にマイクロ波を照射して、同一の温度に加熱するには、反応媒体の量に制限があり、金属ナノ粒子の量産性に劣る。また、マイクロ波を照射した試料を濾過、精製した後に８００℃という高温で熱処理することが必要になり、大気雰囲気での処理ではナノ粒子が酸化される。また、酸化されない雰囲気での熱処理は、金属ナノ粒子の製造費用が高価になる。 Further, Patent Document 3 describes metal nanoparticles by heating a reaction medium composed of a metal oxide or a metal hydroxide, an acidic substance or a basic substance, and an organic solvent containing an organic modifier with a microwave. The manufacturing technology is disclosed. However, in order to uniformly irradiate the reaction medium with microwaves and heat the reaction medium to the same temperature, the amount of the reaction medium is limited, and the mass productivity of the metal nanoparticles is inferior. Further, it is necessary to perform heat treatment at a high temperature of 800 ° C. after filtering and purifying the sample irradiated with microwaves, and the nanoparticles are oxidized by the treatment in the atmospheric atmosphere. In addition, heat treatment in an atmosphere that is not oxidized increases the cost of producing metal nanoparticles.
ナノ粒子が凝集せずに、個々のナノ粒子に分離した該ナノ粒子の集まりとして得られれば、ナノ粒子の固有の性質が工業製品に適応でき、ナノ粒子を工業製品に適応する範囲が広がる。また、金属に限らず、金属酸化物のナノ粒子が製造できれば、ナノ粒子の工業製品への適応範囲がさらに広がる。さらに、ナノ粒子の大きさが小さいほど、ナノ粒子を適応する工業製品の範囲が広がる。しかしながら、ナノ粒子が、極微細で極軽量で比表面積が大きいため、ナノ粒子の大きさが小さくなるほど、ナノ粒子の取り扱いが難しくなる。特に、不純物を含まない金属のナノ粒子は、製造時に活性状態にあるため凝集し易く、一度、凝集した金属のナノ粒子を、個々のナノ粒子に解除することは難しい。これによって、金属のナノ粒子の製造意義が失われる。また、ナノ粒子を製造する際に、ナノ粒子を構成する以外の原子が存在すると、純粋な金属ないしは純粋な金属酸化物のナノ粒子が生成されない。従って、ナノ粒子を製造する際に、異物や不純物の存在や混入は、完全に排除しなければならない。いっぽう、ナノ粒子を化学的に安定な有機化合物で取り囲んで析出させ、この後、ナノ粒子が、不活性で安定したナノ粒子になれば、有機化合物で取り囲んだナノ粒子の集まりは、長期保存が可能になる。さらに、有機化合物の蒸気圧より低い圧力に減圧させ、ナノ粒子を取り囲んだ有機化合物を気化すれば、ナノ粒子が再度活性化することがないため、ナノ粒子が凝集せず、個々のナノ粒子に分離した状態でナノ粒子の集まりが析出する。この結果、ナノ粒子の集まりを、様々な工業製品に適応できる。しかし、こうしたナノ粒子の集まりを製造するに際し、次の９つの課題が発生する。
第一に、安価な原料を用い、極めて簡単な処理でナノ粒子の集まりを製造する。これによって、安価なナノ粒子が製造できる。第二に、不純物を一切含まないナノ粒子を製造する。第三に、製造するナノ粒子の量に制約がない。第四に、金属に限らず、金属酸化物のナノ粒子を製造する。第五に、ナノ粒子の大きさが１０ｎｍ前後と小さい。第六に、ナノ粒子を有機化合物で取り囲んで析出させる。第七に、有機化合物が化学的に安定な物質で、活性状態で析出した金属のナノ粒子が、有機化合物と化学反応を起こさず、その後、金属のナノ粒子が不活性になり、安定化した金属のナノ粒子が、有機化合物で取り囲まれる。第八に、有機化合物が化学的に安定な物質で、ナノ粒子が経時変化せず、また、室温における蒸気圧が低く、長期保存が可能になる。第九に、有機化合物の気化によって、必要な時に必要な量のナノ粒子を、ナノ粒子同士が凝集せず、個々のナノ粒子に分離した該ナノ粒子の集まりとして取り出せる。
本発明における解決すべき課題は、前記した９つの課題を解決して、金属ないしは金属酸化物からなるナノ粒子を製造することにある。
If the nanoparticles are obtained as a collection of nanoparticles separated into individual nanoparticles without agglomeration, the unique properties of the nanoparticles can be applied to industrial products, and the range of applications of nanoparticles to industrial products is expanded. Further, if nanoparticles of metal oxides, not limited to metals, can be produced, the range of application of nanoparticles to industrial products will be further expanded. Furthermore, the smaller the size of the nanoparticles, the wider the range of industrial products to which the nanoparticles are applied. However, since the nanoparticles are extremely fine, extremely lightweight, and have a large specific surface area, the smaller the size of the nanoparticles, the more difficult it is to handle the nanoparticles. In particular, metal nanoparticles containing no impurities are likely to aggregate because they are in an active state at the time of production, and it is difficult to release the once aggregated metal nanoparticles into individual nanoparticles. This loses the significance of producing metal nanoparticles. Further, in the production of nanoparticles, if atoms other than those constituting the nanoparticles are present, nanoparticles of pure metal or pure metal oxide are not produced. Therefore, when manufacturing nanoparticles, the presence or contamination of foreign substances and impurities must be completely eliminated. On the other hand, if the nanoparticles are surrounded by a chemically stable organic compound and precipitated, and then the nanoparticles become inert and stable nanoparticles, the nanoparticles surrounded by the organic compound can be stored for a long time. It will be possible. Furthermore, if the pressure is reduced to a pressure lower than the vapor pressure of the organic compound and the organic compound surrounding the nanoparticles is vaporized, the nanoparticles will not be activated again, so that the nanoparticles will not aggregate and become individual nanoparticles. A collection of nanoparticles precipitates in a separated state. As a result, the collection of nanoparticles can be applied to various industrial products. However, the following nine problems arise in producing such a collection of nanoparticles.
First, it uses inexpensive raw materials and produces a collection of nanoparticles with a very simple process. As a result, inexpensive nanoparticles can be produced. Second, it produces nanoparticles that are completely free of impurities. Third, there are no restrictions on the amount of nanoparticles produced. Fourth, we manufacture nanoparticles of metal oxides, not just metals. Fifth, the size of nanoparticles is as small as around 10 nm. Sixth, the nanoparticles are surrounded by an organic compound and precipitated. Seventh, the organic compound is a chemically stable substance, and the metal nanoparticles precipitated in the active state do not chemically react with the organic compound, and then the metal nanoparticles become inactive and stabilized. Metal nanoparticles are surrounded by organic compounds. Eighth, the organic compound is a chemically stable substance, the nanoparticles do not change with time, the vapor pressure at room temperature is low, and long-term storage is possible. Ninth, by vaporizing the organic compound, the required amount of nanoparticles can be taken out as a collection of the nanoparticles separated into individual nanoparticles without the nanoparticles agglomerating with each other.
The problem to be solved in the present invention is to solve the above-mentioned nine problems to produce nanoparticles made of a metal or a metal oxide.
本発明における熱分解で金属ないしは金属酸化物を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法は、
メタノールに分散するが、メタノールに溶解しない第一の性質と、熱分解で金属ないしは金属酸化物を析出する第二の性質を兼備する金属化合物をメタノールに分散し、該金属化合物のメタノール分散液を作成し、この後、該金属化合物のメタノール分散液からメタノールを気化させ、該金属化合物の結晶の集まりを析出させる、さらに、該金属化合物の結晶の集まりを容器に充填し、該金属化合物の結晶の集まりの表面全体を覆う板材を、該金属化合物の結晶の集まりの上に被せる、この後、該板材の表面全体に圧縮荷重を加え、前記容器内の前記金属化合物の結晶を粉砕する、さらに、前記容器に前後、左右、上下の３方向の衝撃加速度を繰り返し加え、該容器内の前記粉砕された金属化合物の結晶の集まりを再配列させる、この後、前記板材の表面全体に再度前記圧縮荷重を加え、前記金属化合物の結晶の粉砕をさらに進める、さらに、前記容器に前記３方向の衝撃加速度を再度繰り返し加える、こうした前記圧縮荷重を加える処理と前記衝撃加速度を加える処理とからなる一対の処理を繰り返し、前記板材に前記圧縮荷重を加えた際に、該板材からの反発力が発生した時点で、前記一対の処理を停止する、この後、前記板材を前記容器から取り出し、さらに、前記容器に、融点が１５℃より低い第一の性質と、前記金属化合物が溶解及び分散しない第二の性質と、沸点が前記金属化合物の熱分解温度より３０℃以内の温度だけ高い第三の性質と、前記金属化合物の熱分解温度で析出した金属ないしは金属酸化物の微粒子と化学反応を起こさない第四の性質と、吸水性を持たない第五の性質からなる５つの性質を兼備する液体の有機化合物を、前記容器内の前記金属化合物の粉砕された結晶の集まりより多い体積からなる該有機化合物の重量として秤量し、該秤量した液体の有機化合物を前記容器に混合し、前記金属化合物の粉砕された結晶の集まりが、前記液体の有機化合物に分散された第一の懸濁液を作成する、さらに、前記容器内に超音波ホモジナイザー装置を配置し、該超音波ホモジナイザー装置の稼働によって、前記第一の懸濁液中に衝撃波を連続して発生させ、該衝撃波が前記金属化合物の粉砕された結晶の集まりに連続して衝突し、該粉砕された結晶が個々の結晶に分離し、該個々の結晶が、前記液体の有機化合物で囲まれ、該液体の有機化合物中に分散した第二の懸濁液が前記容器内に作成される、熱分解で金属ないしは金属酸化物を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。
In the present invention, the method for producing a suspension in which fine crystals of a metal compound that precipitates a metal or a metal oxide by thermal decomposition are surrounded by a liquid organic compound and dispersed in the liquid organic compound is used.
A metal compound having the first property of being dispersed in methanol but not soluble in methanol and the second property of precipitating a metal or a metal oxide by thermal decomposition is dispersed in methanol, and a methanol dispersion of the metal compound is prepared. After that, methanol is vaporized from the methanol dispersion of the metal compound to precipitate a collection of crystals of the metal compound, and further, the collection of crystals of the metal compound is filled in a container to crystallize the metal compound. A plate material covering the entire surface of the aggregate is placed on the aggregate of crystals of the metal compound, and then a compressive load is applied to the entire surface of the plate material to crush the crystals of the metal compound in the container. , The container is repeatedly subjected to impact acceleration in three directions of front-back, left-right, and up-down to rearrange the collection of crystals of the crushed metal compound in the container, and then the compression is performed again on the entire surface of the plate material. A pair consisting of a process of applying the compressive load and a process of applying the impact acceleration, in which a load is applied to further promote the crushing of the crystal of the metal compound, and the impact acceleration in the three directions is repeatedly applied to the container. The treatment is repeated, and when the compressive load is applied to the plate material, the pair of treatments is stopped when the repulsive force from the plate material is generated. The first property that the melting point is lower than 15 ° C., the second property that the metal compound does not dissolve and disperse, and the third property that the boiling point is higher than the thermal decomposition temperature of the metal compound by a temperature within 30 ° C. A liquid having five properties, that is, a fourth property that does not cause a chemical reaction with fine particles of a metal or metal oxide precipitated at the thermal decomposition temperature of the metal compound, and a fifth property that does not have water absorption. The organic compound is weighed as the weight of the organic compound having a volume larger than the collection of crushed crystals of the metal compound in the container, and the weighed liquid organic compound is mixed in the container to obtain the metal compound. A collection of crushed crystals creates a first suspension dispersed in the liquid organic compound, and an ultrasonic homogenizer device is placed in the container, and the operation of the ultrasonic homogenizer device causes the operation of the ultrasonic homogenizer device. A shock wave was continuously generated in the first suspension, and the shock wave continuously collided with a collection of crushed crystals of the metal compound, and the crushed crystals were separated into individual crystals. The individual crystals are surrounded by the liquid organic compound, and a second suspension dispersed in the liquid organic compound is created in the container. A method for producing a suspension in which fine crystals of a metal compound that precipitates a metal or a metal oxide by thermal decomposition are surrounded by a liquid organic compound and dispersed in the liquid organic compound.
つまり、本製造方法によれば、次の５つの極めて簡単な処理を連続して実施すると、容器内に、２０ｎｍ前後の大きさの微細結晶が液体の有機化合物で囲まれるとともに、該有機化合物中に前記微細結晶が分散した懸濁液が製造される。
第一の処理は、金属化合物を、最も汎用的な溶剤であるメタノールに分散するだけの処理である。第二の処理は、メタノール分散液からメタノールを気化するだけの処理である。第三の処理は、容器に充填した金属化合物の微細結晶の集まりに圧縮荷重を加える処理と、さらに、容器に３方向の衝撃加速度を加える処理とからなる一対の処理を繰り返し、金属化合物の結晶の粉砕を進める処理である。第四の処理は、粉砕が進んだ結晶の集まりが充填された容器に、５つの性質を兼備する有機化合物を充填するだけの処理である。第五の処理は、超音波ホモジナイザー装置の稼働によって、懸濁液に衝撃波を連続して加えるだけの処理である。
これら極めて簡単な５つの処理を連続して実施すると、粉砕された個々の結晶が、液体の有機化合物で囲まれ、該個々の結晶が有機化合物中に分散した懸濁液が容器に製造される。この結果、６段落に記載した第一の課題が解決される。
次に、前記した５つの処理における現象と各々の処理の効果とを説明する。
第一の処理において、熱分解で金属を析出する金属化合物を、最も汎用的な溶剤であるメタノールに分散すると、金属化合物が分子状態となってメタノールに分散する。これに対し、金属化合物がメタノールに溶解すると、金属化合物を構成する金属が金属イオンとなってメタノール中に溶出し、溶解した金属化合物は、溶解前の金属化合物に戻ることができない。このため、金属化合物のメタノール溶解液からメタノールを気化させると、溶解前の金属化合物の結晶が析出しない。従って、メタノールに溶解せず分散する金属化合物を用いる。つまり、金属化合物のメタノール分散液からメタノールを気化させると、分散前の金属化合物が、１００ｎｍより小さい金属化合物の結晶として析出する。
第二の処理において、金属化合物のメタノール分散液からメタノールを気化すると、１００ｎｍより小さい金属化合物の結晶の集まりが析出する。つまり、金属化合物のメタノール分散液において、金属化合物が分子状態となってメタノールに均一に分散しため、メタノールを気化させると、分散前の金属化合物が、１００ｎｍより小さい粒状の結晶として析出する。この結晶は、分子状態でメタノール中に分散した金属化合物が、結晶として析出したため、金属化合物の単分子が形成する結晶が集積した結晶の集まりである。従って、結晶に応力を加えると結晶が粉砕され、微細な結晶になる。いっぽう、結晶が微細になるほど、結晶に応力を加えることが難しくなり、結晶の微細化には限界がある。なお、気化したメタノールは回収機で回収し、再利用する。
第三の処理において、板材で容器内に拘束した金属化合物の結晶の集まりに対し、板材を介して圧縮荷重を加える。この際、結晶の大きさが相対的に大きい結晶ほど粉砕されやすい。このため、相対的に大きい結晶が優先して粉砕され、圧縮荷重が加えられている間は、結晶の粉砕が進む。いっぽう、結晶の集まりにおいては、結晶の粉砕によって新たな空隙が形成され、圧縮荷重が加えられている間は、空隙を埋めるように結晶が移動する。印加する圧縮荷重を停止した後に、容器に前後、左右、上下の３方向の衝撃加速度を繰り返し加える。この際、結晶は、板材で容器内に拘束されているため飛散せず、空隙を埋めるように結晶が移動し、結晶の集まりが容器内で再配列する。さらに、印加する衝撃加速度を停止した後に、再度、板材を介して結晶の集まりに圧縮荷重を加える。この際、より微細になった結晶の集まりに対し、前記した結晶の粉砕が進む。この後、再度、容器に３方向の衝撃加速度を繰り返し加え、微細になった結晶の集まりの再配列を進める。こうした圧縮荷重を加える処理と、３方向の衝撃加速度を加える処理とからなる一対の処理を繰り返す。いっぽう、結晶が微細になるほど、圧縮荷重を加えも、結晶に応力を加えることが難しくなり、結晶の微細化には限界がある。結晶の微細化が限界になると、板材に圧縮荷重を加えても、結晶の粉砕が行われず、板材に反発力が発生する。この時点で、一対の処理を停止する。この結果、結晶の大きさは、結晶が析出した時点の大きさに比べ、１／５に近い２０ｎｍ前後になる。なお、金属化合物の結晶が析出した際に、結晶の大きさにばらつきがあり、また、粉砕よってできた空隙の大きさにもばらつきがある。このため、粉砕が進んだ結晶の集まりの大きさにもばらつきがある。また、板材に加える圧縮荷重は、容器の大きさに応じて、１０－１００ｋｇ重に相当する圧縮荷重を加える。また、容器に加える衝撃加速度は、容器の大きさに応じて、０．３－１．０Ｇの衝撃加速度を加える。
第四の処理において、融点が１５℃より低い第一の性質と、前記金属化合物が溶解及び分散しない第二の性質と、沸点が前記金属化合物の熱分解温度より３０℃以内の温度だけ高い第三の性質と、前記金属化合物の熱分解温度で析出した金属ないしは金属酸化物の微粒子と化学反応を起こさない第四の性質と、吸水性を持たない第五の性質からなる５つの性質を兼備する液体の有機化合物を、容器内の金属化合物の粉砕された結晶の集まりより多い体積からなる該有機化合物を、容器に充填して攪拌すると、粉砕された結晶の集まりが液体の有機化合物に分散された第一の懸濁液が、容器内に製造される。なお、有機化合物の重量を、粉砕された結晶の集まりの重量より多い重量とし加え、第一の懸濁液における粉砕された結晶の分散性を高めた。
第五の処理において、超音波ホモジナイザー装置の稼働によって、第一の懸濁液に衝撃波を連続して加えると、液体の有機化合物を介して、粉砕された結晶の集まりに衝撃波が連続して加わる。つまり、容器内で超音波ホモジナイザー装置を稼働させると、超音波の振動周波数の振動周期に応じて、粗密波からなる超音波が、第一の懸濁液中を連続して伝搬する際に、高圧域と低圧域とが繰り返し発生し、この圧力差が第一懸濁液を構成する有機化合物の分子間力を上回る際に、微細結晶と同程度の大きさで、莫大な数のキャビティ（空洞）が連続して形成される。このキャビティが第一の懸濁液内で膨張し、この後、収縮する現象を繰り返し、次第にキャビティが成長し、一定の大きさ以上にキャビティが膨張すると、莫大な数のキャビティが連続して圧壊する。この際に莫大な数の衝撃波波が連続して第一の懸濁液中に発生する。この衝撃波が液体の有機化合物を介して粉砕された結晶の集まりに加わり、粉砕された結晶同士が直接接触した部位に衝撃波が加わると、粉砕された結晶が殆ど質量を持たないため、粉砕された結晶が容易に分離する。この際、液体の有機化合物の粘度に応じて、液体の有機化合物が分離した結晶に吸着し、分離した結晶が液体の有機化合物で覆われ、この後、分離した結晶同士が直接接触しない。この結果、粉砕された結晶は、懸濁液中で１個１個の結晶に分離され、分離された結晶は、液体の有機化合物で囲まれた第二の懸濁液になる。
これら５つの処理を連続して実施すると、容器内に第二の懸濁液が製造される。いっぽう、粉砕された結晶が２０ｎｍ前後と極めて微細であるため、粉砕された結晶の集まりを経時変化させることなく、長期に保管することは難しい。しかしながら、第二の懸濁液においては、個々の粉砕された結晶を取り囲む液体の有機化合物が、金属化合物に溶解及び分散せず、また、吸水性を持たないため、液体の有機化合物で囲まれた金属化合物の粉砕された結晶は、長期に亘って経時変化しない。さらに、液体の有機化合物は、室温における蒸気圧が著しく小さく、蒸発量は極めて少なく、長期に亘って粉砕された結晶を取り囲んで保存する。この結果、５つの性質を兼備する有機化合物で粉砕された結晶が取り囲まれ、長期に亘って経時変化することなく粉砕された結晶が保存できる。
That is, according to this production method, when the following five extremely simple treatments are continuously carried out, fine crystals having a size of about 20 nm are surrounded by a liquid organic compound in the container, and the organic compound is contained. A suspension in which the fine crystals are dispersed is produced.
The first treatment is a treatment in which the metal compound is simply dispersed in methanol, which is the most general-purpose solvent. The second treatment is a treatment that only vaporizes methanol from the methanol dispersion. The third process repeats a pair of processes consisting of a process of applying a compressive load to a collection of fine crystals of the metal compound filled in the container and a process of applying impact acceleration in three directions to the container, and crystallizes the metal compound. It is a process to proceed with crushing. The fourth treatment is a treatment in which a container filled with a collection of crystals that have been pulverized is simply filled with an organic compound having five properties. The fifth process is a process in which a shock wave is continuously added to the suspension by operating the ultrasonic homogenizer device.
When these five extremely simple treatments are carried out in succession, each crushed crystal is surrounded by a liquid organic compound, and a suspension in which the individual crystals are dispersed in the organic compound is produced in a container. .. As a result, the first problem described in paragraph 6 is solved.
Next, the phenomena in the above-mentioned five processes and the effects of each process will be described.
In the first treatment, when a metal compound that precipitates a metal by thermal decomposition is dispersed in methanol, which is the most general-purpose solvent, the metal compound becomes a molecular state and is dispersed in methanol. On the other hand, when the metal compound is dissolved in methanol, the metal constituting the metal compound becomes a metal ion and elutes into the methanol, and the dissolved metal compound cannot return to the metal compound before dissolution. Therefore, when methanol is vaporized from a solution of the metal compound in methanol, crystals of the metal compound before dissolution do not precipitate. Therefore, a metal compound that is not dissolved in methanol and is dispersed is used. That is, when methanol is vaporized from the methanol dispersion of the metal compound, the metal compound before dispersion precipitates as crystals of the metal compound smaller than 100 nm.
In the second treatment, when methanol is vaporized from the methanol dispersion of the metal compound, a collection of crystals of the metal compound smaller than 100 nm is deposited. That is, in the methanol dispersion of the metal compound, the metal compound becomes a molecular state and is uniformly dispersed in methanol. Therefore, when the methanol is vaporized, the metal compound before dispersion is precipitated as granular crystals smaller than 100 nm. This crystal is a collection of crystals in which crystals formed by a single molecule of a metal compound are accumulated because a metal compound dispersed in methanol in a molecular state is precipitated as a crystal. Therefore, when stress is applied to the crystal, the crystal is crushed into fine crystals. On the other hand, the finer the crystal, the more difficult it is to apply stress to the crystal, and there is a limit to the miniaturization of the crystal. The vaporized methanol is recovered by a recovery machine and reused.
In the third treatment, a compressive load is applied to the aggregate of crystals of the metal compound restrained in the container by the plate material through the plate material. At this time, the crystal having a relatively large crystal size is more likely to be crushed. Therefore, the relatively large crystals are preferentially crushed, and the crushing of the crystals proceeds while the compressive load is applied. On the other hand, in a collection of crystals, new voids are formed by crushing the crystals, and the crystals move so as to fill the voids while the compressive load is applied. After stopping the applied compressive load, impact acceleration in three directions of front-back, left-right, and up-down is repeatedly applied to the container. At this time, since the crystals are restrained in the container by the plate material, they do not scatter, the crystals move so as to fill the voids, and the aggregates of the crystals are rearranged in the container. Further, after stopping the applied impact acceleration, a compressive load is applied to the crystal collection through the plate material again. At this time, the above-mentioned pulverization of the crystals proceeds with respect to the collection of finer crystals. After that, the impact acceleration in three directions is repeatedly applied to the container again to proceed with the rearrangement of the fine crystal aggregates. A pair of processes including the process of applying such a compressive load and the process of applying impact acceleration in three directions are repeated. On the other hand, the finer the crystal, the more difficult it is to apply stress to the crystal even if a compressive load is applied, and there is a limit to the miniaturization of the crystal. When the miniaturization of crystals reaches the limit, even if a compressive load is applied to the plate material, the crystals are not crushed and a repulsive force is generated in the plate material. At this point, the pair of processes is stopped. As a result, the size of the crystal is about 20 nm, which is close to 1/5 of the size at the time when the crystal is precipitated. When the crystals of the metal compound are precipitated, the size of the crystals varies, and the size of the voids formed by pulverization also varies. Therefore, the size of the aggregate of crystals that have been crushed also varies. Further, as the compressive load applied to the plate material, a compressive load corresponding to a weight of 10 to 100 kg is applied depending on the size of the container. The impact acceleration applied to the container is 0.3-1.0 G depending on the size of the container.
