JP2014065632A - Titanium oxide sol and method of producing the same - Google Patents
Titanium oxide sol and method of producing the same Download PDFInfo
- Publication number
- JP2014065632A JP2014065632A JP2012212020A JP2012212020A JP2014065632A JP 2014065632 A JP2014065632 A JP 2014065632A JP 2012212020 A JP2012212020 A JP 2012212020A JP 2012212020 A JP2012212020 A JP 2012212020A JP 2014065632 A JP2014065632 A JP 2014065632A
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- oxide sol
- saccharide
- sol
- mass
- 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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 237
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims abstract description 221
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 81
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 65
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 239000003125 aqueous solvent Substances 0.000 claims abstract description 15
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 14
- 150000002016 disaccharides Chemical class 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims description 17
- 238000004519 manufacturing process Methods 0.000 claims description 15
- 239000005749 Copper compound Substances 0.000 claims description 9
- 150000001880 copper compounds Chemical class 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 238000010979 pH adjustment Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 5
- 230000001603 reducing effect Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 230000002378 acidificating effect Effects 0.000 description 18
- 239000000460 chlorine Substances 0.000 description 16
- 229910052801 chlorine Inorganic materials 0.000 description 16
- 239000010409 thin film Substances 0.000 description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 230000002776 aggregation Effects 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 238000004220 aggregation Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 12
- 238000005259 measurement Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229930006000 Sucrose Natural products 0.000 description 9
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 150000002736 metal compounds Chemical class 0.000 description 9
- 239000005720 sucrose Substances 0.000 description 9
- 239000000853 adhesive Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 description 6
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000008101 lactose Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- -1 silane compound Chemical class 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 4
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910021645 metal ion Chemical group 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 2
- 229930091371 Fructose Natural products 0.000 description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 description 2
- 239000005715 Fructose Substances 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229930182830 galactose Natural products 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 150000002500 ions Chemical group 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- HDTRYLNUVZCQOY-UHFFFAOYSA-N α-D-glucopyranosyl-α-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1C(O)C(O)C(O)C(CO)O1 HDTRYLNUVZCQOY-UHFFFAOYSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-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
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Natural products OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- AVGPOAXYRRIZMM-UHFFFAOYSA-N D-Apiose Natural products OCC(O)(CO)C(O)C=O AVGPOAXYRRIZMM-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-CBPJZXOFSA-N D-Gulose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@H]1O WQZGKKKJIJFFOK-CBPJZXOFSA-N 0.000 description 1
- WQZGKKKJIJFFOK-WHZQZERISA-N D-aldose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-WHZQZERISA-N 0.000 description 1
- WQZGKKKJIJFFOK-IVMDWMLBSA-N D-allopyranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@H](O)[C@@H]1O WQZGKKKJIJFFOK-IVMDWMLBSA-N 0.000 description 1
- LKDRXBCSQODPBY-JDJSBBGDSA-N D-allulose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@H]1O LKDRXBCSQODPBY-JDJSBBGDSA-N 0.000 description 1
