JP4891021B2 - Method for producing niobium oxide fine particles - Google Patents
Method for producing niobium oxide fine particles Download PDFInfo
- Publication number
- JP4891021B2 JP4891021B2 JP2006265748A JP2006265748A JP4891021B2 JP 4891021 B2 JP4891021 B2 JP 4891021B2 JP 2006265748 A JP2006265748 A JP 2006265748A JP 2006265748 A JP2006265748 A JP 2006265748A JP 4891021 B2 JP4891021 B2 JP 4891021B2
- Authority
- JP
- Japan
- Prior art keywords
- acid
- niobium
- dispersion
- oxide fine
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000010419 fine particle Substances 0.000 title claims description 139
- 229910000484 niobium oxide Inorganic materials 0.000 title claims description 81
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 title claims description 81
- 238000004519 manufacturing process Methods 0.000 title claims description 28
- 239000006185 dispersion Substances 0.000 claims description 152
- 239000010955 niobium Substances 0.000 claims description 96
- 229910052758 niobium Inorganic materials 0.000 claims description 93
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 92
- 239000002253 acid Substances 0.000 claims description 88
- 239000002245 particle Substances 0.000 claims description 67
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 62
- 150000001875 compounds Chemical class 0.000 claims description 30
- 238000010335 hydrothermal treatment Methods 0.000 claims description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000007771 core particle Substances 0.000 claims description 15
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229910052787 antimony Inorganic materials 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 229910052718 tin Inorganic materials 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 10
- 229910052721 tungsten Inorganic materials 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003630 growth substance Substances 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- 150000007942 carboxylates Chemical class 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 2
- VBSTXRUAXCTZBQ-UHFFFAOYSA-N 1-hexyl-4-phenylpiperazine Chemical compound C1CN(CCCCCC)CCN1C1=CC=CC=C1 VBSTXRUAXCTZBQ-UHFFFAOYSA-N 0.000 claims description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- JACRWUWPXAESPB-QMMMGPOBSA-N Tropic acid Natural products OC[C@H](C(O)=O)C1=CC=CC=C1 JACRWUWPXAESPB-QMMMGPOBSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- UKXSKSHDVLQNKG-UHFFFAOYSA-N benzilic acid Chemical compound C=1C=CC=CC=1C(O)(C(=O)O)C1=CC=CC=C1 UKXSKSHDVLQNKG-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 87
- 239000000243 solution Substances 0.000 description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 55
- 239000000499 gel Substances 0.000 description 38
- 239000007787 solid Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 22
- 239000007864 aqueous solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 12
- 239000002612 dispersion medium Substances 0.000 description 10
- 150000002822 niobium compounds Chemical class 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- -1 for example Chemical compound 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 235000014413 iron hydroxide Nutrition 0.000 description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 6
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 238000001935 peptisation Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000011362 coarse particle Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000012615 aggregate Substances 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- AOLPZAHRYHXPLR-UHFFFAOYSA-I pentafluoroniobium Chemical compound F[Nb](F)(F)(F)F AOLPZAHRYHXPLR-UHFFFAOYSA-I 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229940058015 1,3-butylene glycol Drugs 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 1
- KSCAZPYHLGGNPZ-UHFFFAOYSA-N 3-chloropropyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CCCCl KSCAZPYHLGGNPZ-UHFFFAOYSA-N 0.000 description 1
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 1
- PLXLQGPXPXIVKM-UHFFFAOYSA-N 3-chloropropyl(tripropoxy)silane Chemical compound CCCO[Si](CCCCl)(OCCC)OCCC PLXLQGPXPXIVKM-UHFFFAOYSA-N 0.000 description 1
- KNTKCYKJRSMRMZ-UHFFFAOYSA-N 3-chloropropyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)CCCCl KNTKCYKJRSMRMZ-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- XITGHTRVSNMXOD-UHFFFAOYSA-N [Nb].ClOCl Chemical compound [Nb].ClOCl XITGHTRVSNMXOD-UHFFFAOYSA-N 0.000 description 1
- RQVFGTYFBUVGOP-UHFFFAOYSA-N [acetyloxy(dimethyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(C)OC(C)=O RQVFGTYFBUVGOP-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- TVJPBVNWVPUZBM-UHFFFAOYSA-N [diacetyloxy(methyl)silyl] acetate Chemical compound CC(=O)O[Si](C)(OC(C)=O)OC(C)=O TVJPBVNWVPUZBM-UHFFFAOYSA-N 0.000 description 1
- VLFKGWCMFMCFRM-UHFFFAOYSA-N [diacetyloxy(phenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C1=CC=CC=C1 VLFKGWCMFMCFRM-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000019437 butane-1,3-diol Nutrition 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 238000006297 dehydration reaction Methods 0.000 description 1
- GENZKBJGWAAVIE-UHFFFAOYSA-N diethoxy-[3-(oxiran-2-ylmethoxy)propyl]-phenylsilane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)CCCOCC1CO1 GENZKBJGWAAVIE-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
- Silicon Compounds (AREA)
Description
本発明は、ニオブ酸分散液に過酸化水素を加えて溶解および／または解膠して得られた溶液を、必要に応じてニオブ化合物以外の化合物の共存下で水熱処理することを特徴とする透明性、安定性、単分散性、紫外線遮蔽性（特に紫外線Ｂ：２９０〜３２０ｎｍ）等に優れたニオブ系酸化物微粒子分散液の製造方法に関する。 The present invention is characterized in that a solution obtained by adding and dissolving and / or peptizing hydrogen peroxide to a niobic acid dispersion is subjected to hydrothermal treatment in the presence of a compound other than a niobium compound as necessary. The present invention relates to a method for producing a niobium-based oxide fine particle dispersion excellent in transparency, stability, monodispersibility, ultraviolet shielding properties (particularly ultraviolet B: 290 to 320 nm) and the like.
従来、ニオブ酸化物ゾルあるいはニオブ酸化物コロイドが触媒、触媒担体、さらには機能性セラミックスとして圧電体、半導体、センサー、オプトエレクトロニクス材、誘電体等に用いられている。このときのニオブ酸化物ゾルあるいはニオブ酸化物コロイドとしては均一で微細な粒子径を有すると共に安定性にも優れたものが要求されている。 Conventionally, niobium oxide sols or niobium oxide colloids have been used as catalysts, catalyst carriers, and functional ceramics for piezoelectric bodies, semiconductors, sensors, optoelectronic materials, dielectrics, and the like. The niobium oxide sol or niobium oxide colloid at this time is required to have a uniform and fine particle size and excellent stability.
例えば、特公平８−７０１号公報（特許文献１）には、ニオブ化合物に強酸を添加して溶解し、これに過酸化水素を加えてペルオキシニオブ酸水溶液とし、５〜５０℃で加熱処理することによってペルオキシニオブ酸ゾル（Ｈ+[Ｎb０2(Ｏ)2]-）を得ることが開示されている。また、安定性が不充分なために安定剤を添加して加熱処理してペルオキシニオブ酸ゾルを得ることが記載されている。
しかしながら、この方法では酸に由来するアニオンや安定剤などを含んでいるために用途が制限されることがあった。また、そのためにペルオキシニオブ酸ゾルを限外濾過膜等で除去・精製する必要があった。
For example, in Japanese Patent Publication No. 8-701 (Patent Document 1), a strong acid is added to a niobium compound and dissolved, and hydrogen peroxide is added thereto to form a peroxyniobic acid aqueous solution, followed by heat treatment at 5 to 50 ° C. To obtain a peroxyniobic acid sol (H + [Nb0 2 (O) 2 ] − ). In addition, it is described that a stabilizer is added and heat treatment is performed due to insufficient stability to obtain a peroxyniobic acid sol.
However, in this method, since an anion derived from an acid, a stabilizer, and the like are included, the use may be limited. For this purpose, it was necessary to remove and purify the peroxyniobic acid sol with an ultrafiltration membrane or the like.
特開平６−３２１５４３号公報（特許文献２）および特開平８−１４３３１４号公報（特許文献３）には、活性な水酸化ニオブ、例えば酸化ニオブをフッ酸で溶解処理し、ついでアンモニアを添加し、濾過洗浄して得た水酸化ニオブスラリーに特定範囲のモル比のシュウ酸、クエン酸を加えて加熱処理する酸化ニオブゾルの製造方法が開示されている。
しかしながら、これらの方法で得られる酸化ニオブゾルは均一かつ微細な粒径で安定性に優れているものの、シュウ酸やクエン酸などの有機質を含有しているために、あるいはフッ素が残留することがあり用途に制限があった。
In JP-A-6-321543 (Patent Document 2) and JP-A-8-143314 (Patent Document 3), an active niobium hydroxide, for example, niobium oxide is dissolved in hydrofluoric acid, and then ammonia is added. A method for producing a niobium oxide sol is disclosed in which oxalic acid and citric acid within a specific range of molar ratio are added to a niobium hydroxide slurry obtained by filtration and washing, followed by heat treatment.
However, although the niobium oxide sol obtained by these methods has a uniform and fine particle size and excellent stability, it may contain organic substances such as oxalic acid and citric acid, or fluorine may remain. There was a limit to the use.
特開平５−２２２５６２号公報（特許文献４）には、ニオブ化合物などの金属塩水溶液を安定化剤を加えることなく電気分解して金属酸化物ゾルを製造する方法が開示されている。この方法で得られる金属酸化物ゾルは透明性が高いために、化粧品調整物用や艶だし上薬などのセラミックス産業に好適に用いられることが記載されている。また、この方法で得られるＴiＯ2ゾルは紫外線防止として化粧品に、あるいは、高屈折率を利用してセラミックスに使用されることが記載されていている。 The JP-5-222 562 (Patent Document 4), a method of electrolysis to the production of metal oxide sol without the addition of stabilizing agent a metal salt aqueous solution such as niobium compound is disclosed. It is described that the metal oxide sol obtained by this method is suitable for the ceramic industry such as for cosmetic preparations and polishes because of its high transparency. Further, it is described that the TiO 2 sol obtained by this method is used in cosmetics for preventing ultraviolet rays or in ceramics utilizing a high refractive index.
本発明は、上記従来技術における問題点を解決するものであり、均一で微細な粒子径を有するとともに安定性にも優れ、特にアニオンや安定剤などの成分を含まないか、含んでいても少ないので除去する必要が無く、このため広範囲な用途に使用できるニオブ系酸化物微粒子分散液の製造方法を提供することを目的としている。 The present invention solves the above-mentioned problems in the prior art, has a uniform and fine particle size and is excellent in stability, and particularly does not contain or contain components such as anions and stabilizers. Therefore, it is not necessary to remove them, and therefore it is an object of the present invention to provide a method for producing a niobium oxide fine particle dispersion that can be used for a wide range of applications.
本発明に係るニオブ系酸化物微粒子分散液の第１の製造方法は、ニオブ酸分散液またはニオブ酸とニオブ以外の元素の化合物の分散液または溶液に過酸化水素を加えて溶解および／または解膠し、得られた溶液を８０〜３００℃で水熱処理することを特徴としている。
本発明に係るニオブ系酸化物微粒子分散液の第２の製造方法は、ニオブ酸分散液に過酸化水素を加えて溶解および／または解膠して得られた溶液と、ニオブ以外の元素の化合物の分散液または溶液に過酸化水素を加えて溶解および／または解膠して得られた溶液とを混合し、８０〜３００℃で水熱処理することを特徴としている。
本発明に係るニオブ系酸化物微粒子分散液の第３の製造方法は、ニオブ酸分散液に過酸化水素を加えて溶解および／または解膠して得られた溶液に、ニオブ以外の元素の化合物の分散液または溶液を混合し、８０〜３００℃で水熱処理することを特徴としている。
The first method for producing a niobium-based oxide fine particle dispersion according to the present invention comprises dissolving and / or dissolving a niobic acid dispersion or a dispersion or solution of a compound of elements other than niobic acid and niobium by adding hydrogen peroxide. The resulting solution is hydrothermally treated at 80 to 300 ° C.