In the fourth treatment, the first property that the melting point is lower than 15 ° C., the second property that the metal compound does not dissolve and disperse, and the boiling point is higher than the thermal decomposition temperature of the metal compound by a temperature within 30 ° C. It has the three properties, the fourth property that does not cause a chemical reaction with the fine particles of the metal or metal oxide precipitated at the thermal decomposition temperature of the metal compound, and the fifth property that does not have water absorption. When the organic compound having a volume larger than that of the crushed crystals of the metal compound in the container is filled in the container and stirred, the crushed crystals are dispersed in the liquid organic compound. The first suspension made is produced in a container. The weight of the organic compound was set to be larger than the weight of the aggregate of crushed crystals, and the dispersibility of the crushed crystals in the first suspension was enhanced.
In the fifth process, when the shock wave is continuously added to the first suspension by the operation of the ultrasonic homogenizer device, the shock wave is continuously added to the group of crushed crystals via the liquid organic compound. .. That is, when the ultrasonic homogenizer device is operated in the container, the ultrasonic waves composed of coarse and dense waves propagate continuously in the first suspension according to the vibration cycle of the vibration frequency of the ultrasonic waves. When the high-pressure region and the low-pressure region repeatedly occur and this pressure difference exceeds the intramolecular force of the organic compounds constituting the first suspension, the size is about the same as that of fine crystals and a huge number of cavities ( Cavities) are formed continuously. When this cavity expands in the first suspension and then contracts repeatedly, the cavity gradually grows, and when the cavity expands beyond a certain size, a huge number of cavities are continuously crushed. do. At this time, a huge number of shock waves are continuously generated in the first suspension. When this shock wave joins a collection of crushed crystals via a liquid organic compound and a shock wave is applied to a site where the crushed crystals are in direct contact with each other, the crushed crystals have almost no mass and are therefore crushed. Crystals separate easily. At this time, depending on the viscosity of the liquid organic compound, the liquid organic compound is adsorbed on the separated crystals, the separated crystals are covered with the liquid organic compound, and then the separated crystals do not come into direct contact with each other. As a result, the crushed crystals are separated into individual crystals in the suspension, and the separated crystals become a second suspension surrounded by a liquid organic compound.
When these five treatments are carried out in succession, a second suspension is produced in the container. On the other hand, since the crushed crystals are extremely fine at around 20 nm, it is difficult to store the crushed crystals for a long period of time without changing them over time. However, in the second suspension, the liquid organic compound surrounding the individual crushed crystals is not dissolved or dispersed in the metal compound and has no water absorbency, so that it is surrounded by the liquid organic compound. The crushed crystals of the metal compound do not change with time over a long period of time. In addition, liquid organic compounds have a significantly lower vapor pressure at room temperature, very little evaporation, and surround and store the crushed crystals for a long period of time. As a result, the crystal crushed by the organic compound having five properties is surrounded, and the crushed crystal can be preserved without changing with time for a long period of time.
７段落に記載した方法で製造した第二の懸濁液から金属ないしは金属酸化物からなるナノ粒子の集まりを析出させる方法は、
７段落に記載した方法で製造した第二の懸濁液の必要となる量を新たな容器に充填し、該新たな容器を、７段落に記載した金属化合物を熱分解させる雰囲気に晒すとともに、該金属化合物が熱分解する温度に昇温する、これによって、前記新たな容器内に、金属ないしは金属酸化物からなるナノ粒子が、７段落に記載した液体の有機化合物に囲まれて析出し、該液体の有機化合物中に前記ナノ粒子の集まりが分散した第三の懸濁液が作成される、この後、該第三の懸濁液が充填された前記新たな容器を真空チャンバー内に移し、真空ポンプによって前記真空チャンバー内の圧力を、該新たな容器内の前記第三の懸濁液の温度における前記液体の有機化合物の蒸気圧より低い圧力に減圧させ、前記第三の懸濁体から前記液体の有機化合物を気化させる、これによって、前記新たな容器に、前記金属ないしは前記金属酸化物からなるナノ粒子の集まりが析出する、７段落に記載した方法で製造した第二の懸濁液から金属ないしは金属酸化物からなるナノ粒子の集まりを析出させる方法。
The method for precipitating a collection of nanoparticles consisting of a metal or a metal oxide from a second suspension produced by the method described in paragraph 7 is
A new container is filled with the required amount of the second suspension produced by the method described in paragraph 7, and the new container is exposed to an atmosphere that thermally decomposes the metal compound described in paragraph 7. The temperature rises to a temperature at which the metal compound thermally decomposes, whereby nanoparticles made of metal or metal oxide are deposited in the new container surrounded by the liquid organic compound described in paragraph 7. A third suspension is created in which a collection of the nanoparticles is dispersed in the liquid organic compound, after which the new container filled with the third suspension is transferred into a vacuum chamber. , The vacuum pump reduces the pressure in the vacuum chamber to a pressure lower than the vapor pressure of the liquid organic compound at the temperature of the third suspension in the new vessel, and the third suspension. The second suspension produced by the method described in paragraph 7, wherein the liquid organic compound is vaporized from the liquid, whereby a collection of nanoparticles composed of the metal or the metal oxide is deposited in the new container. A method of precipitating a collection of nanoparticles consisting of a metal or metal oxide from a liquid.
最初に、７段落に記載した方法で製造した第二の懸濁液の必要となる量を新たな容器に充填し、新たな容器を、金属化合物を熱分解させる雰囲気に晒すとともに、金属化合物が熱分解する温度まで昇温する。金属化合物が熱分解する温度に到達すると、液体の有機化合物で囲まれた金属化合物の粉砕された結晶が、無機物の分子ないしは有機物の分子と金属分子とに分解し、無機物の分子ないしは有機物の分子が気化熱を奪って気化する。この際、無機物ないしは有機物からなる気体の体積が爆発的に膨張し、気体分子が有機化合物を通過して、順次外界に吐き出る。つまり、無機物の分子ないしは有機物の分子の１モルが気化すると、無機物ないしは有機物からなる気体の体積は２２．４リットルを占める。このため、無機物の分子ないしは有機物の分子の気化が始まると、液体の有機化合物で囲まれた無機物ないしは有機物からなる気体は、２０ｎｍ前後の大きさから爆発的に膨張し、気体分子が有機化合物を通過して、順次外界に吐き出る。また、無機物ないしは有機物からなる気体の密度は、液体の有機化合物の密度より２桁小さいため、無機物ないしは有機物からなる気体は、液体の有機化合物内に留まることはできない。この後、無機物の分子ないしは有機物の分子の気化が完了した瞬間に、金属分子の集まりが１０ｎｍ前後の大きさからなる金属ないしは金属酸化物のナノ粒子を形成し、該ナノ粒子が液体の有機化合物に囲まれて析出する。これによって、液体の有機化合物に囲まれて金属ないしは金属酸化物からなるナノ粒子が析出し、該液体の有機化合物中にナノ粒子が分散した第三の懸濁液が作成される。なお、金属化合物が熱分解する際に、第二の懸濁液に含まれ、沸点が金属化合物の熱分解温度より低い、水分、有機物、水酸化物などの不純物は、全て第二の懸濁液から気化し、金属ないしは金属酸化物のナノ粒子が析出する際に、ナノ粒子が不純物を持たない液体の有機化合物に囲まれて析出するため、真性な金属ないしは真性な金属酸化物のナノ粒子として析出する。
いっぽう、真性な金属のナノ粒子は、析出した際は活性状態にあるが、液体の有機化合物とは化学反応を起こさず、析出後には、液体の有機化合物で囲まれて、不活性で安定した金属のナノ粒子になる。また、有機化合物が化学的に安定な物質で、吸水性を持たないため、液体の有機化合物で囲まれたナノ粒子は化学変化しない。この結果、６段落に記載した第二から第八の課題が解決される。なお、容器から気化した無機物ないしは有機物の気体は、回収機で回収し、再利用する。
次に、第三の懸濁液を真空チャンバー内に速やかに移し、真空ポンプによって真空チャンバー内の圧力を、容器内の第三の懸濁液の温度における有機化合物の蒸気圧より低い圧力に減圧させると、第三の懸濁液から有機化合物が気化し、容器内に金属ないしは金属酸化物からなるナノ粒子の集まりが析出する。なお、第三の懸濁液の温度が金属化合物の熱分解温度に近く、また、有機化合物の沸点が金属化合物の熱分解温度より３０℃以内の温度だけ高いため、真空チャンバー内に移された第三の懸濁液における有機化合物の蒸気圧は、数千パスカルを超える蒸気圧持つ。従って、真空チャンバー内の圧力を数千パスカルに近い圧力に減圧するだけで、有機化合物が気化できる。なお、液体の有機化合物で囲まれた金属ないしは金属酸化物からなるナノ粒子は、既に不活性で安定したナノ粒子になっている。従って、有機化合物の蒸気圧より低い圧力に減圧させ、有機化合物を気化させたため、ナノ粒子は昇温の過程を踏んでいないため、容器内に析出した金属ないしは金属酸化物からなるナノ粒子は凝集せず、個々のナノ粒子に分離した該ナノ粒子の集まりとして析出する。従って、個々のナノ粒子に分離した該ナノ粒子の集まりを、容器から取り出せる。この結果、６段落に記載した第九の課題が解決される。
これに対し、第三の懸濁液を有機化合物の沸点に昇温し、有機化合物を気化させると、液体の有機化合物で囲まれた金属ないしは金属酸化物からなるナノ粒子が、金属化合物の熱分解温度より３０℃以内だけ高い温度に昇温され、金属のナノ粒子が析出した際の温度より３０℃以内だけ高い温度に昇温されるため、金属のナノ粒子が再度活性化する。従って、有機化合物が気化した後に、活性化した金属のナノ粒子同士が接触し、金属のナノ粒子同士が凝着する。ナノ粒子の大きさが１０ｎｍ前後と小さいため、凝着した金属のナノ粒子を分離することはできない。このため、第二の懸濁液を用い、金属ないしは金属酸化物からなるナノ粒子の集まりを析出させる方法として、第三の懸濁液を、容器内の第三の懸濁液の温度における有機化合物の蒸気圧より低い圧力に減圧させて、有機化合物を気化させる方法を用いた。
First, the required amount of the second suspension produced by the method described in paragraph 7 is filled in a new container, and the new container is exposed to an atmosphere that pyrolyzes the metal compound, and the metal compound is charged. The temperature is raised to the temperature at which it decomposes thermally. When the temperature at which the metal compound thermally decomposes is reached, the crushed crystals of the metal compound surrounded by the liquid organic compound decompose into inorganic molecules or organic molecules and metal molecules, and the inorganic molecule or organic molecule. Takes away the heat of vaporization and vaporizes. At this time, the volume of the gas composed of an inorganic substance or an organic substance expands explosively, and the gas molecules pass through the organic compound and are sequentially discharged to the outside world. That is, when one mole of an inorganic molecule or an organic molecule is vaporized, the volume of the gas composed of the inorganic or organic substance occupies 22.4 liters. Therefore, when the vaporization of an inorganic molecule or an organic molecule starts, the gas composed of the inorganic substance or the organic substance surrounded by the liquid organic compound expands explosively from a size of about 20 nm, and the gas molecule becomes the organic compound. It passes through and spits out to the outside world in sequence. Further, since the density of the gas composed of an inorganic substance or an organic substance is two orders of magnitude smaller than the density of the liquid organic compound, the gas composed of the inorganic substance or the organic substance cannot stay in the liquid organic compound. After that, at the moment when the vaporization of the molecules of the inorganic substance or the molecule of the organic substance is completed, the aggregates of the metal molecules form metal or metal oxide nanoparticles having a size of about 10 nm, and the nanoparticles are liquid organic compounds. It is surrounded by and precipitates. As a result, nanoparticles composed of a metal or a metal oxide are precipitated surrounded by the liquid organic compound, and a third suspension in which the nanoparticles are dispersed in the liquid organic compound is created. When the metal compound is thermally decomposed, all impurities such as water, organic substances, and hydroxides contained in the second suspension and whose boiling point is lower than the thermal decomposition temperature of the metal compound are suspended in the second suspension. When the nanoparticles of the metal or metal oxide are vaporized from the liquid and precipitated, the nanoparticles are surrounded by liquid organic compounds having no impurities and are precipitated. Therefore, the nanoparticles of the true metal or the true metal oxide are deposited. Precipitate as.
On the other hand, the intrinsic metal nanoparticles are in an active state when precipitated, but do not chemically react with the liquid organic compound, and after the precipitation, they are surrounded by the liquid organic compound and are inactive and stable. It becomes metal nanoparticles. Moreover, since the organic compound is a chemically stable substance and does not have water absorbency, nanoparticles surrounded by the liquid organic compound do not chemically change. As a result, the second to eighth problems described in paragraph 6 are solved. Inorganic or organic gas vaporized from the container is recovered by a recovery machine and reused.
The third suspension is then quickly transferred into the vacuum chamber and the pressure in the vacuum chamber is reduced by a vacuum pump to a pressure lower than the vapor pressure of the organic compound at the temperature of the third suspension in the vessel. Then, the organic compound is vaporized from the third suspension, and a collection of nanoparticles made of metal or metal oxide is deposited in the container. Since the temperature of the third suspension is close to the thermal decomposition temperature of the metal compound and the boiling point of the organic compound is higher than the thermal decomposition temperature of the metal compound by 30 ° C., it was moved into the vacuum chamber. The vapor pressure of the organic compound in the third suspension has a vapor pressure of more than several thousand pascals. Therefore, the organic compound can be vaporized only by reducing the pressure in the vacuum chamber to a pressure close to several thousand pascals. The nanoparticles made of a metal or a metal oxide surrounded by a liquid organic compound have already become inert and stable nanoparticles. Therefore, since the pressure was reduced to a pressure lower than the vapor pressure of the organic compound and the organic compound was vaporized, the nanoparticles did not undergo the process of raising the temperature, and therefore the nanoparticles composed of the metal or the metal oxide deposited in the container aggregated. Instead, it precipitates as a collection of nanoparticles separated into individual nanoparticles. Therefore, a collection of nanoparticles separated into individual nanoparticles can be taken out of the container. As a result, the ninth problem described in paragraph 6 is solved.
On the other hand, when the temperature of the third suspension is raised to the boiling point of the organic compound and the organic compound is vaporized, nanoparticles made of a metal or a metal oxide surrounded by the liquid organic compound are heated by the metal compound. The temperature is raised to a temperature within 30 ° C. higher than the decomposition temperature, and the temperature is raised to a temperature within 30 ° C. higher than the temperature at which the metal nanoparticles are precipitated, so that the metal nanoparticles are activated again. Therefore, after the organic compound is vaporized, the activated metal nanoparticles come into contact with each other and the metal nanoparticles adhere to each other. Since the size of the nanoparticles is as small as about 10 nm, it is not possible to separate the adhered metal nanoparticles. Therefore, as a method of precipitating a collection of nanoparticles composed of a metal or a metal oxide using the second suspension, the third suspension is organic at the temperature of the third suspension in the container. A method was used in which the organic compound was vaporized by reducing the pressure to a pressure lower than the vapor pressure of the compound.
７段落に記載した熱分解で金属を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法は、
７段落に記載した熱分解で金属を析出する金属化合物が、無機物の分子ないしは無機物のイオンが配位子となって金属イオンに配位結合した金属錯イオンを有する無機塩で構成された無機金属化合物であり、７段落に記載した液体の有機化合物が、炭素原子の数が１１－１３からなるアルカン、ないしは、飽和脂肪酸からなるカルボン酸エステル類、ないしは、脂肪族アルコール類に属するいずれか１種類の有機化合物であり、前記無機金属化合物を７段落に記載した熱分解で金属を析出する金属化合物として用い、前記アルカン、ないしは、前記カルボン酸エステル類、ないしは、前記脂肪族アルコール類に属するいずれか１種類の有機化合物を７段落に記載した液体の有機化合物として用い、７段落に記載した懸濁液を製造する方法に従って懸濁液を製造する、７段落に記載した熱分解で金属を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。
The method for producing a suspension in which fine crystals of a metal compound that precipitates a metal by thermal decomposition described in paragraph 7 are surrounded by a liquid organic compound and dispersed in the liquid organic compound is described.
The metal compound that precipitates a metal by thermal decomposition described in paragraph 7 is an inorganic metal composed of an inorganic salt having a metal complex ion coordinated and bonded to the metal ion by using an inorganic molecule or an ion of the inorganic substance as a ligand. One of the liquid organic compounds described in paragraph 7 which belongs to alkanes having 11-13 carbon atoms, carboxylic acid esters composed of saturated fatty acids, or aliphatic alcohols. The organic compound of the above, wherein the inorganic metal compound is used as a metal compound for precipitating a metal by thermal decomposition described in paragraph 7, and belongs to the alkane, the carboxylic acid esters, or the aliphatic alcohols. Using one type of organic compound as the liquid organic compound described in paragraph 7, the suspension is produced according to the method for producing the suspension described in paragraph 7, and the metal is precipitated by the thermal decomposition described in paragraph 7. A method for producing a suspension in which fine crystals of a metal compound are surrounded by a liquid organic compound and dispersed in the liquid organic compound.
つまり、無機物からなる分子ないしは無機物からなるイオンが配位子となって、金属イオンに配位結合した金属錯イオンを有する無機塩からなる無機金属化合物を、還元雰囲気で熱処理すると、最初に配位結合部が分断され、無機物と金属とに分解する。さらに昇温すると、無機物が気化熱を奪って気化し、１８０－２２０℃の温度範囲で無機物の気化が完了して金属が析出する。
すなわち、無機金属化合物を構成するイオンの中で、分子の中央に位置する金属イオンが最も大きく、金属イオンと配位子との距離が最も長い。この無機金属化合物を還元雰囲気で熱処理すると、金属イオンが配位子と結合する配位結合部が最初に分断され、金属と無機物とに分解する。さらに温度が上がると、無機物が気化熱を奪って気化し、無機物の気化が完了すると金属が析出し、熱分解を終える。金属が析出する温度は、金属化合物の熱分解で金属が析出する温度の中で最も低い。従って、熱処理費用が安価で済む。また、金属錯イオンを有する無機塩からなる無機金属化合物は、メタノールに１０重量％近く分散し、メタノールに溶解しない。このため、無機金属化合物は、７段落に記載した熱分解で金属を析出する金属化合物として用いることができる。
すなわち、無機物からなる分子ないしは無機物からなるイオンが配位子になって、金属イオンに配位結合する金属錯イオンは、他の金属錯イオンに比べて合成が容易である。このような金属錯イオンとして、アンモニアＮＨ３が配位子となって金属イオンに配位結合するアンミン金属錯イオン、水Ｈ２Ｏが配位子となって金属イオンに配位結合するアクア金属錯イオン、水酸基ＯＨ―が配位子となって金属イオンに配位結合するヒドロキソ金属錯イオン、塩素イオンＣｌ－が、ないしは塩素イオンＣｌ－とアンモニアＮＨ３とが配位子となって金属イオンに配位結合するクロロ金属錯イオンなどがある。さらに、このような金属錯イオンを有する塩化物、硫酸塩、硝酸塩などの無機塩からなる無機金属化合物は、合成が容易で、無機塩の分子量が小さいため、１８０－２２０℃の温度範囲で無機物の気化が完了し金属を析出する。この金属が析出する温度は、金属化合物の熱分解で金属を析出する温度の中で最も低い。こうした無機金属化合物は、汎用的な工業用の薬品である。
いっぽう、７段落に記載した熱分解で金属を析出する金属化合物として、前記した無機金属化合物を用いることで、７段落に記載した５つの性質を兼備する適切な有機化合物として、炭素原子の数が１１－１３からなるアルカン、ないしは、飽和脂肪酸からなるカルボン酸エステル類、ないしは、脂肪族アルコール類に属する有機化合物が存在する。なお、これらの有機化合物は、汎用的な工業用の有機化合物である。
すなわち、炭素原子の数が１１からなるｎ－ウンデカンＣ１１Ｈ２４は、融点が－２６℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い１９６℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５つの性質を兼備する。なお、蒸気圧は、沸点に近い１９２℃では５３８３パスカルである。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ｎ－ウンデカンが数千パスカルの蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ｎ－ウンデカンを気化することができる。さらに、ｎ－ウンデカンは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
次に、炭素原子の数が１２からなるｎ－ドデカンＣ１２Ｈ２６は、融点が－９．６℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２１６℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５つの性質を兼備する。なお、蒸気圧は、４８℃では１３３パスカルで、無機金属化合物の熱分解温度に近い２０４℃では、蒸気圧は６３１０パスカルである。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ｎ－ドデカンが数千パスカルの蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ｎ－ドデカンを気化することができる。さらに、ｎ－ドデカンは水に殆ど溶けない。このため、常温の近辺では吸水性がない。また、常温の２０℃近辺での蒸気圧が低いため、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
さらに、炭素原子の数が１３からなるｎ－トリデカンＣ１３Ｈ２８は、融点が－５℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２３５℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５つの性質を兼備する。なお、蒸気圧は、無機金属化合物の熱分解温度に近い２１１℃では、５５２０パスカルである。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ｎ－トリデカンが数千パスカルの蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ｎ－トリデカンを気化することができる。さらに、ｎ－トリデカンは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。常温の２０℃近辺での蒸気圧が低いため、蒸発量が極めて僅かな液体である。また、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
さらに、７段落に記載した金属化合物として、前記した無機金属化合物を用いることによって、７段落に記載した５つの性質を兼備する適切な他の有機化合物として、飽和脂肪酸からなるカルボン酸エステル類に属する有機化合物が存在する。
すなわち、デカン酸エステル類の中では、デカン酸メチルＣＨ３（ＣＨ２）８ＣＯＯＣＨ３は、融点が－１２℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２２４℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、１９９℃においては２２１３パスカルで、沸点に近づくにつれ急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、デカン酸メチルが数千パスカルの蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、デカン酸メチルを気化することができる。さらに、デカン酸メチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
次に、デカン酸エチルＣＨ３（ＣＨ２）８ＣＯＯＣ２Ｈ５は、融点が－２０℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２４３℃で、前記無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、デカン酸メチルと同様に、沸点に近づくと急激に増加する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、デカン酸エチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、デカン酸エチルを気化することができる。さらに、デカン酸エチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
いっぽう、ノナン酸エステル類の中で、ノナン酸メチルＣＨ３（ＣＨ２）７ＣＯＯＣＨ３は、融点が－３５℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２１４℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、沸点が無機金属化合物の熱分解温度に近いため、無機金属化合物の熱分解温度では１気圧に近い蒸気圧を持つ。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ノナン酸メチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ノナン酸メチルを気化することができる。さらに、ノナン酸メチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、無機金属化合物の微細結晶を変化させることなく保管できる。
また、ノナン酸エチルＣＨ３（ＣＨ２）７ＣＯＯＣ２Ｈ５は、融点は－４４℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２２０℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、沸点が無機金属化合物の熱分解温度に近いため、無機金属化合物の熱分解温度では１気圧に近い蒸気圧を持つ。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ノナン酸エチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ノナン酸エチルを気化することができる。さらに、ノナン酸エチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
さらに、オクタン酸エステル類の中では、オクタン酸メチルＣＨ３（ＣＨ２）６ＣＯＯＣＨ３は、融点が－４０℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い１９４℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、沸点に近い１９０℃では４４１０パスカルを持つ。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸メチルが数千パスカルの蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸メチルを気化することができる。さらに、オクタン酸メチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
さらに、オクタン酸エチルＣＨ３（ＣＨ２）６ＣＯＯＣ２Ｈ５は、融点が－４８℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２０８℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、６０℃において３２２パスカルで、沸点に近づくと蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸エチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸エチルを気化することができる。さらに、オクタン酸エチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
また、オクタン酸イソプロピルＣＨ３（ＣＨ２）６ＣＯＯＣＨ（ＣＨ３）２は、融点が１２℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２１４℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、沸点が無機金属化合物の熱分解温度に近いため、無機金属化合物の熱分解温度では１気圧に近い蒸気圧を持つ。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸イソプロピルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸イソプロピルを気化することができる。さらに、オクタン酸イソプロピルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
さらに、ヘプタン酸エステル類の中では、ヘプタン酸ブチルＣＨ３（ＣＨ２）５ＣＯＯＣ４Ｈ９は、融点が－６４℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２０７℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、沸点が無機金属化合物の熱分解温度に近いため、無機金属化合物の熱分解温度では１気圧に近い蒸気圧を持つ。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ヘプタン酸ブチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ヘプタン酸ブチルを気化することができる。さらに、ヘプタン酸ブチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
いっぽう、７段落に記載した金属化合物として、前記した無機金属化合物を用いることによって、７段落に記載した５つの性質を兼備する適切な他の有機化合物として、８－２２個の炭素の鎖からなる脂肪族アルコールＣＨ３（ＣＨ２）ｎ－１ＯＨに属する有機化合物が存在する。
すなわち、炭素の鎖が８からなる１－オクタノールＣＨ３（ＣＨ２）７ＯＨは、融点が－１６℃で、無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い１９５℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、１７１℃で３４８パスカル、１９３℃では３７９７パスカルであり、沸点に近づくと蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、１－オクタノールが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、１－オクタノールを気化することができる。さらに、１－オクタノールは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
次に、炭素の鎖が９からなる１－ノナノールＣＨ３（ＣＨ２）８ＯＨは、融点が－７℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２１５℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、１９３℃では１８４２パスカルで、沸点に近づくと蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、１－ノナノールが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、１－ノナノールを気化することができる。さらに、１－ノナノールは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
さらに、炭素の鎖が１０からなる１－デカノールＣＨ３（ＣＨ２）９ＯＨは、融点が－６．４℃で、前記した無機金属化合物が溶解及び分散せず、沸点が無機金属化合物の熱分解温度より高い２３３℃で、無機金属化合物の熱分解で析出する金属からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、１９３℃では９１０パスカルで、沸点に近づくと蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、１－デカノールが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、１－デカノールを気化することができる。さらに、１－デカノールは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、無機金属化合物の微細結晶を変化させることなく保管できる。
以上に説明したように、７段落に記載した熱分解で金属を析出する金属化合物として、前記した無機金属化合物を用いることによって、７段落に記載した５つの性質を兼備する適切な有機化合物として、炭素原子の数が１１－１４からなるアルカン、ないしは、飽和脂肪酸からなるカルボン酸エステル類、ないしは、脂肪族アルコール類に属する有機化合物が存在する。
That is, when a molecule composed of an inorganic substance or an ion composed of an inorganic substance serves as a ligand and an inorganic metal compound composed of an inorganic salt having a metal complex ion coordinated to a metal ion is heat-treated in a reducing atmosphere, the coordination is first performed. The bond is broken and decomposes into an inorganic substance and a metal. When the temperature is further raised, the inorganic substance takes away the heat of vaporization and vaporizes, and the vaporization of the inorganic substance is completed in the temperature range of 180-220 ° C., and the metal precipitates.