- ASNHGEVAWNWCRQ-LJJLCWGRSA-N D-apiofuranose Chemical compound OC[C@@]1(O)COC(O)[C@@H]1O ASNHGEVAWNWCRQ-LJJLCWGRSA-N 0.000 description 1
- ASNHGEVAWNWCRQ-UHFFFAOYSA-N D-apiofuranose Natural products OCC1(O)COC(O)C1O ASNHGEVAWNWCRQ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- HMFHBZSHGGEWLO-SOOFDHNKSA-N D-ribofuranose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H]1O HMFHBZSHGGEWLO-SOOFDHNKSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-NQXXGFSBSA-N D-ribulose Chemical compound OC[C@@H](O)[C@@H](O)C(=O)CO ZAQJHHRNXZUBTE-NQXXGFSBSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-UHFFFAOYSA-N D-threo-2-Pentulose Natural products OCC(O)C(O)C(=O)CO ZAQJHHRNXZUBTE-UHFFFAOYSA-N 0.000 description 1
- ZAQJHHRNXZUBTE-WUJLRWPWSA-N D-xylulose Chemical compound OC[C@@H](O)[C@H](O)C(=O)CO ZAQJHHRNXZUBTE-WUJLRWPWSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- LKDRXBCSQODPBY-AMVSKUEXSA-N L-(-)-Sorbose Chemical compound OCC1(O)OC[C@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-AMVSKUEXSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VSOAQEOCSA-N L-altropyranose Chemical compound OC[C@@H]1OC(O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-VSOAQEOCSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PYMYPHUHKUWMLA-LMVFSUKVSA-N Ribose Natural products OC[C@@H](O)[C@@H](O)[C@@H](O)C=O PYMYPHUHKUWMLA-LMVFSUKVSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021603 Ruthenium iodide Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HDTRYLNUVZCQOY-WSWWMNSNSA-N Trehalose Natural products O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-WSWWMNSNSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- CUGWZRINJNBMDM-UHFFFAOYSA-L [Cu](Cl)Cl.[I] Chemical compound [Cu](Cl)Cl.[I] CUGWZRINJNBMDM-UHFFFAOYSA-L 0.000 description 1
- OIENHJCGDAGWEG-UHFFFAOYSA-N [Ir]=S Chemical compound [Ir]=S OIENHJCGDAGWEG-UHFFFAOYSA-N 0.000 description 1
- DUDJJJCZFBPZKW-UHFFFAOYSA-N [Ru]=S Chemical compound [Ru]=S DUDJJJCZFBPZKW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- HDTRYLNUVZCQOY-LIZSDCNHSA-N alpha,alpha-trehalose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 HDTRYLNUVZCQOY-LIZSDCNHSA-N 0.000 description 1
- HMFHBZSHGGEWLO-UHFFFAOYSA-N alpha-D-Furanose-Ribose Natural products OCC1OC(O)C(O)C1O HMFHBZSHGGEWLO-UHFFFAOYSA-N 0.000 description 1
- SRBFZHDQGSBBOR-STGXQOJASA-N alpha-D-lyxopyranose Chemical compound O[C@@H]1CO[C@H](O)[C@@H](O)[C@H]1O SRBFZHDQGSBBOR-STGXQOJASA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000840 anti-viral effect Effects 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 239000005328 architectural glass Substances 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- SAEBCFDIJRQJQB-UHFFFAOYSA-N carbonic acid;nickel Chemical compound [Ni].OC(O)=O SAEBCFDIJRQJQB-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- XHFVDZNDZCNTLT-UHFFFAOYSA-H chromium(3+);tricarbonate Chemical compound [Cr+3].[Cr+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O XHFVDZNDZCNTLT-UHFFFAOYSA-H 0.000 description 1
- PPUZYFWVBLIDMP-UHFFFAOYSA-K chromium(3+);triiodide Chemical compound I[Cr](I)I PPUZYFWVBLIDMP-UHFFFAOYSA-K 0.000 description 1
- DBULDCSVZCUQIR-UHFFFAOYSA-N chromium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Cr+3].[Cr+3] DBULDCSVZCUQIR-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- XZQOHYZUWTWZBL-UHFFFAOYSA-L chromium(ii) bromide Chemical compound [Cr+2].[Br-].[Br-] XZQOHYZUWTWZBL-UHFFFAOYSA-L 0.000 description 1
- VQWFNAGFNGABOH-UHFFFAOYSA-K chromium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Cr+3] VQWFNAGFNGABOH-UHFFFAOYSA-K 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 229940112669 cuprous oxide Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002454 idoses Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- HTFVQFACYFEXPR-UHFFFAOYSA-K iridium(3+);tribromide Chemical compound Br[Ir](Br)Br HTFVQFACYFEXPR-UHFFFAOYSA-K 0.000 description 1
- IUJMNDNTFMJNEL-UHFFFAOYSA-K iridium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ir+3] IUJMNDNTFMJNEL-UHFFFAOYSA-K 0.000 description 1
- WUHYYTYYHCHUID-UHFFFAOYSA-K iridium(3+);triiodide Chemical compound [I-].[I-].[I-].[Ir+3] WUHYYTYYHCHUID-UHFFFAOYSA-K 0.000 description 1
