JP2006182604A - Method for producing metal oxide sol and metal oxide sol - Google Patents
Method for producing metal oxide sol and metal oxide sol Download PDFInfo
- Publication number
- JP2006182604A JP2006182604A JP2004378396A JP2004378396A JP2006182604A JP 2006182604 A JP2006182604 A JP 2006182604A JP 2004378396 A JP2004378396 A JP 2004378396A JP 2004378396 A JP2004378396 A JP 2004378396A JP 2006182604 A JP2006182604 A JP 2006182604A
- Authority
- JP
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- Prior art keywords
- metal oxide
- oxide sol
- dispersion
- hydroxide gel
- metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 153
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 153
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 108
- 239000002245 particle Substances 0.000 claims abstract description 96
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 28
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 28
- 239000007864 aqueous solution Substances 0.000 claims abstract description 27
- 239000003630 growth substance Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 18
- 230000032683 aging Effects 0.000 claims abstract description 12
- 239000010419 fine particle Substances 0.000 claims abstract description 8
- UNJPQTDTZAKTFK-UHFFFAOYSA-K cerium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ce+3] UNJPQTDTZAKTFK-UHFFFAOYSA-K 0.000 claims abstract description 7
- 229940049676 bismuth hydroxide Drugs 0.000 claims abstract description 6
- TZSXPYWRDWEXHG-UHFFFAOYSA-K bismuth;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Bi+3] TZSXPYWRDWEXHG-UHFFFAOYSA-K 0.000 claims abstract description 6
- 235000014413 iron hydroxide Nutrition 0.000 claims abstract description 6
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims abstract description 6
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 claims abstract description 6
- 150000001785 cerium compounds Chemical class 0.000 claims abstract description 5
- -1 yttrium compound Chemical class 0.000 claims abstract description 5
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 4
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 4
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 4
- 238000010335 hydrothermal treatment Methods 0.000 claims description 26
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 21
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 18
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 18
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 17
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 15
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 15
- 239000002612 dispersion medium Substances 0.000 claims description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 15
- 239000000243 solution Substances 0.000 abstract description 13
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000003513 alkali Substances 0.000 abstract description 5
- 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 32
- 238000000034 method Methods 0.000 description 31
- 239000000126 substance Substances 0.000 description 30
- 239000003957 anion exchange resin Substances 0.000 description 29
- 239000000843 powder Substances 0.000 description 27
- 239000003729 cation exchange resin Substances 0.000 description 25
- 239000000499 gel Substances 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000017 hydrogel Substances 0.000 description 21
- 239000012528 membrane Substances 0.000 description 19
- 238000000108 ultra-filtration Methods 0.000 description 19
- 239000011324 bead Substances 0.000 description 18
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 18
- 239000013078 crystal Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 13
- 238000002242 deionisation method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 238000005259 measurement Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000004576 sand Substances 0.000 description 9
- 239000003456 ion exchange resin Substances 0.000 description 8
- 229920003303 ion-exchange polymer Polymers 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 150000002736 metal compounds Chemical class 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000002425 crystallisation Methods 0.000 description 7
- 230000008025 crystallization Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 229960004106 citric acid Drugs 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000011975 tartaric acid Substances 0.000 description 6
- 235000002906 tartaric acid Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000005341 cation exchange Methods 0.000 description 4
- XMPZTFVPEKAKFH-UHFFFAOYSA-P ceric ammonium nitrate Chemical compound [NH4+].[NH4+].[Ce+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O XMPZTFVPEKAKFH-UHFFFAOYSA-P 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- FMHKPLXYWVCLME-UHFFFAOYSA-N 4-hydroxy-valeric acid Chemical compound CC(O)CCC(O)=O FMHKPLXYWVCLME-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960002303 citric acid monohydrate Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 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
- 230000001678 irradiating effect Effects 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000005304 optical glass Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000001054 red pigment Substances 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 description 2
- RBNPOMFGQQGHHO-UHFFFAOYSA-N -2,3-Dihydroxypropanoic acid Natural products OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 description 1
- VBSTXRUAXCTZBQ-UHFFFAOYSA-N 1-hexyl-4-phenylpiperazine Chemical compound C1CN(CCCCCC)CCN1C1=CC=CC=C1 VBSTXRUAXCTZBQ-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ALRHLSYJTWAHJZ-UHFFFAOYSA-N 3-hydroxypropionic acid Chemical compound OCCC(O)=O ALRHLSYJTWAHJZ-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RBNPOMFGQQGHHO-UWTATZPHSA-N D-glyceric acid Chemical compound OC[C@@H](O)C(O)=O RBNPOMFGQQGHHO-UWTATZPHSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- JACRWUWPXAESPB-QMMMGPOBSA-N Tropic acid Natural products OC[C@H](C(O)=O)C1=CC=CC=C1 JACRWUWPXAESPB-QMMMGPOBSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 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 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 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
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- IINACGXCEZNYTF-UHFFFAOYSA-K trichloroyttrium;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Y+3] IINACGXCEZNYTF-UHFFFAOYSA-K 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Compounds Of Iron (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
Description
本発明は、コロイド領域の安定性に優れた金属酸化物ゾルおよび該金属酸化物ゾルを製造する方法に関する。本発明において金属酸化物ゾルには、酸化セリウムゾル、酸化ビスマスゾル、酸化イットリウムゾル、および酸化鉄ゾルを含む。 The present invention relates to a metal oxide sol excellent in stability of a colloidal region and a method for producing the metal oxide sol. In the present invention, the metal oxide sol includes cerium oxide sol, bismuth oxide sol, yttrium oxide sol, and iron oxide sol.
従来、シリカ、アルミナ、チタニア、ジルコニア、酸化亜鉛、五酸化アンチモン、酸化スズ、酸化セリウム、酸化ビスマス、酸化鉄、酸化イットリウム、シリカ・アルミナ、シリカ・ジルコニアなどの金属酸化物のコロイド粒子が溶媒に分散した金属酸化物ゾルが知られている。
これらの金属酸化物ゾルは屈折率調整材、絶縁材料、導電性材料、顔料、紫外線吸収剤、研磨材、半導体材料、光触媒、イオン交換体、各種フィラー等の材料として多くの分野で用いられている。
具体的には、酸化セリウムゾルはガラス基板、アルミナ基板等の研磨材や、紫外線吸収剤として、酸化ビスマスゾルは液晶の陰イオン交換体（イオンゲッター材）として、また、アンチモンをドープした酸化ビスマスゾルは両イオン交換体（イオンゲッター材）として、酸化鉄ゾルは赤色顔料等として、酸化イットリウムゾルはコンデンサー用誘電体あるいは内部電極、蛍光体、光学ガラス用屈折率調整剤、酸素センサー、セラミックスの焼結助剤、耐火物等として用いられている。
Conventionally, metal oxide colloidal particles such as silica, alumina, titania, zirconia, zinc oxide, antimony pentoxide, tin oxide, cerium oxide, bismuth oxide, iron oxide, yttrium oxide, silica-alumina, silica-zirconia, etc. are used as solvents. Dispersed metal oxide sols are known.
These metal oxide sols are used in many fields as materials such as refractive index adjusting materials, insulating materials, conductive materials, pigments, ultraviolet absorbers, abrasives, semiconductor materials, photocatalysts, ion exchangers, and various fillers. Yes.
Specifically, the cerium oxide sol is a polishing material such as a glass substrate or an alumina substrate, an ultraviolet absorber, the bismuth oxide sol is a liquid crystal anion exchanger (ion getter material), and the antimony-doped bismuth oxide sol is both. As an ion exchanger (ion getter material), iron oxide sol is used as a red pigment, yttrium oxide sol is used as a dielectric for capacitors or internal electrodes, phosphors, refractive index regulators for optical glass, oxygen sensors, ceramics sintering aids It is used as a chemical and refractory.
しかしながら、従来、シリカゾルを除いて均一な粒子径分布で、分散性、安定性等に優れた金属酸化物ゾルを得ることは困難であった。例えば、研磨材として用いた場合はスクラッチが発生したり、充分な研磨速度が得られないことがあった。また、顔料として用いた場合は色相、明度、彩度が不充分であったり、ばらつきの原因となることがあった。
また、従来の無機イオン交換体は粒子径が数１００ｎｍ〜数μオーダーの粉体であり、このような大きな粒子を液晶の配向膜保護層に内填し使用することはできなかった。また、このような大きな粒子を粉砕し微粒子化すると結晶度が低下して著しくイオン交換能が低下したり、粒子径が不均一であるために凝集することがあった。
However, conventionally, it has been difficult to obtain a metal oxide sol having a uniform particle size distribution and excellent dispersibility, stability, etc., excluding silica sol. For example, when used as an abrasive, scratches may occur or a sufficient polishing rate may not be obtained. Further, when used as a pigment, the hue, lightness, and saturation may be insufficient or cause variations.
Further, the conventional inorganic ion exchanger is a powder having a particle diameter of several hundreds nm to several μm, and such large particles cannot be used by being embedded in a protective layer for a liquid crystal alignment film. Further, when such large particles are pulverized to form fine particles, the crystallinity is lowered and the ion exchange ability is remarkably lowered, or the particle diameter is not uniform, and the particles may be aggregated.
本発明は、均一な粒子径分布を有し、安定性に優れた金属酸化物ゾルの製造方法および金属酸化物ゾルを提供することを目的としている。 An object of the present invention is to provide a method for producing a metal oxide sol having a uniform particle size distribution and excellent stability, and a metal oxide sol.
本発明に係る金属酸化物ゾルの製造方法は、下記の工程（ａ）〜（ｅ）からなることを特徴とし、平均粒子径が５〜１５０ｎｍの範囲にある金属酸化物微粒子が分散したゾルを製造するものである。
（ａ）粒子成長調整剤の存在下、セリウム化合物水溶液、ビスマス化合物水溶液、鉄化合物水溶液、イットリウム化合物水溶液のいずれか１種にアルカリ水溶液を加えてセリウム水酸化物ゲルの分散液、ビスマス水酸化物ゲルの分散液、鉄水酸化物ゲルの分散液、イットリウム水酸化物ゲルの分散液のいずれか１種を調製する工程
（ｂ）前記金属水酸化物ゲルの分散液を洗浄する工程
（ｃ）前記洗浄した金属水酸化物ゲルの分散液を熟成する工程
（ｄ）熟成した金属水酸化物ゲルの分散液を洗浄する工程
（ｅ）粒子成長調整剤の存在下、前記洗浄した熟成金属水酸化物ゲルの分散液を水熱処理する工程
The method for producing a metal oxide sol according to the present invention comprises the following steps (a) to (e), and a sol in which metal oxide fine particles having an average particle diameter in the range of 5 to 150 nm are dispersed: To manufacture.
(A) In the presence of a particle growth regulator, an alkaline aqueous solution is added to any one of a cerium compound aqueous solution, a bismuth compound aqueous solution, an iron compound aqueous solution, and an yttrium compound aqueous solution, and a dispersion of cerium hydroxide gel, bismuth hydroxide A step of preparing any one of a gel dispersion, an iron hydroxide gel dispersion, and a yttrium hydroxide gel dispersion (b) a step (c) of washing the metal hydroxide gel dispersion; Aging the washed metal hydroxide gel dispersion (d) washing the aged metal hydroxide gel dispersion (e) washing the aged metal hydroxide in the presence of a particle growth regulator. Hydrothermal treatment of a dispersion of a solid gel
前記工程（ｅ）で得られた金属酸化物微粒子分散ゾルを濃縮または希釈することが好ましい。
前記粒子成長調整剤がカルボン酸またはヒドロキシカルボン酸であることが好ましい。
前記水熱処理を１００〜２５０℃の温度範囲で行うことが好ましい。
前記工程（ｄ）および／または工程（ｅ）を繰り返し行うことが好ましい。
前記工程（ｂ）で金属水酸化物ゲル分散液の電導度を２０μＳ／ｃｍ以下とすることが好ましく、前記工程（ｄ）で金属酸化物分散液の電導度を２００μＳ／ｃｍ以下とすることが好ましい。
前記工程（ｅ）または前記繰り返し実施した工程（ｄ）および／または工程（ｅ）の後、金属酸化物ゾルを乾燥し、３００〜９００℃の範囲で焼成し、得られた微粒子を再び分散媒に分散させることが好ましい。
It is preferable to concentrate or dilute the metal oxide fine particle-dispersed sol obtained in the step (e).
The particle growth regulator is preferably a carboxylic acid or a hydroxycarboxylic acid.
The hydrothermal treatment is preferably performed in a temperature range of 100 to 250 ° C.
It is preferable to repeat the step (d) and / or the step (e).
In the step (b), the conductivity of the metal hydroxide gel dispersion is preferably 20 μS / cm or less, and in the step (d), the conductivity of the metal oxide dispersion is 200 μS / cm or less. preferable.