That is, among the ions constituting the inorganic metal compound, the metal ion located in the center of the molecule is the largest, and the distance between the metal ion and the ligand is the longest. When this inorganic metal compound is heat-treated in a reducing atmosphere, the coordination bond portion in which the metal ion binds to the ligand is first separated and decomposed into a metal and an inorganic substance. When the temperature rises further, the inorganic substance takes away the heat of vaporization and vaporizes, and when the vaporization of the inorganic substance is completed, the metal precipitates and the thermal decomposition is completed. The temperature at which the metal precipitates is the lowest among the temperatures at which the metal precipitates due to the thermal decomposition of the metal compound. Therefore, the heat treatment cost is low. Further, the inorganic metal compound composed of an inorganic salt having a metal complex ion is dispersed in methanol in an amount of about 10% by weight and is not dissolved in methanol. Therefore, the inorganic metal compound can be used as a metal compound that precipitates a metal by the thermal decomposition described in paragraph 7.
That is, a metal complex ion in which a molecule composed of an inorganic substance or an ion composed of an inorganic substance serves as a ligand and is coordinate-bonded to the metal ion is easier to synthesize than other metal complex ions. As such metal complex ions, ammonia NH 3 serves as a ligand to coordinate-bond to metal ions, and water H 2 O serves as a ligand to coordinate-bond to metal ions. Hydroxometal complex ion, chlorine ion Cl- , which is coordinated to a metal ion with a complex ion, hydroxyl group OH- as a ligand, or chlorine ion Cl - and ammonia NH 3 are ligands for a metal ion. There are chlorometal complex ions that coordinate to each other. Furthermore, inorganic metal compounds composed of inorganic salts such as chlorides, sulfates, and nitrates having such metal complex ions are easy to synthesize and have a small molecular weight of the inorganic salts, so that they are inorganic substances in the temperature range of 180-220 ° C. The vaporization of the metal is completed and the metal is deposited. The temperature at which this metal precipitates is the lowest among the temperatures at which the metal precipitates due to the thermal decomposition of the metal compound. Such inorganic metal compounds are general-purpose industrial chemicals.
On the other hand, by using the above-mentioned inorganic metal compound as the metal compound for precipitating metal by thermal decomposition described in paragraph 7, the number of carbon atoms can be increased as an appropriate organic compound having the five properties described in paragraph 7. There are alkanes made of 11-13, carboxylic acid esters made of saturated fatty acids, or organic compounds belonging to aliphatic alcohols. These organic compounds are general-purpose industrial organic compounds.
That is, the n-undecane C 11 H 24 having 11 carbon atoms has a melting point of −26 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is higher than the thermal decomposition temperature of the inorganic metal compound 196. It has the five properties described in paragraph 7, which does not cause a chemical reaction with fine particles made of a metal precipitated by thermal decomposition of an inorganic metal compound and has no water absorption at ° C. The vapor pressure is 5383 Pascal at 192 ° C., which is close to the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the n-undecane has a vapor pressure of several thousand Pascals, so that the vacuum in the vacuum chamber The n-undecane can be vaporized without increasing the degree. Furthermore, n-undecane is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Next, n-dodecane C 12 H 26 having 12 carbon atoms has a melting point of −9.6 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is the thermal decomposition temperature of the inorganic metal compound. At a higher temperature of 216 ° C., it does not chemically react with fine particles made of a metal precipitated by thermal decomposition of an inorganic metal compound, has no water absorption, and has the five properties described in paragraph 7. The vapor pressure is 133 pascals at 48 ° C., and the vapor pressure is 6310 pascals at 204 ° C., which is close to the thermal decomposition temperature of the inorganic metal compound. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the n-dodecane has a vapor pressure of several thousand pascals, so that the vacuum in the vacuum chamber The n-dodecane can be vaporized without increasing the degree. Furthermore, n-dodecane is almost insoluble in water. Therefore, there is no water absorption near room temperature. Further, since the vapor pressure at around 20 ° C. at room temperature is low, the amount of evaporation is extremely small. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Further, n-tridecane C 13 H 28 having 13 carbon atoms has a melting point of −5 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is higher than the thermal decomposition temperature of the inorganic metal compound 235. It has the five properties described in paragraph 7, which does not cause a chemical reaction with fine particles made of a metal precipitated by thermal decomposition of an inorganic metal compound and has no water absorption at ° C. The vapor pressure is 5520 pascals at 211 ° C., which is close to the thermal decomposition temperature of the inorganic metal compound. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the n-tridecane has a vapor pressure of several thousand pascals, so that the vacuum in the vacuum chamber The n-tridecane can be vaporized without increasing the degree. Furthermore, n-tridecane is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. Since the vapor pressure at around 20 ° C. at room temperature is low, the amount of evaporation is extremely small. In addition, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Further, by using the above-mentioned inorganic metal compound as the metal compound described in paragraph 7, it belongs to carboxylic acid esters composed of saturated fatty acids as an appropriate other organic compound having the five properties described in paragraph 7. There are organic compounds.
That is, among the decanoic acid esters, methyl decanoate CH 3 (CH 2 ) 8 COOCH 3 has a melting point of −12 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is the heat of the inorganic metal compound. At 224 ° C., which is higher than the decomposition temperature, it does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound, has no water absorption, and has the properties of 5 described in paragraph 7. The vapor pressure is 2213 pascals at 199 ° C and increases rapidly as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the vacuum in the vacuum chamber is due to the fact that methyl decanoate has a vapor pressure of several thousand pascals. Methyl decanoate can be vaporized without increasing the degree. In addition, methyl decanoate is practically insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Next, ethyl decanoate CH 3 (CH 2 ) 8 COOC 2 H 5 has a melting point of −20 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is higher than the thermal decomposition temperature of the inorganic metal compound 243. It has the properties of 5 described in paragraph 7, which does not cause a chemical reaction with fine particles made of a metal precipitated by thermal decomposition of the inorganic metal compound and has no water absorption at ° C. Vapor pressure, like methyl decanoate, increases sharply as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, ethyl decanoate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Ethyl decanoate can be vaporized without increasing. Furthermore, ethyl decanoate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
On the other hand, among the nonanoic acid esters, methyl nonanoate CH 3 (CH 2 ) 7 COOCH 3 has a melting point of −35 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is the heat of the inorganic metal compound. At 214 ° C., which is higher than the decomposition temperature, it does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound, has no water absorption, and has the properties of 5 described in paragraph 7. Since the vapor pressure has a boiling point close to the thermal decomposition temperature of the inorganic metal compound, the vapor pressure has a vapor pressure close to 1 atm at the thermal decomposition temperature of the inorganic metal compound. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the degree of vacuum in the vacuum chamber is increased because methyl nonanoate has a constant vapor pressure. Methyl nonanoate can be vaporized without increasing it. In addition, methyl nonanoate is practically insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, the fine crystals of the inorganic metal compound can be stored without being changed.
Further, ethyl nonanoate CH 3 (CH 2 ) 7 COOC 2 H 5 has a melting point of −44 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is 220 ° C. higher than the thermal decomposition temperature of the inorganic metal compound. Therefore, it has the properties of 5 described in paragraph 7, which does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound and does not have water absorption. Since the vapor pressure has a boiling point close to the thermal decomposition temperature of the inorganic metal compound, the vapor pressure has a vapor pressure close to 1 atm at the thermal decomposition temperature of the inorganic metal compound. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, ethyl nonanoate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Ethyl nonanoate can be vaporized without increasing. Furthermore, ethyl nonanoate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Further, among the octanoic acid esters, methyl octanoate CH 3 (CH 2 ) 6 COOCH 3 has a melting point of −40 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is the heat of the inorganic metal compound. At 194 ° C., which is higher than the decomposition temperature, it does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound, has no water absorption, and has the properties of 5 described in paragraph 7. The vapor pressure has 4410 pascals at 190 ° C., which is close to the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the vacuum in the vacuum chamber is due to the fact that methyl octanate has a vapor pressure of several thousand pascals. Methyl octanate can be vaporized without increasing the degree. In addition, methyl octanate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Further, ethyl octanoate CH 3 (CH 2 ) 6 COOC 2 H 5 has a melting point of −48 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is 208 ° C. higher than the thermal decomposition temperature of the inorganic metal compound. Therefore, it has the properties of 5 described in paragraph 7, which does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound and does not have water absorption. The vapor pressure is 322 pascals at 60 ° C., and the vapor pressure rapidly increases as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, ethyl octanoate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Ethyl octanate can be vaporized without increasing. Furthermore, ethyl octanoate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Further, isopropyl octanoate CH 3 (CH 2 ) 6 COOCH (CH 3 ) 2 has a melting point of 12 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is higher than the thermal decomposition temperature of the inorganic metal compound 214. It has the properties of 5 described in paragraph 7, which does not cause a chemical reaction with fine particles made of a metal precipitated by thermal decomposition of an inorganic metal compound and has no water absorption at ° C. Since the vapor pressure has a boiling point close to the thermal decomposition temperature of the inorganic metal compound, the vapor pressure has a vapor pressure close to 1 atm at the thermal decomposition temperature of the inorganic metal compound. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, isopropyl octanoate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Isopropyl octanate can be vaporized without increasing. Furthermore, isopropyl octanate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Further, among the heptanic acid esters, butyl heptanate CH 3 (CH 2 ) 5 COOC 4 H 9 has a melting point of −64 ° C., the above-mentioned inorganic metal compound is not dissolved and dispersed, and the boiling point is an inorganic metal compound. At 207 ° C., which is higher than the thermal decomposition temperature of the above, it does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound, has no water absorption, and has the properties of 5 described in paragraph 7. Since the vapor pressure has a boiling point close to the thermal decomposition temperature of the inorganic metal compound, the vapor pressure has a vapor pressure close to 1 atm at the thermal decomposition temperature of the inorganic metal compound. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the butyl heptanate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Butyl heptanate can be vaporized without increasing. Furthermore, butyl heptanate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
On the other hand, by using the above-mentioned inorganic metal compound as the metal compound described in paragraph 7, it is composed of 8-22 carbon chains as another suitable organic compound having the five properties described in paragraph 7. There are organic compounds belonging to the aliphatic alcohol CH 3 (CH 2 ) n-1 OH.
That is, 1-octanol CH 3 (CH 2 ) 7 OH having 8 carbon chains has a melting point of -16 ° C., the inorganic metal compound does not dissolve and disperse, and the boiling point is higher than the thermal decomposition temperature of the inorganic metal compound. At 195 ° C., it does not cause a chemical reaction with fine particles made of a metal precipitated by thermal decomposition of an inorganic metal compound, has no water absorption, and has the properties of 5 described in paragraph 7. The vapor pressure is 348 pascals at 171 ° C. and 3797 pascals at 193 ° C., and the vapor pressure rapidly increases as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, 1-octanol has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. 1-Octanol can be vaporized without increasing. Furthermore, 1-octanol is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Next, 1-nonanol CH 3 (CH 2 ) 8 OH having a carbon chain of 9 has a melting point of −7 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is thermal decomposition of the inorganic metal compound. At 215 ° C., which is higher than the temperature, it does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound, has no water absorption, and has the properties of 5 described in paragraph 7. The vapor pressure is 1842 pascals at 193 ° C., and the vapor pressure rapidly increases as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, 1-nonanol has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. 1-Nonanol can be vaporized without increasing. Furthermore, 1-nonanol is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
Further, 1-decanol CH 3 (CH 2 ) 9 OH having 10 carbon chains has a melting point of −6.4 ° C., the above-mentioned inorganic metal compound does not dissolve and disperse, and the boiling point is the heat of the inorganic metal compound. At 233 ° C., which is higher than the decomposition temperature, it does not cause a chemical reaction with fine particles made of metal deposited by thermal decomposition of an inorganic metal compound, has no water absorption, and has the properties of 5 described in paragraph 7. The vapor pressure is 910 pascals at 193 ° C., and the vapor pressure rapidly increases as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, 1-decanol has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. 1-Decanol can be vaporized without increasing. Moreover, 1-decanol is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the inorganic metal compound can be stored for a long period of time without change.
As described above, by using the above-mentioned inorganic metal compound as the metal compound for precipitating metal by thermal decomposition described in paragraph 7, as an appropriate organic compound having the five properties described in paragraph 7. There are alkanes having 11-14 carbon atoms, carboxylic acid esters consisting of saturated fatty acids, or organic compounds belonging to aliphatic alcohols.
７段落に記載した熱分解で金属を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法は、
７段落に記載した熱分解で金属を析出する金属化合物が、オクチル酸金属化合物であり、７段落に記載した液体の有機化合物が、飽和脂肪酸からなるカルボン酸エステル類に属する１種類の有機化合物であり、前記オクチル酸金属化合物を７段落に記載した熱分解で金属を析出する金属化合物として用い、前記飽和脂肪酸からなるカルボン酸エステル類に属する１種類の有機化合物を７段落に記載した液体の有機化合物として用い、７段落に記載した懸濁液を製造する方法に従って懸濁液を製造する、７段落に記載した熱分解で金属を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。
The method for producing a suspension in which fine crystals of a metal compound that precipitates a metal by thermal decomposition described in paragraph 7 are surrounded by a liquid organic compound and dispersed in the liquid organic compound is described.
The metal compound that precipitates metal by thermal decomposition described in paragraph 7 is an octylate metal compound, and the liquid organic compound described in paragraph 7 is one kind of organic compound belonging to carboxylic acid esters composed of saturated fatty acids. There, the octylate metal compound is used as a metal compound for precipitating metal by thermal decomposition described in paragraph 7, and one kind of organic compound belonging to the carboxylic acid esters composed of saturated fatty acids is described in paragraph 7 as a liquid organic compound. Fine crystals of a metal compound that precipitates a metal by thermal decomposition described in paragraph 7, which is used as a compound and produces a suspension according to the method for producing a suspension described in paragraph 7, are surrounded by a liquid organic compound. , A method for producing a suspension dispersed in a liquid organic compound.
つまり、オクチル酸金属化合物は、大気雰囲気の２９０℃で熱処理すると、金属を析出する。また、メタノールに１０重量％近く分散し、メタノールに溶解しない。従って、オクチル酸金属化合物は、７段落に記載した懸濁液を製造する方法において、２つの性質を兼備する金属化合物である。
すなわち、オクチル酸金属化合物を構成するイオンの中で、金属イオンが最も大きい。従って、オクチル酸のカルボキシル基を構成する酸素イオンが金属イオンに共有結合するオクチル酸金属化合物においては、カルボキシル基を構成する酸素イオンと金属イオンとの距離が、他のイオン同士の距離より長い。こうした分子構造の特徴を持つオクチル酸金属化合物を大気雰囲気で熱処理すると、オクチル酸の沸点の２２８℃を超えると、カルボキシル基を構成する酸素イオンと金属イオンとの結合部が最初に分断され、オクチル酸と金属とに分離する。さらに、オクチル酸が飽和脂肪酸であるため、炭素原子が水素原子に対して過剰となる不飽和構造を持たないため、オクチル酸が気化熱を奪って気化し、気化が完了する２９０℃で金属が析出する。なお、オクチル酸金属化合物を窒素雰囲気で熱処理すると、３３０℃で金属が析出する。
つまり、飽和脂肪酸からなるカルボン酸のカルボキシラートアニオン（Ｒ－ＣＯＯ－）が、金属イオンと共有結合するカルボン酸金属化合物は、熱分解で金属を析出する。こうしたカルボン酸金属化合物として、金属を析出する熱分解温度が低い順に、オクチル酸金属化合物、ラウリン酸金属化合物、ステアリン酸金属化合物がある。従って、熱分解温度が最も低いオクチル酸金属化合物を用いると、７段落に記載した懸濁液が安価に製造できる。なお、ラウリン酸金属化合物とステアリン酸金属化合物は、オクチル酸金属化合物と同様に、メタノールに１０重量％近く分散し、メタノールに溶解しない。
つまり、ラウリン酸の沸点は２９６℃であり、ラウリン酸金属化合物の熱分解温度が３６０℃である。しかし、ラウリン酸金属化合物とステアリン酸金属化合物の熱分解温度が、オクチル酸金属化合物の熱分解温度より高く、金属を析出する原料として、オクチル酸金属化合物を用いるのが望ましい。
なお、不飽和脂肪酸からなるカルボン酸金属化合物は、飽和脂肪酸からなるカルボン酸金属化合物に比べ、炭素原子が水素原子に対して過剰になるため、熱分解によって金属酸化物、例えば、オレイン酸銅の場合は、酸化第一銅Ｃｕ２Ｏと酸化第二銅ＣｕＯとが同時に析出し、酸化第一銅と酸化第二銅とを銅に還元する処理費用を要する。特に、酸化第一銅は、大気雰囲気より酸素がリッチな雰囲気で酸化第二銅に酸化させ、さらに、還元雰囲気で銅に還元させる必要があるため、処理費用がかさむ。
さらに、オクチル酸金属化合物は、容易に合成できる安価な工業用薬品である。すなわち、オクチル酸を強アルカリと反応させるとオクチル酸アルカリ金属化合物が生成される。この後、オクチル酸アルカリ金属化合物を無機金属化合物と反応させると、様々な金属からなるオクチル酸金属化合物が生成される。また、オクチル酸が汎用的な有機酸である。従って、オクチル酸金属化合物は、有機金属化合物の中で最も安価な有機金属化合物である。このため、１２段落で説明した無機金属化合物からなる錯体より熱分解温度が高くなるが、錯体より安価な金属化合物である。
以上に説明したように、オクチル酸金属化合物は、７段落に記載した懸濁液を製造する方法において、２つの性質を兼備する金属化合物であり、また、金属の微粒子の安価な原料になる。
いっぽう、７段落に記載した熱分解で金属を析出する金属化合物として、前記したオクチル酸金属化合物を用いることで、７段落に記載した５つの性質を兼備する適切な有機化合物として、飽和脂肪酸からなるカルボン酸エステル類に属する有機化合物が存在する。該カルボン酸エステル類に属する有機化合物は、汎用的な工業用の有機化合物である。
すなわち、ミリスチン酸エステル類の中で、ミリスチン酸エチルＣＨ３（ＣＨ２）１２ＣＯＯＣ２Ｈ５は、融点が１１℃で、前記したオクチル酸金属化合物が溶解及び分散せず、沸点が２９５℃で、オクチル酸金属化合物の熱分解温度である２９０℃より５℃高く、オクチル酸金属化合物の熱分解温度で析出した金属の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ミリスチン酸エチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ミリスチン酸エチルを気化することができる。さらに、ミリスチン酸エチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、オクチル酸金属化合物の微細結晶を変化させることなく保管できる。
さらに、ミリスチン酸イソプロピルＣＨ３（ＣＨ２）１２ＣＯＯＣ３Ｈ７は、融点が７℃で、前記したオクチル酸金属化合物が溶解及び分散せず、沸点が３２０℃で、オクチル酸金属化合物の熱分解温度である２９０℃より３０℃高く、オクチル酸金属化合物の熱分解温度で析出した金属の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、２３５℃において１７５３パスカルで、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ミリスチン酸イソプロピルが数千パスカルの蒸気圧を持ち、真空チャンバー内の真空度を高めることなく、ミリスチン酸イソプロピルを気化することができる。さらに、ミリスチン酸イソプロピルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘ってオクチル酸金属化合物の微細結晶を変化させることなく保管できる。
次に、ラウリン酸エステル類の中で、ラウリン酸ブチルＣＨ３（ＣＨ２）１０ＣＯＯＣ４Ｈ９は、融点が－１０℃で、沸点が３０６℃で、前記したオクチル酸金属化合物の熱分解温度である２９０℃より１６℃高く、オクチル酸金属化合物の熱分解温度で析出した金属の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、真空チャンバー内の真空度を高めることなく、ラウリン酸ブチルを気化することができる。さらに、ラウリン酸ブチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、オクチル酸金属化合物の微細結晶を変化させることなく保管できる。
また、ラウリン酸２－エチルヘキシルＣＨ３（ＣＨ２）１０ＣＯＯＣ８Ｈ１７は、融点が－３０℃で、沸点が３１５℃で、前記したオクチル酸金属化合物の熱分解温度である２９０℃より２５℃高く、オクチル酸金属化合物の熱分解温度で析出した金属の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ラウリン酸２－エチルヘキシルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ラウリン酸２－エチルヘキシルを気化することができる。さらに、ラウリン酸２－エチルヘキシルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、オクチル酸金属化合物の微細結晶を変化させることなく保管できる。
さらに、オクタン酸エステル類の中で、オクタン酸オクチルＣＨ３（ＣＨ２）７ＣＯＯ（ＣＨ２）６ＣＨ３は、融点が－１８℃で、沸点が３０６℃で、前記したオクチル酸金属化合物の熱分解温度である２９０℃より１６℃高く、オクチル酸金属化合物の熱分解温度で析出した金属の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸オクチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸オクチルを気化することができる。さらに、オクタン酸オクチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、オクチル酸金属化合物の微細結晶を変化させることなく保管できる。
以上に説明したように、７段落に記載した熱分解で金属を析出する金属化合物として、前記したオクチル酸金属化合物を用いることによって、７段落に記載した５つの性質を兼備する適切な有機化合物として、飽和脂肪酸からなるカルボン酸エステル類に属する有機化合物が存在する。
That is, the metal octylate compound precipitates a metal when heat-treated at 290 ° C. in the atmospheric atmosphere. Further, it is dispersed in methanol in an amount of about 10% by weight and does not dissolve in methanol. Therefore, the octylate metal compound is a metal compound having two properties in the method for producing a suspension described in paragraph 7.