A second method for producing a niobium-based oxide fine particle dispersion according to the present invention includes a solution obtained by adding hydrogen peroxide to a niobic acid dispersion and dissolving and / or peptizing, and a compound of an element other than niobium It is characterized in that hydrogen peroxide is added to a dispersion or solution of the above solution and mixed with a solution obtained by dissolving and / or peptizing and hydrothermally treated at 80 to 300 ° C.
A third method for producing a niobium-based oxide fine particle dispersion according to the present invention includes a compound of an element other than niobium in a solution obtained by dissolving and / or peptizing hydrogen peroxide in a niobic acid dispersion. The dispersion liquid or solution is mixed and hydrothermally treated at 80 to 300 ° C.
前記水熱処理を粒子成長調整剤の存在下で行うことが好ましい。
前記ニオブ以外の元素がＦe、Ｃe、Ｓi、Ｚr、Ａl、Ｔi、Ｓｎ、Ｓｂ、Ｗ、Ｚｎから選ばれる１種または２種以上であることが好ましい。
前記水熱処理を種粒子の存在下で行うことが好ましい。
前記水熱処理を核粒子の存在下で行うことができる。
The hydrothermal treatment is preferably performed in the presence of a particle growth regulator.
The element other than niobium is preferably one or more selected from Fe, Ce, Si, Zr, Al, Ti, Sn, Sb, W, and Zn.
The hydrothermal treatment is preferably performed in the presence of seed particles.
The hydrothermal treatment can be performed in the presence of core particles.
前記した製造方法で得られたニオブ系酸化物微粒子分散液には、（１）ニオブ酸分散液、（２）ニオブ酸とニオブ以外の元素の化合物の分散液または溶液、（３）ニオブ以外の元素の化合物の分散液または溶液、のいずれかに過酸化水素を加えて溶解および／または解膠して得られた溶液を混合し、８０〜３００℃で水熱処理することができる。
また、前記製造方法で得られたニオブ系酸化物微粒子分散液には、ニオブ以外の元素の化合物の分散液または溶液を混合し、８０〜３００℃で水熱処理することができる。
前記ニオブ以外の元素がＦe、Ｃe、Ｓi、Ｚr、Ａl、Ｔi、Ｓｎ、Ｓｂ、Ｗ、Ｚｎから選ばれる１種または２種以上であることが好ましい。
The niobium-based oxide fine particle dispersion obtained by the production method described above includes (1) niobic acid dispersion, (2) dispersion or solution of a compound of elements other than niobic acid and niobium, and (3) other than niobium. A solution obtained by dissolving and / or peptizing by adding hydrogen peroxide to either a dispersion or a solution of an elemental compound can be mixed and hydrothermally treated at 80 to 300 ° C.
The niobium-based oxide fine particle dispersion obtained by the above production method can be mixed with a dispersion or solution of a compound of an element other than niobium and hydrothermally treated at 80 to 300 ° C.
The element other than niobium is preferably one or more selected from Fe, Ce, Si, Zr, Al, Ti, Sn, Sb, W, and Zn.
本発明によれば、均一で微細な粒子径を有するとともに安定性にも優れ、特にアニオンや安定剤などの成分を含まないか、含んでいても少ないので除去する必要が無く、このため広範囲な用途に使用できるニオブ系酸化物微粒子分散液の製造方法を提供することができる。
According to the present invention, it has a uniform and fine particle size and is excellent in stability. In particular, it does not need to be removed because it does not contain or does not contain components such as anions and stabilizers. A method for producing a niobium-based oxide fine particle dispersion that can be used for an application can be provided.
以下、本発明のニオブ酸化物微粒子分散ゾルの製造方法について具体的に説明する。
本発明に係るニオブ系酸化物微粒子分散液の製造方法は、ニオブ酸分散液に過酸化水素を加えて溶解および／または解膠して得られた溶液を、必要に応じてニオブ化合物以外の化合物の共存下、８０〜３００℃で水熱処理することを特徴としている。
本発明に用いるニオブ酸は、過酸化水素に溶解および／または解膠することが出来れば特に制限はなく、従来公知のニオブ酸を用いることができる。ここでニオブ酸とはニオブの水酸化物（またはニオブ酸化物の水和物）をいい、Ｎb2Ｏ5・ｎＨ2Ｏで表すことができ、ｎが概ね１〜５の範囲のものをいう。
Hereafter, the manufacturing method of the niobium oxide fine particle dispersion | distribution sol of this invention is demonstrated concretely.
The method for producing a niobium-based oxide fine particle dispersion according to the present invention comprises a solution obtained by adding hydrogen peroxide to a niobic acid dispersion and dissolving and / or peptizing, if necessary, a compound other than a niobium compound. It is characterized by hydrothermal treatment at 80 to 300 ° C. in the presence of.
The niobic acid used in the present invention is not particularly limited as long as it can be dissolved and / or peptized in hydrogen peroxide, and conventionally known niobic acid can be used. Here, niobic acid refers to a hydroxide of niobium (or a hydrate of niobium oxide), which can be represented by Nb 2 O 5 .nH 2 O, where n is approximately in the range of 1 to 5. .
このようなニオブ酸は例えば以下のような方法によって得ることができる。
（１）五塩化ニオブおよび／またはオキシ塩化ニオブを出発原料とし、加水分解した後、洗浄する。
（２）ニオブ金属あるいは酸化ニオブなどを酸で溶解した溶液、または五フッ化ニオブの水溶液を中和および／または加水分解した後、洗浄する。
（３）オルトニオブ酸塩あるいはメタニオブ酸塩の溶液を中和および／または加水分解した後、洗浄する。
Such niobic acid can be obtained, for example, by the following method.
(1) Using niobium pentachloride and / or niobium oxychloride as a starting material, hydrolyzing and then washing.
(2) A solution obtained by dissolving niobium metal or niobium oxide with an acid or an aqueous solution of niobium pentafluoride is neutralized and / or hydrolyzed and then washed.
(3) The solution of orthoniobate or metaniobate is neutralized and / or hydrolyzed and then washed.
上記において、中和あるいは加水分解には、必要に応じて酸またはアルカリを添加することができる。アルカリとしてはアンモニア水が好適である。
また、洗浄はイオン交換樹脂法、フィルター法、限外濾過法などの方法によって行うことができ、洗浄後のニオブ酸中のアルカリおよび酸根はニオブ酸のＮb2Ｏ5に対して０.５重量％以下であることが好ましい。０.５重量％を越えると、最終的に得られるニオブ酸化物微粒子分散ゾル中のアルカリおよび／または酸根が多過ぎてゾルの安定性や透明性が低下したり、また安定性がないなどのために用途が制限される問題がある。
In the above, acid or alkali can be added to neutralization or hydrolysis as necessary. As the alkali, ammonia water is suitable.
Also, washing the ion exchange resin method, filter method, it can be carried out by a method such as ultrafiltration, alkali and acid radicals in niobate after washing 0.5 wt relative to Nb 2 O 5 niobate % Or less is preferable. If it exceeds 0.5% by weight, there will be too much alkali and / or acid radicals in the finally obtained niobium oxide fine particle-dispersed sol, and the stability and transparency of the sol will decrease, and there will be no stability. Therefore, there is a problem that the use is limited.
前記ニオブ以外の元素の化合物の分散液または溶液において、ニオブ以外の元素としてはＦe、Ｃe、Ｓi、Ｚr、Ａl、Ｔi、Ｓｎ、Ｓｂ、Ｗ、Ｚｎから選ばれる１種または２種以上が好適に用いられ、化合物としてはこれら元素の硝酸塩、硫酸塩、塩化物、有機酸塩、酸化物等が用いられる。具体的には、塩化第一鉄、塩化第二鉄、硝酸第二鉄、硝酸セリウム、塩化アルミニウム、硫酸アルミニウム、四塩化チタン、硫酸チタニル、硝酸錫、五塩化アンチモン、タングステン酸アンモニウム、硝酸亜鉛、酸化鉄、酸化セリウム、シリカ、酸化アルミニウム、酸化チタン、酸化錫、酸化アンチモン、酸化タングステン、酸化亜鉛等が挙げられる。ここで、酸化物には水酸化物、水和物を含み、これらのゾルを用いることが好ましい。 In the dispersion or solution of the compound of the element other than niobium, the element other than niobium is preferably one or more selected from Fe, Ce, Si, Zr, Al, Ti, Sn, Sb, W, and Zn. As the compound, nitrates, sulfates, chlorides, organic acid salts, oxides and the like of these elements are used. Specifically, ferrous chloride, ferric chloride, ferric nitrate, cerium nitrate, aluminum chloride, aluminum sulfate, titanium tetrachloride, titanyl sulfate, tin nitrate, antimony pentachloride, ammonium tungstate, zinc nitrate, Examples thereof include iron oxide, cerium oxide, silica, aluminum oxide, titanium oxide, tin oxide, antimony oxide, tungsten oxide, and zinc oxide. Here, the oxide includes a hydroxide and a hydrate, and these sols are preferably used.
本発明方法では、ニオブ酸分散液またはニオブ酸とニオブ以外の元素の化合物の分散液または溶液、あるいはニオブ以外の元素の化合物の分散液または溶液（以下、ニオブ酸等という。）に過酸化水素を加える。過酸化水素の使用量は、ニオブ酸等を酸化物に換算し、合計酸化物１重量部に対して濃度が概ね５〜４０重量％の過酸化水素をＨ2Ｏ2に換算して１.５〜６重量部、好ましくは２〜４重量部加える。
このときのニオブ酸等の濃度は酸化物に換算した濃度で０.５〜１０重量％、好ましくは１〜５重量％となるように調整する。
In the method of the present invention, hydrogen peroxide is added to a niobic acid dispersion or a dispersion or solution of a compound of an element other than niobic acid and niobium, or a dispersion or solution of a compound of an element other than niobium (hereinafter referred to as niobic acid or the like). Add The amount of hydrogen peroxide used is as follows: niobic acid or the like is converted into an oxide, and hydrogen peroxide having a concentration of about 5 to 40% by weight is converted into H 2 O 2 with respect to 1 part by weight of the total oxide. Add 5-6 parts by weight, preferably 2-4 parts by weight.
At this time, the concentration of niobic acid or the like is adjusted to 0.5 to 10% by weight, preferably 1 to 5% by weight in terms of oxide.
ニオブ酸等に対するＨ2Ｏ2の使用量が１.５重量部未満の場合は、ニオブ酸および／またはＨ2Ｏ2に可溶性のニオブ以外の元素の化合物が完全に溶解および／または解膠せず、未反応のニオブ酸等が残存するので好ましくない。
ニオブ酸等に対するＨ2Ｏ2のモル数が６重量部を越えると、溶解および／または解膠する速度は大きく、反応は低温であるいは短時間で終了するが、過剰の過酸化水素が系内に残存することになり、経済的でなく、また水熱処理の際に酸素ガスが発生したり、圧力の上昇を伴う危険がある。
ニオブ酸等に対するＨ2Ｏ2の使用量が上記範囲にあれば、加熱溶解温度にもよるが、ニオブ酸は０.５〜５時間で完全に溶解および／または解膠することができる。
When the amount of H 2 O 2 used relative to niobic acid is less than 1.5 parts by weight, niobic acid and / or compounds of elements other than niobium soluble in H 2 O 2 are completely dissolved and / or peptized. In addition, unreacted niobic acid and the like remain, which is not preferable.