After the step (e) or the repeated step (d) and / or step (e), the metal oxide sol is dried and fired in the range of 300 to 900 ° C., and the obtained fine particles are dispersed again in the dispersion medium. It is preferable to be dispersed.
本発明に係る金属酸化物ゾルは、平均粒子径（Ｄｎ）が５〜１５０ｎｍの範囲にあり、結晶子径（Ｄｘ）が５〜５０ｎｍの範囲にあることを特徴とする酸化セリウム、酸化ビスマス、酸化鉄、酸化イットリウムから選ばれるいずれか１種の金属酸化物粒子が分散した金属酸化物ゾルである。
前記平均粒子径（Ｄn）と結晶子径（Ｄx）との比（Ｄn／Ｄx）が１〜２の範囲にあることが好ましい。
前記金属酸化物ゾルは、前記本発明に係る金属酸化物ゾルの製造方法によって得られたものであることが好ましい。
The metal oxide sol according to the present invention has an average particle diameter (Dn) in the range of 5 to 150 nm and a crystallite diameter (Dx) in the range of 5 to 50 nm, cerium oxide, bismuth oxide, A metal oxide sol in which any one metal oxide particle selected from iron oxide and yttrium oxide is dispersed.
The ratio (D n / D x ) of the average particle diameter (D n ) to the crystallite diameter (D x ) is preferably in the range of 1 to 2.
The metal oxide sol is preferably obtained by the method for producing a metal oxide sol according to the present invention.
本発明方法によれば、結晶性が高く、均一な粒子径分布を有し、しかもコロイド領域の安定性に優れた金属酸化物ゾルを製造することができる。
また、本発明方法によって得られる酸化セリウムゾルは、ガラス基板、アルミナ基板等の研磨材、紫外線吸収剤等として、酸化ビスマスゾルはイオン交換体として、酸化鉄ゾルは赤色顔料として、酸化イットリウムゾルはコンデンサー用誘電体、光学ガラス用屈折率調整剤、酸素センサー、あるいは内部電極、蛍光体等として好適に用いることができる。
According to the method of the present invention, a metal oxide sol having high crystallinity, uniform particle size distribution, and excellent colloidal region stability can be produced.
In addition, the cerium oxide sol obtained by the method of the present invention is used for abrasives such as glass substrates and alumina substrates, ultraviolet absorbers, etc., bismuth oxide sol as an ion exchanger, iron oxide sol as a red pigment, and yttrium oxide sol as a capacitor. It can be suitably used as a dielectric, a refractive index adjusting agent for optical glass, an oxygen sensor, an internal electrode, a phosphor, or the like.
以下、本発明に係る金属酸化物ゾルの製造方法を工程順に説明する。
工程（ａ）
本発明に用いるセリウム化合物としては、硝酸第二セリウムアンモン、硫酸第二セリウムアンモン等が挙げられる。ビスマス化合物としては、硝酸ビスマス５水和物、塩化ビスマス、オキシ塩化ビスマス等が挙げられる。鉄化合物としては、塩化第二鉄６水和物、硝酸第二鉄、硫酸第二鉄、臭化第二鉄等が挙げられる。また、イットリウム化合物としては、硝酸イットリウム６水和物、塩化イットリウム６水和物等が挙げられる。
先ず、前記金属化合物の水溶液を調製する。このときの各金属化合物水溶液の濃度は、酸化物（ＣeＯ2、Ｂi2Ｏ3、Ｆe2Ｏ3、Ｙ2Ｏ3）に換算して０.１〜５重量％、さらには０.２〜３重量％の範囲にあることが好ましい。該濃度が０.１重量％未満の場合は、収率、生産効率が低く、一方、濃度が５重量％を越えると、得られる金属酸化物ゾルの粒子径が不均一となる傾向がある。
Hereinafter, the method for producing a metal oxide sol according to the present invention will be described in the order of steps.
Step (a)
Examples of the cerium compound used in the present invention include ceric ammonium nitrate and ceric ammonium sulfate. Examples of the bismuth compound include bismuth nitrate pentahydrate, bismuth chloride, and bismuth oxychloride. Examples of the iron compound include ferric chloride hexahydrate, ferric nitrate, ferric sulfate, and ferric bromide. Examples of the yttrium compound include yttrium nitrate hexahydrate and yttrium chloride hexahydrate.
First, an aqueous solution of the metal compound is prepared. At this time, the concentration of each aqueous metal compound solution is 0.1 to 5% by weight in terms of oxides (CeO 2 , Bi 2 O 3 , Fe 2 O 3 , Y 2 O 3 ), and further 0.2 to 0.2%. It is preferably in the range of 3% by weight. When the concentration is less than 0.1% by weight, the yield and production efficiency are low. On the other hand, when the concentration exceeds 5% by weight, the particle diameter of the resulting metal oxide sol tends to be non-uniform.
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、ヒドロキシカルボン酸塩が用いられる。
具体的には、蟻酸、酢酸、蓚酸、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。
As the particle growth regulator used in the present invention, carboxylic acid or carboxylate, hydroxycarboxylic acid, hydroxycarboxylate is used.
Specifically, monocarboxylic acids and monocarboxylic acid salts such as formic acid, acetic acid, succinic acid, acrylic acid (unsaturated carboxylic acid), gluconic acid, malic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid And polyvalent carboxylic acids such as sebacic acid, maleic acid, fumaric acid, and phthalic acid, and polyvalent carboxylic acid salts.
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.
工程（ａ）では、金属化合物水溶液に前記粒子成長調整剤または粒子成長調整剤の水溶液を混合する。このときの金属化合物のモル数（Ｍm）と粒子成長調整剤のモル数（Ｃm）とのモル比（Ｃm）／（Ｍm）は０.０１〜１、さらには０.１〜０.５の範囲にあることが好ましい。
前記モル比が０.０１未満の場合は、粗大な金属水酸化物ヒドロゲルが生成したり、不均一な金属水酸化物ヒドロゲルが生成し、このため、後述する工程（ｃ）で水熱処理して得られる金属酸化物ゾルの粒子径が不均一であったり、平均粒子径が１５０ｎｍ以下とならないことがある。一方、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、平均粒子径を小さく抑制する効果がさらに向上することもなく、加えて経済性が低下する問題がある。
In the step (a), the particle growth regulator or the aqueous solution of the particle growth regulator is mixed with the metal compound aqueous solution. At this time, the molar ratio (Cm) / (Mm) of the number of moles of metal compound (Mm) to the number of moles of grain growth regulator (Cm) is 0.01 to 1, more preferably 0.1 to 0.5. It is preferable to be in the range.
When the molar ratio is less than 0.01, a coarse metal hydroxide hydrogel is formed or a heterogeneous metal hydroxide hydrogel is formed. Therefore, hydrothermal treatment is performed in the step (c) described later. The particle diameter of the resulting metal oxide sol may not be uniform or the average particle diameter may not be 150 nm or less. On the other hand, even when the molar ratio exceeds 1, there is a problem that the particle size is not made uniform or the effect of suppressing the average particle size is not further improved, and the economy is lowered.
ついで、粒子成長調整剤を含む金属化合物水溶液を充分に撹拌しながら、これにアルカリ水溶液を加える。
アルカリ水溶液としては、ＮaＯＨ水溶液、ＫＯＨ水溶液等のアルカリ金属水溶液の他アンモニア水、有機アミン水溶液などの塩基性化合物水溶液を用いることができる。
アルカリ水溶液は金属化合物水溶液のｐＨが３〜１２、さらには４〜１１の範囲となるように添加する。ｐＨが３未満の場合は、金属化合物の加水分解が不充分となったり、後述する工程（ｂ）での洗浄が困難となることがあり、一方、ｐＨが１２を越えても後述する工程（ｂ）での洗浄が困難となることがある。
なお、アルカリ水溶液を添加する際の金属化合物水溶液の温度は特に制限はないが、通常１０〜５０℃、さらには１５〜４０℃の範囲にあることが好ましい。
Next, the aqueous alkali compound solution is added to the aqueous metal compound solution containing the particle growth regulator while sufficiently stirring.
As the aqueous alkali solution, an aqueous alkali compound solution such as an aqueous NaOH solution, an aqueous KOH solution or the like, or an aqueous basic compound solution such as aqueous ammonia or organic amine can be used.
The alkaline aqueous solution is added so that the pH of the aqueous metal compound solution is in the range of 3 to 12, more preferably 4 to 11. When the pH is less than 3, the hydrolysis of the metal compound may be insufficient, or washing in the step (b) described later may be difficult. On the other hand, even if the pH exceeds 12, the step described later ( Cleaning in b) may be difficult.
The temperature of the aqueous metal compound solution when adding the alkaline aqueous solution is not particularly limited, but is usually in the range of 10 to 50 ° C, more preferably 15 to 40 ° C.
工程（ｂ）
ついで、生成した金属水酸化物ゲルの分散液を洗浄する。
洗浄方法としては、陽イオン、陰イオン、あるいは塩を除去できれば特に制限はなく、従来公知の方法を採用することができ、例えば、限外濾過膜法、濾過分離法、遠心分離濾過法、イオン交換樹脂法等が挙げられる。
なかでもイオン交換樹脂法は洗浄後のイオン濃度を効果的に低下させることができるので好ましい。この場合、予め限外濾過膜法で洗浄した後、イオン交換樹脂法で洗浄すると効率的である。イオン交換樹脂としては、両イオン交換樹脂を用いるか、陽イオン交換樹脂と陰イオン交換樹脂とを順次用いることができる。
Step (b)
Next, the produced metal hydroxide gel dispersion is washed.
The washing method is not particularly limited as long as it can remove cations, anions, or salts, and a conventionally known method can be adopted. For example, an ultrafiltration membrane method, a filtration separation method, a centrifugal filtration method, an ion Examples include the exchange resin method.
Among these, the ion exchange resin method is preferable because the ion concentration after washing can be effectively reduced. In this case, it is efficient to wash with an ion exchange resin method after washing with an ultrafiltration membrane method in advance. As the ion exchange resin, both ion exchange resins can be used, or a cation exchange resin and an anion exchange resin can be sequentially used.
洗浄後の電導度は２０μＳ／ｃｍ以下、さらには１０μＳ／ｃｍ以下であることが好ましい。洗浄後の電導度が２０μＳ／ｃｍを越えると、粒子成長調整剤の効果が充分得られないか、得られる金属酸化物ゾルの粒子径分布が不均一となる傾向がある。
また、このときの洗浄金属水酸化物ヒドロゲル分散液のｐＨは概ね５〜１０の範囲である。
なお、洗浄したヒドロゲル分散液には、必要に応じて酸化剤を添加して酸化しても良い。例えば、セリウム化合物を加水分解して得られるヒドロゲルは３価のセリウムが残存することがあり、酸素、オゾン、過酸化水素等の酸化剤で酸化して４価とすることが好ましい。
The conductivity after washing is preferably 20 μS / cm or less, more preferably 10 μS / cm or less. When the electric conductivity after washing exceeds 20 μS / cm, the effect of the particle growth regulator cannot be obtained sufficiently, or the particle size distribution of the obtained metal oxide sol tends to be non-uniform.
Moreover, the pH of the cleaning metal hydroxide hydrogel dispersion at this time is generally in the range of 5 to 10.
The washed hydrogel dispersion may be oxidized by adding an oxidizing agent as necessary. For example, a hydrogel obtained by hydrolyzing a cerium compound may retain trivalent cerium, and is preferably made tetravalent by oxidation with an oxidizing agent such as oxygen, ozone, or hydrogen peroxide.
工程（ｃ）
ついで、前記洗浄した金属水酸化物ゲルの分散液を熟成する。
工程（ｂ）で得た洗浄金属水酸化物ゲル分散液の濃度を酸化物に換算して０.１〜２０重量％、さらには０.２〜１５重量％、特に０.５〜１０重量％の範囲に調整することが好ましい。この濃度が０.１重量％未満の場合は、粒子径分布は均一になるものの収率、生産効率が低下する問題がある。一方、濃度が２０重量％を越えると、得られる金属酸化物ゾルに凝集体が生成することがある。
この濃度調整した金属水酸化物ゲル分散液を充分に撹拌しながら昇温して熟成する。該分散液は、昇温する前または昇温中に超音波を照射するなどして金属水酸化物ゲルの凝集体をできるだけ分散させておくことが好ましい。金属水酸化物ゲルの凝集体を分散させておくと、得られる金属酸化物ゾルに粗大粒子が存在することがなく、また粒子径分布がより均一な金属酸化物ゾルが得られる傾向がある。
Step (c)
Next, the dispersion of the washed metal hydroxide gel is aged.