That is, among the ions constituting the octylate metal compound, the metal ion is the largest. Therefore, in the octylate metal compound in which the oxygen ion constituting the carboxyl group of octyl acid is covalently bonded to the metal ion, the distance between the oxygen ion constituting the carboxyl group and the metal ion is longer than the distance between the other ions. When a metal octylate compound having such molecular structure characteristics is heat-treated in an atmospheric atmosphere, when the boiling point of octyl acid exceeds 228 ° C, the bond portion between the oxygen ion constituting the carboxyl group and the metal ion is first separated, and octyl is used. Separates into acid and metal. Furthermore, since octyl acid is a saturated fatty acid, it does not have an unsaturated structure in which carbon atoms are excessive with respect to hydrogen atoms. Precipitate. When the metal octylate compound is heat-treated in a nitrogen atmosphere, the metal precipitates at 330 ° C.
That is, a carboxylic acid metal compound in which a carboxylate anion (R - COO-) of a carboxylic acid composed of a saturated fatty acid is covalently bonded to a metal ion deposits a metal by thermal decomposition. As such a carboxylic acid metal compound, there are an octylate metal compound, a laurate metal compound, and a stearate metal compound in ascending order of the thermal decomposition temperature at which the metal is precipitated. Therefore, if the metal compound octylate having the lowest thermal decomposition temperature is used, the suspension described in paragraph 7 can be produced at low cost. The metal laurate compound and the metal stearate compound, like the metal octylate compound, are dispersed in methanol in an amount of about 10% by weight and are not dissolved in methanol.
That is, the boiling point of lauric acid is 296 ° C, and the thermal decomposition temperature of the metal lauric acid compound is 360 ° C. However, the thermal decomposition temperature of the metal laurate compound and the metal stearate compound is higher than the thermal decomposition temperature of the metal octylate compound, and it is desirable to use the metal octylate compound as a raw material for precipitating the metal.
Since the carboxylic acid metal compound composed of unsaturated fatty acid has an excess of carbon atom with respect to the hydrogen atom as compared with the carboxylic acid metal compound composed of saturated fatty acid, the metal oxide, for example, copper oleate, is subjected to thermal decomposition. In this case, cuprous oxide Cu 2 O and cupric oxide Cu O are deposited at the same time, and a treatment cost for reducing the cuprous oxide and cupric oxide to copper is required. In particular, cuprous oxide needs to be oxidized to cupric oxide in an atmosphere rich in oxygen than the air atmosphere and further reduced to copper in a reducing atmosphere, which increases the processing cost.
Furthermore, octylate metal compounds are inexpensive industrial chemicals that can be easily synthesized. That is, when octyl acid is reacted with a strong alkali, an alkali metal octylate compound is produced. After that, when the alkali metal octylate compound is reacted with the inorganic metal compound, a metal octylate compound composed of various metals is produced. In addition, octyl acid is a general-purpose organic acid. Therefore, the octylate metal compound is the cheapest organometallic compound among the organometallic compounds. Therefore, the thermal decomposition temperature is higher than that of the complex composed of the inorganic metal compound described in paragraph 12, but the metal compound is cheaper than the complex.
As described above, the octylate metal compound is a metal compound having two properties in the method for producing a suspension described in paragraph 7, and is an inexpensive raw material for metal fine particles.
On the other hand, by using the above-mentioned octylate metal compound as the metal compound for precipitating a metal by thermal decomposition described in paragraph 7, it is composed of a saturated fatty acid as an appropriate organic compound having the five properties described in paragraph 7. There are organic compounds belonging to carboxylic acid esters. The organic compound belonging to the carboxylic acid esters is a general-purpose industrial organic compound.
That is, among the myristin acid esters, ethyl myristate CH 3 (CH 2 ) 12 COOC 2 H 5 has a melting point of 11 ° C., the above-mentioned octylate metal compound does not dissolve and disperse, and the boiling point is 295 ° C. , Which is 5 ° C higher than the thermal decomposition temperature of the metal octylate compound of 290 ° C. and does not cause a chemical reaction with the fine particles of the metal precipitated at the thermal decomposition temperature of the metal octylate compound, and has the five properties described in paragraph 7. It is an organic compound. As the vapor pressure approaches the boiling point, the vapor pressure rapidly increases. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, ethyl myristate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Ethyl myristate can be vaporized without increasing. In addition, ethyl myristate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal octylate compound can be stored for a long period of time without being changed.
Further, isopropyl myristate CH 3 (CH 2 ) 12 COOC 3 H 7 has a melting point of 7 ° C., the above-mentioned metal octylate compound is not dissolved and dispersed, and a boiling point of 320 ° C. is such that the metal compound octylate is thermally decomposed. It is an organic compound having the five properties described in paragraph 7, which is 30 ° C. higher than the temperature of 290 ° C. and does not cause a chemical reaction with the fine metal particles precipitated at the thermal decomposition temperature of the metal octylate compound. The vapor pressure is 1753 pascals at 235 ° C., and the vapor pressure increases rapidly as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, isopropyl myristate has a vapor pressure of several thousand pascals and the degree of vacuum in the vacuum chamber. Isopropyl myristate can be vaporized without increasing. In addition, isopropyl myristate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal octylate compound can be stored for a long period of time without change.
Next, among the lauric acid esters, butyl laurate CH 3 (CH 2 ) 10 COOC 4 H 9 has a melting point of −10 ° C. and a boiling point of 306 ° C., and has a thermal decomposition temperature of the above-mentioned octylate metal compound. It is an organic compound having the five properties described in paragraph 7, which is 16 ° C. higher than 290 ° C. and does not cause a chemical reaction with the fine metal particles precipitated at the thermal decomposition temperature of the metal octylate compound. As the vapor pressure approaches the boiling point, the vapor pressure rapidly increases. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, butyl laurate can be vaporized without increasing the degree of vacuum in the vacuum chamber. can. In addition, butyl laurate is practically insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal octylate compound can be stored for a long period of time without being changed.
In addition, 2-ethylhexyl laurate CH 3 (CH 2 ) 10 COOC 8 H 17 has a melting point of −30 ° C. and a boiling point of 315 ° C., which is 25 ° C. from the thermal decomposition temperature of the above-mentioned octylate metal compound of 290 ° C. It is an organic compound having the five properties described in paragraph 7, which is high and does not cause a chemical reaction with the fine particles of the metal precipitated at the thermal decomposition temperature of the metal octylate compound. As the vapor pressure approaches the boiling point, the vapor pressure rapidly increases. Therefore, if the pressure inside the vacuum chamber is reduced with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, 2-ethylhexyl laurate has a constant vapor pressure, so that the vacuum inside the vacuum chamber 2-Ethylhexyl laurate can be vaporized without increasing the degree. Furthermore, 2-ethylhexyl laurate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal octylate compound can be stored for a long period of time without being changed.
Further, among the octanoic acid esters, octyl octylate CH 3 (CH 2 ) 7 COO (CH 2 ) 6 CH 3 has a melting point of -18 ° C. and a boiling point of 306 ° C., and is the above-mentioned octylate metal compound. It is an organic compound having the five properties described in paragraph 7, which is 16 ° C. higher than the thermal decomposition temperature of 290 ° C. and does not cause a chemical reaction with the fine metal particles precipitated at the thermal decomposition temperature of the metal octylate compound. As the vapor pressure approaches the boiling point, the vapor pressure rapidly increases. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, octyl octanoate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Octyl octanate can be vaporized without increasing. Moreover, octyl octanate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal octylate compound can be stored for a long period of time without being changed.
As described above, by using the above-mentioned metal octylate compound as the metal compound for precipitating a metal by thermal decomposition described in paragraph 7, as an appropriate organic compound having the five properties described in paragraph 7. , There are organic compounds belonging to carboxylic acid esters composed of saturated fatty acids.
７段落に記載した熱分解で金属酸化物を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法は、
７段落に記載した熱分解で金属酸化物を析出する金属化合物が、カルボン酸のカルボキシル基を構成する酸素イオンが、金属イオンに配位結合したカルボン酸金属化合物からなる錯体であり、７段落に記載した液体の有機化合物が、飽和脂肪酸からなるカルボン酸エステル類、ないしは、不飽和脂肪酸類に属するいずれか１種類の有機化合物であり、前記カルボン酸金属化合物を７段落に記載した熱分解で金属酸化物を析出する金属化合物として用い、前記カルボン酸エステル類、ないしは、前記不飽和脂肪酸類に属するいずれか１種類の有機化合物を７段落に記載した液体の有機化合物として用い、７段落に記載した懸濁液を製造する方法に従って懸濁液を製造する、７段落に記載した熱分解で金属酸化物を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。
The method for producing a suspension in which fine crystals of a metal compound that precipitates a metal oxide by thermal decomposition described in paragraph 7 are surrounded by a liquid organic compound and dispersed in the liquid organic compound is described.
The metal compound that precipitates the metal oxide by thermal decomposition described in paragraph 7 is a complex composed of the carboxylic acid metal compound in which the oxygen ion constituting the carboxyl group of the carboxylic acid is coordinated and bonded to the metal ion, and is described in paragraph 7. The liquid organic compound described is any one of organic compounds belonging to carboxylic acid esters composed of saturated fatty acids or unsaturated fatty acids, and the said carboxylic acid metal compound is metallized by thermal decomposition described in paragraph 7. It is used as a metal compound that precipitates an oxide, and any one of the organic compounds belonging to the carboxylic acid esters or the unsaturated fatty acids is used as the liquid organic compound described in paragraph 7, and is described in paragraph 7. The fine crystals of the metal compound that precipitates the metal oxide by thermal decomposition described in paragraph 7, which produces the suspension according to the method for producing the suspension, are surrounded by the liquid organic compound and contained in the liquid organic compound. A method for producing a suspension dispersed in a compound.
つまり、カルボン酸金属化合物からなる錯体は、１８０－３３０℃の温度からなる大気雰囲気で熱処理すると、金属酸化物を析出する。また、メタノールに分散し、メタノールに溶解しない。従って、カルボン酸金属化合物からなる錯体は、７段落に記載した懸濁液を製造する方法において、２つの性質を兼備する金属化合物である。
すなわち、カルボン酸のカルボキシラートアニオン（Ｒ－ＣＯＯ－）が配位子となって、金属イオンに近づいて配位結合するカルボン酸金属化合物からなる錯体は、最も大きいイオンである金属イオンにカルボキシラートアニオン（Ｒ－ＣＯＯ－）が近づいて配位結合するため、両者の距離は短くなる。これによって、金属イオンに配位結合するカルボキシラートアニオン（Ｒ－ＣＯＯ－）が、金属イオンの反対側で共有結合するイオンとの距離が最も長くなる。こうした分子構造上の特徴を持つカルボン酸金属化合物は、カルボン酸の沸点を超えると、カルボキシラートアニオン（Ｒ－ＣＯＯ－）が金属イオンの反対側で共有結合するイオンとの結合部が最初に分断され、金属イオンと酸素イオンとの化合物である金属酸化物とカルボン酸とに分解する。さらに昇温すると、カルボン酸が気化熱を奪って気化し、カルボン酸の分子量と、配位結合するカルボン酸の数に応じて、カルボン酸の気化が進み、気化が完了すると、金属酸化物が析出して熱分解を終える。
こうした分子構造上の特徴を持つカルボン酸金属化合物として、酢酸金属化合物、カプリル酸金属化合物、安息香酸金属化合物、ナフテン酸金属化合物などがある。これらカルボン酸金属化合物からなる錯体は、カルボン酸の沸点に応じて、１８０－３３０℃の大気雰囲気で熱分解する。つまり、酢酸の沸点は１１８℃で、カプリル酸の沸点は２３７℃で、安息香酸の沸点は２４９℃である。いっぽう、ナフテン酸は５員環をもつ飽和脂肪酸の混合物で、一般式ではＣｎＨ２ｎ－１ＣＯＯＨで示され、主成分は沸点が２６８℃で、分子量が１７０のＣ９Ｈ１７ＣＯＯＨからなる。このため、ナフテン酸金属化合物の熱分解温度は、カルボン酸金属化合物からなる錯体の中で３３０℃と高い。従って、酢酸金属化合物、カプリル酸金属化合物、安息香酸金属化合物ないしはナフテン酸金属化合物を、７段落に記載した２つの性質を兼備する金属化合物として用いることができる。
いっぽう、酢酸金属化合物の中に、メタノールに溶解する酢酸金属化合物がある。また、熱分解でアモルファス化した金属酸化物を析出する酢酸金属化合物がある。アモルファス化した金属酸化物の組成は一定でない。こうした酢酸金属化合物は、金属酸化物からなる微粒子の原料として用いることができない。さらに、酢酸金属化合物ないしはカプリル酸金属化合物の中に、熱分解で無定形の金属酸化物を析出する酢酸金属化合物ないしはカプリル酸金属化合物がある。こうした酢酸金属化合物ないしはカプリル酸金属化合物は、金属酸化物からなる微粒子の原料として用いることができない。また、酢酸金属化合物とカプリル酸金属化合物と安息香酸金属化合物の中に、酸素イオンが金属イオンに近づいて配位結合して複核錯塩を形成するが、熱分解の途上においては不安定な物質であり、熱分解における取り扱いが難しい酢酸金属化合物、カプリル酸金属化合物ないしは安息香酸金属化合物がある。こうしたカルボン酸金属化合物においては、ナフテン酸金属化合物を金属酸化物からなる微粒子の原料として用いる。従って、熱分解で析出する物質に応じて、カルボン酸金属化合物からなる錯体を、微細結晶の原料として用いる。
さらに、カルボン酸金属化合物からなる錯体は容易に合成できる安価な工業用薬品である。すなわち、カルボン酸を強アルカリと反応させるとカルボン酸アルカリ金属化合物が生成される。この後、カルボン酸アルカリ金属化合物を無機金属化合物と反応させると、様々な金属からなるカルボン酸金属化合物からなる錯体が合成される。また、原料となるカルボン酸は、安価な有機酸である。従って、有機金属化合物の中で最も安価な有機金属化合物である。
以上に説明したように、カルボン酸金属化合物からなる錯体は、７段落に記載した懸濁液を製造する製造方法において、熱分解で金属酸化物を析出する金属化合物であり、また、金属酸化物の微粒子の安価な原料になる。
いっぽう、７段落に記載した熱分解で金属酸化物を析出する金属化合物として、前記したカルボン酸金属化合物からなる錯体を用いることによって、７段落に記載した５つの性質を兼備する適切な有機化合物として、飽和脂肪酸からなるカルボン酸エステル類、ないしは、不飽和脂肪酸類に属する有機化合物が存在する。なお、これらの有機化合物は、汎用的な工業用の有機化合物である。
すなわち、飽和脂肪酸からなるカルボン酸エステル類の中では、オクタン酸エステル類に属するオクタン酸メチルＣＨ３（ＣＨ２）６ＣＯＯＣＨ３は、１２段落に記載したように、融点が－４０℃で、前記したカルボン酸金属化合物からなる錯体が溶解及び分散せず、沸点が前記した酢酸金属化合物の熱分解温度より１９℃高い１９４℃で、酢酸金属化合物の熱分解で析出する金属酸化物からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、沸点が酢酸金属化合物の熱分解温度に近く、沸点に近い１９０℃では４４１０パスカルを持つ。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸メチルが数千パスカル蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸メチルを気化することができる。さらに、オクタン酸メチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、酢酸金属化合物の微細結晶を変化させることなく保管できる。
さらに、オクタン酸エチルＣＨ３（ＣＨ２）６ＣＯＯＣ２Ｈ５は、１２段落に記載したように、融点が－４８℃で、前記した酢酸金属化合物が溶解及び分散せず、沸点が酢酸金属化合物の熱分解温度より２８℃高い２０８℃で、酢酸金属化合物の熱分解で析出する金属酸化物からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、６０℃では３２２パスカルで、沸点に近づくと蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸エチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸エチルを気化することができる。さらに、オクタン酸エチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、酢酸金属化合物の微細結晶を変化させることなく保管できる。
さらに、オクタン酸エステル類の中で、オクタン酸オクチルＣＨ３（ＣＨ２）７ＣＯＯ（ＣＨ２）６ＣＨ３は、１２段落に記載したように、融点が－１８℃で、沸点が３０６℃で、前記したカプリル酸金属化合物の熱分解温度より１１℃高い２９５℃で、カプリル酸金属化合物の熱分解温度で析出した金属酸化物の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸オクチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸オクチルを気化することができる。さらに、オクタン酸オクチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、カプリル酸金属化合物の微細結晶を変化させることなく保管できる。
また、オクタン酸イソプロピルＣＨ３（ＣＨ２）６ＣＯＯＣＨ（ＣＨ３）２は、１２段落に記載したように、融点が１２℃で、前記した酢酸金属化合物が溶解及び分散せず、沸点が酢酸金属化合物の熱分解温度より２４℃高い２１４℃で、酢酸金属化合物の熱分解で析出する金属酸化物からなる微粒子と化学反応を起こさず、吸水性を持たない、７段落に記載した５の性質を兼備する。蒸気圧は、沸点が酢酸金属化合物の熱分解温度に近いため、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オクタン酸イソプロピルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オクタン酸イソプロピルを気化することができる。さらに、オクタン酸イソプロピルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、酢酸金属化合物の微細結晶を変化させることなく保管できる。
さらに、カルボン酸エステル類の中で、ラウリン酸エステル類に属するラウリン酸ブチルＣＨ３（ＣＨ２）１０ＣＯＯＣ４Ｈ９は、１４段落に記載したように、融点が－１０℃で、沸点が３０６℃で、前記したカプリル酸金属化合物の熱分解温度より１１℃高い２９５℃で、カプリル酸金属化合物の熱分解温度で析出した金属酸化物の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ラウリン酸ブチルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ラウリン酸ブチルを気化することができる。さらに、ラウリン酸ブチルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、カプリル酸金属化合物の微細結晶を変化させることなく保管できる。
また、ラウリン酸２－エチルヘキシルＣＨ３（ＣＨ２）１０ＣＯＯＣ８Ｈ１７は、１４段落に記載したように、融点が－３０℃で、沸点が３１５℃で、前記したカプリル酸金属化合物の熱分解温度より２０℃高い２９５℃で、また、前記した安息香酸金属化合物の熱分解温度より５℃高く、カプリル酸金属化合物ないしは安息香酸金属化合物の熱分解温度で析出した金属酸化物の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。また、ラウリン酸２－エチルヘキシルの蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ラウリン酸２－エチルヘキシルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ラウリン酸２－エチルヘキシルを気化することができる。さらに、ラウリン酸２－エチルヘキシルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、カプリル酸金属化合物ないしは安息香酸金属化合物の微細結晶を変化させることなく保管できる。
さらに、ラウリン酸ヘキシルＣＨ３（ＣＨ２）１０ＣＯＯＣＨ３（ＣＨ２）５は、融点が－３℃で、沸点が３３５℃で、前記した安息香酸金属化合物の熱分解温度より２５℃高く、また、前記したナフテン酸金属化合物の熱分解温度より５℃高く、安息香酸金属化合物ないしはナフテン酸金属化合物の熱分解で析出した金属酸化物の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。また、ラウリン酸ヘキシルの蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ラウリン酸ヘキシルが一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ラウリン酸ヘキシルを気化することができる。さらに、ラウリン酸ヘキシルは水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、安息香酸金属化合物ないしはナフテン酸金属化合物の微細結晶を変化させることなく保管できる。
ところで、不飽和脂肪酸類に属する有機化合物の中に、前記したカルボン酸金属化合物からなる錯体を、７段落に記載した熱分解で金属酸化物を析出する金属化合物として用いる際に、７段落に記載した５つの性質を兼備する有機化合物が存在する。
すなわち、ミリストレイン酸ＣＨ３（ＣＨ２）３ＣＨ＝ＣＨ（ＣＨ２）７ＣＯＯＨは、融点が－４℃で、沸点が３３９℃で、前記した安息香酸金属化合物の熱分解温度より２９℃高く、また、前記したナフテン酸金属化合物の熱分解温度である３３０℃より９℃高く、熱分解で析出した金属酸化物の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。ミリストレイン酸の蒸気圧は、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、ミリストレイン酸が一定の蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、ミリストレイン酸を気化することができる。さらに、ミリストレイン酸は水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、安息香酸金属化合物ないしはナフテン酸金属化合物の微細結晶を変化させることなく保管できる。
さらに、オレイン酸ＣＨ３（ＣＨ２）７ＣＨ＝ＣＨ（ＣＨ２）７ＣＯＯＨは、融点が１３．４℃で、沸点が３６０℃で、前記したナフテン酸金属化合物の熱分解温度である３３０℃より３０℃高く、熱分解で析出した金属酸化物の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、２６５℃において２３５７パスカルで、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、オレイン酸が数千パスカルの蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、オレイン酸を気化することができる。さらに、オレイン酸は水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、ナフテン酸金属化合物の微細結晶を変化させることなく保管できる。
また、リノール酸ＣＨ３（ＣＨ２）４（ＣＨ＝ＣＨＣＨ２）２（ＣＨ２）６ＣＯＯＨは、融点が－５℃で、沸点が３６０℃で、前記したナフテン酸金属化合物の熱分解温度である３３０℃より３０℃高く、熱分解で析出した金属酸化物の微粒子と化学反応を起こさない、７段落に記載した５つの性質を兼備する有機化合物である。蒸気圧は、２２９℃において２１３３パスカルで、沸点に近づくほど蒸気圧が急増する。従って、９段落に記載した第三の懸濁液の温度が低下する以前に、真空ポンプで真空チャンバー内を減圧すると、リノール酸が数千パスカルの蒸気圧を持つため、真空チャンバー内の真空度を高めることなく、リノール酸を気化することができる。さらに、リノール酸は水に殆ど溶けない。このため、常温の２０℃近辺で吸水性がない。また、常温の２０℃近辺での蒸気圧が低く、蒸発量が極めて僅かな液体である。さらに、常温の２０℃近辺では化学的に安定している。このため、第二の懸濁液において、長期に亘って、ナフテン酸金属化合物の微細結晶を変化させることなく保管できる。
以上に説明したように、７段落に記載した熱分解で金属酸化物を析出する金属化合物として、前記したカルボン酸金属化合物からなる錯体を用いることによって、７段落に記載した５つの性質を兼備する適切な有機化合物として、飽和脂肪酸からなるカルボン酸エステル類、ないしは、不飽和脂肪酸類に属する有機化合物が存在する。
That is, when the complex made of a carboxylic acid metal compound is heat-treated in an atmospheric atmosphere having a temperature of 180-330 ° C., a metal oxide is precipitated. It also disperses in methanol and does not dissolve in methanol. Therefore, the complex composed of a carboxylic acid metal compound is a metal compound having two properties in the method for producing a suspension described in paragraph 7.
That is, the complex composed of the carboxylic acid metal compound in which the carboxylate anion (R - COO-) of the carboxylic acid serves as a ligand and is coordinated and bonded to the metal ion is carboxylated to the metal ion which is the largest ion. Since the anion (R - COO-) approaches and coordinates, the distance between the two becomes shorter. As a result, the carboxylate anion (R - COO-) coordinated to the metal ion has the longest distance from the ion covalently bonded on the opposite side of the metal ion. When the carboxylic acid metal compound having such molecular structural characteristics exceeds the boiling point of the carboxylic acid, the bond portion with the ion to which the carboxylate anion (R - COO-) is covalently bonded on the opposite side of the metal ion is first split. Then, it decomposes into a metal oxide and a carboxylic acid, which are compounds of a metal ion and an oxygen ion. When the temperature is further raised, the carboxylic acid takes away the heat of vaporization and vaporizes, and the vaporization of the carboxylic acid proceeds according to the molecular weight of the carboxylic acid and the number of carboxylic acids to be coordinated, and when the vaporization is completed, the metal oxide is released. Precipitates and finishes thermal decomposition.
Examples of the carboxylic acid metal compound having such molecular structural characteristics include a metal acetate compound, a capricate metal compound, a benzoate metal compound, and a naphthenate metal compound. The complex composed of these carboxylic acid metal compounds is thermally decomposed in an air atmosphere of 180-330 ° C. depending on the boiling point of the carboxylic acid. That is, the boiling point of acetic acid is 118 ° C, the boiling point of caprylic acid is 237 ° C, and the boiling point of benzoic acid is 249 ° C. On the other hand, naphthenic acid is a mixture of saturated fatty acids having a 5-membered ring, which is generally represented by C n H 2n-1 COOH, and its main component is C 9 H 17 COOH having a boiling point of 268 ° C and a molecular weight of 170. .. Therefore, the thermal decomposition temperature of the metal naphthenate compound is as high as 330 ° C. in the complex composed of the metal carboxylate compound. Therefore, the metal acetate compound, the capricate metal compound, the benzoate metal compound or the naphthenate metal compound can be used as the metal compound having the two properties described in paragraph 7.