When the number of moles of H 2 O 2 with respect to niobic acid or the like exceeds 6 parts by weight, the dissolution and / or peptization rate is large, and the reaction is completed at a low temperature or in a short time. Therefore, there is a risk that oxygen gas is generated during the hydrothermal treatment or that the pressure increases.
If the amount of H 2 O 2 used for niobic acid or the like is within the above range, niobic acid can be completely dissolved and / or peptized in 0.5 to 5 hours, depending on the heating and melting temperature.
また、ニオブ酸等の濃度が酸化物として０.５重量％未満の場合は濃度が低過ぎて生産効率が低く、ニオブ酸等の濃度が酸化物として１０重量％を越えると得られるニオブ系酸化物微粒子分散液の粘度が高くなり過ぎたり、安定性に欠けることがある。 Further, when the concentration of niobic acid or the like is less than 0.5% by weight as an oxide, the concentration is too low and the production efficiency is low, and the niobium-based oxidation obtained when the concentration of niobic acid or the like exceeds 10% by weight as an oxide. The viscosity of the fine particle dispersion may become too high or lack stability.
なお、溶解および／または解膠する際に、必要に応じて加熱することができる。加熱温度としては概ね３０〜１００℃の範囲にあることが好ましい。加熱温度が３０℃未満では溶解、解膠が不充分となることがあり、ついで水熱処理して得られるニオブ系酸化物微粒子分散液中の微粒子の粒子径分布が不均一になり易い。また、溶解および／または解膠時間が長くなり過ぎて生産効率が低下する。一方、加熱温度が１００℃を越えた場合、溶解および／または解膠時間が短くなるものの、ついで水熱処理して得られるニオブ系酸化物微粒子分散液の微粒子の粒子径分布が不均一になる傾向がある。 In addition, it can heat as needed when melt | dissolving and / or peptizing. The heating temperature is preferably in the range of approximately 30 to 100 ° C. When the heating temperature is less than 30 ° C., dissolution and peptization may be insufficient, and the particle size distribution of the fine particles in the niobium oxide fine particle dispersion obtained by hydrothermal treatment tends to be non-uniform. Also, the dissolution and / or peptization time becomes too long and the production efficiency is lowered. On the other hand, when the heating temperature exceeds 100 ° C., the dissolution and / or peptization time is shortened, but then the particle size distribution of the fine particles of the niobium-based oxide fine particle dispersion obtained by hydrothermal treatment tends to be non-uniform. There is.
本発明の第１の製造方法は、前記したように、ニオブ酸分散液またはニオブ酸とニオブ以外の元素の化合物の分散液または溶液に過酸化水素を加えて溶解および／または解膠して得られた溶液を８０〜３００℃で水熱処理する。
第２の製造方法は、ニオブ酸分散液に過酸化水素を加えて溶解および／または解膠して得られた溶液と、ニオブ以外の元素の化合物の分散液または溶液に過酸化水素を加えて溶解および／または解膠して得られた溶液とを混合し、８０〜３００℃で水熱処理する。
第３の製造方法は、ニオブ酸分散液に過酸化水素を加えて溶解および／または解膠して得られた溶液に、ニオブ以外の元素の化合物の分散液または溶液を混合し、８０〜３００℃で水熱処理する。
As described above, the first production method of the present invention is obtained by dissolving and / or peptizing by adding hydrogen peroxide to a niobic acid dispersion or a dispersion or solution of a compound of elements other than niobic acid and niobium. The obtained solution is hydrothermally treated at 80 to 300 ° C.
In the second production method, hydrogen peroxide is added to a solution obtained by dissolving and / or peptizing hydrogen peroxide in a niobic acid dispersion and a dispersion or solution of a compound of an element other than niobium. The solution obtained by dissolution and / or peptization is mixed and hydrothermally treated at 80 to 300 ° C.
In the third production method, a dispersion or solution of a compound of an element other than niobium is mixed with a solution obtained by adding and dissolving and / or peptizing hydrogen peroxide to a niobic acid dispersion. Hydrothermal treatment at ℃.
上記において、ニオブ酸とニオブ以外の元素の化合物とを用いる場合、最終的に得られるニオブ系酸化物微粒子中のＮｂ2Ｏ5の含有量が５０重量％以上、さらには７０重量％以上であることが好ましい。ニオブ系酸化物微粒子中のＮｂ2Ｏ5の含有量が５０重量％未満の場合は得られるニオブ系酸化物微粒子の半導体、光学特性、誘電体特性、紫外線遮蔽特性、耐光性、耐候性等が不充分となることがある。 In the above, when niobic acid and a compound of an element other than niobium are used, the content of Nb 2 O 5 in the finally obtained niobium-based oxide fine particles is 50% by weight or more, further 70% by weight or more. It is preferable. When the content of Nb 2 O 5 in the niobium-based oxide fine particles is less than 50% by weight, the obtained niobium-based oxide fine particles have semiconductor, optical properties, dielectric properties, ultraviolet shielding properties, light resistance, weather resistance, etc. It may be insufficient.
水熱処理温度が８０℃未満の場合はニオブ酸の脱水による酸化物化が充分進行せず、得られるニオブ系酸化物微粒子分散液は安定性に欠けることがあり、水熱処理温度が８０〜３００℃の範囲にあれば、粒子径が均一で、安定性に優れたニオブ系酸化物微粒子分散液が得られる。好ましい水熱処理温度は１００〜２５０℃の範囲である。 When the hydrothermal treatment temperature is less than 80 ° C, niobic acid is not sufficiently oxidized by dehydration, and the resulting niobium-based oxide fine particle dispersion may lack stability, and the hydrothermal treatment temperature is 80 to 300 ° C. Within the range, a niobium oxide fine particle dispersion having a uniform particle diameter and excellent stability can be obtained. A preferable hydrothermal treatment temperature is in the range of 100 to 250 ° C.
前記した水熱処理は粒子成長調整剤の存在下で行うことが好ましい。
本発明に用いる粒子成長調整剤としては、カルボン酸またはカルボン酸塩、ヒドロキシカルボン酸（１分子内にカルボキシル基とアルコール性水酸基とを有する）、ヒドロキシカルボン酸塩が用いられる。
The hydrothermal treatment described above is preferably performed in the presence of a particle growth regulator.
As the particle growth regulator used in the present invention, carboxylic acid or carboxylate, hydroxycarboxylic acid (having a carboxyl group and an alcoholic hydroxyl group in one molecule), and hydroxycarboxylate are used.
具体的には、蟻酸、酢酸、アクリル酸（不飽和カルボン酸）、グルコン酸等のモノカルボン酸およびモノカルボン酸塩、リンゴ酸、シュウ酸、マロン酸、コハク酸、グルタール酸、アジピン酸、セバシン酸、マレイン酸、フマル酸、フタル酸、などの多価カルボン酸および多価カルボン酸塩等が挙げられる。
また、α−乳酸、β−乳酸、γ−ヒドロキシ吉草酸、グリセリン酸、酒石酸、クエン酸、トロパ酸、ベンジル酸のヒドロキシカルボン酸およびヒドロキシカルボン酸塩が挙げられる。
Specifically, formic acid, acetic acid, A acrylic acid (unsaturated carboxylic acid), monocarboxylic acids and monocarboxylic acid salts such as gluconic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Examples thereof include polyvalent carboxylic acids such as sebacic acid, maleic acid, fumaric acid, and phthalic acid, and polyvalent carboxylates.
Further, α-lactic acid, β-lactic acid, γ-hydroxyvaleric acid, glyceric acid, tartaric acid, citric acid, tropic acid, hydroxycarboxylic acid and hydroxycarboxylate of benzylic acid can be mentioned.
このような粒子成長調整剤は、ニオブ酸を調製する際にニオブ化合物に加えて加水分解してもよく、調製したニオブ酸等に加えてもよく、また過酸化水素を加えて溶解、解膠した後に加えてもよい。
粒子成長調整剤の使用量は、ニオブ化合物、ニオブ酸、ニオブ以外の元素の化合物の合計モル数（Ｎm）と粒子成長調整剤のモル数（Ｐm）とのモル比（Ｐm）／（Ｎm）が０.０１〜１、さらには０.１〜０.５の範囲にあることが好ましい。
Such a particle growth regulator may be hydrolyzed in addition to the niobium compound when preparing niobic acid, or may be added to the prepared niobic acid or the like, or dissolved or peptized by adding hydrogen peroxide. It may be added after.
The amount of the particle growth regulator used is the molar ratio (Pm) / (Nm) of the total number of moles (Nm) of niobium compounds, niobic acid, and compounds of elements other than niobium and the number of moles of grain growth regulator (Pm). Is preferably in the range of 0.01 to 1, more preferably 0.1 to 0.5.
前記モル比が０.０１未満の場合は粒子成長調整剤が不足し、水熱処理して得られるニオブ系酸化物微粒子の粒子径が不均一であったり、粗大な粒子が生成することがある。
前記モル比が１を越えてもさらに粒子径を均一にしたり、粗大粒子の生成を抑制する効果が向上することもなく、加えて粒子成長調整剤が多いことおよび収率が低下することがあり、経済性が低下する問題がある。
When the molar ratio is less than 0.01, the particle growth regulator is insufficient, and the niobium oxide fine particles obtained by hydrothermal treatment may have non-uniform particle diameters or coarse particles.
Even if the molar ratio exceeds 1, the particle size is not made uniform or the effect of suppressing the formation of coarse particles is not improved, and in addition, the amount of the particle growth regulator may be increased and the yield may be lowered. There is a problem that the economy is lowered.
本発明では、前記水熱処理を種粒子の存在下で行うことが好ましい。
種粒子としてはＡｌなどの周期律表第III族、Ｔi、Ｚr、Ｓi、Ｓnなどの第IV族、Ｖ、Ｎb、Ｓbなどの第Ｖ族、Ｗなどの第VI族、およびＦeなどの第VIII族から選ばれた１種または２種以上の元素の無機化合物が用いられる。
In the present invention, the hydrothermal treatment is preferably performed in the presence of seed particles.
Seed particles include group III of the periodic table such as Al, group IV such as Ti, Zr, Si and Sn, group V such as V, Nb and Sb, group VI such as W, and group such as Fe. An inorganic compound of one or more elements selected from Group VIII is used.
無機化合物の形態としては、塩、酸化物、水酸化物またはオキシ酸あるいはオキシ酸塩等が用いられ、好ましくは、酸化物、水酸化物またはオキシ酸等のゲルまたはゾルを用いる。なかでもゾルは分散性、安定性、粒子径の均一性が高く、均一な粒子径のニオブ系酸化物微粒子を得ることができる。
種粒子の平均粒径は５ｎｍ未満であることが好ましいが、特に０．５〜３ｎｍの範囲にあることが好ましい。
As the form of the inorganic compound, salts, oxides, hydroxides, oxyacids or oxyacid salts are used, and preferably gels or sols of oxides, hydroxides or oxyacids are used. Among them, the sol has high dispersibility, stability, and uniform particle size, and niobium-based oxide fine particles having a uniform particle size can be obtained.
The average particle size of the seed particles is preferably less than 5 nm, and particularly preferably in the range of 0.5 to 3 nm.
また、種粒子の使用量はニオブ化合物、ニオブ酸、ニオブ以外の元素の化合物の酸化物としての合計重量の１〜３０重量％、さらには２〜２０重量％の範囲にあることが好ましい。
種粒子の使用量が１重量％未満の場合は粒子径を均一にする効果が不充分となることがあり、種粒子の使用量が３０重量％を超えると種粒子がニオブ化合物以外の場合にニオブ系酸化物の含有量が不充分となり、得られるニオブ系酸化物微粒子の半導体、光学特性、誘電体特性、紫外線遮蔽特性、耐光性、耐候性等が低下し用途が制限されることがある。
Moreover, it is preferable that the usage-amount of a seed particle exists in the range of 1-30 weight% of the total weight as an oxide of the compound of niobium compound, niobic acid, and elements other than niobium, Furthermore, it is 2-20 weight%.