The concentration of the washed metal hydroxide gel dispersion obtained in step (b) is 0.1 to 20% by weight, further 0.2 to 15% by weight, especially 0.5 to 10% by weight, in terms of oxide. It is preferable to adjust to the range. When this concentration is less than 0.1% by weight, the particle size distribution becomes uniform, but there is a problem that the yield and production efficiency are lowered. On the other hand, if the concentration exceeds 20% by weight, aggregates may be formed in the resulting metal oxide sol.
This concentration-adjusted metal hydroxide gel dispersion is heated and aged with sufficient stirring. In the dispersion, it is preferable to disperse the metal hydroxide gel aggregate as much as possible by irradiating ultrasonic waves before or during the temperature rise. When the metal hydroxide gel aggregates are dispersed, coarse particles are not present in the obtained metal oxide sol, and a metal oxide sol having a more uniform particle size distribution tends to be obtained.
熟成温度は１００〜２５０℃、さらには１２０〜２００℃の範囲にあることが好ましい。熟成温度が１００℃未満の場合は、粒子成長に長時間を要したり、分散が不十分で凝集した粒子が残存したり、所望の粒子径の金属酸化物ゾルを得ることが困難であったり、さらに、結晶化が不十分なために光触媒性能、半導体性能、センサー機能等に優れた金属酸化物ゾルが得られないことがある。熟成温度が２５０℃を越えても粒子成長時間がさらに短くなる効果は小さく、場合によっては粒子径分布が不均一になったり、粗大な粒子が生成することがある。
なお、熟成時間は特に制限はなく、処理温度によって異なるが、通常０.５〜１２時間である。
The aging temperature is preferably 100 to 250 ° C, more preferably 120 to 200 ° C. When the aging temperature is less than 100 ° C., it takes a long time to grow the particles, or the aggregated particles remain insufficiently dispersed, or it is difficult to obtain a metal oxide sol having a desired particle size. Furthermore, since the crystallization is insufficient, a metal oxide sol excellent in photocatalytic performance, semiconductor performance, sensor function and the like may not be obtained. Even if the aging temperature exceeds 250 ° C., the effect of further shortening the particle growth time is small, and in some cases, the particle size distribution may be non-uniform or coarse particles may be generated.
The aging time is not particularly limited and is usually 0.5 to 12 hours, although it varies depending on the treatment temperature.
工程（ｄ）
ついで、工程（ｃ）で得られた熟成した金属水酸化物ゲル分散液を洗浄する。
洗浄方法としては、限外濾過膜法、イオン交換樹脂法等を採用することができる。好適な例として、限外濾過膜法による洗浄の前および／または後にイオン交換樹脂による洗浄を行うこともできる。イオン交換樹脂法は洗浄後のイオン濃度を効果的に低下させることができるので好ましい。
ここで得られる金属酸化物ゲル分散液の電導度は概ね２００μＳ／ｃｍ以下であることが好ましい。また、金属酸化物ゲル分散液のｐＨは概ね６〜９の範囲であることが好ましい。金属酸化物ゲル分散液の電導度およびｐＨが前記範囲にあると金属酸化物ゲル分散液は安定性に優れている。
Step (d)
Next, the aged metal hydroxide gel dispersion obtained in step (c) is washed.
As a cleaning method, an ultrafiltration membrane method, an ion exchange resin method, or the like can be employed. As a preferred example, washing with an ion exchange resin can be performed before and / or after washing by an ultrafiltration membrane method. The ion exchange resin method is preferable because the ion concentration after washing can be effectively reduced.
The conductivity of the metal oxide gel dispersion obtained here is preferably about 200 μS / cm or less. The pH of the metal oxide gel dispersion is preferably in the range of 6-9. When the conductivity and pH of the metal oxide gel dispersion are in the above ranges, the metal oxide gel dispersion is excellent in stability.
工程（ｅ）
ついで、粒子成長調整剤の存在下、前記洗浄した熟成金属水酸化物ゲルの分散液を水熱処理する。
洗浄した熟成金属水酸化物ゲル分散液に粒子成長調整剤または粒子成長調整剤の水溶液を添加する。粒子成長調整剤としては前記したと同様のものを用いることができる。
このときの粒子成長調整剤の添加量は、金属水酸化物ゲル分散液中の換算金属酸化物ＭＯ（ＣeＯ2、Ｂi2Ｏ3、Ｆe2Ｏ3、Ｙ2Ｏ3）のモル数（Ｍmc）と粒子成長調整剤のモル数（Ｃmc）とのモル比Ｃmc／Ｍmcが、０.０５〜０.８、さらには０.１〜０.５の範囲にあることが好ましい。前記モル比Ｃmc／Ｍmcが０.０５未満の場合は、得られる金属酸化物ゾル中に凝集体が生成したり、平均粒子径が１５０ｎｍ以下の金属酸化物ゾルを得るのが困難となることがある。前記モル比Ｃmc／Ｍmcが０.８を越えると、粒子成長あるいは結晶化が大きく抑制されるために所望の粒子径に成長させるのに長時間を要したり、結晶化（結晶子径の成長）が不充分なためか所望の屈折率あるいは所望の粒子径の金属酸化物ゾルを得ることが困難となることがある。
Step (e)
Next, the washed aged metal hydroxide gel dispersion is hydrothermally treated in the presence of a particle growth regulator.
A particle growth regulator or an aqueous solution of a particle growth regulator is added to the washed aged metal hydroxide gel dispersion. As the particle growth regulator, the same ones as described above can be used.
The amount of the particle growth regulator added at this time is the number of moles (Mmc) of the converted metal oxide MO (CeO 2 , Bi 2 O 3 , Fe 2 O 3 , Y 2 O 3 ) in the metal hydroxide gel dispersion. ) And the number of moles (Cmc) of the grain growth regulator is preferably in the range of 0.05 to 0.8, more preferably 0.1 to 0.5. When the molar ratio Cmc / Mmc is less than 0.05, aggregates may be generated in the obtained metal oxide sol, or it may be difficult to obtain a metal oxide sol having an average particle size of 150 nm or less. is there. If the molar ratio Cmc / Mmc exceeds 0.8, particle growth or crystallization is greatly suppressed, so that it takes a long time to grow to a desired particle size or crystallization (growth of crystallite size). ) Is insufficient, it may be difficult to obtain a metal oxide sol having a desired refractive index or a desired particle size.
ついで、粒子成長調整剤を含む金属水酸化物ゲル分散液を充分に撹拌しながら昇温して、水熱処理をする。
水熱処理温度は１００〜２５０℃、さらには１２０〜２００℃の範囲にあることが好ましい。水熱処理温度が１００℃未満の場合は、結晶化および粒子成長に長時間を要したり、屈折率の高い金属酸化物粒子の分散したゾルを得ることが困難となることがある。水熱処理温度が２５０℃を越えても結晶化および粒子成長時間がさらに短くなる効果は小さく、場合によっては粒子径分布が不均一になったり、粗大な粒子が生成することがある。
なお、水熱処理時間は特に制限はなく、処理温度によって異なるが、通常０.５〜１２時間である。
Next, the metal hydroxide gel dispersion containing the particle growth regulator is heated with sufficient stirring and subjected to hydrothermal treatment.
The hydrothermal treatment temperature is preferably in the range of 100 to 250 ° C, more preferably 120 to 200 ° C. When the hydrothermal treatment temperature is less than 100 ° C., it may take a long time for crystallization and particle growth, or it may be difficult to obtain a sol in which metal oxide particles having a high refractive index are dispersed. Even if the hydrothermal treatment temperature exceeds 250 ° C., the effect of further shortening the crystallization and particle growth time is small, and in some cases, the particle size distribution may be non-uniform or coarse particles may be generated.
The hydrothermal treatment time is not particularly limited and is usually 0.5 to 12 hours, although it varies depending on the treatment temperature.
工程（ｅ）で得られた金属酸化物ゾルは、そのまま用いることもできるが、必要に応じて、濃縮または希釈して用いることができる。
濃縮する方法として、従来公知の方法を採用することができ、例えば、ロータリーエバポレーター等で加熱濃縮してもよく、さらには減圧下で加熱濃縮してもよく、限外濾過膜法で濃縮することもできる。
このようにして得られた金属酸化物ゾルの電導度は５００μＳ／ｃｍ以下、さらには３００μＳ／ｃｍ以下であることが好ましい。金属酸化物ゾルの電導度が５００μＳ／ｃｍを越えると、安定性が不充分となることがある。また、このときの金属酸化物ゾルのｐＨは概ね２〜８の範囲である。
Although the metal oxide sol obtained in the step (e) can be used as it is, it can be concentrated or diluted as necessary.
As a method of concentration, a conventionally known method can be employed. For example, it may be concentrated by heating with a rotary evaporator or the like, or further concentrated under reduced pressure, or concentrated by an ultrafiltration membrane method. You can also.
The electric conductivity of the metal oxide sol thus obtained is preferably 500 μS / cm or less, more preferably 300 μS / cm or less. If the conductivity of the metal oxide sol exceeds 500 μS / cm, the stability may be insufficient. Further, the pH of the metal oxide sol at this time is approximately in the range of 2-8.
このときの金属酸化物ゾルの安定なｐＨ範囲はゾルの種類によって異なり、酸化セリウムゾルのｐＨは概ね３〜５の範囲である。酸化ビスマスゾルのｐＨは概ね７〜８の範囲にあることが好ましい。酸化イットリウム、酸化鉄ゾルについては酸性側で粒子の安定性が低下する傾向にあるため、得られたゾルを電導度が２００μＳ／ｃｍ以下となるまで洗浄した後、アンモニア等のアルカリ性物質でｐＨ調整することが好ましい。この場合、電導度が５００を超えることがあり、このときの酸化イットリウム、 酸化鉄ゾルのｐＨは概ね７〜１１の範囲となることがある。
また、得られた金属酸化物ゾルは、使用に際し、必要に応じて電導度、ｐＨを調整して用いることができる。例えば、酸化セリウムゾルは研磨材としても用いられることがあり、この場合、アルカリ側で使用するためにＫＯＨ等のアルカリ性物質でｐＨ調整することができ、この場合の酸化セリウムゾルの電導度は５００μＳ／ｃｍ以下、ｐＨは概ね７〜１１の範囲である。
The stable pH range of the metal oxide sol at this time varies depending on the type of sol, and the pH of the cerium oxide sol is generally in the range of 3 to 5. The pH of the bismuth oxide sol is preferably approximately in the range of 7-8. For yttrium oxide and iron oxide sols, the stability of the particles tends to decrease on the acidic side, so the obtained sol is washed until the conductivity becomes 200 μS / cm or less, and then adjusted with an alkaline substance such as ammonia. It is preferable to do. In this case, the electrical conductivity may exceed 500, and the pH of the yttrium oxide and iron oxide sol at this time may be approximately in the range of 7-11.
In addition, the obtained metal oxide sol can be used by adjusting the conductivity and pH as necessary. For example, cerium oxide sol may be used as an abrasive, and in this case, pH can be adjusted with an alkaline substance such as KOH for use on the alkali side. In this case, the conductivity of cerium oxide sol is 500 μS / cm. Hereinafter, the pH is generally in the range of 7-11.
本発明の金属酸化物ゾルの製造方法では、前記工程（ｅ）の後、工程（ｄ）および／または工程（ｅ）を繰り返し実施することができる。
繰り返し行う工程（ｄ）の洗浄方法と工程（ｅ）の熟成方法とは、前記したと同様に行うことができる。工程（ｄ）を繰り返し行うことによって安定性が向上し、工程（ｅ）を繰り返し行うことによって結晶性の向上、結晶子径の成長効果が得られる。
前記工程（ｄ）および／または（ｅ）工程を繰り返し実施した後の金属酸化物ゾルの電導度は１００μＳ／ｃｍ以下、ｐＨは概ね３〜８の範囲であることが好ましい。金属酸化物ゾルの電導度およびｐＨがこの範囲にあると金属酸化物ゾルはさらに安定性に優れている。
In the method for producing a metal oxide sol of the present invention, the step (d) and / or the step (e) can be repeatedly performed after the step (e).
The washing method in the repeated step (d) and the aging method in the step (e) can be performed in the same manner as described above. By repeating the step (d), the stability is improved, and by repeating the step (e), the crystallinity is improved and the effect of growing the crystallite diameter is obtained.
It is preferable that the electric conductivity of the metal oxide sol after repeating the step (d) and / or the step (e) is 100 μS / cm or less, and the pH is in the range of 3 to 8. When the conductivity and pH of the metal oxide sol are in this range, the metal oxide sol is further excellent in stability.