- GSNZLGXNWYUHMI-UHFFFAOYSA-N iridium(3+);trinitrate Chemical compound [Ir+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GSNZLGXNWYUHMI-UHFFFAOYSA-N 0.000 description 1
- VNVQLDDPGAWSSB-UHFFFAOYSA-H iridium(3+);trisulfate Chemical compound [Ir+3].[Ir+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNVQLDDPGAWSSB-UHFFFAOYSA-H 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 1
- BJHIKXHVCXFQLS-PQLUHFTBSA-N keto-D-tagatose Chemical compound OC[C@@H](O)[C@H](O)[C@H](O)C(=O)CO BJHIKXHVCXFQLS-PQLUHFTBSA-N 0.000 description 1
- TYQCGQRIZGCHNB-JLAZNSOCSA-N l-ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(O)=C(O)C1=O TYQCGQRIZGCHNB-JLAZNSOCSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- QWYFOIJABGVEFP-UHFFFAOYSA-L manganese(ii) iodide Chemical compound [Mn+2].[I-].[I-] QWYFOIJABGVEFP-UHFFFAOYSA-L 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 150000002972 pentoses Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- MMRXYMKDBFSWJR-UHFFFAOYSA-K rhodium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Rh+3] MMRXYMKDBFSWJR-UHFFFAOYSA-K 0.000 description 1
- KTEDZFORYFITAF-UHFFFAOYSA-K rhodium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Rh+3] KTEDZFORYFITAF-UHFFFAOYSA-K 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 1
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 description 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- CADICXFYUNYKGD-UHFFFAOYSA-N sulfanylidenemanganese Chemical compound [Mn]=S CADICXFYUNYKGD-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- NRUVOKMCGYWODZ-UHFFFAOYSA-N sulfanylidenepalladium Chemical compound [Pd]=S NRUVOKMCGYWODZ-UHFFFAOYSA-N 0.000 description 1
- BVJAAVMKGRODCT-UHFFFAOYSA-N sulfanylidenerhodium Chemical compound [Rh]=S BVJAAVMKGRODCT-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- 229910052718 tin Inorganic materials 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
- RYSQYJQRXZRRPH-UHFFFAOYSA-J tin(4+);dicarbonate Chemical compound [Sn+4].[O-]C([O-])=O.[O-]C([O-])=O RYSQYJQRXZRRPH-UHFFFAOYSA-J 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 125000000647 trehalose group Chemical group 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、酸化チタン粒子が水性溶媒に分散した酸化チタンゾルと、この酸化チタンゾルの製造方法に関するものである。 The present invention relates to a titanium oxide sol in which titanium oxide particles are dispersed in an aqueous solvent, and a method for producing the titanium oxide sol.
酸化チタンを用いた光触媒は、安価で化学的安定性に優れ、高い光触媒活性（有機化合物分解性、抗菌性等）を有し、人体に無害であること等により、光触媒等として広く用いられている。そして、酸化チタン粒子を溶媒に分散させてなる酸化チタンゾルは、有機化合物分解、抗菌、紫外線吸収、汚れ防止、親水、防曇等の各種機能性コーティング剤原料として好適に利用される。
酸化チタンゾルは、種々の方法によって製造される。例えば、酸化チタンゾルは、イルメナイト鉱石を硫酸に溶解し、溶解した硫酸チタニアゾルを濃縮後、種結晶を入れて加水分解させ、酸化チタンゾルを得る硫酸法、ルチル鉱にコークスと塩素を加え塩素化し、生成した四塩化チタンを酸化させ、酸化チタンゾルを得る塩素法によって製造することができる（以下、それぞれ「硫酸法」及び「塩素法」ということがある）。また、酸化チタンゾルは、特許文献１に記載されているように、四塩化チタン水溶液の加水分解によっても製造することができる（以下、「液相法」ということがある）。
Photocatalysts using titanium oxide are widely used as photocatalysts because they are inexpensive, excellent in chemical stability, have high photocatalytic activity (decomposability of organic compounds, antibacterial properties, etc.) and are harmless to the human body. Yes. A titanium oxide sol obtained by dispersing titanium oxide particles in a solvent is suitably used as a raw material for various functional coating agents such as organic compound decomposition, antibacterial, ultraviolet absorption, antifouling, hydrophilicity, and antifogging.
Titanium oxide sol is produced by various methods. For example, titanium oxide sol is produced by dissolving ilmenite ore in sulfuric acid, concentrating the dissolved titania sulfate sol, then adding seed crystals to hydrolyze to obtain titanium oxide sol, and chlorinating by adding coke and chlorine to rutile ore. The titanium tetrachloride can be oxidized to produce a titanium oxide sol by the chlorine method (hereinafter, sometimes referred to as “sulfuric acid method” and “chlorine method”, respectively). Further, as described in Patent Document 1, the titanium oxide sol can also be produced by hydrolysis of an aqueous titanium tetrachloride solution (hereinafter sometimes referred to as “liquid phase method”).