When the amount of seed particles used is less than 1% by weight, the effect of making the particle diameter uniform may be insufficient. When the amount of seed particles used exceeds 30% by weight, the seed particles are other than niobium compounds. Insufficient niobium-based oxide content may reduce the semiconductor, optical properties, dielectric properties, ultraviolet shielding properties, light resistance, weather resistance, etc. of the resulting niobium-based oxide fine particles, thereby limiting the application. .
さらに、本発明では、水熱処理を前記種粒子に代えて核粒子の存在下で行うことができる。
核粒子としては、前記種粒子と同種の粒子であって、平均粒子径が５〜５０ｎｍ、好ましくは１０〜３０ｎｍの範囲にある酸化物または水酸化物の粒子が用いられる。
Furthermore, in the present invention, hydrothermal treatment can be performed in the presence of core particles instead of the seed particles.
As the core particles, oxide or hydroxide particles having the same kind as the seed particles and having an average particle diameter of 5 to 50 nm, preferably 10 to 30 nm are used.
核粒子の使用量はニオブ化合物、ニオブ酸、ニオブ以外の元素の化合物の酸化物としての合計重量の５〜５０重量％、さらには１０〜３０重量％の範囲にあることが好ましい。 特に、最終的に得られるニオブ系酸化物微粒子中のＮｂ2Ｏ5の含有量が５０重量％以上であることが好ましい。ニオブ系酸化物微粒子中のＮｂ2Ｏ5の含有量が５０重量％未満の場合は得られるニオブ系酸化物微粒子の半導体、光学特性、誘電体特性、紫外線遮蔽特性、耐光性、耐候性等が不充分となることがある。 The amount of the core particles used is preferably in the range of 5 to 50% by weight, more preferably 10 to 30% by weight, based on the total weight of oxides of niobium compounds, niobic acid, and compounds of elements other than niobium. In particular, the content of Nb 2 O 5 in the finally obtained niobium-based oxide fine particles is preferably 50% by weight or more. When the content of Nb 2 O 5 in the niobium-based oxide fine particles is less than 50% by weight, the obtained niobium-based oxide fine particles have semiconductor, optical properties, dielectric properties, ultraviolet shielding properties, light resistance, weather resistance, etc. It may be insufficient.
さらに、本発明では、前記のようにして得られたニオブ系酸化物微粒子分散液に、（１）ニオブ酸分散液、（２）ニオブ酸とニオブ以外の元素の化合物の分散液または溶液、（３）ニオブ以外の元素の化合物の分散液または溶液、のいずれかに過酸化水素を加えて溶解および／または解膠して得られた溶液を混合し、８０〜３００℃で水熱処理してニオブ系酸化物微粒子分散液を調製することもできる。
さらに、ニオブ系酸化物微粒子分散液に、（４）ニオブ以外の元素の化合物の分散液または溶液を混合し、８０〜３００℃で水熱処理してニオブ系酸化物微粒子分散液を調製することもできる。
Furthermore, in the present invention, the niobium-based oxide fine particle dispersion obtained as described above is added to (1) a niobic acid dispersion, (2) a dispersion or solution of a compound of elements other than niobic acid and niobium, 3) A solution obtained by adding hydrogen peroxide to any dispersion or solution of a compound of an element other than niobium and dissolving and / or peptizing the mixture is mixed and hydrothermally treated at 80 to 300 ° C. to form niobium. A system oxide fine particle dispersion can also be prepared.
Furthermore, a niobium-based oxide fine particle dispersion may be prepared by mixing a dispersion or solution of a compound of an element other than niobium (4) with a niobium-based oxide fine particle dispersion and hydrothermally treating at 80 to 300 ° C. it can.
これらの製造方法により、ニオブ系酸化物微粒子がコアで、ニオブ酸等を溶解および／または解膠した溶液に由来する酸化物でコア粒子を被覆してシェルを形成したコア−シェル構造を有するニオブ系酸化物微粒子の分散液が得られる。
例えば、（１）の場合はコア粒子としてのニオブ系酸化物微粒子をニオブ酸化物で被覆したニオブ系酸化物微粒子が得られ、（２）の場合はコア粒子としてのニオブ系酸化物微粒子をニオブ酸とニオブ以外の元素の複合酸化物で被覆したニオブ系酸化物微粒子が得られ、（３）および（４）の場合はコア粒子としてのニオブ系酸化物微粒子を、ニオブ酸化物を含まない酸化物、複合酸化物で被覆したニオブ系酸化物微粒子が得られる。
Niobium having a core-shell structure in which a niobium-based oxide fine particle is a core and a core is coated with an oxide derived from a solution in which niobic acid or the like is dissolved and / or peptized to form a shell. A dispersion of system oxide fine particles is obtained.
For example, in the case of (1), niobium-based oxide fine particles obtained by coating niobium-based oxide fine particles as core particles with niobium oxide are obtained. In the case of (2), niobium-based oxide fine particles as core particles are converted to niobium. Niobium oxide fine particles coated with a complex oxide of an element other than acid and niobium can be obtained. In the cases (3) and (4), niobium oxide fine particles as core particles are oxidized without containing niobium oxide. And niobium oxide fine particles coated with the composite oxide.
上記におけるニオブ以外の元素がＦe、Ｃe、Ｓi、Ｚr、Ａl、Ｔi、Ｓｎ、Ｓｂ、Ｗ、Ｚｎから選ばれる１種または２種以上であることが好ましく、ニオブ以外の元素の化合物としては前記と同様の化合物が用いられる。 The element other than niobium in the above is preferably one or more selected from Fe, Ce, Si, Zr, Al, Ti, Sn, Sb, W, and Zn. Similar compounds are used.
水熱処理温度は、前記と同様８０〜３００℃、さらには１００〜２５０℃の範囲にあることが好ましい。
水熱処理温度が８０℃未満の場合はニオブ酸等の酸化物の緻密な被覆層（シェル）の形成ができない場合があり、水熱処理温度が３００℃を超えると得られるニオブ系酸化物微粒子が凝集することがある。
The hydrothermal treatment temperature is preferably in the range of 80 to 300 ° C, more preferably 100 to 250 ° C, as described above.
When the hydrothermal treatment temperature is less than 80 ° C., a dense coating layer (shell) of an oxide such as niobic acid may not be formed. When the hydrothermal treatment temperature exceeds 300 ° C., the resulting niobium oxide fine particles aggregate. There are things to do.
上記のようにして得られたニオブ系酸化物微粒子分散液は、必要に応じてイオン交換樹脂などにより残存するイオンを除去して用いることもできる。しかしながら、本発明で得られるニオブ酸化物微粒子分散液には不純物やイオンが洗浄工程で予め低減されているので必ずしもその必要はない。
前記の方法で得られたニオブ酸化物微粒子分散液は、ロータリーエバポレーターなどでメタノール、エタノールなどのアルコール、１，３-ブチレングリコールなどのグルコール類やグリセリンなど所望の溶媒に置換して用いることもできる。また、得られたニオブ酸化物微粒子分散液は分散媒が有機溶媒であっても非常に安定であり、凝集したり、ゲル化したり、沈殿が生ずることはない。
The niobium-based oxide fine particle dispersion obtained as described above can be used after removing remaining ions with an ion exchange resin or the like, if necessary. However, the niobium oxide fine particle dispersion obtained in the present invention is not necessarily required because impurities and ions are reduced in advance in the washing step.
The niobium oxide fine particle dispersion obtained by the above method can be used by substituting with a desired solvent such as alcohols such as methanol and ethanol, glycols such as 1,3-butylene glycol, and glycerin using a rotary evaporator or the like. . The obtained niobium oxide fine particle dispersion is very stable even when the dispersion medium is an organic solvent, and does not aggregate, gel, or precipitate.
本発明の製造方法によって得られるニオブ系酸化物微粒子分散液の微粒子の平均粒子径は概ね１〜１００ｎｍ、好ましくは２〜６０ｎｍの範囲にある。
平均粒子径が１ｎｍ未満の場合は、安定性が不充分となり濃度の高い微粒子分散ゾルを得ることができないことがあり、平均粒子径が１００ｎｍを越えると、粒子が大き過ぎて沈降したり、透明性が不充分となることがある。
また、上記のようにして得られたニオブ酸化物微粒子分散液は、そのまま各種用途に用いることもできるし、必要に応じて希釈したり濃縮して用いることもできる。
The average particle size of the fine particles of the niobium-based oxide fine particle dispersion obtained by the production method of the present invention is generally in the range of 1 to 100 nm, preferably 2 to 60 nm.
If the average particle size is less than 1 nm, the stability may be insufficient and a high-density fine particle-dispersed sol may not be obtained. If the average particle size exceeds 100 nm, the particles are too large to settle or transparent. May be insufficient.
Moreover, the niobium oxide fine particle dispersion obtained as described above can be used for various purposes as it is, or can be diluted or concentrated as necessary.
このようなニオブ系酸化物微粒子分散液の濃度は、酸化物として５〜４０重量％、さらには１０〜３０重量％の範囲にあることが好ましい。
ニオブ系酸化物微粒子分散液の濃度が酸化物として５重量％未満の場合は実用性に劣り、ニオブ系酸化物微粒子分散液の濃度が酸化物として４０重量％を越えると分散媒によっても異なるが安定性が不充分となることがある。
The concentration of such a niobium-based oxide fine particle dispersion is preferably in the range of 5 to 40% by weight, more preferably 10 to 30% by weight as an oxide.
When the concentration of the niobium-based oxide fine particle dispersion is less than 5% by weight as an oxide, the practicality is inferior. Stability may be insufficient.
本発明では、得られたニオブ系酸化物微粒子分散液を乾燥し、必要に応じて焼成してニオブ系酸化物微粒子として用いることができる。
乾燥温度は、ニオブ酸化物微粒子粉体が得られれば特に制限はなく、通常室温〜１２０℃で乾燥する。
ついで、必要に応じて焼成することができるが、このときの温度は概ね３００〜７００℃の範囲である。このような温度範囲で焼成すると酸化物化あるいは成分によっては結晶化が充分進行し、光学特性、紫外線遮蔽性、耐候性等に優れたニオブ系酸化物微粒子を得ることができる。７００℃を越える高温で焼成すると、粒子径にもよるが粒子が凝集したり互いに融着することがある。
In the present invention, the obtained niobium-based oxide fine particle dispersion can be dried and calcined as necessary to be used as niobium-based oxide fine particles.
The drying temperature is not particularly limited as long as niobium oxide fine particle powder can be obtained, and it is usually dried at room temperature to 120 ° C.
Then, it can be fired as necessary, but the temperature at this time is generally in the range of 300 to 700 ° C. When firing in such a temperature range, oxidization or crystallization sufficiently proceeds depending on the component, and niobium oxide fine particles having excellent optical characteristics, ultraviolet shielding properties, weather resistance, and the like can be obtained. When fired at a high temperature exceeding 700 ° C., the particles may be agglomerated or fused to each other depending on the particle diameter.
さらに、ニオブ系酸化物微粒子はシランカップリング剤等の加水分解性有機ケイ素化合物で表面処理したり表面被覆して用いることもできる。表面処理方法あるいは表面被覆方法としては特に制限はなく、例えば、分散液中に加水分解性有機ケイ素化合物を添加し、所定温度、所定時間反応させることによって、表面が有機シラン化合物で被覆される。
ここで用いられる加水分解性有機ケイ素化合物の種類は、用途に応じて適宜選定される。
Furthermore, the niobium-based oxide fine particles can be used by surface treatment or surface coating with a hydrolyzable organosilicon compound such as a silane coupling agent. The surface treatment method or the surface coating method is not particularly limited, and for example, the surface is coated with an organosilane compound by adding a hydrolyzable organosilicon compound to the dispersion and reacting for a predetermined time at a predetermined temperature.