On the other hand, among the metal acetate compounds, there is a metal acetate compound that dissolves in methanol. In addition, there are metal acetate compounds that precipitate metal oxides that are amorphized by thermal decomposition. The composition of the amorphized metal oxide is not constant. Such a metal acetate compound cannot be used as a raw material for fine particles made of a metal oxide. Further, among the metal acetate compounds or caprice metal compounds, there are metal acetate compounds or caprice metal compounds that precipitate atypical metal oxides by thermal decomposition. Such a metal acetate compound or a metal caprylic acid compound cannot be used as a raw material for fine particles made of a metal oxide. In addition, oxygen ions approach the metal ions and coordinate to form a dinuclear complex salt in the metal acetate compound, the capricate metal compound, and the benzoate metal compound, but they are unstable substances during thermal decomposition. There are metal acetate compounds, metal caprylate compounds, and metal benzoate compounds that are difficult to handle in thermal decomposition. In such a metal carboxylate compound, the metal naphthenate compound is used as a raw material for fine particles made of a metal oxide. Therefore, a complex composed of a metal carboxylate compound is used as a raw material for fine crystals, depending on the substance precipitated by thermal decomposition.
Further, a complex composed of a metal carboxylate compound is an inexpensive industrial chemical that can be easily synthesized. That is, when a carboxylic acid is reacted with a strong alkali, a carboxylic acid alkali metal compound is produced. After that, when the carboxylic acid alkali metal compound is reacted with the inorganic metal compound, a complex made of a carboxylic acid metal compound made of various metals is synthesized. The carboxylic acid used as a raw material is an inexpensive organic acid. Therefore, it is the cheapest organometallic compound among the organometallic compounds.
As described above, the complex composed of the carboxylate metal compound is a metal compound that precipitates a metal oxide by thermal decomposition in the production method for producing the suspension described in paragraph 7, and is also a metal oxide. It is an inexpensive raw material for fine particles.
On the other hand, as the metal compound that precipitates the metal oxide by thermal decomposition described in paragraph 7, by using the complex composed of the above-mentioned carboxylic acid metal compound, as an appropriate organic compound having the five properties described in paragraph 7. , Carboxylic acid esters composed of saturated fatty acids, or organic compounds belonging to unsaturated fatty acids. These organic compounds are general-purpose industrial organic compounds.
That is, among the carboxylic acid esters composed of saturated fatty acids, the octanoic acid methyl CH 3 (CH 2 ) 6 COOCH 3 belonging to the octanoic acid esters has a melting point of −40 ° C. and is described above. The complex made of the carboxylic acid metal compound did not dissolve and disperse, and the fine particles made of the metal oxide precipitated by the thermal decomposition of the metal acetate compound at 194 ° C, which is 19 ° C higher than the thermal decomposition temperature of the metal acetate compound described above. It does not cause a chemical reaction and has no water absorption, and has the properties of 5 described in paragraph 7. The vapor pressure has a boiling point close to the thermal decomposition temperature of the metal acetate compound, and has 4410 pascals at 190 ° C. close to the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the degree of vacuum in the vacuum chamber is high because methyl octanate has a vapor pressure of several thousand pascals. Methyl octanoate can be vaporized without increasing. In addition, methyl octanate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal acetate compound can be stored for a long period of time without change.
Further, ethyl octanoate CH 3 (CH 2 ) 6 COOC 2 H 5 has a melting point of −48 ° C., the above-mentioned metal acetate compound does not dissolve and disperse, and the boiling point is a metal acetate compound, as described in paragraph 12. At 208 ° C, which is 28 ° C higher than the thermal decomposition temperature of the above, it does not chemically react with fine particles composed of metal oxides precipitated by thermal decomposition of metal acetate compounds, does not have water absorption, and has the properties of 5 described in paragraph 7. do. The vapor pressure is 322 pascals at 60 ° C., and the vapor pressure rapidly increases as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, ethyl octanoate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Ethyl octanate can be vaporized without increasing. Furthermore, ethyl octanoate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal acetate compound can be stored for a long period of time without change.
Furthermore, among the octanoic acid esters, octyl octanoate CH 3 (CH 2 ) 7 COO (CH 2 ) 6 CH 3 has a melting point of -18 ° C and a boiling point of 306 ° C, as described in paragraph 12. , The five properties described in paragraph 7 that do not cause a chemical reaction with the fine particles of the metal oxide precipitated at the thermal decomposition temperature of the caprilate metal compound at 295 ° C, which is 11 ° C higher than the thermal decomposition temperature of the caprilate metal compound described above. It is an organic compound that also has. As the vapor pressure approaches the boiling point, the vapor pressure rapidly increases. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, octyl octanoate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Octyl octanate can be vaporized without increasing. Moreover, octyl octanate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the caprylic acid metal compound can be stored for a long period of time without change.
Further, as described in paragraph 12, isopropyl octanoate CH 3 (CH 2 ) 6 COOCH (CH 3 ) 2 has a melting point of 12 ° C., the above-mentioned metal acetate compound does not dissolve and disperse, and the boiling point is metal acetate. At 214 ° C, which is 24 ° C higher than the thermal decomposition temperature of the compound, the properties of 5 described in paragraph 7 that do not chemically react with the fine particles of the metal oxide precipitated by the thermal decomposition of the metal acetate compound and do not have water absorption are exhibited. Combine. Since the boiling point of the steam pressure is close to the thermal decomposition temperature of the metal acetate compound, when the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, isopropyl octanoate is released. Since it has a constant vapor pressure, isopropyl octanoate can be vaporized without increasing the degree of vacuum in the vacuum chamber. Furthermore, isopropyl octanate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal acetate compound can be stored for a long period of time without change.
Further, among the carboxylic acid esters, the butyl laurate CH 3 (CH 2 ) 10 COOC 4 H 9 , which belongs to the lauric acid esters, has a melting point of −10 ° C. and a boiling point of 306, as described in paragraph 14. 5 described in paragraph 7, which does not cause a chemical reaction with the fine particles of the metal oxide precipitated at the thermal decomposition temperature of the caprilate metal compound at 295 ° C., which is 11 ° C. higher than the thermal decomposition temperature of the caprylic acid metal compound described above. It is an organic compound that has two properties. As the vapor pressure approaches the boiling point, the vapor pressure rapidly increases. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the butyl laurate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Butyl laurate can be vaporized without increasing. In addition, butyl laurate is practically insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the caprylic acid metal compound can be stored for a long period of time without change.
Further, 2-ethylhexyl laurate CH 3 (CH 2 ) 10 COOC 8 H 17 has a melting point of −30 ° C. and a boiling point of 315 ° C., as described in paragraph 14, and thermally decomposes the above-mentioned caprylic acid metal compound. Chemical reaction with fine particles of metal oxide precipitated at 295 ° C, which is 20 ° C higher than the temperature, and 5 ° C higher than the thermal decomposition temperature of the above-mentioned metal benzoate compound, and at the thermal decomposition temperature of the metal caprylate compound or metal benzoate compound. It is an organic compound having the five properties described in paragraph 7 that does not cause the above. In addition, the vapor pressure of 2-ethylhexyl laurate increases rapidly as it approaches the boiling point. Therefore, if the pressure inside the vacuum chamber is reduced with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, 2-ethylhexyl laurate has a constant vapor pressure, so that the vacuum inside the vacuum chamber 2-Ethylhexyl laurate can be vaporized without increasing the degree. Furthermore, 2-ethylhexyl laurate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal caprylate compound or the metal benzoate compound can be stored for a long period of time without change.
Further, hexyl laurate CH 3 (CH 2 ) 10 COOCH 3 (CH 2 ) 5 has a melting point of -3 ° C and a boiling point of 335 ° C, which is 25 ° C higher than the thermal decomposition temperature of the benzoate metal compound described above, and also. , 5 ° C. higher than the thermal decomposition temperature of the metal naphthenate compound described above, and does not cause a chemical reaction with the fine particles of the metal oxide precipitated by the thermal decomposition of the metal benzoate compound or the metal naphthenate compound. It is an organic compound that has both properties. In addition, the vapor pressure of hexyl laurate increases rapidly as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the hexyl laurate has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Hexyl laurate can be vaporized without increasing. In addition, hexyl laurate is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the benzoate metal compound or the naphthenate metal compound can be stored for a long period of time without change.
By the way, when the above-mentioned complex composed of a carboxylate metal compound is used as a metal compound for precipitating a metal oxide by thermal decomposition described in paragraph 7 among organic compounds belonging to unsaturated fatty acids, it is described in paragraph 7. There are organic compounds that have the above five properties.
That is, myristoleic acid CH 3 (CH 2 ) 3 CH = CH (CH 2 ) 7 COOH has a melting point of -4 ° C and a boiling point of 339 ° C, which is 29 ° C higher than the thermal decomposition temperature of the benzoate metal compound described above. Further, it has the five properties described in paragraph 7 that are 9 ° C. higher than the thermal decomposition temperature of the metal naphthenate compound of 330 ° C. and do not cause a chemical reaction with the fine particles of the metal oxide precipitated by the thermal decomposition. It is an organic compound. The vapor pressure of myristoleic acid increases rapidly as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, myristoleic acid has a constant vapor pressure, so that the degree of vacuum in the vacuum chamber is increased. Myristoleic acid can be vaporized without increasing it. In addition, myristoleic acid is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the benzoate metal compound or the naphthenate metal compound can be stored for a long period of time without change.
Further, CH 3 (CH 2 ) oleate 7 CH = CH (CH 2 ) 7 COOH has a melting point of 13.4 ° C., a boiling point of 360 ° C., and a thermal decomposition temperature of the above-mentioned metal naphthenate compound of 330 ° C. It is an organic compound having the five properties described in paragraph 7, which is higher than 30 ° C. and does not cause a chemical reaction with the fine particles of the metal oxide precipitated by thermal decomposition. The vapor pressure is 2357 pascals at 265 ° C., and the vapor pressure rapidly increases as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the oleic acid has a vapor pressure of several thousand pascals, so that the degree of vacuum in the vacuum chamber is high. Oleic acid can be vaporized without increasing the amount of vacuum. Moreover, oleic acid is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal naphthenate compound can be stored for a long period of time without change.
Further, CH 3 (CH 2 ) 4 (CH = CHCH 2 ) 2 (CH 2 ) 6 COOH linoleic acid has a melting point of −5 ° C. and a boiling point of 360 ° C. at the thermal decomposition temperature of the metal naphthenate compound described above. It is an organic compound having the five properties described in paragraph 7, which is 30 ° C. higher than a certain 330 ° C. and does not cause a chemical reaction with the fine particles of the metal oxide precipitated by thermal decomposition. The vapor pressure is 2133 pascals at 229 ° C., and the vapor pressure increases rapidly as it approaches the boiling point. Therefore, if the vacuum chamber is depressurized with a vacuum pump before the temperature of the third suspension described in paragraph 9 drops, the linoleic acid has a vapor pressure of several thousand pascals, so that the degree of vacuum in the vacuum chamber is high. The linoleic acid can be vaporized without increasing the amount of linoleic acid. In addition, linoleic acid is almost insoluble in water. Therefore, there is no water absorption at around 20 ° C. at room temperature. In addition, it is a liquid having a low vapor pressure at around 20 ° C. at room temperature and an extremely small amount of evaporation. Furthermore, it is chemically stable at around 20 ° C. at room temperature. Therefore, in the second suspension, the fine crystals of the metal naphthenate compound can be stored for a long period of time without change.
As described above, by using the complex composed of the above-mentioned carboxylic acid metal compound as the metal compound for precipitating the metal oxide by the thermal decomposition described in paragraph 7, the five properties described in paragraph 7 are combined. Suitable organic compounds include carboxylic acid esters composed of saturated fatty acids or organic compounds belonging to unsaturated fatty acids.
実施形態１
本実施形態は、１２段落で説明した熱分解で金属を析出する無機金属化合物に関わる実施形態である。本発明における金属化合物は、第一にメタノールに分散し、メタノールに溶解せず、第二に熱分解で金属を析出する２つの性質を兼備する。ここでは金属を銀とし、銀化合物を例にして説明する。
最初に、メタノールに分散し、メタノールに溶解しない銀化合物を説明する。硝酸銀はメタノールに溶解し、銀イオンが溶出し、多くの銀イオンが銀微粒子の析出に参加できない。従って、銀化合物は溶剤に溶解せず、溶剤に分散する性質を持つことが必要になる。また、酸化銀、塩化金、硫酸銀、水酸化銀、炭酸銀などの無機銀化合物はメタノールに分散しない。このため、前記した無機金化合物は、銀化合物として適切でない。
いっぽう、銀化合物は銀を析出する性質を持つ。銀化合物から銀が生成される化学反応の中で、最も簡単な化学反応のひとつに熱分解反応がある。さらに、銀化合物の熱分解温度が低ければ、熱処理温度が低くなり、第二の懸濁液が安価に製造できる。いっぽう、無機物からなる分子ないしは無機物からなるイオンが配位子となって、銀イオンに配位結合する銀錯イオンを有する無機金化合物からなる銀錯体は、無機物の分子量が小さければ、還元雰囲気での熱分解温度は低い。また、他の銀錯イオンを有する錯体より合成が容易で安価な工業用薬品である。
すなわち、銀錯体を構成する分子の中で銀イオンが最も大きい。ちなみに、銀原子の単結合の共有結合半径は１２８ｐｍであり、窒素原子の単結合の共有結合半径の７１ｐｍであり、酸素原子の単結合の共有結合半径は６３ｐｍである。このため、配位子が銀イオンに配位結合する配位結合部の距離が最も長い。従って、無機金化合物からなる銀錯体は、還元雰囲気の熱処理によって、最初に配位結合部が分断され、銀と無機物とに分解し、無機物の気化が完了した後に銀が析出する。
このような無機金化合物からなる銀錯体として、アンモニアＮＨ３が配位子となって銀イオンに配位結合するジアンミン銀イオン［Ａｇ（ＮＨ３）２］＋を有する銀錯体と、シアン化物イオンＣＮ－が配位子となって銀イオンに配位結合するジシアノ銀イオン［Ａｇ（ＣＮ）２］－を有する銀錯体は、配位子が低分子量で、配位子の数が少ないため、他の銀錯イオンを有する銀錯体に比べて、合成が容易であり安価に製造できる。こうした銀錯イオンを有する無機金属化合物からなる錯体は、無機物の分子量が小さいため、還元性雰囲気で熱処理すると、配位結合部位が最初に分断され、２００℃程度の低い温度で無機物の気化が完了して銀が析出する。また、メタノールに１０重量％近くの分散濃度まで分散する。このような銀錯体として、例えば、塩化ジアンミン銀［Ａｇ（ＮＨ３）２］Ｃｌ、硫酸ジアンミン銀［Ａｇ（ＮＨ３）２］２ＳＯ４、硝酸ジアンミン銀［Ａｇ（ＮＨ３）２］ＮＯ３などがある。
また、熱分解で銅を析出する無機銅化合物からなる銅錯体として、アンモニアＮＨ３が配位子となって銅イオンに配位結合するテトラアンミン銅イオン［Ｃｕ（ＮＨ３）４］２＋を有する銅錯体や、ヘキサアンミン銅イオン［Ｃｕ（ＮＨ３）６］２＋を有する銅錯体や、塩素イオンＣｌ－が配位子になって銅イオンに配位結合するテトラクロロ銅イオン［ＣｕＣｌ４］２－を有する銅錯体は、配位子が低分子量で配位子の数が少ないため、他の銅錯イオンを有する錯体に比べて合成が容易であり、安価に製造できる。こうした銅錯イオンを有する無機金属化合物からなる錯体は、無機物の分子量が小さいため、還元性雰囲気で熱処理すると、配位結合部位が最初に分断され、２００℃程度の比較的低い温度で熱分解が完了する。また、メタノールに１０重量％近くの分散濃度まで分散する。このような銅錯体として、例えば、テトラアンミン銅硝酸塩［Ｃｕ（ＮＨ３）４］（ＮＯ３）２やヘキサアンミン銅硫酸塩［Ｃｕ（ＮＨ３）６］ＳＯ４がある。
同様に、熱分解でニッケルを析出し、メタノールに１０重量％近くの分散濃度まで分散する、無機ニッケル化合物からなるニッケル錯体として、例えば、ヘキサアンミンニッケル塩化物［Ｎｉ（ＮＨ３）６］Ｃｌ２がある。
また、熱分解でコバルトを析出し、メタノールに１０重量％近くの分散濃度まで分散する、無機コバルト化合物からなるコバルト錯体として、例えば、ヘキサアンミンコバルト塩化物［Ｃｏ（ＮＨ３）６］Ｃｌ３や、ヘキサアンミンコバルト硝酸塩［Ｃｏ（ＮＨ３）６］（ＮＯ３）３がある。
さらに、熱分解でイリジウムを析出し、メタノールに１０重量％近くの分散濃度まで分散する、無機イリジウム化合物からなるイリジウム錯体として、例えば、ヘキサアンミンイリジウム塩化物［Ｉｒ（ＮＨ３）６］Ｃｌ３がある。
同様に、熱分解でルテニウムを析出し、メタノールに１０重量％近くの分散濃度まで分散する、無機ルテニウム化合物からなるルテニウム錯体として、例えば、ヘキサアンミンルテニウム塩化物［Ｒｕ（ＮＨ３）６］Ｃｌ３がある。
さらに、熱分解でロジウムを析出し、メタノールに１０重量％近くの分散濃度まで分散する、無機ロジウム化合物からなるロジウム錯体として、例えば、ヘキサアンミンロジウム塩化物ヘキサアンミンイリジウム塩化物［Ｒｈ（ＮＨ３）６］Ｃｌ３がある。
同様に、熱分解で白金を析出し、メタノールに１０重量％近くの分散濃度まで分散する、無機白金化合物からなる白金錯体として、例えば、トランス－ジアンミンジクロロ白金［ＰｔＣｌ２（ＮＨ３）２］がある。
さらに、熱分解でパラジウムを析出し、メタノールに１０重量％近くの分散濃度まで分散する、無機パラジウム化合物からなるパラジウム錯体として、例えば、ジアンミンジクロロパラジウム［ＰｄＣｌ２（ＮＨ３）２］がある。
以上に説明したように、無機物のイオンないしは無機物の分子が配位子になって、金属イオンに配位結合する金属錯イオンを有する無機塩からなる無機金属化合物は、配位子が低分子量で、配位子の数が少なく、無機塩の分子量が小さいため、熱分解温度が最も低く、合成が容易で最も安価な金属錯体である。従って、金属のナノ粒子の優れた原料になる。
Embodiment 1
This embodiment is an embodiment relating to an inorganic metal compound that precipitates a metal by thermal decomposition described in paragraph 12. The metal compound in the present invention first has two properties of being dispersed in methanol, not dissolving in methanol, and secondly precipitating a metal by thermal decomposition. Here, the metal is silver, and a silver compound will be described as an example.
First, a silver compound that is dispersed in methanol and insoluble in methanol will be described. Silver nitrate dissolves in methanol, silver ions elute, and many silver ions cannot participate in the precipitation of silver fine particles. Therefore, it is necessary that the silver compound has the property of being insoluble in the solvent and being dispersed in the solvent. Further, inorganic silver compounds such as silver oxide, gold chloride, silver sulfate, silver hydroxide and silver carbonate do not disperse in methanol. Therefore, the above-mentioned inorganic gold compound is not suitable as a silver compound.
On the other hand, silver compounds have the property of precipitating silver. Among the chemical reactions that produce silver from silver compounds, one of the simplest chemical reactions is the thermal decomposition reaction. Further, if the thermal decomposition temperature of the silver compound is low, the heat treatment temperature is low, and the second suspension can be produced at low cost. On the other hand, a silver complex composed of an inorganic gold compound having a silver complex ion coordinated to a silver ion with a molecule composed of an inorganic substance or an ion composed of an inorganic substance as a ligand can be used in a reducing atmosphere if the molecular weight of the inorganic substance is small. The thermal decomposition temperature of is low. In addition, it is an industrial chemical that is easier to synthesize and cheaper than other complexes having silver complex ions.
That is, the silver ion is the largest among the molecules constituting the silver complex. Incidentally, the covalent radius of the single bond of the silver atom is 128 pm, the covalent radius of the single bond of the nitrogen atom is 71 pm, and the covalent radius of the single bond of the oxygen atom is 63 pm. Therefore, the distance of the coordination bond portion where the ligand is coordinate-bonded to the silver ion is the longest. Therefore, in the silver complex composed of the inorganic gold compound, the coordination bond portion is first divided by the heat treatment in the reducing atmosphere, the silver and the inorganic substance are decomposed, and the silver is precipitated after the vaporization of the inorganic substance is completed.
As a silver complex composed of such an inorganic gold compound, a silver complex having a diammine silver ion [Ag (NH 3 ) 2 ] + in which ammonia NH 3 acts as a ligand and is coordinated and bonded to a silver ion, and a cyanide ion. A silver complex having a dicyanosilver ion [ Ag (CN) 2 ] -with CN- as a ligand and coordinating with a silver ion has a low molecular weight ligand and a small number of ligands. Compared with other silver complexes having silver complex ions, it is easier to synthesize and can be manufactured at low cost. Since the complex composed of such an inorganic metal compound having silver complex ions has a small molecular weight of the inorganic substance, the coordination bond site is first divided when heat-treated in a reducing atmosphere, and the vaporization of the inorganic substance is completed at a low temperature of about 200 ° C. Then silver is deposited. Further, it is dispersed in methanol to a dispersion concentration of nearly 10% by weight. Examples of such silver complexes include silver diammine chloride [Ag (NH 3 ) 2 ] Cl, silver diammine sulfate [Ag (NH 3 ) 2 ] 2 SO 4 , and silver diammine nitrate [Ag (NH 3 ) 2 ] NO 3 . and so on.
Further, as a copper complex composed of an inorganic copper compound that precipitates copper by thermal decomposition, copper having a tetraammine copper ion [Cu (NH 3 ) 4 ] 2+ in which ammonia NH 3 acts as a ligand and is coordinated and bonded to a copper ion. A complex, a copper complex having a hexaammine copper ion [Cu (NH 3 ) 6 ] 2+ , or a tetrachloro copper ion [CuCl 4 ] 2 -coordinating with a copper ion in which the chlorine ion Cl − acts as a ligand. Since the copper complex having a copper complex has a low molecular weight and a small number of ligands, it can be easily synthesized and inexpensively produced as compared with other complexes having a copper complex ion. Since the complex composed of such an inorganic metal compound having a copper complex ion has a small molecular weight of the inorganic substance, when the heat treatment is performed in a reducing atmosphere, the coordination bond site is first divided and thermal decomposition occurs at a relatively low temperature of about 200 ° C. Complete. Further, it is dispersed in methanol to a dispersion concentration of nearly 10% by weight. Examples of such a copper complex include tetraammine copper nitrate [Cu (NH 3 ) 4 ] (NO 3 ) 2 and hexaammine copper sulfate [Cu (NH 3 ) 6 ] SO 4 .
Similarly, as a nickel complex composed of an inorganic nickel compound that precipitates nickel by thermal decomposition and disperses in methanol to a dispersion concentration of nearly 10% by weight, for example, hexaammine nickel chloride [Ni (NH 3 ) 6 ] Cl 2 There is.
Further, as a cobalt complex composed of an inorganic cobalt compound that precipitates cobalt by thermal decomposition and disperses it in methanol to a dispersion concentration of nearly 10% by weight, for example, hexaamminecobalt chloride [Co (NH 3 ) 6 ] Cl 3 or , Hexamminecobalt nitrate [Co (NH 3 ) 6 ] (NO 3 ) 3 .
Further, as an iridium complex composed of an inorganic iridium compound that precipitates iridium by thermal decomposition and disperses it in methanol to a dispersion concentration of nearly 10% by weight, for example, hexaammine iridium chloride [Ir (NH 3 ) 6 ] Cl 3 is used. be.
Similarly, as a ruthenium complex composed of an inorganic ruthenium compound that precipitates ruthenium by thermal decomposition and disperses it in methanol to a dispersion concentration of nearly 10% by weight, for example, hexaammine ruthenium chloride [Ru (NH 3 ) 6 ] Cl 3 There is.