硫酸法や塩素法によって得られた酸化チタンゾルは、ゾル中に硫酸又は塩酸が含まれるために、一般にｐＨは１〜４程度と低い。また、液相法によって得られた酸化チタンゾルも、四塩化チタンの加水分解により生成する塩酸のために、一般にｐＨは１〜４程度と低い。そのため、中性又はアルカリ性の酸化チタンゾルを製造する場合には、アルカリ溶液でｐＨを調製することが考えられる。しかしながら、このようにアルカリ溶液で中和していくと、酸化チタン粒子の等電点付近において酸化チタン粒子が強く凝集してしまうという問題がある。この問題を解決するために、種々の技術が検討されている。
例えば、特許文献２には、ヒドロキシカルボン酸で分散安定化されたアナターゼ型結晶性酸化チタンゾルが記載されている。
特許文献３には、加水分解性シラン、チタン化合物、及び金属酸化物微粒子が混合されたコーティング用組成物が記載されている。
また、高分子分散剤を用い、その立体的な障害で分散性を維持する手法も広く知られている（非特許文献１）。
The titanium oxide sol obtained by the sulfuric acid method or the chlorine method generally has a low pH of about 1 to 4 because sulfuric acid or hydrochloric acid is contained in the sol. In addition, the titanium oxide sol obtained by the liquid phase method also has a pH as low as about 1 to 4 due to hydrochloric acid produced by hydrolysis of titanium tetrachloride. Therefore, when producing a neutral or alkaline titanium oxide sol, it is conceivable to adjust the pH with an alkaline solution. However, when neutralized with an alkali solution in this way, there is a problem that the titanium oxide particles strongly aggregate near the isoelectric point of the titanium oxide particles. In order to solve this problem, various techniques have been studied.
For example, Patent Document 2 describes an anatase type crystalline titanium oxide sol dispersed and stabilized with hydroxycarboxylic acid.
Patent Document 3 describes a coating composition in which a hydrolyzable silane, a titanium compound, and metal oxide fine particles are mixed.
In addition, a technique of using a polymer dispersant and maintaining dispersibility due to its steric hindrance is also widely known (Non-patent Document 1).
特許文献２のように、酸化チタン粒子をヒドロキシカルボン酸で分散させた酸化チタンゾルは、製造プロセスが煩雑である上に、分散性が十分ではなく、さらに水酸化ナトリウム等のアルカリ金属の水酸化物でｐＨを調整するとゾルが不安定化しゲル化や沈殿を生じる。また、アルカリ溶液で中和して中性やアルカリ性にする際に、ヒドロキシカルボン酸の分だけアルカリ溶液量の必要量が多くなる。
特許文献３のように、酸化チタン粒子を加水分解性シラン等で分散させる場合、分散性が十分ではなく、特に、高濃度ゾルにすると凝集し易い。
ｐＨを調整する際に高分子分散剤を用い、その立体的な障害で分散性を維持しようとすると、数百ｎｍ程度の粒子からなるゾルにはある程度の効果が期待できるものの、数十ｎｍ程度の粒子からなる高分散ゾルに対しては、理由は定かではないが高分子系分散剤を高分散ゾル中に添加した段階で激しく凝集してしまい、再分散化が非常に困難である。
このため、上記のヒドロキシカルボン酸、シラン化合物や高分子系分散剤を用いることなく酸化チタンゾルの分散性を向上させる技術が望まれている。
As in Patent Document 2, a titanium oxide sol in which titanium oxide particles are dispersed with a hydroxycarboxylic acid has a complicated manufacturing process and is not sufficiently dispersible. Further, an alkali metal hydroxide such as sodium hydroxide is used. If the pH is adjusted with, the sol becomes unstable and gelation or precipitation occurs. Moreover, when neutralizing with an alkaline solution and making it neutral or alkaline, the required amount of the alkaline solution is increased by the amount of the hydroxycarboxylic acid.
As in Patent Document 3, when the titanium oxide particles are dispersed with hydrolyzable silane or the like, the dispersibility is not sufficient.