The kind of the hydrolyzable organosilicon compound used here is appropriately selected according to the application.
表面改質用加水分解性有機ケイ素化合としては、具体的には、テトラメトキシシラン、テトラエトキシシランなどのテトラアルコキシシラン類、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリアセトキシシラン、メチルトリプロポキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリアセトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリアセトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−クロロプロピルトリエトキシシラン、γ−クロロプロピルトリプロポキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−（β−グリシドキシエトキシ）プロピルトリメトキシシラン、γ−メタクリルオキシプロピルトリメトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−メルカプトプロピルトリ工トキシシランなどのトリアルコキシまたはトリアシルオキシシラン類、およびジメチルジメトキシシラン、ジメチルジエトキシシラン、フェニルメチルジエトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルフェニルジエトキシシラン、γ−クロロプロピルメチルジメトキシシラン、ジメチルジアセトキシシラン、γ−メタクリルオキシプロピルメチルジメトキシシラン、γ−メルカプトプロビルメチルジメトキシシラン、γ−アミノプロピルメチルジメトキシシランなどのジアルコキシシランまたはジアシルオキシシラン類またはトリメチルクロロシランなどが挙げられ、単独または２種以上組合せることも可能である。 Specific examples of hydrolyzable organosilicon compounds for surface modification include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriacetoxysilane, and methyltripropoxy. Silane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriacetoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, γ-chloropropyltripropoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- (β- Trialkoxy or triacyloxysilanes such as lysidoxyethoxy) propyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and dimethyldimethoxysilane, dimethyldi Ethoxysilane, phenylmethyldiethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylphenyldiethoxysilane, γ-chloropropylmethyldimethoxysilane, dimethyldiacetoxysilane, γ-methacryloxypropylmethyldimethoxy Dialkoxysilanes or diacyloxysilanes such as silane, γ-mercaptopropyl methyldimethoxysilane, γ-aminopropylmethyldimethoxysilane Or trimethylchlorosilane, and the like can be used alone or in combination of two or more.
ニオブ系酸化物微粒子の表面をより良く改質するには、上記加水分解性有機ケイ素化合物のアルコール溶液とニオブ系酸化物微粒子分散液とを混合し、必要に応じて加水分解触媒として酸またはアルカリを加え、一定温度、一定時間反応させた後、混合液中の水を分離することによって有機溶剤に分散したニオブ系酸化物微粒子ができる。この表面改質により、ニオブ系酸化物微粒子は有機溶媒中での分散安定性が向上する。 In order to better modify the surface of the niobium-based oxide fine particles, the alcohol solution of the hydrolyzable organosilicon compound and the niobium-based oxide fine particle dispersion are mixed, and an acid or alkali is used as a hydrolysis catalyst as necessary. And reacting at a constant temperature for a certain period of time, and then separating the water in the mixed solution to produce niobium oxide fine particles dispersed in an organic solvent. This surface modification improves the dispersion stability of the niobium-based oxide fine particles in the organic solvent.
以下に本発明を実施例により説明するが、本発明はこれら実施例に限定されるものではない。 EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
ニオブ系酸化物微粒子(A1)分散液の調製
濃度３５.３重量％のＫＮbＯ3溶液１９１７ｇと水２３０８３ｇを混合し、濃度２.７１重量％のＫＮbＯ3溶液とし、これに１mol／Lの酢酸を添加し、中和した。この時のｐＨは５.５であった。これを濾過し、蒸留水で洗浄してニオブ酸のゲル１９９０ｇを得た。このゲルの固形分濃度は、Ｎb2Ｏ5換算で２４.０１重量％であった。
得られたニオブ酸のゲル１４６０ｇに水３３５４０ｇを添加し、充分撹拌した後、濃度３５重量％の過酸化水素水４０００ｇを加え、８０℃で２時間加熱溶解した。得られた溶液に水を加え、Ｎb2Ｏ5換算で濃度０.５重量％とした後、オートクレーブにて１５０℃で１８時間水熱処理を行った。
Nb based oxide particles (A1) were mixed to prepare a concentration 35.3% by weight of the KNbO 3 solution 1917g of water 23083g of the dispersion, the concentration of 2.71 wt% of KNbO 3 solution, to which the 1 mol / L acetic acid Added and neutralized. The pH at this time was 5.5. This was filtered and washed with distilled water to obtain 1990 g of niobic acid gel. The solid content concentration of this gel was 24.01% by weight in terms of Nb 2 O 5 .
After adding 33540 g of water to 1460 g of the resulting niobic acid gel and stirring sufficiently, 4000 g of 35% by weight hydrogen peroxide was added and dissolved by heating at 80 ° C. for 2 hours. Water was added to the resulting solution to adjust the concentration to 0.5% by weight in terms of Nb 2 O 5 , and then hydrothermal treatment was performed at 150 ° C. for 18 hours in an autoclave.
ついで、これを濃縮し、Ｎb2Ｏ5換算で濃度１０重量％のニオブ系酸化物微粒子(A1)水分散液３５００ｇを得た。
ついで、ニオブ系酸化物微粒子(A1)分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(A1)メタノール分散液を得た。
Next, this was concentrated to obtain 3500 g of an aqueous dispersion of niobium oxide fine particles (A1) having a concentration of 10% by weight in terms of Nb 2 O 5 .
Next, a portion of the niobium-based oxide fine particle (A1) dispersion is replaced with methanol as the dispersion medium and concentrated to obtain a niobium-based oxide fine particle (A1) methanol dispersion having a solid content of 20% by weight. Obtained.
前記各粒子について平均粒子径をレーザー法（ＰＡＲＴＩＣＬＥ ＳＩＺＩＮＧ ＳＹＳＴＥＭ社製：ＮＩＣＯＭＰ３８０）にて測定し、粒子径の均一性を観察し、さらに粒子中の酸根を測定し、結果を表１に示した。また、各分散液について安定性、透明性、粒子の屈折率を評価し、結果１を表に示した。
測定方法と評価基準を以下に示すが、後述する実施例２以下の実施例と比較例においても、これらの測定方法と評価基準により各粒子の測定、評価を行った。
The average particle size of each of the particles was measured by a laser method (manufactured by PARTICS SIZING SYSTEM: NICOM 380), the uniformity of the particle size was observed, and the acid radicals in the particles were measured. The results are shown in Table 1. Moreover, stability, transparency, and the refractive index of particle | grains were evaluated about each dispersion liquid, and the result 1 was shown in the table | surface.
Measurement methods and evaluation criteria are shown below. In Examples 2 and below, which will be described later, and comparative examples, each particle was measured and evaluated according to these measurement methods and evaluation criteria.
粒子径の均一性
ニオブ系酸化物微粒子(A1)メタノール分散液から採取したニオブ系酸化物微粒子(A1)の透過型電子顕微鏡写真を撮影し、以下の基準で評価した。
平均粒子径の１／２以下の粒子または２倍以上の粒子が殆ど認められない ： ○
平均粒子径の１／２以下の粒子または２倍以上の粒子が僅かに認められる ： △
平均粒子径の１／２以下の粒子または２倍以上の粒子が明らかに認められる ： Ｘ
Uniform Niobium Oxide Fine Particles (A1) Transmission electron micrographs of niobium oxide fine particles (A1) collected from a methanol dispersion were taken and evaluated according to the following criteria.
Almost no particles smaller than 1/2 of the average particle diameter or particles larger than 2 times are recognized: ○
Slightly less than 1/2 the average particle size or more than twice the average particle size: Δ
Particles with an average particle size of ½ or less or twice or more are clearly recognized: X
水分散液安定性の測定
Ｎb2Ｏ5換算で濃度１０重量％に希釈して調整した直後のニオブ酸化物微粒子分散液の粘度と、これを５０℃で１０日間加熱した後の粘度とを測定し、以下の基準で評価した。
粘度上昇率１０％未満 ： ○
粘度上昇率１０〜５０％未満： △
粘度上昇率５０％以上 ： ×
Measurement of water dispersion stability Measure the viscosity of the niobium oxide fine particle dispersion immediately after being diluted to 10% by weight in terms of Nb 2 O 5 and adjusting the viscosity after heating it at 50 ° C. for 10 days. And evaluated according to the following criteria.
Viscosity increase rate less than 10%: ○
Viscosity increase rate less than 10-50%: Δ
Viscosity increase rate 50% or more: ×
メタノール分散液安定性の測定
Ｎb2Ｏ5換算で濃度２０重量％に調整した直後のニオブ酸化物微粒子分散液の粘度と、これを５０℃で１０日間加熱した後の粘度とを測定し、以下の基準で評価した。
粘度上昇率１０％未満 ： ◎
粘度上昇率１０〜２０％未満 ： ○
粘度上昇率２０〜５０％未満 ： △
粘度上昇率５０％以上 ： ×
Measurement of Stability of Methanol Dispersion The viscosity of the niobium oxide fine particle dispersion immediately after being adjusted to a concentration of 20% by weight in terms of Nb 2 O 5 and the viscosity after heating this at 50 ° C. for 10 days were measured. Evaluation based on the criteria.
Viscosity increase rate is less than 10%: ◎
Viscosity increase rate less than 10-20%: ○
Viscosity increase rate 20 to less than 50%: Δ
Viscosity increase rate 50% or more: ×
透明性の測定
Ｎb2Ｏ5換算で濃度０.１重量％に調整したニオブ酸化物微粒子分散液を、厚さ１０ｍｍの石英セルに入れ、透過率測定装置（日本分光（株）製：Ｖ−５５０、波長550ｎｍ）で透過率を測定し、以下の基準で評価した。
透過率９０％以上 ： ○
透過率９０％未満 ： ×
Transparency Measurement A niobium oxide fine particle dispersion liquid adjusted to a concentration of 0.1% by weight in terms of Nb 2 O 5 was put into a 10 mm thick quartz cell, and a transmittance measuring device (manufactured by JASCO Corporation: V- The transmittance was measured at 550 and a wavelength of 550 nm, and evaluated according to the following criteria.
Transmission 90% or more: ○
Transmittance less than 90%: ×
ニオブ系酸化物微粒子(A2)分散液の調製
実施例１の１mol／Lの酢酸溶液を１mol／Lのシュウ酸に代えた以外は実施例１と同様にして、ニオブ系酸化物微粒子(A2)水分散液およびニオブ系酸化物微粒子(A2) メタノール分散液を得た。
Preparation of Niobium Oxide Fine Particles (A2) Dispersion Niobium Oxide Fine Particles (A2) In the same manner as in Example 1 except that the 1 mol / L acetic acid solution of Example 1 was replaced with 1 mol / L oxalic acid. An aqueous dispersion and niobium oxide fine particles (A2) in methanol were obtained.
ニオブ系酸化物微粒子(A3)分散液の調製
実施例１の１mol／Lの酢酸溶液を１mol／Lの塩酸に代えた以外は実施例１と同様にして、ニオブ系酸化物微粒子(A3)水分散液およびニオブ系酸化物微粒子(A3)メタノール分散液を得た。
Preparation of Niobium Oxide Fine Particles (A3) Dispersion Niobium Oxide Fine Particles (A3) water in the same manner as in Example 1 except that the 1 mol / L acetic acid solution of Example 1 was replaced with 1 mol / L hydrochloric acid. A dispersion and a niobium oxide fine particle (A3) methanol dispersion were obtained.