さらに、本発明の金属酸化物ゾルの製造方法では、前記工程（ｅ）または前記繰り返し実施した工程（ｄ）および／または工程（ｅ）の後、金属酸化物ゾルを乾燥し、金属酸化物ゾルの種類によっても異なるが３００〜９００℃、より好ましくは５００〜８００℃の範囲で焼成し、焼成して得た微粉末を再び分散液に分散させて金属酸化物ゾルとすることができる。 Furthermore, in the method for producing a metal oxide sol of the present invention, the metal oxide sol is dried after the step (e) or the step (d) and / or the step (e), which are repeatedly performed, Although it depends on the type, the powder is calcined in the range of 300 to 900 ° C., more preferably 500 to 800 ° C., and the fine powder obtained by calcining can be dispersed again in the dispersion to obtain a metal oxide sol.
乾燥方法としては従来公知の方法を採用することができ、例えば、ロータリーエバポレーターを用いて、あるいは加熱して濃縮し、通常１００℃〜２００℃で乾燥して分散媒を除去する。
乾燥した金属酸化物微粉末の焼成温度が３００℃未満の場合は、前記工程（ｅ）、必要に応じて工程（ｅ）を繰り返した場合と結晶度があまり変わらない。焼成温度が９００℃を超えると、結晶度は高くなるが粒子径、結晶子径が大きくなり過ぎたり、粒子が凝集することがあり、用途が限定されることがある。例えば、分散安定性、透明性等が低下し、被膜の強度あるいは透明性を必要とする被膜の形成には不向きである。
As a drying method, a conventionally known method can be employed. For example, the solution is concentrated by using a rotary evaporator or by heating, and usually dried at 100 ° C. to 200 ° C. to remove the dispersion medium.
When the firing temperature of the dried metal oxide fine powder is less than 300 ° C., the crystallinity is not much different from that when the step (e) and the step (e) are repeated as necessary. When the firing temperature exceeds 900 ° C., the crystallinity increases, but the particle diameter and crystallite diameter may become too large, and the particles may aggregate, limiting the application. For example, the dispersion stability, transparency and the like are lowered, and it is not suitable for forming a film that requires the strength or transparency of the film.
焼成した金属酸化物微粉末は分散媒に分散させ、必要に応じて分散機にて分散させて、金属酸化物ゾルを得ることができる。
分散媒としては、水および／または有機溶媒を用いることができ、有機溶媒としてはアルコール類、グリコール類、エステル類、エーテル類、ケトン類等が挙げられる。
焼成した金属酸化物微粉末の分散液の濃度は所望の濃度に調整することができるが、通常５〜３０重量％の範囲で用いられる。
また、必要に応じて分散機にて分散させる場合、金属酸化物微粉末の分散液の濃度は、分散機の種類によっても異なるが、５〜３０重量％、さらには１０〜２５重量％の範囲にあることが好ましい。分散液の濃度が５重量％未満の場合は、分散効率が悪くなり、場合によっては未分散の凝集物が残ることがある。一方、分散液の濃度が３０重量％を超えると、分散した粒子が再凝集を起こすことがあり、高分散の金属酸化物ゾルが得られない場合がある。
さらに、得られた金属酸化物ゾルは、必要に応じて前記工程（ｄ）と同様にして洗浄してもよい。
The fired metal oxide fine powder can be dispersed in a dispersion medium and dispersed with a disperser as necessary to obtain a metal oxide sol.
As the dispersion medium, water and / or an organic solvent can be used. Examples of the organic solvent include alcohols, glycols, esters, ethers, and ketones.
Although the density | concentration of the dispersion liquid of the baked metal oxide fine powder can be adjusted to a desired density | concentration, it is normally used in 5-30 weight%.
In addition, when dispersed with a disperser as required, the concentration of the metal oxide fine powder dispersion varies depending on the type of the disperser, but is in the range of 5 to 30% by weight, more preferably 10 to 25% by weight. It is preferable that it exists in. When the concentration of the dispersion is less than 5% by weight, the dispersion efficiency is deteriorated, and in some cases, undispersed aggregates may remain. On the other hand, if the concentration of the dispersion exceeds 30% by weight, the dispersed particles may reaggregate, and a highly dispersed metal oxide sol may not be obtained.
Further, the obtained metal oxide sol may be washed in the same manner as in the step (d) as necessary.
このようにして得られた金属酸化物ゾルの平均粒子径（Ｄn）は５〜１５０ｎｍ、さらには１０〜５０ｎｍの範囲にあることが好ましい。平均粒子径（Ｄn）が５ｎｍ未満の場合は、金属酸化物の結晶化が不充分なためか目的とする機能が発現しない傾向にある。平均粒子径（Ｄn）が１５０ｎｍを越えるものは得られたとしても、金属酸化物ゾルが白濁したり透明性が低く、用途に制限がある。
なお、上記金属酸化物ゾルの平均粒子径（Ｄn）は、数平均粒子径を意味しており、例えば動的光散乱法粒度測定装置（大塚電子（株）PAR-III）によって測定することができる。
The average particle size (D n ) of the metal oxide sol thus obtained is preferably in the range of 5 to 150 nm, more preferably 10 to 50 nm. When the average particle diameter (D n ) is less than 5 nm, the target function tends not to be exhibited because the crystallization of the metal oxide is insufficient. Even if an average particle diameter (D n ) exceeding 150 nm is obtained, the metal oxide sol becomes cloudy or has low transparency, and there is a limit to applications.
The average particle diameter of the metal oxide sol (D n) is meant the number average particle size, for example, be measured by dynamic light scattering particle size measuring apparatus (Otsuka Electronics (Ltd.) PAR-III) Can do.
金属酸化物ゾルの分散質である金属酸化物粒子の結晶子径（Ｄx）は５〜５０ｎｍ、さらには１０〜３０ｎｍの範囲にあることが好ましい。結晶子径（Ｄx）が５ｎｍ未満の場合は、結晶化、屈折率共に不充分であり、また、分散安定性も不充分となることがある。結晶子径（Ｄx）が５０ｎｍを超えるものは、得られるゾルの透明性が低下し、用途に制限がある。 The crystallite diameter (D x ) of the metal oxide particles as the dispersoid of the metal oxide sol is preferably in the range of 5 to 50 nm, more preferably 10 to 30 nm. When the crystallite diameter (D x ) is less than 5 nm, both crystallization and refractive index are insufficient, and dispersion stability may be insufficient. When the crystallite diameter (D x ) exceeds 50 nm, the transparency of the obtained sol is lowered, and the application is limited.
なお、結晶子径（Ｄx）は、Ｘ線回折により、メインピークの半価幅（β）より、Ｓｃｈｅｒｒｅｒの式Ｄ＝λ／βｃｏｓθ（Ｄ：結晶子径（Å）、λ＝Ｘ線波長（Å）、θ＝反射角）より求めることができる。
各金属酸化物ゾルのメインピークのミラー指数（ｈ、ｋ、ｌ）は以下の通りである。
ＣeＯ2：ミラー指数（ｈ＝１、ｋ＝１、ｌ＝１）
Ｂi2Ｏ3：ミラー指数（ｈ＝１、ｋ＝２、ｌ＝０）
Ｆe2Ｏ3：ミラー指数（ｈ＝１、ｋ＝０、ｌ＝４）
Ｙ2Ｏ3：ミラー指数（ｈ＝２、ｋ＝２、ｌ＝２）
The crystallite diameter (D x ) is determined by X-ray diffraction from the half-value width (β) of the main peak. Scherrer's formula D = λ / βcos θ (D: crystallite diameter (Å), λ = X-ray wavelength (Å), θ = reflection angle).
The Miller index (h, k, l) of the main peak of each metal oxide sol is as follows.
CeO 2 : Miller index (h = 1, k = 1, l = 1)
Bi 2 O 3 : Miller index (h = 1, k = 2, l = 0)
Fe 2 O 3 : Miller index (h = 1, k = 0, l = 4)
Y 2 O 3 : Miller index (h = 2, k = 2, l = 2)
本発明で得られた上記水を分散媒とする金属酸化物ゾルは、必要に応じてアルコール、グリコール、エステル、エーテル、ケトン等の有機溶媒に置換して金属酸化物オルガノゾルとすることもできる。このような金属酸化物オルガノゾルは、例えば、樹脂基材あるいは光学材料としての樹脂レンズ基材等のハードコート膜の屈折率調整剤、反射防止膜等に好適に用いることができる。
本発明に係る金属酸化物ゾルの製造方法で得られた金属酸化物ゾルは、標準屈折率液法で測定した屈折率が１.７〜２.２の範囲にある。
The metal oxide sol obtained with the present invention using water as a dispersion medium can be replaced with an organic solvent such as alcohol, glycol, ester, ether, ketone, or the like, if necessary, to obtain a metal oxide organosol. Such a metal oxide organosol can be suitably used, for example, as a refractive index adjusting agent for a hard coat film such as a resin substrate or a resin lens substrate as an optical material, an antireflection film, or the like.
The metal oxide sol obtained by the method for producing a metal oxide sol according to the present invention has a refractive index measured by a standard refractive index liquid method in the range of 1.7 to 2.2.
つぎに、本発明に係る金属酸化物ゾルは、平均粒子径（Ｄn）が５〜１５０ｎｍの範囲にあり、結晶子径（Ｄx）が５〜５０ｎｍの範囲にある金属酸化物粒子が分散したものである。金属酸化物粒子の平均粒子径および結晶子径が前記範囲にあれば、金属酸化物粒子の粒子径分布が均一で、分散安定性に優れ、結晶性が高く高屈折率である。
平均粒子径のより好ましい範囲は１０〜５０ｎｍであり、結晶子径のより好ましい範囲は１０〜３０ｎｍである。
また、前記平均粒子径（Ｄn）と結晶子径（Ｄx）との比（Ｄn／Ｄx）が１〜２、さらには１〜１．６の範囲にあることが好ましい。該比（Ｄn／Ｄx）が１未満となることはなく、比（Ｄn／Ｄx）が２を超えると、粒子の凝集が進んでいることを示し、前記した目的とする性能を充分発揮できないことがある。
Next, in the metal oxide sol according to the present invention, metal oxide particles having an average particle diameter (D n ) in the range of 5 to 150 nm and a crystallite diameter (D x ) in the range of 5 to 50 nm are dispersed. It is a thing. When the average particle diameter and crystallite diameter of the metal oxide particles are in the above ranges, the particle size distribution of the metal oxide particles is uniform, excellent in dispersion stability, high in crystallinity, and high in refractive index.
A more preferable range of the average particle diameter is 10 to 50 nm, and a more preferable range of the crystallite diameter is 10 to 30 nm.
Further, the ratio of the average particle diameter and (D n) and crystallite size (D x) (D n / D x) is 1-2, more preferably in the range of 1 to 1.6. The ratio (D n / D x) is never less than 1, the ratio (D n / D x) is more than 2, indicates that progressed agglomeration of the particles, the performance of the above objects It may not be able to fully demonstrate.
例えば、酸化セリウムゾルの場合は、光学用途において均一な被膜を得ることが困難となることがあり、研磨用途の場合、充分な研磨レートが得られない場合や傷が発生ずることがある。また、酸化ビスマスゾルの場合、液晶配向膜の保護層に内填した場合保護膜に凹凸が発生したり、配向膜を損傷する場合がある。さらに、酸化イットリウムゾルの場合、均一な被膜が得られないため光学用途、その他の用途に制限が生じることがある。酸化鉄ゾルの場合はヘーズが高くなったり、色調が劣る傾向にある。
このような金属酸化物ゾルは、前記した本発明に係る金属酸化物ゾルの製造方法により得られる。
For example, in the case of cerium oxide sol, it may be difficult to obtain a uniform film in optical applications, and in the case of polishing applications, a sufficient polishing rate may not be obtained or scratches may not occur. In the case of bismuth oxide sol, when the protective layer of the liquid crystal alignment film is embedded, the protective film may be uneven, or the alignment film may be damaged. Furthermore, in the case of an yttrium oxide sol, a uniform film cannot be obtained, so that there may be limitations in optical applications and other applications. In the case of iron oxide sol, the haze tends to be high or the color tone tends to be inferior.
Such a metal oxide sol can be obtained by the above-described method for producing a metal oxide sol according to the present invention.