When a polymer dispersant is used to adjust the pH and the dispersibility is maintained by the steric hindrance, a sol composed of particles of about several hundred nm can be expected to have a certain effect, but about several tens of nm. The reason for the high-dispersion sol composed of the above-mentioned particles is not clear for reasons, but vigorously agglomerates when the polymer-based dispersant is added to the high-dispersion sol, and redispersion is very difficult.
For this reason, the technique which improves the dispersibility of a titanium oxide sol, without using said hydroxycarboxylic acid, a silane compound, and a polymeric dispersing agent is desired.
本発明は、このような状況下になされたものであり、酸性領域及びアルカリ領域のいずれにおいても酸化チタン粒子の凝集が少なく分散性の高い酸化チタンゾル及びその製造方法を提供することを目的とする。 The present invention has been made under such circumstances, and an object of the present invention is to provide a titanium oxide sol having a high degree of dispersibility with little aggregation of titanium oxide particles in both an acidic region and an alkaline region, and a method for producing the same. .
本発明者らは、鋭意研究の結果、酸化チタンゾルに特定の糖類を含有することにより、酸性領域及びアルカリ領域のいずれにおいても分散性の高い酸化チタンゾルを得ることができることを見出した。本発明は、かかる知見に基づいて完成したものである。 As a result of intensive studies, the present inventors have found that a titanium oxide sol having high dispersibility can be obtained in both the acidic region and the alkaline region by containing a specific saccharide in the titanium oxide sol. The present invention has been completed based on such findings.
すなわち、本発明は次の［１］〜［１３］を提供するものである。
［１］酸化チタン粒子（Ａ）、水性溶媒（Ｂ）、並びに単糖類及び二糖類の少なくとも１種からなる糖類（Ｃ）を含有する酸化チタンゾル。
［２］前記糖類（Ｃ）が還元性を有する糖類である、［１］に記載の酸化チタンゾル。
［３］糖類（Ｃ）がグルコースである、請求項［１］又は［２］に記載の酸化チタンゾル。
［４］酸化チタン粒子（Ａ）１００質量部に対する糖類（Ｃ）の割合が５〜５０質量部である、［１］〜［３］のいずれかに記載の酸化チタンゾル。
［５］助触媒（Ｄ）を含有する、［１］〜［４］のいずれかに記載の酸化チタンゾル。
［６］助触媒（Ｄ）が銅化合物である、［５］に記載の酸化チタンゾル。
［７］酸化チタン粒子（Ａ）１００質量部に対する助触媒（Ｄ）の割合が０．０１〜１０質量部である、［５］又は［６］に記載の酸化チタンゾル。
［８］前記酸化チタン粒子（Ａ）が、ブルッカイト型酸化チタンである、［１］〜［７］のいずれかに記載の酸化チタンゾル。
［９］酸化チタン粒子（Ａ）の平均粒径が５〜１５０ｎｍである、［１］〜［８］のいずれかに記載の酸化チタンゾル。
［１０］ｐＨが９〜１３である、［１］〜［９］のいずれかに記載の酸化チタンゾル。
［１１］酸化チタン粒子（Ａ）及び水性溶媒（Ｂ）を含む原料ゾルに、単糖類及び二糖類の少なくとも１種からなる糖類（Ｃ）を添加する糖類添加工程を含む酸化チタンゾルの製造方法。
［１２］前記糖類添加工程の後に、アルカリ又は酸を添加してｐＨを調製するｐＨ調整工程を含む、［１１］に記載の酸化チタンゾルの製造方法。
［１３］前記原料ゾルのｐＨが１〜５であり、前記ｐＨ調整工程で酸化チタンゾルのｐＨを９〜１３に調製する、［１２］に記載の酸化チタンゾルの製造方法。
That is, the present invention provides the following [1] to [13].
[1] A titanium oxide sol containing titanium oxide particles (A), an aqueous solvent (B), and a saccharide (C) composed of at least one of monosaccharide and disaccharide.
[2] The titanium oxide sol according to [1], wherein the saccharide (C) is a reducing saccharide.
[3] The titanium oxide sol according to [1] or [2], wherein the saccharide (C) is glucose.
[4] The titanium oxide sol according to any one of [1] to [3], wherein the ratio of the saccharide (C) to 100 parts by mass of the titanium oxide particles (A) is 5 to 50 parts by mass.
[5] The titanium oxide sol according to any one of [1] to [4], which contains a promoter (D).
[6] The titanium oxide sol according to [5], wherein the promoter (D) is a copper compound.