ニオブ系酸化物微粒子(A4)分散液の調製
実施例１で得たニオブ酸化物微粒子(A1) メタノール分散液１０００ｇと純水１０００ｇを反応容器にとり、６３℃に加熱した後、撹拌しながらテトラエトキシシランとメタノール（重量比１５３／１０００）の混合液２リットルを除々に添加した。添加終了後、さらに溶液の温度を６３℃に維持して熟成し、ついでメタノールで溶媒置換するとともに濃縮し、固形分濃度３０.５重量％のテトラエトキシシランで表面改質されたニオブ系酸化物微粒子(A4) メタノール分散液を得た。
Preparation of Niobium Oxide Fine Particles (A4) Dispersion Niobium Oxide Fine Particles (A1) obtained in Example 1 1000 g of methanol dispersion and 1000 g of pure water were placed in a reaction vessel, heated to 63 ° C., and then stirred with tetraethoxy 2 liters of a mixed solution of silane and methanol (weight ratio 153/1000) was gradually added. After completion of the addition, the temperature of the solution is further maintained at 63 ° C. for aging, and then the solvent is replaced with methanol and concentrated, and the surface is modified with tetraethoxysilane having a solid concentration of 30.5% by weight. Fine particles (A4) A methanol dispersion was obtained.
ニオブ系酸化物微粒子(A5)分散液の調製
実施例４のテトラエキトキシシランをメチルトリメトキシシランに代えた以外は実施例４と同様にして、メチルトリメトキシシランで表面改質されたニオブ系酸化物微粒子(A5) メタノール分散液を得た。
Preparation of Niobium Oxide Fine Particle (A5) Dispersion A niobium-based surface modified with methyltrimethoxysilane in the same manner as in Example 4 except that the tetraethoxysilane in Example 4 was replaced with methyltrimethoxysilane. Fine oxide particles (A5) A methanol dispersion was obtained.
ニオブ系酸化物微粒子(A6)分散液の調製
実施例４のテトラエキトキシシランをγ−グリシドキシプロピルトリエトキシシランに代えた以外は実施例４と同様にして、γ−グリシドキシプロピルトリエトキシシランで表面改質されたニオブ系酸化物微粒子(A6) メタノール分散液を得た。
Preparation of Niobium Oxide Fine Particles (A6) Dispersion γ-Glycidoxypropyltrimethyl was prepared in the same manner as in Example 4 except that tetraethoxysilane in Example 4 was replaced with γ-glycidoxypropyltriethoxysilane. Niobium oxide fine particles (A6) methanol-dispersed with surface modification with ethoxysilane were obtained.
ニオブ系酸化物微粒子(A7)分散液の調製
五フッ化ニオブ７０６.９１ｇを水に溶解し、これに濃度１５重量％のアンモニア水４.６９Lを４０分間で添加した。これを濾過、洗浄し、２０００ｇのニオブ酸のゲルを得た。このゲルの固形分濃度は、Ｎb2Ｏ5換算で２５.０重量％であった。
得られたニオブ酸のゲル１３００ｇに水３３５４０ｇを添加し、充分撹拌した後、濃度３５重量％の過酸化水素水３０００ｇを加え、８０℃で２時間加熱溶解した。得られた溶液に水を加え、Ｎb2Ｏ5換算で濃度０.５重量％とした後、オートクレーブにて２００℃で１８時間水熱処理を行った。
Preparation of Niobium Oxide Fine Particle (A7) Dispersion 706.91 g of niobium pentafluoride was dissolved in water, and 4.69 L of aqueous ammonia having a concentration of 15% by weight was added thereto over 40 minutes. This was filtered and washed to obtain 2000 g of niobic acid gel. The solid content concentration of this gel was 25.0% by weight in terms of Nb 2 O 5 .
After adding 33540 g of water to 1300 g of the resulting niobic acid gel and stirring sufficiently, 3000 g of 35% by weight hydrogen peroxide solution was added and dissolved by heating at 80 ° C. for 2 hours. Water was added to the obtained solution to adjust the concentration to 0.5% by weight in terms of Nb 2 O 5 , and then hydrothermal treatment was performed at 200 ° C. for 18 hours in an autoclave.
ついで、これを濃縮し、Ｎb2Ｏ5換算で濃度１０重量％のニオブ系酸化物微粒子(A7)水分散液３５００ｇを得た。
ついで、ニオブ系酸化物微粒子(A7)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(A7) メタノール分散液を得た。
Next, this was concentrated to obtain 3500 g of an aqueous dispersion of niobium oxide fine particles (A7) having a concentration of 10% by weight in terms of Nb 2 O 5 .
Next, a portion of the aqueous dispersion of niobium-based oxide fine particles (A7) is substituted with methanol as the dispersion medium and concentrated to give niobium-based oxide fine particles (A7) methanol dispersion having a solid content of 20% by weight. Got.
ニオブ系酸化物微粒子(A8)分散液の調製
実施例７で得たメタノール分散ニオブ酸化物微粒子(A7)分散液を用いた以外は実施例４と同様にして、テトラエトキシシランで表面改質されたニオブ系酸化物微粒子(A8) メタノール分散液を得た。
Preparation of Niobium Oxide Fine Particle (A8) Dispersion The surface was modified with tetraethoxysilane in the same manner as in Example 4 except that the methanol-dispersed niobium oxide fine particle (A7) dispersion obtained in Example 7 was used. Niobium oxide fine particles (A8) A methanol dispersion was obtained.
ニオブ系酸化物微粒子(A9)分散液の調製
五塩化ニオブを水にて加水分解し、濾過洗浄して、２７８０ｇのニオブ酸のゲルを得た。このゲルの固形分濃度は、Ｎb2Ｏ5換算で２２.７重量％であった。このニオブ酸のゲルをＮb2Ｏ5換算で５００ｇとなるように計り取り、１０Lのビーカーに入れ、更に濃度３５重量％の過酸化水素水１８００ｇを入れ、撹拌しながら加熱し、７０℃で２時間溶解した。ついで、これに水２０００ｇを加えて７０℃で１時間加熱し再び水を加えＮb2Ｏ5換算濃度で１重量％の溶液とし、これをオートクレーブに入れ、２２０℃で１５時間水熱処理を行った。
Preparation of Niobium Oxide Fine Particle (A9) Dispersion Niobium pentachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of a niobic acid gel. The solid content concentration of this gel was 22.7% by weight in terms of Nb 2 O 5 . This niobic acid gel is weighed to 500 g in terms of Nb 2 O 5 , placed in a 10 L beaker, further charged with 1800 g of 35% by weight hydrogen peroxide, heated with stirring, and heated at 70 ° C. for 2 Dissolved for hours. Next, 2000 g of water was added thereto, heated at 70 ° C. for 1 hour, water was added again to obtain a 1% by weight solution in terms of Nb 2 O 5 concentration, and this was placed in an autoclave and subjected to hydrothermal treatment at 220 ° C. for 15 hours. .
ついで、これを濃縮し、Ｎb2Ｏ5換算で濃度１０重量％のニオブ系酸化物微粒子(A9)水分散液５００ｇを得た。
ついで、ニオブ系酸化物微粒子(A9)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(A9) メタノール分散液を得た。
Next, this was concentrated to obtain 500 g of an aqueous dispersion of niobium oxide fine particles (A9) having a concentration of 10% by weight in terms of Nb 2 O 5 .
Next, a part of the aqueous dispersion of niobium oxide fine particles (A9) is substituted with methanol for the dispersion medium and concentrated to give a niobium oxide fine particles (A9) methanol dispersion having a solid concentration of 20% by weight. Got.
ニオブ系酸化物微粒子(A10)分散液の調製
五塩化ニオブを水にて加水分解し、濾過洗浄して、２７８０ｇのニオブ酸のゲルを得た。
このゲルの固形分濃度は、Ｎb2Ｏ5換算で２２.７重量％であった。このニオブ酸のゲルをＮb2Ｏ5換算で５００ｇとなるように計り取り、水２２７９７ｇの入った５０L容器に入れ、更に濃度３５重量％の過酸化水素水５７１４ｇを入れ、撹拌しながら加熱し、７０℃で２時間溶解した。
ついで、これに水１９２８６ｇを加えＮb2Ｏ5換算濃度で１重量％の溶液とした。ついで、これにコア粒子として平均粒子径７ｎｍでありＳiＯ2濃度が１５重量％のシリカゾル３３３ｇと水４６６２ｇとを混合し、オートクレーブに入れ、２２０℃で１５時間水熱処理を行った。
Preparation of Niobium Oxide Fine Particle (A10) Dispersion Niobium pentachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of a niobic acid gel.
The solid content concentration of this gel was 22.7% by weight in terms of Nb 2 O 5 . This niobic acid gel is weighed to 500 g in terms of Nb 2 O 5 , placed in a 50 L container containing 22797 g of water, further charged with 5714 g of 35% by weight hydrogen peroxide, and heated with stirring. It melt | dissolved at 70 degreeC for 2 hours.
Subsequently, 19286 g of water was added thereto to make a 1% by weight solution in terms of Nb 2 O 5 concentration. Subsequently, 333 g of silica sol having an average particle diameter of 7 nm as core particles and an SiO 2 concentration of 15% by weight and 4662 g of water were mixed, placed in an autoclave, and hydrothermally treated at 220 ° C. for 15 hours.
ついで、これを濃縮し、(Ｎb2Ｏ5＋ＳiＯ2)換算で濃度１０重量％のニオブ系酸化物微粒子(A10)水分散液５５００ｇを得た。
ついで、ニオブ系酸化物微粒子(A10)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％の複合酸化物微粒子(A10) メタノール分散液を得た。
Next, this was concentrated to obtain 5500 g of a niobium oxide fine particle (A10) aqueous dispersion having a concentration of 10% by weight in terms of (Nb 2 O 5 + SiO 2 ).
Next, for a part of the aqueous dispersion of niobium oxide fine particles (A10), the water of the dispersion medium is replaced with methanol and concentrated to obtain a composite oxide fine particle (A10) methanol dispersion having a solid content concentration of 20% by weight. Obtained.
ニオブ系酸化物微粒子(A11)分散液の調製
五塩化ニオブと塩化第二鉄を水にて加水分解し、濾過洗浄して、２７８０ｇのニオブ酸と鉄の水酸化物の混合ゲルを得た。このゲルの固形分濃度は、(Ｎb2Ｏ5＋Fe2Ｏ3)換算で２３.５重量％であった。このニオブ酸と鉄の水酸化物の混合ゲルを(Ｎb2Ｏ5＋Fe2Ｏ3)換算で５００ｇとなるように計り取り、水２２８７２ｇの入った５０L容器に入れ、更に濃度３５重量％の過酸化水素水５７１４ｇを入れ、撹拌しながら加熱し、７０℃で２時間溶解した後、これに水１９２８６ｇを加え(Ｎb2Ｏ5＋Fe2Ｏ3)換算濃度で１重量％の溶液とした。 ついで、これに、コア粒子として平均粒子径７ｎｍでありSiＯ2濃度が１５重量％のシリカゾル３３３ｇと水４６６２ｇとを混合し、これをオートクレーブに入れ、２２０℃で１５時間水熱処理を行った。
Preparation of Niobium Oxide Fine Particle (A11) Dispersion Niobium pentachloride and ferric chloride were hydrolyzed with water, washed by filtration, and 2780 g of a mixed gel of niobic acid and iron hydroxide was obtained. The solid content concentration of this gel was 23.5% by weight in terms of (Nb 2 O 5 + Fe 2 O 3 ). This mixed gel of niobic acid and iron hydroxide was weighed so as to be 500 g in terms of (Nb 2 O 5 + Fe 2 O 3 ), put into a 50 L container containing 22872 g of water, and an excess of 35% by weight concentration. 5714 g of hydrogen oxide water was added, heated with stirring, dissolved at 70 ° C. for 2 hours, and then 19286 g of water was added thereto to give a 1% by weight solution in terms of (Nb 2 O 5 + Fe 2 O 3 ). Subsequently, 333 g of silica sol having an average particle diameter of 7 nm as core particles and a SiO 2 concentration of 15% by weight and 4662 g of water were mixed, and the mixture was placed in an autoclave and subjected to hydrothermal treatment at 220 ° C. for 15 hours.