金属酸化物ゾル(1)の調製
純水１７４２ｇにリンゴ酸１．３４ｇ（Ｃｍ＝０．０１）を溶解し、これに硝酸第二セリウムアンモン（Ｃｅ（ＮＯ3）4・２ＮＨ4ＮＯ3）５７．３ｇ（Ｍｍ＝０.１）を溶解させた。（Ｃｍ／Ｍｍ＝０．１）
ついで濃度１０重量％のＫＯＨ水溶液３６５ｇを添加してセリウム水酸化物ヒドロゲル分散液（ＣｅＯ2濃度１重量％）を調製した。このときの分散液のｐＨは１１．７、温度は２８℃であった。
ついで、これを静置、沈降させ上澄み液を除き、純水にて１％濃度に調整した。
ついで、限外ろ過膜で電導度が２８０μＳ／ｃｍになるまで洗浄した。
次に、このセリウム水酸化物ヒドロゲル分散液（ＣｅＯ2濃度１重量％）に陽イオン交換脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。
ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして洗浄したセリウム水酸化物ヒドロゲル分散液（ＣｅＯ2濃度１重量％）の電導度は１μＳ／ｃｍ、ｐＨ＝７であった。
ついでセリウム水酸化物ヒドロゲル分散液に濃度３５重量％の過酸化水素水１．４ｇを加え８０℃で３０分間酸化処理を行った。
Preparation of metal oxide sol (1) 1.34 g of malic acid (Cm = 0.01) was dissolved in 1742 g of pure water, and ceric ammonium nitrate (Ce (NO 3 ) 4 .2NH 4 NO 3 ) 57 was dissolved therein. .3 g (Mm = 0.1) was dissolved. (Cm / Mm = 0.1)
Subsequently, a cerium hydroxide hydrogel dispersion (CeO 2 concentration 1 wt%) was prepared by adding 365 g of a 10 wt% KOH aqueous solution. At this time, the pH of the dispersion was 11.7, and the temperature was 28 ° C.
Subsequently, this was left still and settled, the supernatant was removed, and the concentration was adjusted to 1% with pure water.
Subsequently, it was washed with an ultrafiltration membrane until the electric conductivity reached 280 μS / cm.
Next, 95 g of cation exchange fat (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the cerium hydroxide hydrogel dispersion (CeO 2 concentration 1 wt%) to deionize.
Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The conductivity of the cerium hydroxide hydrogel dispersion thus washed (CeO 2 concentration 1% by weight) was 1 μS / cm and pH = 7.
Next, 1.4 g of hydrogen peroxide solution having a concentration of 35% by weight was added to the cerium hydroxide hydrogel dispersion, followed by oxidation at 80 ° C. for 30 minutes.
ついで純水１７４２ｇを加え、オートクレーブに充填し、２００℃で２時間熟成した。このとき、電導度は２２μＳ／ｃｍ、ｐＨは９であった。
ついで陽イオン交換樹脂（三菱化学（株）：ＳＫ１−ＢＨ）９５ｇを加え脱イオンし、陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンし、陰イオン交換樹脂を分離した。このときの電導度は１μＳ／ｃｍ、ｐＨは８であった。
Next, 1742 g of pure water was added, the autoclave was filled and aged at 200 ° C. for 2 hours. At this time, the conductivity was 22 μS / cm and the pH was 9.
Next, 95 g of a cation exchange resin (Mitsubishi Chemical Corporation: SK1-BH) was added for deionization, and after separating the cation exchange resin, 50 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization. Ionized and separated the anion exchange resin. At this time, the conductivity was 1 μS / cm and the pH was 8.
次に、上記熟成し洗浄した分散液に濃度２重量％のリンゴ酸６７ｇ（Ｃｍ／Ｍｍ＝０．１）を加え、超音波を１時間照射して分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。この時の電導度は３６０μＳ／ｃｍ、ｐＨは２．９であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）９５ｇを加え脱イオンを行い、陰イオン交換樹脂を分離した後、純水３７５０ｇを供給しながら限外濾過膜法で洗浄し、濃縮して濃度１５重量％の金属酸化物ゾル(1)を調製した。
金属酸化物ゾル(1)の電導度は３５μＳ／ｃｍ、ｐＨは３．８であり、微粒子の平均粒子径は２２ｎｍ、結晶子径は１８．５ｎｍ、Ｄｎ／Ｄｘは１．２であった。
また、以下のようにして屈折率を測定し、金属酸化物ゾル(1)の調製条件と測定結果を表１〜３に示した。
Next, 67 g (Cm / Mm = 0.1) of malic acid having a concentration of 2% by weight was added to the above-mentioned aged and washed dispersion, and after ultrasonic treatment for 1 hour, the autoclave was filled. Hydrothermal treatment was performed at 200 ° C. for 2 hours. At this time, the electric conductivity was 360 μS / cm and the pH was 2.9.
95 g of anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) is added to the hydrothermally treated dispersion and deionized to separate the anion exchange resin. Then, 3750 g of pure water is supplied and an ultrafiltration membrane method is used. It was washed and concentrated to prepare a metal oxide sol (1) having a concentration of 15% by weight.
The conductivity of the metal oxide sol (1) was 35 μS / cm, the pH was 3.8, the average particle size of the fine particles was 22 nm, the crystallite size was 18.5 nm, and Dn / Dx was 1.2.
Further, the refractive index was measured as follows, and the preparation conditions and measurement results of the metal oxide sol (1) are shown in Tables 1 to 3.
屈折率の測定
（１）金属酸化物ゾル(1)をエバポレーターに採り、分散媒を蒸発させる。
（２）１２０℃で乾燥し、粉末とする。
（３）屈折率が既知の標準屈折率液を２，３滴ガラス基板状に滴下し、これに金属酸化物粉末を混合する。
（４）上記（３）の操作を種々の標準屈折率液で行い、混合液が透明になったときの標準屈折率液の屈折率を金属酸化物粒子の屈折率とする。
Measurement of Refractive Index (1) The metal oxide sol (1) is taken in an evaporator and the dispersion medium is evaporated.
(2) Dry at 120 ° C. to obtain a powder.
(3) A standard refractive index liquid with a known refractive index is dropped into a glass substrate shape in a few drops, and a metal oxide powder is mixed therewith.
(4) The operation of (3) above is performed with various standard refractive index liquids, and the refractive index of the standard refractive index liquid when the mixed liquid becomes transparent is used as the refractive index of the metal oxide particles.
金属酸化物ゾル(2)の調製
実施例１と同様にして水熱処理し、洗浄した分散液を１００℃で１５時間乾燥した後、８００℃で２時間焼成して酸化セリウムの結晶粉末を得た。
次に、純水２６６ｇに酒石酸４．１ｇを溶解し、酸化セリウム結晶粉末４６．９ｇを添加し、これに濃度４８重量％のＮａＯＨ水溶液４．５ｇを添加した分散液をサンドミルに充填し、ジルコニアビーズ１７１３ｇを加えて６０分間粉砕を行った。
ついでジルコニアビーズを分離し酸化セリウムの分散液を得た。このとき、濃度は１５重量％、電導度は９．５ｍＳ／ｃｍ、ｐＨは１０．６であった。
ついで、酸化セリウムの分散液に陽イオン交換樹脂（三菱化学（株）：ＳＫ１−ＢＨ）９５ｇを加え脱イオンし、陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。さらに、上記陽イオン交換樹脂および陰イオン交換樹脂による脱イオン工程を繰り返し行い、濃度１５重量％の金属酸化物ゾル(2)を調製した。金属酸化物ゾル(2)の電導度は２００μＳ／ｃｍ、ｐＨは６であり、平均粒子径は５０ｎｍ、結晶子径は３３ｎｍ、Ｄｎ／Ｄｘは１．５であった。また、屈折率を測定し、測定結果を表３に示した。
Preparation of Metal Oxide Sol (2) Hydrothermally treated in the same manner as in Example 1. The washed dispersion was dried at 100 ° C. for 15 hours and then calcined at 800 ° C. for 2 hours to obtain a cerium oxide crystal powder. .
Next, 4.1 g of tartaric acid was dissolved in 266 g of pure water, 46.9 g of cerium oxide crystal powder was added, and a dispersion obtained by adding 4.5 g of NaOH aqueous solution having a concentration of 48 wt% was charged in a sand mill, and zirconia was added. 1713 g of beads were added and pulverized for 60 minutes.
Next, zirconia beads were separated to obtain a dispersion of cerium oxide. At this time, the concentration was 15% by weight, the conductivity was 9.5 mS / cm, and the pH was 10.6.
Next, 95 g of a cation exchange resin (Mitsubishi Chemical Corporation: SK1-BH) was added to the cerium oxide dispersion to deionize the cation exchange resin, and then the anion exchange resin (Mitsubishi Chemical Corporation) : SANUPC) was added and deionized. Further, the deionization step using the cation exchange resin and the anion exchange resin was repeated to prepare a metal oxide sol (2) having a concentration of 15% by weight. The conductivity of the metal oxide sol (2) was 200 μS / cm, the pH was 6, the average particle size was 50 nm, the crystallite size was 33 nm, and Dn / Dx was 1.5. Further, the refractive index was measured, and the measurement results are shown in Table 3.
（特徴：実施例１で水熱処理なし）
金属酸化物ゾル(R1)の調製
実施例１と同様に熟成し、イオン交換樹脂で洗浄した後、水熱処理を行わずに限外濾過膜で濃縮して濃度１５重量％の金属酸化物ゾル(R1)を調製した。
金属酸化物ゾル(R1)の電導度は１μＳ／ｃｍ、ｐＨは８であり、平均粒子径は１６ｎｍ、結晶子径は７ｎｍ、Ｄｎ／Ｄｘは２．３であった。また、屈折率を測定し、測定結果を表３に示した。
(Feature: No hydrothermal treatment in Example 1)
Preparation of Metal Oxide Sol (R1) Aged as in Example 1, washed with ion exchange resin, concentrated with an ultrafiltration membrane without hydrothermal treatment, and a metal oxide sol having a concentration of 15% by weight ( R1) was prepared.
The conductivity of the metal oxide sol (R1) was 1 μS / cm, pH was 8, the average particle size was 16 nm, the crystallite size was 7 nm, and Dn / Dx was 2.3. Further, the refractive index was measured, and the measurement results are shown in Table 3.
（特徴：実施例２で水熱処理なし）
金属酸化物ゾル(R2)の調製
実施例１と同様にして熟成、洗浄した分散液（水熱処理を行わなかった。）を１００℃で１５時間乾燥した後、８００℃で２時間焼成して酸化セリウムの結晶粉末を得た。
次に、純水２６６ｇに酒石酸４．１ｇを溶解し、酸化セリウム結晶粉末４６．９ｇを添加し、これに濃度４８重量％のＮａＯＨ水溶液４．５ｇを添加した分散液をサンドミルに充填し、ジルコニアビーズ１７１３ｇを加えて６０分間粉砕を行った。
ついでジルコニアビーズを分離し酸化セリウムの分散液を得た。このとき、濃度は１５重量％、電導度は７ｍＳ／ｃｍ、ｐＨは９．５であった。
ついで、酸化セリウムの分散液に陽イオン交換樹脂（三菱化学（株）：ＳＫ１−ＢＨ）９５ｇを加え脱イオンし、陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。さらに、上記陽イオン交換樹脂および陰イオン交換樹脂による脱イオン工程を繰り返し行い、濃度１５重量％の金属酸化物ゾル(R2)を調製した。金属酸化物ゾル(R2)の電導度は１５０μＳ／ｃｍ、ｐＨは６．５であり、平均粒子径は５８ｎｍ、結晶子径は２９ｎｍ、Ｄｎ／Ｄｘは２．０であった。また、屈折率を測定し、測定結果を表３に示した。
(Feature: No hydrothermal treatment in Example 2)
Preparation of Metal Oxide Sol (R2) A dispersion liquid which was aged and washed in the same manner as in Example 1 (no hydrothermal treatment was performed) was dried at 100 ° C. for 15 hours and then calcined at 800 ° C. for 2 hours to oxidize. A cerium crystal powder was obtained.
Next, 4.1 g of tartaric acid was dissolved in 266 g of pure water, 46.9 g of cerium oxide crystal powder was added, and a dispersion obtained by adding 4.5 g of NaOH aqueous solution having a concentration of 48 wt% was charged in a sand mill, and zirconia was added. 1713 g of beads were added and pulverized for 60 minutes.
Next, zirconia beads were separated to obtain a dispersion of cerium oxide. At this time, the concentration was 15% by weight, the conductivity was 7 mS / cm, and the pH was 9.5.
Next, 95 g of a cation exchange resin (Mitsubishi Chemical Corporation: SK1-BH) was added to the cerium oxide dispersion to deionize the cation exchange resin, and then the anion exchange resin (Mitsubishi Chemical Corporation) : SANUPC) was added and deionized. Further, the deionization step using the cation exchange resin and the anion exchange resin was repeated to prepare a metal oxide sol (R2) having a concentration of 15% by weight. The conductivity of the metal oxide sol (R2) was 150 μS / cm, pH was 6.5, the average particle size was 58 nm, the crystallite size was 29 nm, and Dn / Dx was 2.0. Further, the refractive index was measured, and the measurement results are shown in Table 3.