[7] The titanium oxide sol according to [5] or [6], wherein the ratio of the promoter (D) to 100 parts by mass of the titanium oxide particles (A) is 0.01 to 10 parts by mass.
[8] The titanium oxide sol according to any one of [1] to [7], wherein the titanium oxide particles (A) are brookite-type titanium oxide.
[9] The titanium oxide sol according to any one of [1] to [8], wherein the titanium oxide particles (A) have an average particle diameter of 5 to 150 nm.
[10] The titanium oxide sol according to any one of [1] to [9], which has a pH of 9 to 13.
[11] A method for producing a titanium oxide sol comprising a saccharide addition step of adding a saccharide (C) comprising at least one monosaccharide and disaccharide to a raw material sol containing titanium oxide particles (A) and an aqueous solvent (B).
[12] The method for producing a titanium oxide sol according to [11], further including a pH adjusting step of adjusting the pH by adding an alkali or an acid after the sugar addition step.
[13] The method for producing a titanium oxide sol according to [12], wherein the raw material sol has a pH of 1 to 5, and the pH of the titanium oxide sol is adjusted to 9 to 13 in the pH adjusting step.
本発明によれば、酸性領域及びアルカリ領域のいずれにおいても分散性の高い酸化チタンゾル及びその製造方法を提供することができる。 According to the present invention, it is possible to provide a titanium oxide sol having high dispersibility in both an acidic region and an alkaline region and a method for producing the same.
［酸化チタンゾル］
本発明の酸化チタンゾルは、酸化チタン粒子（Ａ）、水性溶媒（Ｂ）、並びに単糖類及び二糖類の少なくとも１種からなる糖類（Ｃ）を含有するものである。
本発明の酸化チタンゾルは、酸性領域及びアルカリ領域のいずれにおいても分散性に優れ、また糖類（Ｃ）を添加した後であれば酸性領域及びアルカリ性領域の一方から他方にｐＨ調製しても、分散性が維持される。その理由は明らかではないが、次のとおりであると推測される。
酸化チタンゾル中において、糖類（Ｃ）が酸化チタン粒子（Ａ）の表面に吸着して水和層を形成し、酸化チタン粒子（Ａ）同士の凝集を防止又は抑制することにより、酸化チタン粒子（Ａ）が良好に分散するものと考えられる。
また、酸性領域及びアルカリ性領域の一方から他方にｐＨ調製を行う過程で、酸化チタンの等電点を経由するが、糖類（Ｃ）が存在しない状態で等電点に至ると、酸化チタン粒子（Ａ）同士が強く凝集するため、等電点の経由後においても、この凝集状態が維持され、十分に再分散することができない。また、ボールミル処理等を行ったとしても再分散化は非常に困難である。一方、本発明によると、酸化チタン粒子（Ａ）の表面に糖類（Ｃ）が存在するため、等電点に至ったときに、酸化チタン粒子（Ａ）同士は凝集することが無いか又は凝集するにしてもその凝集力は弱い。従って、等電点の経由後において、酸化チタン粒子（Ａ）は、良好な分散が維持されるか又は弱い凝集状態が解除されて十分に再分散するものと考えられる。
次に、酸化チタンゾルの各成分について説明する。
[Titanium oxide sol]
The titanium oxide sol of the present invention contains titanium oxide particles (A), an aqueous solvent (B), and a saccharide (C) composed of at least one of monosaccharide and disaccharide.
The titanium oxide sol of the present invention is excellent in dispersibility in both the acidic region and the alkaline region, and can be dispersed even if the pH is adjusted from one of the acidic region and the alkaline region to the other if the saccharide (C) is added. Sex is maintained. The reason is not clear, but it is assumed that it is as follows.
In the titanium oxide sol, the saccharide (C) is adsorbed on the surface of the titanium oxide particles (A) to form a hydrated layer, thereby preventing or suppressing the aggregation of the titanium oxide particles (A). A) is considered to be well dispersed.
Further, in the process of adjusting the pH from one of the acidic region and the alkaline region to the other, it passes through the isoelectric point of titanium oxide, but when it reaches the isoelectric point in the absence of saccharide (C), titanium oxide particles ( Since A) agglomerates strongly, this agglomerated state is maintained even after passing through the isoelectric point and cannot be sufficiently redispersed. Further, even if ball milling or the like is performed, redispersion is very difficult. On the other hand, according to the present invention, since the saccharide (C) is present on the surface of the titanium oxide particles (A), the titanium oxide particles (A) are not aggregated or aggregated when reaching the isoelectric point. Even so, its cohesion is weak. Therefore, it is considered that after passing through the isoelectric point, the titanium oxide particles (A) are sufficiently dispersed by maintaining good dispersion or releasing the weak aggregation state.