Further, as a rhodium complex composed of an inorganic rhodium compound that precipitates rhodium by thermal decomposition and disperses it in methanol to a dispersion concentration of nearly 10% by weight, for example, hexaammine rhodium chloride hexaammine iridium chloride [Rh (NH 3 ). 6 ] There is Cl 3 .
Similarly, as a platinum complex composed of an inorganic platinum compound that precipitates platinum by thermal decomposition and disperses it in methanol to a dispersion concentration of nearly 10% by weight, for example, trans-diamminedichloroplatinum [PtCl 2 (NH 3 ) 2 ] is used. be.
Further, as a palladium complex composed of an inorganic palladium compound that precipitates palladium by thermal decomposition and disperses it in methanol to a dispersion concentration of nearly 10% by weight, for example, there is diamminedichloropalladium [PdCl 2 (NH 3 ) 2 ].
As described above, an inorganic metal compound composed of an inorganic salt having a metal complex ion in which an inorganic ion or an inorganic molecule acts as a ligand and coordinate-bonds to the metal ion has a low molecular weight ligand. Since the number of ligands is small and the molecular weight of the inorganic salt is small, it has the lowest thermal decomposition temperature, is easy to synthesize, and is the cheapest metal complex. Therefore, it is an excellent raw material for metal nanoparticles.
実施形態２
本実施形態は、１４段落で説明した熱分解で金属を析出するオクチル酸金属化合物に関わる実施形態である。本発明における金属化合物は、第一にメタノールに分散し、メタノールに溶解せず、第二に熱分解で金属を析出する２つの性質を兼備する。ここでは、金属を銅とし、銅化合物について説明する。
最初に、メタノールに分散し、メタノールに溶解しない銅化合物を説明する。塩化銅、硫酸銅、硝酸銅などの無機銅化合物はメタノールに溶解し、銅イオンが溶出してしまい、多くの銅イオンが銅微粒子の析出に参加できなくなる。従って、銅化合物は溶剤に溶解せず、溶剤に分散する性質を持つことが必要になる。また、酸化銅、塩化銅、硫化銅などの無機銅化合物は、最も汎用的な溶剤であるメタノールに分散しない。このため、これらの無機銅化合物は、メタノールに分散する性質を持つ銅化合物として適切でない。
いっぽう分子量が小さい無機物の分子ないしは無機イオンが、銅イオンに配位結合する銅錯イオンを有する錯体として、１２段落で説明したアンミン銅錯体やクロロ銅錯体がある。これらの錯体は、汎用的な有機酸からなる有機銅化合物に比べると高価である。
有機銅化合物は銅を析出する。有機銅化合物から銅が生成される化学反応の中で、最も簡単な化学反応のひとつに熱分解反応がある。さらに、有機酸が汎用的な有機酸で、有機銅化合物の合成が容易でれば、有機銅化合物が安価に製造できる。さらに、有機銅化合物の熱分解温度が低ければ、銅を安価な熱処理費用で析出できる。こうした性質を兼備する有機銅化合物に、カルボン酸Ｒ－ＣＯＯＨのカルボキシラートアニオン（Ｒ－ＣＯＯ－）が銅イオンに共有結合するカルボン酸銅化合物がある。つまり、カルボン酸銅化合物を構成するイオンの中で、最も大きいイオンは銅イオンである。従って、カルボン酸のカルボキシラートアニオンが、銅イオンに共有結合すれば、銅イオンとカルボキシラートアニオンとの距離が、イオン同士の距離の中で最も長い。こうしたカルボン酸銅化合物を大気雰囲気で昇温させると、カルボン酸の沸点を超えると、カルボン酸と銅とに分解する。さらに昇温すると、カルボン酸が飽和脂肪酸で構成されれば、カルボン酸が気化熱を伴って気化し、カルボン酸の気化した後に銅が析出する。なお、還元雰囲気でのカルボン酸銅化合物の熱分解は、大気雰囲気での熱分解より高温側で進むため、大気雰囲気での熱分解のほうが熱処理費用は安価で済む。またカルボン酸が不飽和脂肪酸であれば、炭素原子が水素原子に対して過剰になるため、不飽和脂肪酸からなるカルボン酸銅化合物が熱分解すると、酸化銅が析出する。
いっぽう、カルボン酸銅化合物の中で、カルボン酸のカルボキシラートアニオンが配位子となって銅イオンに近づいて配位結合するカルボン酸銅は、銅イオンとカルボキシラートアニオンとの距離が短くなり、反対に、カルボキシラートアニオンにおける酸素イオンが銅イオンと反対側で結合するイオンとの距離が最も長くなる。このような分子構造の特徴を持つカルボン酸銅化合物の熱分解反応は、カルボキシラートアニオンにおける酸素イオンが銅イオンと反対側で結合するイオンとの結合部が最初に分断され、この結果、酸化銅が析出する。このカルボン酸銅化合物は、１７段落に説明したカルボン酸金属化合物に属する。
さらに、カルボン酸銅化合物は、カルボン酸が最も汎用的な有機酸であるため、合成が容易で最も安価な有機銅化合物である。つまり、カルボン酸を水酸化ナトリウムなどの強アルカリ溶液中で反応させると、カルボン酸アルカリ金属化合物が生成される。このカルボン酸アルカリ金属化合物を、硫酸銅などの無機銅化合物と反応させると、カルボン酸銅化合物が生成される。このため、有機銅化合物の中で最も安価である。
カルボン酸銅化合物の組成式はＣｕ（ＣＯＯＲ）２で表わせられる。Ｒは炭化水素で、この組成式はＣｍＨｎである（ここでｍとｎとは整数）。カルボン酸銅化合物を構成する物質の中で、組成式の中央に位置する銅イオンＣｕ２＋が最も大きい。従って、銅イオンＣｕ２＋とカルボキシラートアニオン（Ｒ－ＣＯ２
－）とが共有結合する場合は、銅イオンＣｕ２＋とカルボキシラートアニオン（Ｒ－ＣＯ２
－）との距離が最大になる。この理由は、銅原子の２重結合における共有結合半径は１１５ｐｍであり、酸素原子の２重結合における共有結合半径は５７ｐｍであり、炭素原子の２重結合における共有結合半径は６７ｐｍであることによる。このため、このような分子構造の特徴を持つカルボン酸銅化合物は、カルボン酸の沸点を超えると、結合距離が最も長い銅イオンとカルボキシラートアニオン（Ｒ－ＣＯ２
－）との結合部が最初に分断され、銅とカルボン酸とに分離する。さらに昇温すると、カルボン酸が飽和脂肪酸であれば、カルボン酸が気化熱を伴って気化し、カルボン酸の気化が完了した後に銅が析出する。こうしたカルボン酸銅化合物として、オクチル酸銅、ラウリン酸銅、ステアリン酸銅などがある。このようなカルボン酸銅化合物の多くは、金属石鹸として市販されている安価な工業用薬品である。
さらに飽和脂肪酸の沸点が低ければ、カルボン酸銅化合物は低い温度で熱分解し、銅を析出させる熱処理費用が安価で済む。飽和脂肪酸を構成する炭化水素が長鎖構造である場合は、長鎖が長いほど、つまり、飽和脂肪酸の分子量が大きいほど、飽和脂肪酸の沸点が高くなり、飽和脂肪酸の気化熱が大きいため、熱分解温度が高くなる。ちなみに、分子量が２００．３であるラウリン酸の大気圧での沸点は２９６℃であり、分子量が２８４．５であるステアリン酸の大気圧での沸点は３６１℃である。
これに対し、分岐鎖構造を有する飽和脂肪酸は、直鎖構造の飽和脂肪酸より鎖の長さが短く、沸点がさらに低くなり、気化熱も小さい。これによって、分岐鎖構造を有する飽和脂肪酸からなるカルボン酸銅化合物は、さらに低い温度で熱分解温度する。また、分岐鎖構造を有する飽和脂肪酸は極性を持つため、分岐鎖構造を有する飽和脂肪酸からなるカルボン酸銅化合物も極性を持ち、メタノールなどの極性を持つ有機溶剤に相対的に高い割合で分散する。このような分岐構造の飽和脂肪酸としてオクチル酸がある。オクチル酸は構造式がＣＨ３（ＣＨ２）３ＣＨ（Ｃ２Ｈ５）ＣＯＯＨで示され、ＣＨでＣＨ３（ＣＨ２）３とＣ２Ｈ５とのアルカンに分岐され、ＣＨにカルボキシル基ＣＯＯＨが結合する。オクチル酸の大気圧での沸点は２２８℃であり、ラウリン酸より沸点が６８℃低い。このため、銅を析出する原料として、オクチル酸銅Ｃｕ（Ｃ７Ｈ１５ＣＯＯ）２が望ましい。オクチル酸銅は、大気雰囲気において２９０℃で熱分解が完了して銅が析出し、メタノールに１０重量％近く分散する。
また、アルミニウムを析出する原料としてオクチル酸アルミニウムＡｌ（Ｃ７Ｈ１５ＣＯＯ）３が、鉄を析出する原料としてオクチル酸鉄Ｆｅ（Ｃ７Ｈ１５ＣＯＯ）３が、ニッケルを析出する原料としてオクチル酸ニッケルＮｉ（Ｃ７Ｈ１５ＣＯＯ）２が、コバルトを析出する原料としてオクチル酸コバルトＣｏ（Ｃ７Ｈ１５ＣＯＯ）２が、マンガンを析出する原料としてオクチル酸マンガンＭｎ（Ｃ７Ｈ１５ＣＯＯ）２が、亜鉛を析出する原料としてオクチル酸亜鉛Ｚｎ（Ｃ７Ｈ１５ＣＯＯ）２が、錫を析出する原料としてオクチル酸錫Ｓｎ（Ｃ７Ｈ１５ＣＯＯ）２が、カルシウムを析出する原料としてオクチル酸カルシウムＣａ（Ｃ７Ｈ１５ＣＯＯ）２が望ましい。これらのオクチル酸金属化合物は、いずれもメタノールに１０重量％近い割合で分散する。
Embodiment 2
This embodiment is an embodiment relating to a metal octylate compound that precipitates a metal by thermal decomposition described in paragraph 14. The metal compound in the present invention first has two properties of being dispersed in methanol, not dissolving in methanol, and secondly precipitating a metal by thermal decomposition. Here, copper is used as the metal, and a copper compound will be described.
First, a copper compound that is dispersed in methanol and insoluble in methanol will be described. Inorganic copper compounds such as copper chloride, copper sulfate, and copper nitrate are dissolved in methanol, copper ions are eluted, and many copper ions cannot participate in the precipitation of copper fine particles. Therefore, it is necessary that the copper compound has the property of being insoluble in the solvent and being dispersed in the solvent. Inorganic copper compounds such as copper oxide, copper chloride and copper sulfide do not disperse in methanol, which is the most versatile solvent. Therefore, these inorganic copper compounds are not suitable as copper compounds having the property of dispersing in methanol.
On the other hand, as a complex having a copper complex ion in which an inorganic molecule or an inorganic ion having a small molecular weight is coordinate-bonded to a copper ion, there are an ammine copper complex and a chlorocopper complex described in paragraph 12. These complexes are more expensive than organic copper compounds consisting of general-purpose organic acids.
Organic copper compounds precipitate copper. Among the chemical reactions in which copper is produced from an organic copper compound, one of the simplest chemical reactions is a thermal decomposition reaction. Further, if the organic acid is a general-purpose organic acid and the synthesis of the organic copper compound is easy, the organic copper compound can be produced at low cost. Further, if the thermal decomposition temperature of the organic copper compound is low, copper can be deposited at a low heat treatment cost. Among the organic copper compounds having such properties, there is a copper carboxylate compound in which the carboxylate anion (R - COO-) of the carboxylate R-COOH is covalently bonded to the copper ion. That is, among the ions constituting the copper carboxylate compound, the largest ion is a copper ion. Therefore, if the carboxylate anion of the carboxylic acid is covalently bonded to the copper ion, the distance between the copper ion and the carboxylate anion is the longest among the distances between the ions. When the temperature of such a carboxylic acid copper compound is raised in an atmospheric atmosphere, when the boiling point of the carboxylic acid is exceeded, the carboxylic acid and copper are decomposed. When the temperature is further raised, if the carboxylic acid is composed of saturated fatty acids, the carboxylic acid is vaporized with heat of vaporization, and copper is precipitated after the vaporization of the carboxylic acid. Since the thermal decomposition of the copper carboxylate compound in the reducing atmosphere proceeds on the higher temperature side than the thermal decomposition in the atmospheric atmosphere, the thermal decomposition in the atmospheric atmosphere requires less heat treatment cost. If the carboxylic acid is an unsaturated fatty acid, the carbon atom becomes excessive with respect to the hydrogen atom. Therefore, when the copper carboxylic acid compound composed of the unsaturated fatty acid is thermally decomposed, copper oxide is precipitated.
On the other hand, among the copper carboxylate compounds, the carboxylate anion of the carboxylate acts as a ligand, and the copper carboxylate that approaches and coordinates with the copper ion has a shorter distance between the copper ion and the carboxylate anion. Conversely, the oxygen ion in the carboxylate anion has the longest distance between the copper ion and the ion bonded on the opposite side. In the thermal decomposition reaction of a copper carboxylate compound having such a characteristic of molecular structure, the bond portion of the carboxylate anion with the ion to which the oxygen ion is bonded on the opposite side to the copper ion is first divided, and as a result, copper oxide is formed. Precipitates. This copper carboxylate compound belongs to the metal carboxylate compound described in paragraph 17.
Further, the copper carboxylic acid compound is an organic copper compound that is easy to synthesize and is the cheapest because the carboxylic acid is the most general-purpose organic acid. That is, when a carboxylic acid is reacted in a strong alkaline solution such as sodium hydroxide, an alkali metal carboxylate compound is produced. When this alkali metal carboxylate compound is reacted with an inorganic copper compound such as copper sulfate, a copper carboxylate compound is produced. Therefore, it is the cheapest among organic copper compounds.
The composition formula of the copper carboxylate compound is represented by Cu (COOR) 2 . R is a hydrocarbon, and the composition formula is C m H n (where m and n are integers). Among the substances constituting the copper carboxylate compound, the copper ion Cu 2+ located in the center of the composition formula is the largest. Therefore, when the copper ion Cu 2+ and the carboxylate anion (R - CO 2- ) are covalently bonded, the distance between the copper ion Cu 2+ and the carboxylate anion (R - CO 2- ) becomes maximum. The reason for this is that the covalent radius in the double bond of the copper atom is 115 pm, the covalent radius in the double bond of the oxygen atom is 57 pm, and the covalent radius in the double bond of the carbon atom is 67 pm. .. Therefore, in the carboxylic acid copper compound having such a characteristic of the molecular structure, when the boiling point of the carboxylic acid is exceeded, the bond portion between the copper ion having the longest bond distance and the carboxylate anion (R - CO 2- ) is first. It is divided into copper and carboxylic acid. When the temperature is further raised, if the carboxylic acid is a saturated fatty acid, the carboxylic acid is vaporized with heat of vaporization, and copper is precipitated after the vaporization of the carboxylic acid is completed. Examples of such a copper carboxylate compound include copper octylate, copper laurate, and copper stearate. Most of such copper carboxylates are inexpensive industrial chemicals commercially available as metal soaps.
Further, if the boiling point of the saturated fatty acid is low, the copper carboxylate compound is thermally decomposed at a low temperature, and the heat treatment cost for precipitating copper can be reduced. When the hydrocarbons constituting the saturated fatty acid have a long chain structure, the longer the chain, that is, the larger the molecular weight of the saturated fatty acid, the higher the boiling point of the saturated fatty acid, and the greater the heat of vaporization of the saturated fatty acid. The decomposition temperature becomes high. Incidentally, the boiling point of lauric acid having a molecular weight of 200.3 at atmospheric pressure is 296 ° C, and the boiling point of stearic acid having a molecular weight of 284.5 at atmospheric pressure is 361 ° C.
On the other hand, the saturated fatty acid having a branched chain structure has a shorter chain length, a lower boiling point, and a smaller heat of vaporization than the saturated fatty acid having a linear structure. As a result, the copper carboxylate compound composed of saturated fatty acids having a branched chain structure is thermally decomposed at a lower temperature. Further, since the saturated fatty acid having a branched chain structure has a polarity, the copper carboxylate compound composed of the saturated fatty acid having a branched chain structure also has a polarity and is dispersed in a relatively high proportion in a polar organic solvent such as methanol. .. Octylic acid is a saturated fatty acid having such a branched structure. The structural formula of octyl acid is represented by CH 3 (CH 2 ) 3 CH (C 2 H 5 ) COOH, and CH is branched into an alkane of CH 3 (CH 2 ) 3 and C 2 H 5 , and a carboxyl group is added to CH. COOH binds. The boiling point of octyl acid at atmospheric pressure is 228 ° C, which is 68 ° C lower than that of lauric acid. Therefore, copper Cu (C 7 H 15 COO) 2 octylate is desirable as a raw material for precipitating copper. Pyrolysis of copper octylate is completed at 290 ° C. in the atmosphere, and copper is precipitated and dispersed in methanol in an amount of about 10% by weight.
Further, aluminum octylate Al (C 7 H 15 COO) 3 as a raw material for precipitating aluminum, iron Fe (C 7 H 15 COO) 3 octylate as a raw material for precipitating iron, and octyl acid as a raw material for precipitating nickel. Nickel Ni (C 7 H 15 COO) 2 is a raw material for precipitating cobalt. Cobalt octylate Co (C 7 H 15 COO) 2 is a raw material for precipitating manganese. Manganese octylate Mn (C 7 H 15 COO) 2 However, zinc octylate Zn (C 7 H 15 COO) 2 as a raw material for precipitating zinc and tin octylate Sn (C 7 H 15 COO) 2 as a raw material for precipitating tin are used as a raw material for precipitating calcium. Calcium Ca (C 7 H 15 COO) 2 is desirable. All of these metal octylate compounds are dispersed in methanol at a ratio of close to 10% by weight.
実施形態３
本実施形態は、１６段落で説明した熱分解で金属酸化物を析出するカルボン酸金属化合物からなる錯体に関わる実施形態である。本発明における金属化合物は、第一にメタノールに分散し、メタノールに溶解せず、第二に熱分解で金属酸化物を析出する２つの性質を兼備する。ここでは、金属酸化物を酸化チタンＴｉＯ２とし、チタン化合物の実施形態から説明する。
最初に、メタノールに分散するチタン化合物を説明する。塩化チタンはメタノールに溶解する。酸化チタンはメタノールに分散しない。このため、これら低分子量の無機チタン化合物は、メタノールに分散しない。
なお、１８段落で説明した無機物の分子ないしは無機物のイオンからなる配位子が、チタンイオンに配位結合したチタン錯イオンとして、チタン錯イオン［ＴｉＣｌ４Ｏ］２－を有する無機金属化合物があるが、配位結合が安定でない。
次に、有機チタン化合物について説明する。有機チタン化合物は、熱分解によって二酸化チタンＴｉＯ２を析出する。有機チタン化合物から酸化チタンが生成される化学反応の中で、最も簡単な化学反応のひとつに熱分解反応がある。つまり、有機チタン化合物を昇温するだけで、熱分解によって酸化チタンが析出する。さらに、有機チタン化合物の合成が容易でれば、有機チタン化合物が安価に製造できる。これらの性質を兼備する有機チタン化合物に、カルボン酸チタン化合物がある。
つまり、カルボン酸チタン化合物を構成する物質の中で、最も大きい共有結合半径を持つ物質はチタンイオンＴｉ４＋である。いっぽう、チタンイオンＴｉ４＋とカルボキシラートアニオン（Ｒ－ＣＯ２
－）とが共有結合するカルボン酸チタン化合物は、チタンイオンと酸素イオンとの距離が最大になるため、熱分解でチタンを析出する。このため、熱分解で酸化チタンを析出するカルボン酸チタン化合物は、チタンイオンＴｉ４＋にカルボキシラートアニオン（Ｒ－ＣＯ２
－）が近づき、これによって、カルボキシラートアニオン（Ｒ－ＣＯ２
－）がチタンイオンＴｉ４＋の反対側で結合するイオンと結合する距離が最も長くなる。つまり、カルボキシラートアニオン（Ｒ－ＣＯ２
－）がチタンイオンＴｉ４＋の反対側で結合するイオンと結合する部位が最も長く、最初にこの結合部が分断され、チタンイオンと結合した酸素イオン、つまり、酸化チタンＴｉＯ２とカルボン酸とに分解する。このような分子構造上の特徴を持つカルボン酸チタン化合物として、カルボキシラートアニオン（Ｒ－ＣＯ２
－）が配位子になってチタンイオンＴｉ４＋に配位結合するカルボン酸チタン化合物がある。
また、有機チタン化合物の中でカルボン酸チタン化合物は、合成が容易で、有機酸の沸点が低くければ熱分解温度が比較的低い。このため、カルボキシラートアニオン（Ｒ－ＣＯ２
－）が、配位子となって金属イオンに近づいて配位結合するカルボン酸金属化合物からなる錯体は、安価な工業用薬品であり、熱処理費用も安価で済む。従って、カルボキシラートアニオン（Ｒ－ＣＯ２
－）がチタンイオンに配位結合したカルボン酸チタン化合物は、熱分解で酸化チタンを析出する安価な工業用薬品である。
こうしたカルボン酸チタン化合物として、酢酸チタン、カプリル酸チタン、安息香酸チタン、ナフテン酸チタンなどが挙げられる。しかし、酢酸チタンとカプリル酸チタンは、配位結合が安定していないため、熱分解で酸化チタンを析出しない。いっぽう、安息香酸の沸点は２４９℃であり、テトラ安息香酸チタンＴｉ（Ｃ６Ｈ５ＣＯＯ）４は大気雰囲気の３１０℃で熱分解して酸化チタンを析出し、ナフテン酸チタンより熱分解温度が低い。
また、カルボン酸バナジウム化合物の中で、ナフテン酸バナジウムを除くカルボン酸バナジウム化合物は、配位結合が安定していないため、熱分解で酸化バナジウムを析出しない。いっぽう、ナフテン酸は５員環をもつ飽和脂肪酸の混合物で、一般式がＣｎＨ２ｎ－１ＣＯＯＨで示され、主成分の沸点が２６８℃で、分子量が１７０のＣ９Ｈ１７ＣＯＯＨからなる。従って、ナフテン酸バナジウムは大気雰囲気の３３０℃で熱分解して、酸化バナジウムを析出する。
なお、カルボン酸のカルボキシラートアニオン（Ｒ－ＣＯ２
－）が配位子になって、金属イオンに配位結合するカルボン酸金属化合物は有機金属化合物からなる錯体である。一方、１８段落で説明した錯体は、無機物の分子ないしは無機物のイオンが配位子となって、金属イオンに配位結合する金属錯イオンを有する無機金属化合物からなる錯体である。また、配位子と金属錯イオンと結合する無機物とが、カルボン酸に比べて分子量が小さいため、無機金属化合物からなる錯体の熱分解温度は、カルボン酸金属化合物の熱分解温度より低い。
Embodiment 3
This embodiment is an embodiment relating to a complex composed of a carboxylic acid metal compound that precipitates a metal oxide by thermal decomposition described in paragraph 16. The metal compound in the present invention first has two properties of being dispersed in methanol, not dissolving in methanol, and secondly precipitating a metal oxide by thermal decomposition. Here, the metal oxide is titanium oxide TiO 2 , and the description will be made from the embodiment of the titanium compound.
First, a titanium compound dispersed in methanol will be described. Titanium chloride is soluble in methanol. Titanium oxide does not disperse in methanol. Therefore, these low molecular weight inorganic titanium compounds are not dispersed in methanol.
In addition, there is an inorganic metal compound having a titanium complex ion [TiCl 4 O] 2- as a titanium complex ion in which a ligand composed of an inorganic molecule or an inorganic ion described in paragraph 18 is coordinated and bonded to the titanium ion. However, the coordination bond is not stable.
Next, the organic titanium compound will be described. The organic titanium compound precipitates titanium dioxide TiO 2 by thermal decomposition. Among the chemical reactions that produce titanium oxide from organic titanium compounds, one of the simplest chemical reactions is the thermal decomposition reaction. That is, titanium oxide is deposited by thermal decomposition only by raising the temperature of the organic titanium compound. Further, if the organic titanium compound can be easily synthesized, the organic titanium compound can be produced at low cost. An organic titanium compound having these properties is a titanium carboxylate compound.