（特徴：実施例２で熟成、水熱処理なし）
金属酸化物ゾル(R3)の調製
実施例１と同様にして調合、洗浄したヒドロゲル分散液を１００℃で１５時間乾燥した後、８００℃で２時間焼成して酸化セリウムの結晶粉末を得た。
次に、純水２６６ｇに酒石酸４．１ｇを溶解し、酸化セリウム結晶粉末４６．９ｇを添加し、これに濃度４８重量％のＮａＯＨ水溶液４．５ｇを添加した分散液をサンドミルに充填し、ジルコニアビーズ１７１３ｇを加えて６０分間粉砕を行った。
ついでジルコニアビーズを分離し酸化セリウムの分散液を得た。このとき、濃度は１５重量％、電導度は６ｍＳ／ｃｍ、ｐＨは８．９であった。
ついで、酸化セリウムの分散液に陽イオン交換樹脂（三菱化学（株）：ＳＫ１−ＢＨ）９５ｇを加え脱イオンし、陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。さらに、上記陽イオン交換樹脂および陰イオン交換樹脂による脱イオン工程を繰り返し行い、濃度１５重量％の金属酸化物ゾル(R3)を調製した。金属酸化物ゾル(R3)の電導度は１００μＳ／ｃｍ、ｐＨは６．６であり、平均粒子径は７８ｎｍ、結晶子径は２８ｎｍ、Ｄｎ／Ｄｘは２．８であった。また、屈折率を測定し、測定結果を表３に示した。
(Feature: Aging in Example 2, no hydrothermal treatment)
Preparation of Metal Oxide Sol (R3) A hydrogel dispersion prepared and washed in the same manner as in Example 1 was dried at 100 ° C. for 15 hours and then calcined at 800 ° C. for 2 hours to obtain a cerium oxide crystal powder.
Next, 4.1 g of tartaric acid was dissolved in 266 g of pure water, 46.9 g of cerium oxide crystal powder was added, and a dispersion obtained by adding 4.5 g of NaOH aqueous solution having a concentration of 48 wt% was charged in a sand mill, and zirconia was added. 1713 g of beads were added and pulverized for 60 minutes.
Next, zirconia beads were separated to obtain a dispersion of cerium oxide. At this time, the concentration was 15% by weight, the conductivity was 6 mS / cm, and the pH was 8.9.
Next, 95 g of a cation exchange resin (Mitsubishi Chemical Corporation: SK1-BH) was added to the cerium oxide dispersion to deionize the cation exchange resin, and then the anion exchange resin (Mitsubishi Chemical Corporation) : SANUPC) was added and deionized. Further, the deionization step using the cation exchange resin and the anion exchange resin was repeated to prepare a metal oxide sol (R3) having a concentration of 15% by weight. The conductivity of the metal oxide sol (R3) was 100 μS / cm, pH was 6.6, the average particle size was 78 nm, the crystallite size was 28 nm, and Dn / Dx was 2.8. Further, the refractive index was measured, and the measurement results are shown in Table 3.
金属酸化物ゾル(3)の調製
純水４４９３ｇに酒石酸３．２ｇ（Ｃｍ＝０．０２１）を溶解し、これに硝酸ビスマス５水和物（Ｂｉ（ＮＯ3）3・５Ｈ2Ｏ）１０４．１５ｇ（Ｍｍ＝０．１０７）を添加した。（Ｃｍ／Ｍｍ＝０．２）
ついで濃度６１重量％の硝酸４００ｇを添加して硝酸ビスマスを溶解させた後、濃度１０重量％のＫＯＨ水溶液２６３６ｇを添加してビスマス水酸化物ヒドロゲル分散液（Ｂｉ2Ｏ3濃度１重量％）を調製した。このときの分散液のｐＨは１２．３、温度は３０℃であった。ついで、これを静置、沈降させ上澄み液を除き、純水にて濃度を１重量％に調整し、限外ろ過膜で電導度が２８０μＳ／ｃｍになるまで洗浄した。
次に、ビスマス水酸化物ヒドロゲル分散液（Ｂｉ2Ｏ3濃度１重量％）に陽イオン交換脂（三菱化学（株）：ＳＫ１−ＢＨ）１５０ｇを加え脱イオンし、陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１００ｇを加え脱イオンし、ついで陰イオン交換樹脂を分離した後、陽イオン交換樹脂（三菱化学（株）：ＳＫ１−ＢＨ）９５ｇを加え脱イオンし、陽イオン交換樹脂を分離した。
このようにして得られた洗浄ビスマス水酸化物ヒドロゲル分散液（Ｂｉ2Ｏ3濃度１重量％）の電導度は１５μＳ／ｃｍ、ｐＨ＝９．３であった。
Preparation of Metal Oxide Sol (3) 3.2 g (Cm = 0.021) of tartaric acid was dissolved in 4493 g of pure water, and bismuth nitrate pentahydrate (Bi (NO 3 ) 3 .5H 2 O) 104. 15 g (Mm = 0.107) was added. (Cm / Mm = 0.2)
Next, 400 g of nitric acid having a concentration of 61% by weight was added to dissolve bismuth nitrate, and 2636 g of a 10% by weight aqueous KOH solution was added to prepare a bismuth hydroxide hydrogel dispersion (Bi 2 O 3 concentration 1% by weight). Prepared. At this time, the pH of the dispersion was 12.3 and the temperature was 30 ° C. Subsequently, this was allowed to stand and settle, the supernatant was removed, the concentration was adjusted to 1% by weight with pure water, and the mixture was washed with an ultrafiltration membrane until the conductivity reached 280 μS / cm.
Next, 150 g of cation exchange fat (Mitsubishi Chemical Corporation: SK1-BH) was added to the bismuth hydroxide hydrogel dispersion (Bi 2 O 3 concentration 1% by weight) and deionized to separate the cation exchange resin. Thereafter, 100 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added for deionization, and after the anion exchange resin was separated, 95 g of a cation exchange resin (Mitsubishi Chemical Corporation: SK1-BH) was added. In addition, deionization was performed to separate the cation exchange resin.
The conductivity of the thus obtained washed bismuth hydroxide hydrogel dispersion (Bi 2 O 3 concentration 1% by weight) was 15 μS / cm and pH = 9.3.
ついでオートクレーブに充填し、１５０℃で２時間熟成した後、陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）１００ｇを加え脱イオンし、陰イオン交換樹脂を分離後、陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）８０ｇを加え脱イオンし、陽イオン交換樹脂を分離した。このときの電導度は２．３μＳ／ｃｍ、ｐＨは９であった。
次に、上記熟成し洗浄した分散液に濃度２重量％の酒石酸８０ｇ（Ｃｍ／Ｍｍ＝０．１）を加え、超音波を１時間照射して分散処理をした後、オートクレーブに充填し、１５０℃で２時間水熱処理をした。この時の電導度は５００μＳ／ｃｍ、ｐＨは２．６であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）９５ｇを加え脱イオンを行い、陰イオン交換樹脂を分離後、陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）８０ｇを加え脱イオンし、陽イオン交換樹脂を分離した。このときの電導度は５０μＳ／ｃｍ、ｐＨは８であった。
ついで純水４５００ｇを供給しながら限外濾過膜法で洗浄し、その後濃縮し、濃度１５重量％の金属酸化物ゾル(3)を調製した。
金属酸化物ゾル(3)の電導度は３５μＳ／ｃｍ、ｐＨは７．７であり、平均粒子径は２２ｎｍ、結晶子径は１２ｎｍ、Ｄｎ／Ｄｘは１．８であった。
Next, after filling in an autoclave and aging at 150 ° C. for 2 hours, 100 g of anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to deionize, and after separating the anion exchange resin, the cation exchange resin (Mitsubishi) 80 g of Chemical Co., Ltd. (SK1-BH) was added and deionized to separate the cation exchange resin. At this time, the electric conductivity was 2.3 μS / cm and the pH was 9.
Next, 80 g of tartaric acid having a concentration of 2 wt% (Cm / Mm = 0.1) is added to the above-mentioned dispersion that has been aged and washed, and subjected to dispersion treatment by irradiating with ultrasonic waves for 1 hour, and then filled into an autoclave. Hydrothermal treatment was carried out at 2 ° C. for 2 hours. The electric conductivity at this time was 500 μS / cm, and the pH was 2.6.
95 g of an anion exchange resin (Mitsubishi Chemical Corp .: SANUPC) is added to the hydrothermally treated dispersion to perform deionization, and after the anion exchange resin is separated, a cation exchange resin (Mitsubishi Chemical Corp .: SK1- BH) 80 g was added and deionized to separate the cation exchange resin. At this time, the conductivity was 50 μS / cm and the pH was 8.
Next, 4500 g of pure water was supplied and washed with an ultrafiltration membrane method, followed by concentration to prepare a metal oxide sol (3) having a concentration of 15% by weight.
The conductivity of the metal oxide sol (3) was 35 μS / cm, pH was 7.7, the average particle size was 22 nm, the crystallite size was 12 nm, and Dn / Dx was 1.8.
金属酸化物ゾル(4)の調製
実施例３と同様にして水熱処理し、洗浄した分散液を１００℃で１５時間乾燥した後、６００℃で２時間焼成して酸化ビスマスの結晶粉末を得た。この酸化ビスマス結晶粉末１２ｇをエタノール２１６ｇに添加した分散液をサンドミルに充填し、ガラスビーズ６２８ｇを加えて２１０分間粉砕を行った。
ついでガラスビーズを分離し、ロータリーエバポレーターにて１５重量％まで濃縮して金属酸化物ゾル(4)を調製した。金属酸化物ゾル(4)中の微粒子の平均粒子径は５６ｎｍ、結晶子径は２８ｎｍ、Ｄｎ／Ｄｘは２．０であった。
Preparation of Metal Oxide Sol (4) Hydrothermally treated in the same manner as in Example 3. The washed dispersion was dried at 100 ° C. for 15 hours and then calcined at 600 ° C. for 2 hours to obtain bismuth oxide crystal powder. . A dispersion obtained by adding 12 g of this bismuth oxide crystal powder to 216 g of ethanol was filled in a sand mill, and 628 g of glass beads were added and pulverized for 210 minutes.
Next, the glass beads were separated and concentrated to 15% by weight with a rotary evaporator to prepare a metal oxide sol (4). The average particle size of the fine particles in the metal oxide sol (4) was 56 nm, the crystallite size was 28 nm, and Dn / Dx was 2.0.
（特徴：実施例３で水熱処理なし）
金属酸化物ゾル(R4)の調製
実施例３と同様に熟成、洗浄した分散液を限外濾過膜法で濃縮し濃度１５重量％の金属酸化物ゾル(R4)を調製した。
金属酸化物ゾル(R4)の電導度は３０μＳ／ｃｍ、ｐＨは８．６であり、平均粒子径は３６ｎｍ、結晶子径は１５ｎｍ、Ｄｎ／Ｄｘは２．４であった。
(Feature: No hydrothermal treatment in Example 3)
Preparation of Metal Oxide Sol (R4) A dispersion aged and washed in the same manner as in Example 3 was concentrated by an ultrafiltration membrane method to prepare a metal oxide sol (R4) having a concentration of 15% by weight.
The conductivity of the metal oxide sol (R4) was 30 μS / cm, pH was 8.6, the average particle size was 36 nm, the crystallite size was 15 nm, and Dn / Dx was 2.4.
（特徴：実施例４で水熱処理なし）
金属酸化物ゾル(R5)の調製
実施例３と同様にして熟成し、洗浄した分散液を１００℃で１５時間乾燥した後、６００℃で２時間焼成して酸化ビスマスの結晶粉末を得た。
次に、エタノール２１６ｇに濃度１重量％のアンチモン酸１２ｇを添加し、これに酸化ビスマス結晶粉末１２ｇを添加した分散液をサンドミルに充填し、ガラスビーズ６２８ｇを加えて２１０分間粉砕を行った。
ついでガラスビーズを分離し、ロータリーエバポレーターにて１５重量％まで濃縮して金属酸化物ゾル(R5)を調製した。金属酸化物ゾル(R5)の平均粒子径は４２ｎｍ、結晶子径は１９ｎｍ、Ｄｎ／Ｄｘは２．２であった。
(Feature: No hydrothermal treatment in Example 4)
Preparation of Metal Oxide Sol (R5) Aged and washed in the same manner as in Example 3, the dried dispersion was dried at 100 ° C. for 15 hours and then calcined at 600 ° C. for 2 hours to obtain bismuth oxide crystal powder.
Next, 12 g of antimonic acid having a concentration of 1% by weight was added to 216 g of ethanol, and a dispersion obtained by adding 12 g of bismuth oxide crystal powder to this was filled in a sand mill, and 628 g of glass beads were added and pulverized for 210 minutes.
Subsequently, the glass beads were separated and concentrated to 15% by weight with a rotary evaporator to prepare a metal oxide sol (R5). The average particle size of the metal oxide sol (R5) was 42 nm, the crystallite size was 19 nm, and Dn / Dx was 2.2.