Next, each component of the titanium oxide sol will be described.
＜酸化チタン粒子（Ａ）＞
酸化チタン粒子（Ａ）の結晶型は、ブルッカイト型、アナターゼ型及びルチル型の１種でも２種以上であってもよい。
酸化チタン粒子（Ａ）の平均粒径（散乱強度分布における５０％累積粒子径：Ｄ５０）は、５〜１５０ｎｍであることが好ましい。５ｎｍ以上であると、凝集することなく良好に分散する。１５０ｎｍ以下であると、沈降することなく良好に分散する。この観点から、平均粒径は、７〜１２５ｎｍであることがより好ましく、１０〜１００ｎｍであることが更に好ましい。なお、平均粒径（Ｄ５０）は、レーザードップラー式粒度分布計や動的光散乱式粒度分布計等によって測定することができる。
酸化チタン粒子（Ａ）の比表面積は、１０〜３００ｍ2／ｇであることが好ましい。１０ｍ2／ｇ以上であると、沈降することなく良好に分散する。３００ｍ2／ｇ以下であると、凝集することなく良好に分散する。この観点から、比表面積は、１５〜２５０ｍ2／ｇであることがより好ましく、２０〜２００ｍ2／ｇであることが更に好ましい。ここで、比表面積とは、ＢＥＴ法によって測定された比表面積のことである。
<Titanium oxide particles (A)>
The crystal form of the titanium oxide particles (A) may be one or more of brookite type, anatase type and rutile type.
The average particle size (50% cumulative particle size in the scattering intensity distribution: D50) of the titanium oxide particles (A) is preferably 5 to 150 nm. When it is 5 nm or more, it is well dispersed without agglomeration. When it is 150 nm or less, it is well dispersed without settling. In this respect, the average particle diameter is more preferably 7 to 125 nm, and still more preferably 10 to 100 nm. The average particle size (D50) can be measured by a laser Doppler particle size distribution meter, a dynamic light scattering particle size distribution meter, or the like.
The specific surface area of the titanium oxide particles (A) is preferably 10 to 300 m 2 / g. When it is 10 m 2 / g or more, it is well dispersed without settling. When it is 300 m 2 / g or less, it disperses well without aggregation. In this respect, the specific surface area is more preferably 15~250m 2 / g, and further preferably from 20 to 200 m 2 / g. Here, the specific surface area is a specific surface area measured by the BET method.
酸化チタンゾル中における酸化チタン粒子（Ａ）の含有量は、３〜３０質量％が好ましい。３質量％以上であると、相対的に水性溶媒の量が少なくなり、酸化チタンゾルの使用時に水性溶媒を乾燥等によって除去する時間が短くてすみ、また、酸化チタンゾルの容量を小さくすることができる。３０質量％以下であると、分散性が良好になる。この観点から、酸化チタンゾル中における酸化チタン粒子（Ａ）の含有量は、４〜２５質量％がより好ましく、５〜２０質量％が更に好ましい。 The content of the titanium oxide particles (A) in the titanium oxide sol is preferably 3 to 30% by mass. When the amount is 3% by mass or more, the amount of the aqueous solvent is relatively reduced, the time for removing the aqueous solvent by drying or the like when using the titanium oxide sol can be shortened, and the capacity of the titanium oxide sol can be reduced. . Dispersibility will become favorable in it being 30 mass% or less. In this respect, the content of the titanium oxide particles (A) in the titanium oxide sol is more preferably 4 to 25% by mass, and further preferably 5 to 20% by mass.
酸化チタン粒子（Ａ）の製造方法は、特に限定は無く、前述した公知の硫酸法、塩酸法、液相法等によって製造すればよい。なお、液相法の詳細は、特許文献１に記載されているとおりである。 The production method of the titanium oxide particles (A) is not particularly limited, and may be produced by the known sulfuric acid method, hydrochloric acid method, liquid phase method and the like described above. The details of the liquid phase method are as described in Patent Document 1.