That is, among the substances constituting the titanium carboxylate compound, the substance having the largest covalent radius is titanium ion Ti 4+ . On the other hand, the titanium carboxylate compound in which the titanium ion Ti 4+ and the carboxylate anion (R - CO 2- ) are covalently bonded has the maximum distance between the titanium ion and the oxygen ion, so that titanium is precipitated by thermal decomposition. Therefore, in the titanium carboxylate compound that precipitates titanium oxide by thermal decomposition, the carboxylate anion (R-CO 2- ) approaches the titanium ion Ti 4+ , so that the carboxylate anion (R -CO 2- ) becomes titanium. The distance to bond with the ion bound on the opposite side of the ion Ti 4+ is the longest. That is, the site where the carboxylate anion (R - CO 2- ) binds to the ion bonded on the opposite side of the titanium ion Ti 4+ is the longest, and this bonding part is first divided and the oxygen ion bonded to the titanium ion, that is, , Decomposes into titanium oxide TiO 2 and carboxylic acid. As a titanium carboxylate compound having such molecular structural characteristics, there is a titanium carboxylate compound in which a carboxylate anion (R - CO 2- ) serves as a ligand and is coordinated to the titanium ion Ti 4+ .
Further, among the organic titanium compounds, the titanium carboxylate compound is easy to synthesize, and if the boiling point of the organic acid is low, the thermal decomposition temperature is relatively low. Therefore, a complex composed of a carboxylate metal compound in which a carboxylate anion (R - CO 2- ) serves as a ligand and is coordinated and bonded to a metal ion is an inexpensive industrial chemical and has a high heat treatment cost. It's cheap. Therefore, the titanium carboxylate compound in which the carboxylate anion (R - CO 2- ) is coordinated to the titanium ion is an inexpensive industrial chemical that precipitates titanium oxide by thermal decomposition.
Examples of such titanium carboxylate compounds include titanium acetate, titanium caprylate, titanium benzoate, and titanium naphthenate. However, titanium acetate and titanium caprylate do not precipitate titanium oxide by thermal decomposition because the coordination bond is not stable. On the other hand, the boiling point of benzoic acid is 249 ° C, and titanium tetrabenzoate Ti (C 6 H 5 COO) 4 is thermally decomposed at 310 ° C in the air atmosphere to precipitate titanium oxide, which has a higher thermal decomposition temperature than titanium naphthenate. low.
Further, among the vanadium carboxylic acid compounds, the vanadium carboxylate compound other than vanadium naphthenate does not precipitate vanadium oxide by thermal decomposition because the coordination bond is not stable. On the other hand, naphthenic acid is a mixture of saturated fatty acids having a 5-membered ring, the general formula is represented by Cn H 2n -1 COOH, the boiling point of the main component is 268 ° C, and the molecular weight is 170 C 9 H 17 COOH. .. Therefore, vanadium naphthenate is thermally decomposed at 330 ° C. in the atmospheric atmosphere to precipitate vanadium oxide.
The carboxylate metal compound in which the carboxylate anion (R - CO 2- ) of the carboxylic acid serves as a ligand and is coordinated to the metal ion is a complex composed of an organic metal compound. On the other hand, the complex described in paragraph 18 is a complex composed of an inorganic metal compound having a metal complex ion coordinate-bonded to a metal ion by using an inorganic molecule or an inorganic ion as a ligand. Further, since the inorganic substance bonded to the ligand and the metal complex ion has a smaller molecular weight than the carboxylic acid, the thermal decomposition temperature of the complex composed of the inorganic metal compound is lower than the thermal decomposition temperature of the carboxylic acid metal compound.
実施例１
本実施例は、熱分解で銀を析出する無機銀化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する。無機銀化合物として、１７段落の実施形態１で説明した塩化ジアンミン銀（例えば、田中貴金属工業株式会社の製品）を用いた。また、液体の有機化合物として、１２段落に記載した炭素原子の数が１１からなるｎ－ウンデカン（例えば、ＥＮＥＯＳ株式会社の製品）を用いた。
最初に、容器に２．５リットルのメタノールを充填し、塩化ジアンミン銀の１７７．５ｇ（１モルに相当する）をメタノールに分散した。さらに、容器を６５℃に昇温し、メタノールを気化し、塩化ジアンミン銀の結晶を析出させた。この後、塩化ジアンミン銀の結晶の集まりを、１０ｃｍ×１０ｃｍ×２ｃｍの容器に移した。さらに、塩化ジアンミン銀の結晶の集まりの上に、１０ｃｍ×１０ｃｍ×１ｃｍの板を被せ、板の上に１０ｋｇの重りを載せ、この後、重りを取り除き、容器に対し、前後、左右、上下の３方向の０．３Ｇからなる衝撃加速度を繰り返し加えた。こうした圧縮荷重を加える処理と衝撃加速度を加える処理とを、３回繰り返した後に、重りを板の上に載せたが、板が全く沈まなかったため、処理を停止した。この後、板を容器から取り外し、容器に、９３ｇのｎ－ウンデカンを混合し、第一の懸濁液を作成した。なお、ｎ－ウンデカンの体積は、塩化ジアンミン銀の体積より２７％多い。この後、容器内に、超音波ホモジナイザー装置（例えば、ヤマト科学株式会社の製品ＬＵＨ３００）のホーンを浸漬させ、２０ｋＨｚの超音波振動を容器内の第一の懸濁体に２分間加え、容器内に第二の懸濁液を作成した。
なお、圧縮荷重を加える処理と衝撃加速度を加える処理とを終えた塩化ジアンミン銀の結晶の一部を取り出し、電子顕微鏡で、試料の観察と分析とを行なった。電子顕微鏡は、ＪＦＥテクノリサーチ株式会社の極低加速電圧ＳＥＭを用いた。この装置は、１００Ｖからの極低加速電圧による表面観察が可能で、試料に導電性の被膜を形成せずに直接試料の表面が観察できる特徴を持つ。
試料からの反射電子線の９００－１０００Ｖの間にある２次電子線を取り出し画像処理を行なった。試料は２０ｎｍ前後の大きさからなる有機物の集まりで形成されていた。このため、塩化ジアンミン銀の結晶は、２０ｎｍ前後の大きさに粉砕された。
Example 1
In this embodiment, fine crystals of an inorganic silver compound that precipitates silver by thermal decomposition are surrounded by a liquid organic compound to produce a suspension dispersed in the liquid organic compound. As the inorganic silver compound, silver diammine chloride described in Embodiment 1 of paragraph 17 (for example, a product of Tanaka Kikinzoku Kogyo Co., Ltd.) was used. Further, as the liquid organic compound, n-undecane having 11 carbon atoms (for example, a product of ENEOS Co., Ltd.) described in paragraph 12 was used.
First, the container was filled with 2.5 liters of methanol and 177.5 g (corresponding to 1 mol) of silver diammine chloride was dispersed in methanol. Further, the temperature of the container was raised to 65 ° C., methanol was vaporized, and silver chloride diammine crystals were precipitated. After this, a collection of silver chloride diammine crystals was transferred to a 10 cm × 10 cm × 2 cm container. Further, a 10 cm × 10 cm × 1 cm plate is placed on a collection of silver chloride diammine crystals, a 10 kg weight is placed on the plate, and then the weight is removed, and the container is placed in front / back, left / right, up / down. Impact acceleration consisting of 0.3 G in three directions was repeatedly applied. After repeating the process of applying the compressive load and the process of applying the impact acceleration three times, the weight was placed on the plate, but the process was stopped because the plate did not sink at all. After this, the plate was removed from the container and 93 g of n-undecane was mixed in the container to prepare the first suspension. The volume of n-undecane is 27% larger than the volume of silver chloride. After that, the horn of an ultrasonic homogenizer device (for example, product LUH300 of Yamato Scientific Co., Ltd.) is immersed in the container, and ultrasonic vibration of 20 kHz is applied to the first suspension in the container for 2 minutes, and the inside of the container is added. A second suspension was made in.
A part of the diammine silver chloride crystal after the treatment of applying the compressive load and the treatment of applying the impact acceleration was taken out, and the sample was observed and analyzed with an electron microscope. As the electron microscope, an extremely low acceleration voltage SEM manufactured by JFE Techno Research Co., Ltd. was used. This device is capable of observing the surface with an extremely low acceleration voltage from 100 V, and has the feature that the surface of the sample can be directly observed without forming a conductive film on the sample.
The secondary electron beam between 900 and 1000 V of the backscattered electron beam from the sample was taken out and image-processed. The sample was formed of a collection of organic substances having a size of about 20 nm. Therefore, the silver chloride diammine crystals were pulverized to a size of about 20 nm.
実施例２
本実施例は、実施例１で製造した懸濁液から、銀のナノ粒子の集まりを析出させる。
実施例１で製造した懸濁液の一部を容器に移し、該容器をアンモニアガス雰囲気の焼成炉に配置し、１８０℃まで昇温し、１８０℃に５分間放置させた。その後、容器を真空ベルジャー内に配置させ、真空ベルジャー内の圧力を１００パスカルまで減圧し、ｎ－ウンデカンを気化した。さらに、真空ベルジャーを大気圧に戻し、容器内の試料を、実施例１で用いた電子顕微鏡で観察と分析を行った。
この結果、試料は、１０ｎｍ前後の大きさからなる銀のナノ粒子の集まりであった。なお、容器を僅かに動かしただけで、容器内のナノ粒子が簡単に動いたため、銀のナノ粒子は凝集せず、個々のナノ粒子が分離していると思われる。図１に、析出した銀のナノ粒子の集まりを、模式的に図示する。１は銀のナノ粒子である。
なお、ｎ－ウンデカンの沸点は１９６℃で、塩化ジアンミン銀の熱分解温度１８０℃より１６℃だけ高い。従って、塩化ジアンミン銀の微細結晶を熱分解した懸濁液を、速やかに真空ベルジャー内に移せば、懸濁液の温度の低下は抑制され、ｎ－ウンデカンは一定の蒸気圧を持つ。このため、真空ベルジャー内の圧力を１００パスカルまで減圧させ、ｎ－ウンデカンを確実に懸濁液から気化させた。
なお、銀は比抵抗が低く、比較的酸化されにくい物質であるため、電子配線などの導電材料として用いられる。例えば、銀のナノ粒子は、比表面積が大きいため、銀のナノ粒子を昇温すると、活性化されたナノ粒子になり、低温で融着しやすい性質を持つ。このため、活性化した銀のナノ粒子の融点が下がり、鉛フリーのはんだ代替材料として用いられる。また、インクジェットプリンタなどを用いた印刷法による電子配線の形成に用いられる。
また、銀イオンの抗菌性はよく知られているが、銀をナノ粒子化すると、比表面積が著しく増大し、表面原子の増大によって銀のイオン化が促進され、銀の抗菌性がさらに高まり、抗菌材への応用が可能になる。さらに、貴金属はバルクでは安定な物質であるが、ナノ粒子化することにより強い触媒活性を発現する。従って、銀のナノ粒子は、様々な触媒作用を持つ工業製品への応用が可能になる。
Example 2
In this example, a collection of silver nanoparticles is precipitated from the suspension produced in Example 1.
A part of the suspension produced in Example 1 was transferred to a container, the container was placed in a firing furnace in an ammonia gas atmosphere, the temperature was raised to 180 ° C., and the mixture was allowed to stand at 180 ° C. for 5 minutes. Then, the container was placed in a vacuum bell jar, the pressure in the vacuum bell jar was reduced to 100 Pascal, and n-undecane was vaporized. Further, the vacuum bell jar was returned to atmospheric pressure, and the sample in the container was observed and analyzed with the electron microscope used in Example 1.
As a result, the sample was a collection of silver nanoparticles having a size of about 10 nm. Since the nanoparticles in the container moved easily by moving the container slightly, it seems that the silver nanoparticles did not aggregate and the individual nanoparticles were separated. FIG. 1 schematically illustrates a collection of precipitated silver nanoparticles. 1 is a silver nanoparticle.
The boiling point of n-undecane is 196 ° C, which is 16 ° C higher than the thermal decomposition temperature of silver chloride 180 ° C. Therefore, if the suspension obtained by thermally decomposing fine crystals of silver diammine chloride is rapidly transferred into a vacuum bell jar, the decrease in the temperature of the suspension is suppressed, and n-undecane has a constant vapor pressure. Therefore, the pressure in the vacuum bell jar was reduced to 100 Pascal to ensure that n-undecane was vaporized from the suspension.
Since silver has a low resistivity and is relatively difficult to oxidize, it is used as a conductive material for electronic wiring and the like. For example, since silver nanoparticles have a large specific surface area, when the temperature of silver nanoparticles is raised, they become activated nanoparticles and have a property of being easily fused at a low temperature. Therefore, the melting point of the activated silver nanoparticles is lowered, and it is used as a lead-free solder substitute material. It is also used to form electronic wiring by a printing method using an inkjet printer or the like.
In addition, although the antibacterial properties of silver ions are well known, when silver is made into nanoparticles, the specific surface area is significantly increased, and the increase in surface atoms promotes the ionization of silver, further enhancing the antibacterial properties of silver, and antibacterial properties. It can be applied to materials. Furthermore, although noble metals are stable substances in bulk, they exhibit strong catalytic activity when they are made into nanoparticles. Therefore, silver nanoparticles can be applied to industrial products having various catalytic actions.
実施例３
本実施例は、１８段落に記載した熱分解で銅を析出するオクチル酸銅（例えば、三津和化学薬品株式会社の製品）の微細結晶が、１４段落に記載したラウリン酸ブチル（例えば、富士フイルム和光純薬株式会社の製品）で囲まれ、ラウリン酸ブチルに分散した懸濁液を製造する。
最初に、容器に２リットルのメタノールを充填し、オクチル酸銅の１４０ｇ（０．４モルに相当する）をメタノールに分散した。さらに、容器を６５℃に昇温し、メタノールを気化し、オクチル酸銅の結晶を析出させた。この後、オクチル酸銅の結晶の集まりを、１０ｃｍ×１０ｃｍ×２ｃｍの容器に移した。さらに、オクチル酸銅の結晶の集まりの上に、１０ｃｍ×１０ｃｍ×１ｃｍの板を被せ、板の上に１０ｋｇの重りを載せ、さらに、重りを取り除き、容器に対し、前後、左右、上下の３方向の０．３Ｇからなる衝撃加速度を繰り返し加えた。こうした圧縮荷重を加える処理と衝撃加速度を加える処理とを、３回繰り返した後に、重りを板の上に載せたが、板が全く沈まなかったため、処理を停止した。この後、板を容器から取り外し、容器に、１５０ｇのラウリン酸ブチルを混合し、第一の懸濁液を作成した。なお、ラウリン酸ブチルの体積は、オクチル酸銅の体積より３５％多い。この後、容器内に、実施例１で用いた超音波ホモジナイザー装置のホーンを浸漬させ、２０ｋＨｚの超音波振動を容器内の第一の懸濁体に２分間加え、容器内に第二の懸濁液を作成した。
なお、実施例１と同様に、粉砕したオクチル酸銅の結晶の一部を取り出し、電子顕微鏡で、試料の観察と分析とを行なった。試料は２０ｎｍ前後の大きさからなる有機物で形成されていた。このため、オクチル酸銅の結晶は、２０ｎｍ前後の大きさに粉砕された。
Example 3
In this embodiment, the fine crystals of copper octylate (for example, a product of Mitsuwa Chemical Industries, Ltd.) that precipitates copper by thermal decomposition described in paragraph 18 are the butyl laurate described in paragraph 14 (for example, Wako Pure Chemical Industries, Ltd.). A suspension surrounded by Wako Pure Chemical Industries, Ltd.) and dispersed in butyl laurate is produced.
First, the container was filled with 2 liters of methanol and 140 g (corresponding to 0.4 mol) of copper octylate was dispersed in methanol. Further, the temperature of the container was raised to 65 ° C., methanol was vaporized, and copper octylate crystals were precipitated. After this, a collection of copper octylate crystals was transferred to a 10 cm × 10 cm × 2 cm container. Furthermore, a plate of 10 cm × 10 cm × 1 cm is placed on a collection of copper octylate crystals, a weight of 10 kg is placed on the plate, and the weight is removed. Impact acceleration consisting of 0.3 G in the direction was repeatedly applied. After repeating the process of applying the compressive load and the process of applying the impact acceleration three times, the weight was placed on the plate, but the process was stopped because the plate did not sink at all. After this, the plate was removed from the container and 150 g of butyl laurate was mixed in the container to prepare the first suspension. The volume of butyl laurate is 35% larger than the volume of copper octylate. After that, the horn of the ultrasonic homogenizer device used in Example 1 is immersed in the container, ultrasonic vibration of 20 kHz is applied to the first suspension in the container for 2 minutes, and the second suspension in the container. A turbid liquid was created.
In addition, in the same manner as in Example 1, a part of the crushed copper octylate crystal was taken out, and the sample was observed and analyzed with an electron microscope. The sample was formed of an organic substance having a size of about 20 nm. Therefore, the copper octylate crystals were pulverized to a size of about 20 nm.
実施例４
本実施例は、実施例３で製造した懸濁液から、銅のナノ粒子の集まりを析出させる。
実施例３で製造した懸濁液の一部を容器に移し、該容器を大気雰囲気の焼成炉に配置し、２９０℃まで昇温し、２９０℃に１分間放置させた。その後、容器を真空ベルジャー内に配置させ、真空ベルジャー内の圧力を１００パスカルまで減圧し、ラウリン酸ブチルを気化した。さらに、真空ベルジャーを大気圧に戻し、容器内の試料を、実施例１で用いた電子顕微鏡で観察と分析を行った。
この結果、試料は、１０ｎｍ前後の大きさからなる銅のナノ粒子の集まりであった。なお、容器を僅かに動かしただけで、容器内のナノ粒子が簡単に動いたため、銅のナノ粒子は凝集せず、個々のナノ粒子が分離していると思われる。
なお、ラウリン酸ブチルの沸点は３０６℃で、オクチル酸銅の熱分解温度２９０℃より１６℃だけ高い。従って、オクチル酸銅の微細結晶を熱分解した懸濁液を、速やかに真空ベルジャー内に移せば、懸濁液の温度の低下は抑制され、ラウリン酸ブチルは一定の蒸気圧を持つ。このため、真空ベルジャー内の圧力を１００パスカルまで減圧させ、ラウリン酸ブチルを確実に懸濁液から気化させた。
なお、銅のナノ粒子の原料であるオクチル酸銅は、銀のナノ粒子の原料である塩化ジアンミン銀より安価である。従って、銅のナノ粒子の集まりは、実施例２で作成した銀のナノ粒子の集まりより安価である。また、銅のナノ粒子は、銀のナノ粒子と同様に、比表面積が大きいため、銅のナノ粒子を昇温すると、活性化されたナノ粒子になり、低温で融着する性質を持つため、銀のナノ粒子と同様にバルクより著しく低温で接合する接合材として用いることができる。従って、銅のナノ粒子は、銀のナノ粒子と同様に、鉛フリーのはんだ代替材料として用いられる。また、インクジェットプリンタなどを用いた印刷法による電子配線の形成に用いられる。
Example 4
In this example, a collection of copper nanoparticles is precipitated from the suspension produced in Example 3.
A part of the suspension produced in Example 3 was transferred to a container, the container was placed in a firing furnace in an air atmosphere, the temperature was raised to 290 ° C, and the mixture was allowed to stand at 290 ° C for 1 minute. Then, the container was placed in a vacuum bell jar, the pressure in the vacuum bell jar was reduced to 100 Pascal, and butyl laurate was vaporized. Further, the vacuum bell jar was returned to atmospheric pressure, and the sample in the container was observed and analyzed with the electron microscope used in Example 1.
As a result, the sample was a collection of copper nanoparticles having a size of about 10 nm. Since the nanoparticles in the container moved easily by moving the container slightly, it seems that the copper nanoparticles did not aggregate and the individual nanoparticles were separated.
The boiling point of butyl laurate is 306 ° C, which is 16 ° C higher than the thermal decomposition temperature of copper octylate of 290 ° C. Therefore, if a suspension obtained by thermally decomposing fine crystals of copper octylate is rapidly transferred into a vacuum bell jar, a decrease in the temperature of the suspension is suppressed, and butyl laurate has a constant vapor pressure. Therefore, the pressure in the vacuum bell jar was reduced to 100 Pascal to ensure that butyl laurate was vaporized from the suspension.
Copper octylate, which is a raw material for copper nanoparticles, is cheaper than silver diammine chloride, which is a raw material for silver nanoparticles. Therefore, the collection of copper nanoparticles is cheaper than the collection of silver nanoparticles prepared in Example 2. Further, since copper nanoparticles have a large specific surface area like silver nanoparticles, when the temperature of copper nanoparticles is raised, they become activated nanoparticles and have the property of being fused at a low temperature. Similar to silver nanoparticles, it can be used as a bonding material for bonding at a significantly lower temperature than bulk. Therefore, copper nanoparticles, like silver nanoparticles, are used as lead-free solder alternatives. It is also used to form electronic wiring by a printing method using an inkjet printer or the like.
実施例５
本実施例は、１９段落に記載した熱分解で酸化チタンを析出するテトラ安息香酸チタン（例えば、シグマ・アルドリッチ社の製品）の微細結晶が、１６段落に記載したラウリン酸ヘキシル（例えば、高級アルコール工業株式会社の製品）に分散した懸濁液を製造する。
最初に、容器に２リットルのメタノールを充填し、テトラ安息香酸チタンの１６０ｇ（０．３モルに相当する）をメタノールに分散した。さらに、容器を６５℃に昇温し、メタノールを気化し、テトラ安息香酸チタンの結晶を析出させた。この後、テトラ安息香酸チタンの結晶の集まりを、１０ｃｍ×１０ｃｍ×２ｃｍの容器に移した。さらに、テトラ安息香酸チタンの結晶の集まりの上に、１０ｃｍ×１０ｃｍ×１ｃｍの板を被せ、板の上に１０ｋｇの重りを載せ、さらに、重りを取り除き、容器に対し、前後、左右、上下の３方向の０．３Ｇからなる衝撃加速度を繰り返し加えた。こうした圧縮荷重を加える処理と衝撃加速度を加える処理とを、３回繰り返した後に、重りを板の上に載せたが、板が全く沈まなかったため、処理を停止した。この後、板を容器から取り外し、容器に、１５０ｇのラウリン酸ヘキシルを混合し、第一の懸濁液を作成した。なお、ラウリン酸ヘキシルの体積は、テトラ安息香酸チタンの体積より２２％多い。この後、容器内に、実施例１で用いた超音波ホモジナイザー装置のホーンを浸漬させ、２０ｋＨｚの超音波振動を容器内の第一の懸濁体に２分間加え、容器内に第二の懸濁液を作成した。
なお、実施例１と同様に、粉砕したテトラ安息香酸チタンの結晶の一部を取り出し、電子顕微鏡で、試料の観察と分析とを行なった。試料は２０ｎｍ前後の大きさからなる有機物で形成されていた。このため、テトラ安息香酸チタンの結晶は、２０ｎｍ前後の大きさに粉砕された。
Example 5
In this example, the fine crystals of titanium tetrabenzoate (eg, a product of Sigma-Aldrich) that precipitates titanium oxide by thermal decomposition described in paragraph 19 are the hexyl laurate (eg, higher alcohol) described in paragraph 16. Manufacture a suspension dispersed in (a product of Kogyo Co., Ltd.).
First, the container was filled with 2 liters of methanol and 160 g (corresponding to 0.3 mol) of titanium tetrabenzoate was dispersed in methanol. Further, the temperature of the container was raised to 65 ° C., methanol was vaporized, and crystals of titanium tetrabenzoate were precipitated. After this, the collection of crystals of titanium tetrabenzoate was transferred to a container of 10 cm × 10 cm × 2 cm. Furthermore, a 10 cm × 10 cm × 1 cm plate is placed on a collection of titanium tetrabenzoate crystals, a 10 kg weight is placed on the plate, the weight is removed, and the container is placed in front / back, left / right, and up / down. Impact acceleration consisting of 0.3 G in three directions was repeatedly applied. After repeating the process of applying the compressive load and the process of applying the impact acceleration three times, the weight was placed on the plate, but the process was stopped because the plate did not sink at all. After this, the plate was removed from the container and 150 g of hexyl laurate was mixed in the container to prepare the first suspension. The volume of hexyl laurate is 22% larger than the volume of titanium tetrabenzoate. After that, the horn of the ultrasonic homogenizer device used in Example 1 is immersed in the container, ultrasonic vibration of 20 kHz is applied to the first suspension in the container for 2 minutes, and the second suspension in the container. A turbid liquid was created.