ついで、これを濃縮し、(Ｎb2Ｏ5＋Fe2Ｏ3＋SiＯ2)換算で濃度１０重量％のニオブ系酸化物微粒子(A11)水分散液５２３８ｇを得た。
ついで、ニオブ系酸化物微粒子(A11)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(A11) メタノール分散液を得た。
Subsequently, this was concentrated to obtain 5238 g of an aqueous dispersion of niobium oxide fine particles (A11) having a concentration of 10% by weight in terms of (Nb 2 O 5 + Fe 2 O 3 + SiO 2 ).
Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A11) is substituted with methanol for the water in the dispersion medium and concentrated to give a niobium-based oxide fine particles (A11) methanol dispersion having a solid concentration of 20% by weight. Got.
ニオブ系酸化物微粒子(A12)分散液の調製
（コア粒子の調製）
実施例３と同様にして、コア粒子用のニオブ系酸化物微粒子(A3)水分散液を得た。ニオブ系酸化物微粒子の平均粒径は２０ｎｍであった。
（ジルコニウム化合物溶解液の調製）
オキシ塩化ジルコニウム１７１ｇを水１２８ｇに加えたZrＯ2濃度２重量％の水溶液に１５％アンモニア水を添加し、ｐＨ８．５のスラリーを得た。このスラリーを濾過して洗浄し、ZrＯ2として１０重量％のケーキを得た。このケーキ６０ｇに水３．０８ｋｇを加え、さらにＫＯＨ水溶液を加えてアルカリ性にした後、これに過酸化水素１２０ｇを加えて加熱し、ZrＯ2として２重量％のジルコニウムの過酸化水素溶解水溶液２９９ｇを調製した。
（ケイ酸液の調製）
市販の水ガラスを水で希釈したのち、陽イオン交換樹脂で脱アルカリし、ＳｉＯ2濃度２重量％のケイ酸液９２６ｇを調製した。
Preparation of niobium oxide fine particles (A12) dispersion (preparation of core particles)
In the same manner as in Example 3, an aqueous dispersion of niobium-based oxide fine particles (A3) for core particles was obtained. The average particle diameter of the niobium-based oxide fine particles was 20 nm.
(Preparation of zirconium compound solution)
15% ammonia water was added to an aqueous solution having a ZrO 2 concentration of 2% by weight obtained by adding 171 g of zirconium oxychloride to 128 g of water to obtain a slurry having a pH of 8.5. The slurry was filtered and washed to obtain a 10% by weight cake as ZrO 2 . After adding 3.08 kg of water to 60 g of this cake and adding KOH aqueous solution to make it alkaline, 120 g of hydrogen peroxide was added thereto and heated to give 299 g of 2 wt% zirconium hydrogen peroxide-dissolved aqueous solution as ZrO 2. Prepared.
(Preparation of silicic acid solution)
A commercially available water glass was diluted with water and then dealkalized with a cation exchange resin to prepare 926 g of a silicic acid solution having a SiO 2 concentration of 2% by weight.
上記で調製したコア粒子用のニオブ系酸化物微粒子(A3)分散液３５００ｇに水１４ｋｇを加えて固形分濃度２重量％にした後９０℃に加熱し、ジルコニウムの過酸化水素溶解水溶液２９９ｇとケイ酸液９２６ｇを混合した。ついで、この混合液をオートクレーブ中で２００℃で１８時間水熱処理を行った後、濃縮して固形分濃度１０重量％の淡乳白色をした透明な酸化ニオブ粒子を酸化ケイ素、酸化ジルコニウムからなる複合酸化物で被覆したニオブ系酸化物微粒子(A12)水分散液を得た。
ついで、ニオブ系酸化物微粒子(A12)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(A12) メタノール分散液を得た。
14 kg of water was added to 3500 g of the niobium oxide fine particle (A3) dispersion for core particles prepared above to obtain a solid concentration of 2% by weight, and then heated to 90 ° C., and 299 g of a hydrogen peroxide-dissolved aqueous solution of zirconium and silica. 926 g of acid solution was mixed. Next, this mixed solution was hydrothermally treated at 200 ° C. for 18 hours in an autoclave, and then concentrated to convert the transparent niobium oxide particles having a solid content concentration of 10% by weight into light milky white composite oxide composed of silicon oxide and zirconium oxide. An aqueous dispersion of niobium oxide fine particles (A12) coated with a product was obtained.
Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A12) is substituted with methanol for the dispersion medium and concentrated to give niobium-based oxide fine particles (A12) methanol dispersion having a solid concentration of 20% by weight. Got.
ニオブ系酸化物微粒子(A13)分散液の調製
（コア粒子の調製）
四塩化チタンを水にて加水分解し、濾過洗浄して、２７８０ｇのチタン酸のゲルを得た。このゲルの固形分濃度は、TiＯ2換算で９．４重量％であった。このチタン酸のゲルをTiＯ2換算で５００ｇとなるように計り取り、水２２８７２ｇの入った５０L容器に入れ、更に濃度３５重量％の過酸化水素水５７１４ｇを入れ、撹拌しながら加熱し、９０℃で２時間溶解した。ついで、これに水１９２８６ｇを加えTiＯ2換算濃度で０．５重量％の溶液とした。これをオートクレーブに入れ、１５０℃で１５時間水熱処理を行った。ついで、これを濃縮し、TiＯ2換算で濃度１．５重量％、平均粒径１２ｎｍの酸化チタン微粒子分散液５２３８ｇを得た。
Preparation of niobium oxide fine particles (A13) dispersion (preparation of core particles)
Titanium tetrachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of titanic acid gel. The solid content concentration of this gel was 9.4% by weight in terms of TiO 2 . This titanic acid gel was weighed to 500 g in terms of TiO 2 , placed in a 50 L container containing 22882 g of water, and 5714 g of 35% by weight hydrogen peroxide solution was added and heated with stirring to 90 ° C. For 2 hours. Subsequently, 19286 g of water was added thereto to obtain a 0.5% by weight solution in terms of TiO 2 concentration. This was put into an autoclave and hydrothermally treated at 150 ° C. for 15 hours. Subsequently, this was concentrated to obtain 5238 g of a titanium oxide fine particle dispersion having a concentration of 1.5% by weight in terms of TiO 2 and an average particle diameter of 12 nm.
（ニオブ化合物溶解液の調製）
五塩化ニオブを水にて加水分解し、濾過洗浄して、２７８０ｇのニオブ酸のゲルを得た。このゲルの固形分濃度は、Ｎb2Ｏ5換算で２２.７重量％であった。このニオブ酸のゲルをＮb2Ｏ5換算で５００ｇとなるように計り取り、水２２７９７ｇの入った５０L容器に入れ、更に濃度３５重量％の過酸化水素水５７１４ｇを入れ、撹拌しながら加熱し、７０℃で２時間溶解した。ついで、これに水１９２８６ｇを加えＮb2Ｏ5換算濃度で１重量％のニオブの過酸化水素溶解水溶液とした。
(Preparation of niobium compound solution)
Niobium pentachloride was hydrolyzed with water, filtered and washed to obtain 2780 g of niobic acid gel. The solid content concentration of this gel was 22.7% by weight in terms of Nb 2 O 5 . This niobic acid gel is weighed to 500 g in terms of Nb 2 O 5 , placed in a 50 L container containing 22797 g of water, further charged with 5714 g of 35% by weight hydrogen peroxide, and heated with stirring. It melt | dissolved at 70 degreeC for 2 hours. Next, 19286 g of water was added thereto to obtain a 1% by weight niobium hydrogen peroxide-dissolved aqueous solution in terms of Nb 2 O 5 concentration.
（ジルコニウム化合物溶解液の調製）
オキシ塩化ジルコニウム１７１０ｇを水１２８０ｇに加えたZrＯ2濃度２重量％の水溶液に１５％アンモニア水を添加し、ｐＨ８．５のスラリーを得た。このスラリーを濾過して洗浄し、ZrＯ2として１０重量％のケーキを得た。このケーキ６００ｇに水３０．８ｋｇを加え、さらにＫＯＨ水溶液を加えてアルカリ性にしたのち、これに過酸化水素１２００ｇを加えて加熱し、ZrＯ2として２重量％のジルコニウムの過酸化水素溶解水溶液２９９０ｇを調製した。
(Preparation of zirconium compound solution)
15% ammonia water was added to an aqueous solution having a ZrO 2 concentration of 2 wt% in which 1710 g of zirconium oxychloride was added to 1280 g of water to obtain a slurry having a pH of 8.5. The slurry was filtered and washed to obtain a 10% by weight cake as ZrO 2 . After adding 30.8 kg of water to 600 g of this cake and adding KOH aqueous solution to make it alkaline, 1200 g of hydrogen peroxide was added thereto and heated, and 2990 g of hydrogen peroxide-dissolved aqueous solution of 2 wt% zirconium as ZrO 2 was added. Prepared.
上記で調製したコア粒子用の酸化チタン微粒子分散液５２３８ｇを９０℃に加熱し、ニオブの過酸化水素溶解水溶液とジルコニウムの過酸化水素溶解水溶液２９９０ｇを混合し、ついで、この混合液をオートクレーブ中で１８０℃で１８時間水熱処理を行った後、濃縮して固形分濃度１０重量％の淡乳白色をした透明な酸化チタン微粒子をニオブ酸化物と酸化ジルコニウムとからなる複合酸化物で被覆したニオブ系酸化物微粒子(A13)水分散液を得た。
ついで、ニオブ系酸化物微粒子(A13)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(A13) メタノール分散液を得た。
5238 g of the titanium oxide fine particle dispersion for core particles prepared above is heated to 90 ° C. and mixed with a hydrogen peroxide-dissolved aqueous solution of niobium and 2990 g of a hydrogen peroxide-dissolved aqueous solution of zirconium, and this mixture is then placed in an autoclave. After hydrothermal treatment at 180 ° C. for 18 hours, niobium-based oxidation in which transparent titanium oxide fine particles with a concentration of 10% by weight and solid milk concentration are coated with a composite oxide composed of niobium oxide and zirconium oxide. Fine particle (A13) aqueous dispersion was obtained.
Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A13) is substituted with methanol for the dispersion medium and concentrated to obtain a niobium-based oxide fine particles (A13) methanol dispersion having a solid content of 20% by weight. Got.
ニオブ系酸化物微粒子(A14)分散液の調製
濃度３５.３重量％のＫＮbＯ3溶液１９１７ｇと水２３０８３ｇを混合し、濃度２.７１重量％のＫＮbＯ3溶液とし、これに１mol／Lの酢酸を添加し、中和した。この時のｐＨは５.５であった。これを濾過し、蒸留水で洗浄してニオブ酸のゲル１９９０ｇを得た。このゲルの固形分濃度は、Ｎb2Ｏ5換算で２４.０１重量％であった。
Nb based oxide particles (A14) were mixed to prepare a concentration 35.3% by weight of the KNbO 3 solution 1917g of water 23083g of the dispersion, the concentration of 2.71 wt% of KNbO 3 solution, to which the 1 mol / L acetic acid Added and neutralized. The pH at this time was 5.5. This was filtered and washed with distilled water to obtain 1990 g of niobic acid gel. The solid content concentration of this gel was 24.01% by weight in terms of Nb 2 O 5 .