（特徴：実施例４で熟成、水熱処理なし）
金属酸化物ゾル(R6)の調製
実施例４と同様にして調合、洗浄したヒドロゲル分散液を１００℃で１５時間乾燥した後、６００℃で２時間焼成して酸化ビスマスの結晶粉末を得た。
次に、エタノール２１６ｇに濃度１重量％のアンチモン酸１２ｇを添加し、これに酸化ビスマス結晶粉末１２ｇを添加した分散液をサンドミルに充填し、ガラスビーズ６２８ｇを加えて２１０分間粉砕を行った。
ついでガラスビーズを分離し、ロータリーエバポレーターにて１５重量％まで濃縮して金属酸化物ゾル(R6)を調製した。金属酸化物ゾル(R6)の平均粒子径は４５ｎｍ、結晶子径は１６ｎｍ、Ｄｎ／Ｄｘは２．８であった。
(Feature: Aging in Example 4, no hydrothermal treatment)
Preparation of Metal Oxide Sol (R6) A hydrogel dispersion prepared and washed in the same manner as in Example 4 was dried at 100 ° C. for 15 hours and then calcined at 600 ° C. for 2 hours to obtain a bismuth oxide crystal powder.
Next, 12 g of antimonic acid having a concentration of 1% by weight was added to 216 g of ethanol, and a dispersion obtained by adding 12 g of bismuth oxide crystal powder to this was filled in a sand mill, and 628 g of glass beads were added and pulverized for 210 minutes.
Next, the glass beads were separated and concentrated to 15% by weight with a rotary evaporator to prepare a metal oxide sol (R6). The metal oxide sol (R6) had an average particle size of 45 nm, a crystallite size of 16 nm, and Dn / Dx of 2.8.
金属酸化物ゾル(５)の調製
純水２８４３ｇにクエン酸一水和物５．４８ｇ（Ｃｍ＝０．０２６）を溶解し、これに硝酸イットリウム６水和物（Ｙ（ＮＯ3）3・６Ｈ2Ｏ）１００ｇ（Ｍｍ＝０．２６）を溶解させた（Ｃｍ／Ｍｍ＝０．１）。
ついで濃度１０重量％のＫＯＨ水溶液４６５ｇを添加してイットリウム水酸化物ヒドロゲル分散液（Ｙ2Ｏ3濃度２重量％）を調製した。このときの分散液のｐＨは１２．０、温度は２０℃であった。
ついで、これを静置、沈降させ上澄み液を除き、純水にて２％濃度に調整した。
次に、このイットリウム水酸化物ヒドロゲル分散液（Ｙ2Ｏ3濃度２重量％）に陽イオン交換脂（三菱化学（株）製：ＳＫ１−ＢＨ）９５ｇを加え脱イオンした。
ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）：ＳＡＮＵＰＣ）５０ｇを加え脱イオンした。このようにして洗浄したイットリウム水酸化物ヒドロゲル分散液（Ｙ2Ｏ3濃度２重量％）の電導度は７．５μＳ／ｃｍ、ｐＨ＝１０であった。
Preparation of metal oxide sol (5) 5.48 g (Cm = 0.026) of citric acid monohydrate was dissolved in 2843 g of pure water, and yttrium nitrate hexahydrate (Y (NO 3 ) 3 · 6H) was dissolved therein. 2 O) 100 g (Mm = 0.26) was dissolved (Cm / Mm = 0. 1).
Then, 465 g of a 10 wt% KOH aqueous solution was added to prepare a yttrium hydroxide hydrogel dispersion (Y 2 O 3 concentration 2 wt%). At this time, the pH of the dispersion was 12.0, and the temperature was 20 ° C.
Subsequently, this was left still and settled, the supernatant was removed, and the concentration was adjusted to 2% with pure water.
Next, 95 g of cation exchange fat (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the yttrium hydroxide hydrogel dispersion (Y 2 O 3 concentration 2% by weight) to deionize.
Next, after the cation exchange resin was separated, 50 g of an anion exchange resin (Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The conductivity of the yttrium hydroxide hydrogel dispersion (Y 2 O 3 concentration 2% by weight) thus washed was 7.5 μS / cm and pH = 10.
ついでオートクレーブに充填し、２００℃で２時間熟成した。このとき、電導度は４７．５μＳ／ｃｍ、ｐＨは７．５であった。
ついで陰イオン交換樹脂（三菱化学（株）：ＳＡＮＵＰＣ）５０ｇを加え脱イオンし、陰イオン交換樹脂を分離した。
このときの電導度は７．６μＳ／ｃｍ、ｐＨは９であった。
次に、上記熟成し洗浄した分散液に濃度２重量％のクエン酸２７４ｇ（Ｃｍ／Ｍｍ＝０．１）を加え、超音波を１時間照射して分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。この時の電導度は５００μＳ／ｃｍ、ｐＨは２．６であった。水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）９５ｇを加え脱イオンを行い、陰イオン交換樹脂を分離した後、陽イオン交換樹脂（三菱化学（株）：ＳＫ１−ＢＨ）５０ｇを加え脱イオンし、限外濾過膜法で濃縮して濃度１０重量％の金属酸化物ゾル(5)を調製した。金属酸化物ゾル(5)の電導度は４５μＳ／ｃｍ、ｐＨは８であり、平均粒子径は１８ｎｍ、結晶子径は１２ｎｍ、Ｄｎ／Ｄｘは１．５であった。また、屈折率を測定し、測定結果を表３に示した。
Next, the autoclave was filled and aged at 200 ° C. for 2 hours. At this time, the conductivity was 47.5 μS / cm and the pH was 7.5.
Subsequently, 50 g of an anion exchange resin (Mitsubishi Chemical Corporation: SANUPC) was added and deionized to separate the anion exchange resin.
At this time, the conductivity was 7.6 μS / cm and the pH was 9.
Next, 274 g of citric acid having a concentration of 2% by weight (Cm / Mm = 0.1) was added to the above ripened and washed dispersion, and after ultrasonic treatment for 1 hour, the dispersion was treated, and then filled into an autoclave. Hydrothermal treatment was performed at 200 ° C. for 2 hours. The electric conductivity at this time was 500 μS / cm, and the pH was 2.6. 95 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) is added to the hydrothermally treated dispersion to perform deionization, and the anion exchange resin is separated, and then the cation exchange resin (Mitsubishi Chemical Corporation: SK1- BH) 50 g was added, deionized, and concentrated by an ultrafiltration membrane method to prepare a metal oxide sol (5) having a concentration of 10% by weight. The conductivity of the metal oxide sol (5) was 45 μS / cm, the pH was 8, the average particle size was 18 nm, the crystallite size was 12 nm, and Dn / Dx was 1.5. Further, the refractive index was measured, and the measurement results are shown in Table 3.
金属酸化物ゾル(6)の調製
実施例５と同様にして水熱処理し、洗浄した分散液を１００℃で１５時間乾燥した後、７００℃で２時間焼成して酸化イットリウムの結晶粉末を得た。
次に、純水４０９ｇにクエン酸４．２ｇを溶解し、酸化イットリウム結晶粉末２３ｇを添加し、これに濃度２８．８重量％のアンモニア１８ｇを添加した分散液をサンドミルに充填し、ガラスビーズ９９９ｇを加えて１８０分間粉砕を行った。
ついでガラスビーズを分離し酸化イットリウムの分散液を得た。このとき、濃度は５重量％、電導度は０．９５ｍＳ／ｃｍ、ｐＨは１１．５であった。
ついで濃度２８．８重量％のアンモニア水にてｐＨを１０に調整した水３６００ｇを供給しながら限外濾過膜法で洗浄し、その後濃縮し濃度１０重量％の金属酸化物ゾル(6)を調整した。金属酸化物ゾル(6)の電導度は０．５ｍＳ／ｃｍ、ｐＨは１０であり、平均粒子径は２２ｎｍ、結晶子径は１８ｎｍ、Ｄｎ／Ｄｘは１．２であった。また、屈折率を測定し、測定結果を表３に示した。
Preparation of Metal Oxide Sol (6) Hydrothermally treated in the same manner as in Example 5. The washed dispersion was dried at 100 ° C. for 15 hours and then calcined at 700 ° C. for 2 hours to obtain yttrium oxide crystal powder. .
Next, 4.2 g of citric acid was dissolved in 409 g of pure water, 23 g of yttrium oxide crystal powder was added, and a dispersion obtained by adding 18 g of ammonia having a concentration of 28.8 wt% was charged into a sand mill, and 999 g of glass beads were added. And pulverized for 180 minutes.
Then, the glass beads were separated to obtain a dispersion of yttrium oxide. At this time, the concentration was 5% by weight, the conductivity was 0.95 mS / cm, and the pH was 11.5.
Next, it was washed by ultrafiltration membrane method while supplying 3600 g of water adjusted to pH 10 with ammonia water having a concentration of 28.8 wt%, and then concentrated to prepare a metal oxide sol (6) having a concentration of 10 wt%. did. The electric conductivity of the metal oxide sol (6) was 0.5 mS / cm, pH was 10, the average particle size was 22 nm, the crystallite size was 18 nm, and Dn / Dx was 1.2. Further, the refractive index was measured, and the measurement results are shown in Table 3.
（特徴：実施例５で水熱処理なし）
金属酸化物ゾル(R7)の調製
実施例５と同様に熟成、洗浄し、限外濾過膜法で濃縮して濃度１０重量％の金属酸化物ゾル(R7)を調製した。金属酸化物ゾル(R7)の電導度は３０μＳ／ｃｍ、ｐＨは９、であり、平均粒子径は１７ｎｍ、結晶子径は７ｎｍ、Ｄｎ／Ｄｘは２．４であった。また、屈折率を測定し、測定結果を表３に示した。
(Feature: No hydrothermal treatment in Example 5)
Preparation of Metal Oxide Sol (R7) Aged, washed and concentrated by the ultrafiltration membrane method in the same manner as in Example 5 to prepare a metal oxide sol (R7) having a concentration of 10% by weight. The conductivity of the metal oxide sol (R7) was 30 μS / cm, the pH was 9, the average particle size was 17 nm, the crystallite size was 7 nm, and Dn / Dx was 2.4. Further, the refractive index was measured, and the measurement results are shown in Table 3.
（特徴：実施例６で水熱処理なし）
金属酸化物ゾル(R8)の調製
実施例６と同様にして熟成、洗浄した分散液を１００℃で１５時間乾燥した後、７００℃で２時間焼成して酸化イットリウムの結晶粉末を得た。
次に、純水４０９ｇにクエン酸４．２ｇを溶解し、酸化イットリウム結晶粉末２３ｇを添加し、これに濃度２８．８重量％のアンモニア１８ｇを添加した分散液をサンドミルに充填し、ガラスビーズ９９９ｇを加えて１８０分間粉砕を行った。
ついでガラスビーズを分離し酸化イットリウムの分散液を得た。このときの濃度は５重量％、電導度は０．６３ｍＳ／ｃｍ、ｐＨは１１であった。
ついで濃度２８．８重量％のアンモニアにてｐＨを１０に調整した純水３６００ｇを供給しながら限外濾過膜法で洗浄し、その後濃縮して濃度１０重量％の金属酸化物ゾル(R8)を調製した。金属酸化物ゾル(R8)の電導度は０．４ｍＳ／ｃｍ、ｐＨは１０であり、平均粒子径は４２ｎｍ、結晶子径は１９ｎｍ、Ｄｎ／Ｄｘは２．２であった。また、屈折率を測定し、測定結果を表３に示した。
(Feature: No hydrothermal treatment in Example 6)
Preparation of Metal Oxide Sol (R8) A dispersion which was aged and washed in the same manner as in Example 6 was dried at 100 ° C. for 15 hours and then calcined at 700 ° C. for 2 hours to obtain a crystalline powder of yttrium oxide.
Next, 4.2 g of citric acid was dissolved in 409 g of pure water, 23 g of yttrium oxide crystal powder was added, and a dispersion obtained by adding 18 g of ammonia having a concentration of 28.8 wt% was charged into a sand mill, and 999 g of glass beads were added. And pulverized for 180 minutes.
Then, the glass beads were separated to obtain a dispersion of yttrium oxide. The concentration at this time was 5% by weight, the conductivity was 0.63 mS / cm, and the pH was 11.
Next, 3600 g of pure water whose pH was adjusted to 10 with ammonia having a concentration of 28.8% by weight was supplied, washed with an ultrafiltration membrane method, and then concentrated to obtain a metal oxide sol (R8) having a concentration of 10% by weight. Prepared. The conductivity of the metal oxide sol (R8) was 0.4 mS / cm, the pH was 10, the average particle size was 42 nm, the crystallite size was 19 nm, and Dn / Dx was 2.2. Further, the refractive index was measured, and the measurement results are shown in Table 3.