In the same manner as in Example 1, a part of the crushed titanium crystals of tetrabenzoate was taken out, and the sample was observed and analyzed with an electron microscope. The sample was formed of an organic substance having a size of about 20 nm. Therefore, the crystals of titanium tetrabenzoate were pulverized to a size of about 20 nm.
実施例６
本実施例は、実施例５で製造した懸濁液から、酸化チタンのナノ粒子の集まりを析出させる。
実施例５で製造した懸濁液の一部を容器に移し、該容器を大気雰囲気の焼成炉に配置し、３１０℃まで昇温し、３１０℃に１分間放置させた。その後、容器を真空ベルジャー内に配置させ、真空ベルジャー内の圧力を５０パスカルまで減圧し、ラウリン酸ヘキシルを気化した。さらに、真空ベルジャーを大気圧に戻し、容器内の試料を、実施例１で用いた電子顕微鏡で観察と分析を行った。
この結果、試料は、１０ｎｍ前後の大きさからなる酸化チタンのナノ粒子の集まりであった。なお、容器を僅かに動かしただけで、容器内のナノ粒子が簡単に動いたため、酸化チタンのナノ粒子は凝集せず、個々のナノ粒子が分離していると思われる。
さらに、極低加速電圧ＳＥＭの機能にＥＢＳＰ解析機能を付加し、酸化チタンの結晶構造の解析を行なった。酸化チタンは、正方晶系のアナターゼ型であった。アナターゼ型の酸化チタンは、光触媒活性を持ち、粒子が小さいほど比表面積が大きいため活性度が高い。このため、抗菌、脱臭、大気浄化、セルフクリーニング膜などへの適応が考えられる。本実施例で作成した酸化チタンのナノ粒子は、このような製品への応用が可能になる。
なお、ラウリン酸ヘキシルの沸点は３３５℃で、テトラ安息香酸チタンの熱分解温度３１０℃より２５℃だけ高い。従って、テトラ安息香酸チタンの微細結晶を熱分解した懸濁液を、速やかに真空ベルジャー内に移せば、懸濁液の温度の低下は抑制され、ラウリン酸ヘキシルは一定の蒸気圧を持つ。このため、真空ベルジャー内の圧力を５０パスカルまで減圧させ、ラウリン酸ヘキシルを確実に懸濁液から気化させた。
Example 6
In this example, a collection of titanium oxide nanoparticles is precipitated from the suspension produced in Example 5.
A part of the suspension produced in Example 5 was transferred to a container, the container was placed in a baking furnace in an air atmosphere, the temperature was raised to 310 ° C., and the mixture was allowed to stand at 310 ° C. for 1 minute. Then, the container was placed in a vacuum bell jar, the pressure in the vacuum bell jar was reduced to 50 pascals, and hexyl laurate was vaporized. Further, the vacuum bell jar was returned to atmospheric pressure, and the sample in the container was observed and analyzed with the electron microscope used in Example 1.
As a result, the sample was a collection of titanium oxide nanoparticles having a size of about 10 nm. Since the nanoparticles in the container moved easily by moving the container slightly, it seems that the nanoparticles of titanium oxide did not aggregate and the individual nanoparticles were separated.
Furthermore, the EBSP analysis function was added to the function of the ultra-low acceleration voltage SEM, and the crystal structure of titanium oxide was analyzed. Titanium oxide was a tetragonal anatase type. Anatase-type titanium oxide has photocatalytic activity, and the smaller the particles, the larger the specific surface area, and therefore the higher the activity. Therefore, it can be applied to antibacterial, deodorizing, air purification, self-cleaning membranes, etc. The titanium oxide nanoparticles produced in this example can be applied to such products.
The boiling point of hexyl laurate is 335 ° C, which is 25 ° C higher than the thermal decomposition temperature of titanium tetrabenzoate, 310 ° C. Therefore, if the suspension obtained by thermally decomposing fine crystals of titanium tetrabenzoate is rapidly transferred into a vacuum bell jar, the decrease in the temperature of the suspension is suppressed, and the hexyl laurate has a constant vapor pressure. Therefore, the pressure in the vacuum bell jar was reduced to 50 pascals to ensure that hexyl laurate was vaporized from the suspension.
以上に説明した実施例は、熱分解で銀、銅、酸化チタンのいずれかを析出する金属化合物の微細結晶を、沸点が、金属化合物の熱分解温度より３０℃以内の温度だけ高い液体の有機化合物に分散した懸濁液の製造方法に係り、また、該懸濁液を用いて、金属ないしは金属酸化物からなるナノ粒子の集まりを析出させる方法に関わる。
いっぽう、塩化ジアンミン銀の微細結晶をｎ－ウンデカンに分散した懸濁液は、一つの事例に過ぎず、実施例１に限定されることはない。つまり、無機物からなる分子ないしは無機物からなるイオンが配位子となって、金属イオンに配位結合する金属錯イオンからなる金属錯体は、１７段落に説明したように、様々な無機金化合物からなる金属錯体が存在する。また、無機金化合物からなる金属錯体の微細結晶を分散させる液体の有機化合物は、１２段落に記載したように、様々な有機化合物が存在する。従って、実施例１は、懸濁液を製造する一つの事例に過ぎず、実施例１に限定されることはない。また、実施例２で記載した方法に従って懸濁液を処理すれば、金属のナノ粒子が液体の有機化合物で取り囲んで析出し、この後、液体の有機化合物を真空チャンバー内で気化すると、様々な金属からナノ粒子が凝集せずに、個々の金属ナノ粒子の集まりが得られる。従って、実施例２は、銀のナノ粒子が凝集せずに、個々の銀のナノ粒子の集まりが得られる一つの事例に過ぎず、様々な金属からナノ粒子が凝集せずに、個々の金属のナノ粒子の集まりが得られる。
また、オクチル酸銅をラウリン酸ブチルに分散した懸濁液は、一つの事例に過ぎず、実施例３に限定されることはない。つまり、熱分解で金属を析出するオクチル酸金属化合物は、１８段落に説明したように、様々なオクチル酸金属化合物が存在する。また、オクチル酸金属化合物を分散させる液体の有機化合物は、１４段落に記載したように、様々な有機化合物が存在する。従って、実施例３は、懸濁液を製造する一つの事例に過ぎず、実施例３に限定されることはない。また、実施例４で記載した方法に従って懸濁液を処理すれば、金属のナノ粒子が液体の有機化合物で取り囲んで析出し、この後、液体の有機化合物を真空チャンバー内で気化すると、様々な金属からナノ粒子が凝集せずに、個々の金属ナノ粒子の集まりが得られる。従って、実施例４は、金属のナノ粒子が凝集せずに、個々の金属のナノ粒子の集まりが得られる一つの事例に過ぎず、実施例４に限定されない。
さらに、テトラ安息香酸チタンをラウリン酸ヘキシルに分散した懸濁液は、一つの事例に過ぎず、実施例５に限定されることはない。つまり、熱分解で金属酸化物を析出するカルボン酸金属化合物は、１９段落に説明したように、様々なカルボン酸金属化合物が存在する。また、カルボン酸金属化合物を分散させる液体の有機化合物は、１６段落に記載したように、様々な有機化合物が存在する。従って、実施例５は、熱分解で金属酸化物を析出するカルボン酸金属化合物を、液体の有機化合物に分散した懸濁液を製造する一つの事例に過ぎず、実施例５に限定されることはない。また、実施例６で記載した方法に従って懸濁液を処理すれば、金属酸化物のナノ粒子が液体の有機化合物で取り囲んで析出し、この後、液体の有機化合物を真空チャンバー内で気化すると、様々な金属酸化物からナノ粒子が得られる。従って、実施例６は、金属酸化物のナノ粒子の集まりが得られる一つの事例に過ぎず、実施例６に限定されることはない。
本発明に依れば、金属ないしは金属酸化物のナノ粒子が凝集せず、個々のナノ粒子に分離しているため、ナノ粒子の集まりは、様々な工業製品への応用が可能になる。さらに、ナノ粒子の大きさは、１０ｎｍ前後と小さい。従って、本発明は、様々な工業用製品に応用できるナノ粒子の製造に係る発明である。
In the examples described above, fine crystals of a metal compound that precipitates any of silver, copper, and titanium oxide by thermal decomposition are liquid organic having a boiling point higher than the thermal decomposition temperature of the metal compound by a temperature within 30 ° C. It relates to a method for producing a suspension dispersed in a compound, and also to a method for precipitating a collection of nanoparticles composed of a metal or a metal oxide using the suspension.
On the other hand, the suspension in which fine crystals of silver diammine chloride are dispersed in n-undecane is only one example, and is not limited to Example 1. That is, as described in paragraph 17, a metal complex composed of a metal complex ion in which a molecule composed of an inorganic substance or an ion composed of an inorganic substance serves as a ligand and is coordinate-bonded to the metal ion is composed of various inorganic gold compounds. There is a metal complex. Further, as described in paragraph 12, various organic compounds exist as liquid organic compounds in which fine crystals of a metal complex composed of an inorganic gold compound are dispersed. Therefore, Example 1 is merely one example of producing a suspension, and is not limited to Example 1. Further, when the suspension is treated according to the method described in Example 2, metal nanoparticles are surrounded by a liquid organic compound and precipitated, and then the liquid organic compound is vaporized in a vacuum chamber in various ways. A collection of individual metal nanoparticles is obtained without the nanoparticles being aggregated from the metal. Therefore, Example 2 is only one example in which a collection of individual silver nanoparticles can be obtained without agglomeration of silver nanoparticles, and the nanoparticles from various metals do not agglomerate and are individual metals. A collection of nanoparticles is obtained.
Further, the suspension in which copper octylate is dispersed in butyl laurate is only one example, and is not limited to Example 3. That is, as the octylate metal compound that precipitates a metal by thermal decomposition, various octylate metal compounds exist as described in paragraph 18. Further, as the liquid organic compound in which the metal octylate compound is dispersed, various organic compounds exist as described in paragraph 14. Therefore, Example 3 is merely one example of producing a suspension, and is not limited to Example 3. Further, when the suspension is treated according to the method described in Example 4, metal nanoparticles are surrounded by a liquid organic compound and precipitated, and then the liquid organic compound is vaporized in a vacuum chamber in various ways. A collection of individual metal nanoparticles is obtained without the nanoparticles being aggregated from the metal. Therefore, Example 4 is only one case in which a collection of individual metal nanoparticles can be obtained without agglomeration of metal nanoparticles, and is not limited to Example 4.
Furthermore, the suspension in which titanium tetrabenzoate is dispersed in hexyl laurate is only one case, and is not limited to Example 5. That is, as the carboxylic acid metal compound that precipitates the metal oxide by thermal decomposition, various carboxylic acid metal compounds exist as described in paragraph 19. Further, as the liquid organic compound in which the metal carboxylate compound is dispersed, various organic compounds exist as described in paragraph 16. Therefore, Example 5 is only one example of producing a suspension in which a metal carboxylate compound that precipitates a metal oxide by thermal decomposition is dispersed in a liquid organic compound, and is limited to Example 5. There is no. Further, when the suspension is treated according to the method described in Example 6, the nanoparticles of the metal oxide are surrounded by the liquid organic compound and precipitated, and then the liquid organic compound is vaporized in the vacuum chamber. Nanoparticles can be obtained from various metal oxides. Therefore, Example 6 is only one example in which a collection of nanoparticles of a metal oxide can be obtained, and is not limited to Example 6.
According to the present invention, nanoparticles of metal or metal oxide are not aggregated but separated into individual nanoparticles, so that the aggregate of nanoparticles can be applied to various industrial products. Furthermore, the size of the nanoparticles is as small as around 10 nm. Therefore, the present invention is an invention relating to the production of nanoparticles that can be applied to various industrial products.
１ 銀のナノ粒子
1 Silver nanoparticles
Claims (5)
メタノールに分散するが、メタノールに溶解しない第一の性質と、熱分解で金属ないしは金属酸化物を析出する第二の性質を兼備する金属化合物をメタノールに分散し、該金属化合物のメタノール分散液を作成し、この後、該金属化合物のメタノール分散液からメタノールを気化させ、該金属化合物の結晶の集まりを析出させる、さらに、該金属化合物の結晶の集まりを容器に充填し、該金属化合物の結晶の集まりの表面全体を覆う板材を、該金属化合物の結晶の集まりの上に被せる、この後、該板材の表面全体に圧縮荷重を加え、前記容器内の前記金属化合物の結晶を粉砕する、さらに、前記容器に前後、左右、上下の３方向の衝撃加速度を繰り返し加え、該容器内の前記粉砕された金属化合物の結晶の集まりを再配列させる、この後、前記板材の表面全体に再度前記圧縮荷重を加え、前記金属化合物の結晶の粉砕をさらに進める、さらに、前記容器に前記３方向の衝撃加速度を再度繰り返し加える、こうした前記圧縮荷重を加える処理と前記衝撃加速度を加える処理とからなる一対の処理を繰り返し、前記板材に前記圧縮荷重を加えた際に、該板材からの反発力が発生した時点で、前記一対の処理を停止する、この後、前記板材を前記容器から取り出し、さらに、前記容器に、融点が１５℃より低い第一の性質と、前記金属化合物が溶解及び分散しない第二の性質と、沸点が前記金属化合物の熱分解温度より３０℃以内の温度だけ高い第三の性質と、前記金属化合物の熱分解温度で析出した金属ないしは金属酸化物の微粒子と化学反応を起こさない第四の性質と、吸水性を持たない第五の性質からなる５つの性質を兼備する液体の有機化合物を、前記容器内の前記金属化合物の粉砕された結晶の集まりより多い体積からなる該有機化合物の重量として秤量し、該秤量した液体の有機化合物を前記容器に混合し、前記金属化合物の粉砕された結晶の集まりが、前記液体の有機化合物に分散された第一の懸濁液を作成する、さらに、前記容器内に超音波ホモジナイザー装置を配置し、該超音波ホモジナイザー装置の稼働によって、前記第一の懸濁液中に衝撃波を連続して発生させ、該衝撃波が前記金属化合物の粉砕された結晶の集まりに連続して衝突し、該粉砕された結晶が個々の結晶に分離し、該個々の結晶が、前記液体の有機化合物で囲まれ、該液体の有機化合物中に分散した第二の懸濁液が前記容器内に作成される、熱分解で金属ないしは金属酸化物を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。 A method for producing a suspension in which fine crystals of a metal compound that precipitates a metal or a metal oxide by thermal decomposition are surrounded by a liquid organic compound and dispersed in the liquid organic compound is used.
A metal compound having the first property of being dispersed in methanol but not soluble in methanol and the second property of precipitating a metal or a metal oxide by thermal decomposition is dispersed in methanol, and a methanol dispersion of the metal compound is prepared. After that, methanol is vaporized from the methanol dispersion of the metal compound to precipitate a collection of crystals of the metal compound, and further, the collection of crystals of the metal compound is filled in a container to crystallize the metal compound. A plate material covering the entire surface of the aggregate is placed on the aggregate of crystals of the metal compound, and then a compressive load is applied to the entire surface of the plate material to crush the crystals of the metal compound in the container. , The container is repeatedly subjected to impact acceleration in three directions of front-back, left-right, and up-down to rearrange the collection of crystals of the crushed metal compound in the container, and then the compression is performed again on the entire surface of the plate material. A pair consisting of a process of applying the compressive load and a process of applying the impact acceleration, in which a load is applied to further promote the crushing of the crystal of the metal compound, and the impact acceleration in the three directions is repeatedly applied to the container. The treatment is repeated, and when the compressive load is applied to the plate material, the pair of treatments is stopped when the repulsive force from the plate material is generated. The first property that the melting point is lower than 15 ° C., the second property that the metal compound does not dissolve and disperse, and the third property that the boiling point is higher than the thermal decomposition temperature of the metal compound by a temperature within 30 ° C. A liquid having five properties, that is, a fourth property that does not cause a chemical reaction with fine particles of a metal or metal oxide precipitated at the thermal decomposition temperature of the metal compound, and a fifth property that does not have water absorption. The organic compound is weighed as the weight of the organic compound having a volume larger than the collection of crushed crystals of the metal compound in the container, and the weighed liquid organic compound is mixed in the container to obtain the metal compound. A collection of crushed crystals creates a first suspension dispersed in the liquid organic compound, and an ultrasonic homogenizer device is placed in the container, and the operation of the ultrasonic homogenizer device causes the operation of the ultrasonic homogenizer device. A shock wave was continuously generated in the first suspension, and the shock wave continuously collided with a collection of crushed crystals of the metal compound, and the crushed crystals were separated into individual crystals. The individual crystals are surrounded by the liquid organic compound, and a second suspension dispersed in the liquid organic compound is created in the container. A method for producing a suspension in which fine crystals of a metal compound that precipitates a metal or a metal oxide by thermal decomposition are surrounded by a liquid organic compound and dispersed in the liquid organic compound.
請求項１に記載した方法で製造した第二の懸濁液の必要となる量を新たな容器に充填し、該新たな容器を、請求項１に記載した金属化合物を熱分解させる雰囲気に晒すとともに、該金属化合物が熱分解する温度に昇温する、これによって、前記新たな容器内に、金属ないしは金属酸化物からなるナノ粒子が、請求項１に記載した液体の有機化合物に囲まれて析出し、該液体の有機化合物中に前記ナノ粒子の集まりが分散した第三の懸濁液が作成される、この後、該第三の懸濁液が充填された前記新たな容器を真空チャンバー内に移し、真空ポンプによって前記真空チャンバー内の圧力を、該新たな容器内の前記第三の懸濁液の温度における前記液体の有機化合物の蒸気圧より低い圧力に減圧させ、前記第三の懸濁体から前記液体の有機化合物を気化させる、これによって、前記新たな容器に、前記金属ないしは前記金属酸化物からなるナノ粒子の集まりが析出する、請求項１に記載した方法で製造した第二の懸濁液から金属ないしは金属酸化物からなるナノ粒子の集まりを析出させる方法。 The method for precipitating a collection of nanoparticles made of a metal or a metal oxide from a second suspension produced by the method according to claim 1 is
A new container is filled with the required amount of the second suspension produced by the method according to claim 1, and the new container is exposed to an atmosphere that thermally decomposes the metal compound according to claim 1. At the same time, the temperature is raised to a temperature at which the metal compound is thermally decomposed, whereby nanoparticles made of a metal or a metal oxide are surrounded by the liquid organic compound according to claim 1 in the new container. A third suspension is created that precipitates and the aggregates of the nanoparticles are dispersed in the liquid organic compound, after which the new container filled with the third suspension is placed in a vacuum chamber. The pressure in the vacuum chamber is reduced to a pressure lower than the vapor pressure of the liquid organic compound at the temperature of the third suspension in the new container by a vacuum pump. The method according to claim 1, wherein the liquid organic compound is vaporized from the suspension, whereby a collection of nanoparticles composed of the metal or the metal oxide is deposited in the new container. (2) A method of precipitating a collection of nanoparticles composed of a metal or a metal oxide from a suspension.
請求項１に記載した熱分解で金属を析出する金属化合物が、無機物の分子ないしは無機物のイオンが配位子となって金属イオンに配位結合した金属錯イオンを有する無機塩で構成された無機金属化合物であり、請求項１に記載した液体の有機化合物が、炭素原子の数が１１－１３からなるアルカン、ないしは、飽和脂肪酸からなるカルボン酸エステル類、ないしは、脂肪族アルコール類に属するいずれか１種類の有機化合物であり、前記無機金属化合物を、請求項１に記載した熱分解で金属を析出する金属化合物として用い、前記アルカン、ないしは、前記カルボン酸エステル類、ないしは、前記脂肪族アルコール類に属するいずれか１種類の有機化合物を、請求項１に記載した液体の有機化合物として用い、請求項１に記載した懸濁液を製造する方法に従って懸濁液を製造する、請求項１に記載した熱分解で金属を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。 The method for producing a suspension in which fine crystals of a metal compound that precipitates a metal by thermal decomposition according to claim 1 are surrounded by a liquid organic compound and dispersed in the liquid organic compound is used.
The metal compound that precipitates a metal by thermal decomposition according to claim 1 is an inorganic substance composed of an inorganic salt having a metal complex ion coordinated and bonded to the metal ion by using an inorganic molecule or an ion of the inorganic substance as a ligand. The liquid organic compound according to claim 1, which is a metal compound, belongs to an alkane having 11 to 13 carbon atoms, a carboxylic acid ester composed of a saturated fatty acid, or an aliphatic alcohol. It is one kind of organic compound, and the inorganic metal compound is used as the metal compound for precipitating a metal by the thermal decomposition according to claim 1, and the alkane, the carboxylic acid esters, or the aliphatic alcohols. The method according to claim 1, wherein any one of the organic compounds belonging to the above is used as the liquid organic compound according to claim 1 and the suspension is produced according to the method for producing the suspension according to claim 1. A method for producing a suspension in which fine crystals of a metal compound that precipitates metal by thermal decomposition are surrounded by a liquid organic compound and dispersed in the liquid organic compound.
請求項１に記載した熱分解で金属を析出する金属化合物が、オクチル酸金属化合物であり、請求項１に記載した液体の有機化合物が、飽和脂肪酸からなるカルボン酸エステル類に属する１種類の有機化合物であり、前記オクチル酸金属化合物を、請求項１に記載した熱分解で金属を析出する金属化合物として用い、前記飽和脂肪酸からなるカルボン酸エステル類に属する１種類の有機化合物を、請求項１に記載した液体の有機化合物として用い、請求項１に記載した懸濁液を製造する方法に従って懸濁液を製造する、請求項１に記載した熱分解で金属を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。 The method for producing a suspension in which fine crystals of a metal compound that precipitates a metal by thermal decomposition according to claim 1 are surrounded by a liquid organic compound and dispersed in the liquid organic compound is used.
The metal compound that precipitates metal by thermal decomposition according to claim 1 is an octylate metal compound, and the liquid organic compound according to claim 1 is one kind of organic belonging to carboxylic acid esters composed of saturated fatty acids. Claim 1 is a compound, wherein the octylate metal compound is used as the metal compound for precipitating a metal by thermal decomposition according to claim 1, and one kind of organic compound belonging to the carboxylic acid esters composed of the saturated fatty acid is used. The fine crystals of a metal compound that precipitates a metal by thermal decomposition according to claim 1, wherein the suspension is produced according to the method for producing a suspension according to claim 1, which is used as the liquid organic compound according to claim 1. , A method of producing a suspension surrounded by a liquid organic compound and dispersed in the liquid organic compound.
請求項１に記載した熱分解で金属酸化物を析出する金属化合物が、カルボン酸のカルボキシル基を構成する酸素イオンが、金属イオンに配位結合したカルボン酸金属化合物からなる錯体であり、請求項１に記載した液体の有機化合物が、飽和脂肪酸からなるカルボン酸エステル類、ないしは、不飽和脂肪酸類に属するいずれか１種類の有機化合物であり、前記カルボン酸金属化合物を、請求項１に記載した熱分解で金属酸化物を析出する金属化合物として用い、前記カルボン酸エステル類、ないしは、前記不飽和脂肪酸類に属するいずれか１種類の液体の有機化合物を、請求項１に記載した液体の有機化合物として用い、請求項１に記載した懸濁液を製造する方法に従って懸濁液を製造する、請求項１に記載した熱分解で金属酸化物を析出する金属化合物の微細結晶が、液体の有機化合物で囲まれ、該液体の有機化合物中に分散した懸濁液を製造する方法。
The method for producing a suspension in which fine crystals of a metal compound that precipitates a metal oxide by thermal decomposition according to claim 1 are surrounded by a liquid organic compound and dispersed in the liquid organic compound is used.
The metal compound that precipitates a metal oxide by thermal decomposition according to claim 1 is a complex composed of a carboxylic acid metal compound in which oxygen ions constituting the carboxyl group of the carboxylic acid are coordinated and bonded to the metal ions. The liquid organic compound described in 1 is any one organic compound belonging to carboxylic acid esters composed of saturated fatty acids or unsaturated fatty acids, and the carboxylic acid metal compound is described in claim 1. The liquid organic compound according to claim 1, which is used as a metal compound for precipitating a metal oxide by thermal decomposition, and any one of the liquid organic compounds belonging to the carboxylic acid esters or the unsaturated fatty acids is used. The fine crystals of the metal compound that precipitates the metal oxide by thermal decomposition according to claim 1, wherein the suspension is produced according to the method for producing the suspension according to claim 1, are liquid organic compounds. A method of producing a suspension surrounded by and dispersed in the liquid organic compound.
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