（種粒子分散液の調製）
ニオブ酸のゲルの一部４９８ｇに水を加えてＮb2Ｏ5換算で濃度２重量％のニオブ酸のゲル分散液とし、これに２０分間超音波を照射してニオブ酸の種粒子分散液５９７８ｇを調製した。種粒子の平均粒子径は約１ｎｍであった。
残りのニオブ酸のゲル１４９２ｇに水３５８２３ｇを添加し、充分撹拌した後、濃度３５重量％の過酸化水素水６０００ｇを加え、８０℃で２時間加熱溶解した。得られた溶液に水を加え、Ｎb2Ｏ5換算で濃度０.５重量％とした後、これに種粒子分散液５９７８ｇを加え、オートクレーブにて１８０℃で１８時間水熱処理を行った。
(Preparation of seed particle dispersion)
Water is added to a portion of 498 g of niobic acid gel to form a niobic acid gel dispersion having a concentration of 2% by weight in terms of Nb 2 O 5 , and this is irradiated with ultrasonic waves for 20 minutes to obtain 5978 g of niobic acid seed particle dispersion. Was prepared. The average particle size of the seed particles was about 1 nm.
35823 g of water was added to 1492 g of the remaining niobic acid gel, and after sufficient stirring, 6000 g of 35% by weight hydrogen peroxide water was added and dissolved by heating at 80 ° C. for 2 hours. Water was added to the resulting solution to adjust the concentration to 0.5% by weight in terms of Nb 2 O 5 , 5978 g of seed particle dispersion was added thereto, and hydrothermal treatment was performed at 180 ° C. for 18 hours in an autoclave.
ついで、これを濃縮し、Ｎb2Ｏ5換算で濃度１０重量％のニオブ系酸化物微粒子(A14)水分散液３５００ｇを得た。
ついで、ニオブ系酸化物微粒子(A14)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(A14) メタノール分散液を得た。
Subsequently, this was concentrated to obtain 3500 g of an aqueous dispersion of niobium oxide fine particles (A14) having a concentration of 10% by weight in terms of Nb 2 O 5 .
Next, a part of the aqueous dispersion of niobium-based oxide fine particles (A14) is substituted with methanol as the dispersion medium and concentrated to give a niobium-based oxide fine particles (A14) methanol dispersion having a solid content concentration of 20% by weight. Got.
ニオブ系酸化物微粒子(R1)分散液の調製
濃度３５.３重量％のＫＮbＯ3溶液１９１７ｇと水２３０８３ｇを混合し、濃度２.７１重量％のＫＮbＯ3溶液とし、これに１mol／Lの酢酸を添加し、中和した。この時のｐＨは５.５であった。これを濾過し、蒸留水で洗浄してニオブ酸のゲル１９９０ｇを得た。このゲルの固形分濃度は、Ｎb2Ｏ5換算で２４.０１重量％であった。
得られたニオブ酸のゲル１４６０ｇに水３３５４０ｇを添加し、超音波を照射しながら充分撹拌した後、８０℃で２時間熟成し、これに水を加え、Ｎb2Ｏ5換算で濃度０.５重量％とした後、オートクレーブにて１５０℃で１８時間水熱処理を行った。
Nb based oxide particles (R1) were mixed to prepare a concentration 35.3% by weight of the KNbO 3 solution 1917g of water 23083g of the dispersion, the concentration of 2.71 wt% of KNbO 3 solution, to which the 1 mol / L acetic acid Added and neutralized. The pH at this time was 5.5. This was filtered and washed with distilled water to obtain 1990 g of niobic acid gel. The solid content concentration of this gel was 24.01% by weight in terms of Nb 2 O 5 .
33540 g of water was added to 1460 g of the resulting niobic acid gel, stirred well while irradiating with ultrasonic waves, and then aged at 80 ° C. for 2 hours. Water was added thereto, and the concentration was 0.5 in terms of Nb 2 O 5. After the weight percentage, hydrothermal treatment was performed at 150 ° C. for 18 hours in an autoclave.
ついで、これを濃縮し、Ｎb2Ｏ5換算で濃度１０重量％のニオブ系酸化物微粒子(R1)水分散液としたが、該微粒子が短時間に沈降し比較的安定な分散液は得られなかった。凝集した粗大な粒子が認められた。 Next, this was concentrated to obtain an aqueous dispersion of niobium oxide fine particles (R1) having a concentration of 10% by weight in terms of Nb 2 O 5 , but the fine particles settled in a short time, and a relatively stable dispersion was obtained. There wasn't. Aggregated coarse particles were observed.
ニオブ系酸化物微粒子(R2)分散液の調製
五塩化ニオブと塩化第二鉄を水にて加水分解し、濾過洗浄して、２７８０ｇのニオブ酸と鉄の水酸化物の混合ゲルを得た。このゲルの固形分濃度は、(Ｎb2Ｏ5＋Fe2Ｏ3)換算で２３.５重量％であった。このニオブ酸と鉄の水酸化物の混合ゲルを(Ｎb2Ｏ5＋Fe2Ｏ3)換算で５００ｇとなるように計り取り、水２２８７２ｇの入った５０L容器に入れ、超音波を照射しながら充分撹拌した後、７０℃で２時間熟成し、これに水１９２８６ｇを加え(Ｎb2Ｏ5＋Fe2Ｏ3)換算濃度で１重量％の溶液とした。ついで、これに、平均粒子径７ｎｍでありSiＯ2濃度が１５重量％のシリカゾル３３３ｇと水４６６２ｇとを混合し、これをオートクレーブに入れ、２２０℃で１５時間水熱処理を行った。
Preparation of Niobium Oxide Fine Particle (R2) Dispersion Niobium pentachloride and ferric chloride were hydrolyzed with water, washed by filtration, and 2780 g of a mixed gel of niobic acid and iron hydroxide was obtained. The solid content concentration of this gel was 23.5% by weight in terms of (Nb 2 O 5 + Fe 2 O 3 ). This mixed gel of niobic acid and iron hydroxide was weighed to 500 g in terms of (Nb 2 O 5 + Fe 2 O 3 ), placed in a 50 L container containing 22872 g of water, and sufficiently irradiated with ultrasound. After stirring, the mixture was aged at 70 ° C. for 2 hours, and 19286 g of water was added thereto to give a 1% by weight solution in terms of (Nb 2 O 5 + Fe 2 O 3 ). Subsequently, 333 g of silica sol having an average particle diameter of 7 nm and an SiO 2 concentration of 15% by weight and 4662 g of water were mixed, put into an autoclave, and hydrothermally treated at 220 ° C. for 15 hours.
ついで、これを濃縮し、Ｎb2Ｏ5換算で濃度１０重量％のニオブ系酸化物微粒子(R2)水分散液としたが、該微粒子が短時間に沈降し比較的安定な分散液は得られなかった。溶液中には粗大な粒子が生成していた。また、シリカ粒子に微細なニオブ酸と鉄の水酸化物の混合ゲルが付着した粒子、ニオブ酸と鉄の水酸化物とからなる凝集した粒子が認められた。 Subsequently, this was concentrated to obtain an aqueous dispersion of niobium oxide fine particles (R2) having a concentration of 10% by weight in terms of Nb 2 O 5 , but the fine particles settled in a short time to obtain a relatively stable dispersion. There wasn't. Coarse particles were generated in the solution. Further, particles in which a mixed gel of fine niobic acid and iron hydroxide adhered to silica particles and agglomerated particles composed of niobic acid and iron hydroxide were observed.
ニオブ系酸化物微粒子(R3)分散液の調製
特許文献１（特公平８−７０１号公報）の実施例１に準拠して、ニオブ系酸化物微粒子(R3)分散液を調製した。
濃度３５.３重量％のＫＮbＯ3溶液１９１７ｇと水２３０８３ｇを混合し、濃度２.７１重量％のＫＮbＯ3溶液とし、これに１mol／Lの酢酸を添加し、中和した。この時のｐＨは５.５であった。これを濾過し、蒸留水で洗浄してニオブ酸のゲル１９９０ｇを得た。このゲルの固形分濃度は、Ｎb2Ｏ5換算で２４.０１重量％であった。このニオブ酸のゲルを乾燥して水酸化ニオブを調製した。
Preparation of Niobium Oxide Fine Particle (R3) Dispersion A niobium oxide fine particle (R3) dispersion was prepared in accordance with Example 1 of Patent Document 1 (Japanese Patent Publication No. 8-701).
Mixing the KNbO 3 solution 1917g of water 23083g of concentration 35.3% by weight, a concentration 2.71% by weight of the KNbO 3 solution, to which was added acetic acid 1 mol / L, and neutralized. The pH at this time was 5.5. This was filtered and washed with distilled water to obtain 1990 g of niobic acid gel. The solid content concentration of this gel was 24.01% by weight in terms of Nb 2 O 5 . The niobic acid gel was dried to prepare niobium hydroxide.
このようにして調製した水酸化ニオブ１４８．２ｇを純水１８７．５ｍｌに分散させ、これに濃度３５重量％の塩酸１０４．３ｇを加えた後、撹拌しながら濃度３５重量％の過酸化水素水７７．７ｇを徐々に加え、純水６７２．９ｇを追加して水酸化ニオブをペルオキシニオブ錯体に変化させペルオキシニオブの錯体水溶液を調製した。この水溶液を４５℃の温度に、４８時間保持してペルオキシニオブ酸ゾルを調製した。 After 148.2 g of niobium hydroxide thus prepared was dispersed in 187.5 ml of pure water, 104.3 g of 35% by weight hydrochloric acid was added thereto, and then 35% by weight of hydrogen peroxide solution with stirring. 77.7 g was gradually added, and 672.9 g of pure water was added to change niobium hydroxide to a peroxyniobium complex to prepare a complex aqueous solution of peroxyniobium. This aqueous solution was kept at a temperature of 45 ° C. for 48 hours to prepare a peroxyniobic acid sol.
ついで、生成したペルオキシニオブ酸ゾルに６Ｎアンモニア水を滴下してそのｐＨを１．５に調整し、限外濾過膜法で精製して塩素イオン等の不純イオンを除去するとともに濃縮し、Ｎb2Ｏ5換算で濃度１０重量％のニオブ系酸化物微粒子(R3)水分散液を調製した。
ついで、ニオブ系酸化物微粒子(R3)水分散液の一部について、分散媒の水をメタノールで置換するとともに濃縮して、固形分濃度２０重量％のニオブ系酸化物微粒子(R3) メタノール分散液を得た。
Next, 6N ammonia water is added dropwise to the generated peroxyniobic acid sol to adjust its pH to 1.5, and it is purified by an ultrafiltration membrane method to remove impurity ions such as chloride ions and concentrate, and Nb 2 An aqueous dispersion of niobium oxide fine particles (R3) having a concentration of 10% by weight in terms of O 5 was prepared.
Next, a part of the aqueous dispersion of niobium oxide fine particles (R3) is substituted with methanol for the water in the dispersion medium and concentrated to give a niobium oxide fine particles (R3) methanol dispersion having a solid concentration of 20% by weight. Got.
本発明の製造方法により得られるニオブ酸化物微粒子分散ゾルは、触媒、触媒担体、さらには機能性セラミックスとして圧電体、半導体、センサー、オプトエレクトロニクス材、誘電体等の他、化粧料成分としても有用である。 The niobium oxide fine particle-dispersed sol obtained by the production method of the present invention is useful as a cosmetic component in addition to a piezoelectric material, a semiconductor, a sensor, an optoelectronic material, a dielectric material, etc. as a catalyst, catalyst carrier, and functional ceramics. It is.
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