（特徴：実施例６で熟成、水熱処理なし）
金属酸化物ゾル(R9)の調製
実施例６と同様にして調合、洗浄したヒドロゲル分散液を１００℃で１５時間乾燥した後、７００℃で２時間焼成して酸化イットリウムの結晶粉末を得た。
次に、純水４０９ｇにクエン酸４．２ｇを溶解し、酸化イットリウム結晶粉末２３ｇを添加し、これに濃度２８．８重量％のアンモニア１８ｇを添加した分散液をサンドミルに充填し、ガラスビーズ９９９ｇを加えて１８０分間粉砕を行った。
ついでガラスビーズを分離し酸化イットリウムの分散液を得た。このときの濃度は５重量％、電導度は０．５ｍＳ／ｃｍ、ｐＨは１０．５であった。
ついで濃度２８．８重量％のアンモニアにてｐＨを１０に調整した純水３６００ｇを供給しながら限外濾過膜法で洗浄し、その後濃縮し濃度１０重量％の金属酸化物ゾル(R9)を調製した。金属酸化物ゾル(R9)の電導度は０．４２ｍＳ／ｃｍ、ｐＨは１０であり、平均粒子径は４０ｎｍ、結晶子径は１５ｎｍ、Ｄｎ／Ｄｘは２．７であった。また、屈折率を測定し、測定結果を表３に示した。
(Feature: Aging in Example 6, no hydrothermal treatment)
Preparation of Metal Oxide Sol (R9) A hydrogel dispersion prepared and washed in the same manner as in Example 6 was dried at 100 ° C. for 15 hours and then calcined at 700 ° C. for 2 hours to obtain a crystalline powder of yttrium oxide.
Next, 4.2 g of citric acid was dissolved in 409 g of pure water, 23 g of yttrium oxide crystal powder was added, and a dispersion obtained by adding 18 g of ammonia having a concentration of 28.8 wt% was charged into a sand mill, and 999 g of glass beads were added. And pulverized for 180 minutes.
Then, the glass beads were separated to obtain a dispersion of yttrium oxide. The concentration at this time was 5% by weight, the conductivity was 0.5 mS / cm, and the pH was 10.5.
Next, 3600 g of pure water whose pH was adjusted to 10 with ammonia having a concentration of 28.8% by weight was supplied, washed with an ultrafiltration membrane method, and then concentrated to prepare a metal oxide sol (R9) having a concentration of 10% by weight. did. The conductivity of the metal oxide sol (R9) was 0.42 mS / cm, pH was 10, the average particle size was 40 nm, the crystallite size was 15 nm, and Dn / Dx was 2.7. Further, the refractive index was measured, and the measurement results are shown in Table 3.
金属酸化物ゾル(7)の調製
純水２４５８ｇにクエン酸一水和物４．９７ｇ（Ｃｍ＝０．０２４）を溶解し、これに塩化第二鉄６水和物（ＦｅＣｌ3・６Ｈ2０）６４ｇ（Ｍｍ＝０.２４）を溶解させた。（Ｃｍ／Ｍｍ＝０．１）
ついで濃度１０重量％のＫＯＨ水溶液４３４ｇを添加して鉄水酸化物ヒドロゲル分散液（Ｆｅ2Ｏ3濃度１．５重量％）を調製した。このときの分散液のｐＨは１０．６、温度は２８℃であった。
ついで、これを静置、沈降させ上澄み液を除き、純水にて１．５％濃度に調整した。
ついで、限外ろ過膜で電導度が２８０μＳ／ｃｍになるまで洗浄した。
次に、この鉄水酸化物ヒドロゲル分散液（Ｆｅ2Ｏ3濃度１．５重量％）に陽イオン交換脂（三菱化学（株）製：ＳＫ１−ＢＨ）１５０ｇを加え脱イオンした。ついで陽イオン交換樹脂を分離した後、陰イオン交換樹脂（三菱化学（株）：ＳＡＮＵＰＣ）１００ｇを加え脱イオンした。このようにして洗浄した鉄水酸化物ヒドロゲル分散液（Ｆｅ2Ｏ3濃度１．５重量％）の電導度は１．１μＳ／ｃｍ、ｐＨ＝８であった。
Preparation of metal oxide sol (7) 4.97 g of citric acid monohydrate (Cm = 0.024) was dissolved in 2458 g of pure water, and ferric chloride hexahydrate (FeCl 3 .6H 2 0) was dissolved therein. ) 64 g (Mm = 0.24) was dissolved. (Cm / Mm = 0.1)
Subsequently, 434 g of 10% by weight KOH aqueous solution was added to prepare an iron hydroxide hydrogel dispersion (Fe 2 O 3 concentration 1.5% by weight). At this time, the pH of the dispersion was 10.6 and the temperature was 28 ° C.
Subsequently, this was left still and settled, the supernatant was removed, and the concentration was adjusted to 1.5% with pure water.
Subsequently, it was washed with an ultrafiltration membrane until the electric conductivity reached 280 μS / cm.
Next, 150 g of cation exchange fat (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added to the iron hydroxide hydrogel dispersion (Fe 2 O 3 concentration 1.5 wt%) to deionize. Next, after separating the cation exchange resin, 100 g of an anion exchange resin (Mitsubishi Chemical Corporation: SANUPC) was added for deionization. The conductivity of the iron hydroxide hydrogel dispersion thus washed (Fe 2 O 3 concentration 1.5 wt%) was 1.1 μS / cm and pH = 8.
ついでオートクレーブに充填し、２００℃で２時間熟成した。このとき、電導度は９０μＳ／ｃｍ、ｐＨは４．１であった。
ついで陰イオン交換樹脂（三菱化学（株）：ＳＡＮＵＰＣ）９５ｇを加え脱イオンし、陰イオン交換樹脂を分離した後、陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）５０ｇを加え脱イオンし、陰イオン交換樹脂を分離した。このときの電導度は２μＳ／ｃｍ、ｐＨは６であった。
Next, the autoclave was filled and aged at 200 ° C. for 2 hours. At this time, the conductivity was 90 μS / cm and the pH was 4.1.
Next, 95 g of anion exchange resin (Mitsubishi Chemical Corporation: SANUPC) was added and deionized to separate the anion exchange resin, and then 50 g of cation exchange resin (manufactured by Mitsubishi Chemical Corporation: SK1-BH) was added for deionization. Ionized and separated the anion exchange resin. At this time, the conductivity was 2 μS / cm and the pH was 6.
次に、上記熟成し洗浄した分散液に濃度２重量％のクエン酸２４９ｇ（Ｃｍ／Ｍｍ＝０．１）を加え、超音波を１時間照射して分散処理をした後、オートクレーブに充填し、２００℃で２時間水熱処理をした。この時の電導度は４８０μＳ／ｃｍ、ｐＨは２．４であった。
水熱処理した分散液に陰イオン交換樹脂（三菱化学（株）製：ＳＡＮＵＰＣ）９５ｇを加え脱イオンし、陰イオン交換樹脂を分離した後、陽イオン交換樹脂（三菱化学（株）製：ＳＫ１−ＢＨ）５０ｇを加え脱イオンし、陽イオン交換樹脂を分離し、限外濾過膜法で濃縮し濃度１０重量％の金属酸化物ゾル(7)を調製した。金属酸化物ゾル(7)の電導度は２５μＳ／ｃｍ、ｐＨは７であり、平均粒子径は７７ｎｍ、結晶子径は３９ｎｍ、Ｄｎ／Ｄｘは２．０であった。
Next, 249 g of citric acid having a concentration of 2% by weight (Cm / Mm = 0.1) was added to the above ripened and washed dispersion, and after ultrasonic treatment for 1 hour, the autoclave was filled. Hydrothermal treatment was performed at 200 ° C. for 2 hours. The electric conductivity at this time was 480 μS / cm, and the pH was 2.4.
95 g of an anion exchange resin (manufactured by Mitsubishi Chemical Corporation: SANUPC) was added to the hydrothermally treated dispersion to deionize it, and the anion exchange resin was separated. BH) 50 g was added to deionize, the cation exchange resin was separated, and concentrated by an ultrafiltration membrane method to prepare a metal oxide sol (7) having a concentration of 10% by weight. The conductivity of the metal oxide sol (7) was 25 μS / cm, pH was 7, the average particle size was 77 nm, the crystallite size was 39 nm, and Dn / Dx was 2.0.
（特徴：実施例７で水熱処理なし）
金属酸化物ゾル(R10)の調製
実施例７と同様にして熟成、洗浄し、ついで限外濾過膜法で濃縮し濃度１０重量％の金属酸化物ゾル(R10)を調製した。金属酸化物ゾル(R10)の電導度は１３μＳ／ｃｍ、ｐＨは７であり、平均粒子径は６３ｎｍ、結晶子径は２５ｎｍ、Ｄｎ／Ｄｘは２．５であった。
(Feature: No hydrothermal treatment in Example 7)
Preparation of Metal Oxide Sol (R10) Aged and washed in the same manner as in Example 7, and then concentrated by an ultrafiltration membrane method to prepare a metal oxide sol (R10) having a concentration of 10% by weight. The conductivity of the metal oxide sol (R10) was 13 μS / cm, pH was 7, the average particle size was 63 nm, the crystallite size was 25 nm, and Dn / Dx was 2.5.
Claims (11)
（ａ）粒子成長調整剤の存在下、セリウム化合物水溶液、ビスマス化合物水溶液、鉄化合物水溶液、イットリウム化合物水溶液のいずれか１種にアルカリ水溶液を加えてセリウム水酸化物ゲルの分散液、ビスマス水酸化物ゲルの分散液、鉄水酸化物ゲルの分散液、イットリウム水酸化物ゲルの分散液のいずれか１種を調製する工程
（ｂ）前記金属水酸化物ゲルの分散液を洗浄する工程
（ｃ）前記洗浄した金属水酸化物ゲルの分散液を熟成する工程
（ｄ）熟成した金属水酸化物ゲルの分散液を洗浄する工程
（ｅ）粒子成長調整剤の存在下、前記洗浄した熟成金属水酸化物ゲルの分散液を水熱処理する工程
A method for producing a sol in which metal oxide fine particles having an average particle diameter in the range of 5 to 150 nm are dispersed, comprising the following steps (a) to (e).
(A) In the presence of a particle growth regulator, an alkaline aqueous solution is added to any one of a cerium compound aqueous solution, a bismuth compound aqueous solution, an iron compound aqueous solution, and an yttrium compound aqueous solution, and a dispersion of cerium hydroxide gel, bismuth hydroxide A step of preparing any one of a gel dispersion, an iron hydroxide gel dispersion, and a yttrium hydroxide gel dispersion (b) a step (c) of washing the metal hydroxide gel dispersion; Aging the washed metal hydroxide gel dispersion (d) washing the aged metal hydroxide gel dispersion (e) washing the aged metal hydroxide in the presence of a particle growth regulator. Hydrothermal treatment of a dispersion of a solid gel
The method for producing a metal oxide sol according to claim 1, wherein the metal oxide fine particle-dispersed sol obtained in the step (e) is concentrated or diluted.
The method for producing a metal oxide sol according to claim 1 or 2, wherein the particle growth regulator is a carboxylic acid or a hydroxycarboxylic acid.
The method for producing a metal oxide sol according to any one of claims 1 to 3, wherein the hydrothermal treatment is performed in a temperature range of 100 to 250 ° C.
The method for producing a zirconia sol according to any one of claims 1 to 4, wherein the step (d) and / or the step (e) are repeated.
The method for producing a metal oxide sol according to any one of claims 1 to 5, wherein the conductivity of the metal hydroxide gel dispersion is set to 20 µS / cm or less in the step (b).
The method for producing a metal oxide sol according to any one of claims 1 to 6, wherein the conductivity of the metal oxide dispersion is set to 200 µS / cm or less in the step (d).
After the step (e) or the repeated step (d) and / or step (e), the metal oxide sol is dried and fired in the range of 300 to 900 ° C., and the obtained fine particles are dispersed again in the dispersion medium. The method for producing a metal oxide sol according to claim 1, wherein the metal oxide sol is dispersed in a metal oxide sol.
Any one selected from cerium oxide, bismuth oxide, iron oxide and yttrium oxide, wherein the average particle size (Dn) is in the range of 5 to 150 nm and the crystallite size (Dx) is in the range of 5 to 50 nm. A metal oxide sol in which one kind of metal oxide particles is dispersed.
10. The metal oxide sol according to claim 9, wherein a ratio (D n / D x ) of the average particle diameter (D n ) to the crystallite diameter (D x ) is in a range of 1 to 2.
The metal oxide sol according to claim 9 or 10, obtained by the method for producing a metal oxide sol according to any one of claims 1 to 8.
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