＜水性溶媒（Ｂ）＞
水性溶媒（Ｂ）は、水及び水と相溶する有機溶媒の少なくとも１種であり、糖類（Ｃ）、アルカリ、酸が溶解するものが好ましい。具体的には水、アルコール、ケトン類等が挙げられる。なかでも、水又はアルコール類を用いることが環境面から好ましい。有機溶媒の中では、アルコール類を用いることが好ましい。例えば、アルコールとしては、メタノール、エタノール、ノルマルプロピルアルコール、イソプロピルアルコール等が挙げられる。ケトンとしては、メチルエチルケトン、アセトン（ジメチルケトン）、ジエチルケトン、メチルイソブチルケトン等が挙げられる。水とこれらの混合物であっても良い。
<Aqueous solvent (B)>
The aqueous solvent (B) is at least one of water and an organic solvent that is compatible with water, and those in which saccharide (C), alkali, and acid are dissolved are preferable. Specific examples include water, alcohol, and ketones. Especially, it is preferable from an environmental viewpoint to use water or alcohol. Among organic solvents, it is preferable to use alcohols. For example, as alcohol, methanol, ethanol, normal propyl alcohol, isopropyl alcohol, etc. are mentioned. Examples of the ketone include methyl ethyl ketone, acetone (dimethyl ketone), diethyl ketone, and methyl isobutyl ketone. It may be water and a mixture thereof.
＜糖類（Ｃ）＞
糖類（Ｃ）は、単糖類及び二糖類の少なくとも１種である。これら単糖類及び二糖類によると、酸化チタンゾル中において、糖類（Ｃ）が酸化チタン粒子（Ａ）の表面に吸着して水和層を形成し、酸化チタン粒子（Ａ）同士の凝集を防止又は抑制すると考えられ、その結果酸化チタン粒子（Ａ）を良好に分散できる。
また糖類を含むため、酸化チタンの凝集を抑制する以外に、後述する助触媒等の金属化合物も高分散化できる。その反応機構として、糖類と金属イオンとが錯体を形成し、その後金属化合物を加水分解等で酸化チタン上に析出させると、反応が緩やかに進行し又は金属化合物同士の凝集が抑制されることが考えられる。これにより、糖類（Ｃ）は、酸化チタンのみならず金属助触媒の高分散化にも寄与する。
<Sugar (C)>
The saccharide (C) is at least one of monosaccharide and disaccharide. According to these monosaccharides and disaccharides, in the titanium oxide sol, the saccharide (C) is adsorbed on the surface of the titanium oxide particles (A) to form a hydrated layer to prevent aggregation of the titanium oxide particles (A). As a result, the titanium oxide particles (A) can be well dispersed.
Moreover, since it contains saccharides, in addition to suppressing aggregation of titanium oxide, a metal compound such as a cocatalyst described later can be highly dispersed. As the reaction mechanism, when a saccharide and a metal ion form a complex, and then the metal compound is precipitated on titanium oxide by hydrolysis or the like, the reaction proceeds slowly or aggregation of the metal compounds is suppressed. Conceivable. Thereby, saccharide | sugar (C) contributes also to high dispersion | distribution of not only titanium oxide but a metal promoter.
単糖類には特に制限はないが、価格や入手の容易性の観点から、グルコース、フルクトース、ガラクトース、マンノース、アロース、タロース、グロース、アルトロース、イドース、プシコース、ソルボース及びタガトースのような六炭糖並びにリボース、アラビノース、キシロース、リキソース、アピオース、リブロース及びキシルロースのような五炭糖からなる群から選択される１種又は２種以上が好ましく、グルコース、フルクトース、ガラクトース及びキシロースがより好ましく、グルコースが更に好ましい。これら単糖類は還元性を有するために酸化防止剤としても機能する。したがって、酸化チタン粒子の光触媒作用を向上させるために酸化チタンゾル中に任意に添加される助触媒（Ｄ）が、酸化して劣化したり変色したりすることが防止又は抑制される。 Monosaccharides are not particularly limited, but hexoses such as glucose, fructose, galactose, mannose, allose, talose, gulose, altrose, idose, psicose, sorbose, and tagatose are not limited in terms of price and availability. And one or more selected from the group consisting of pentoses such as ribose, arabinose, xylose, lyxose, apiose, ribulose and xylulose, preferably glucose, fructose, galactose and xylose, more preferably glucose preferable. Since these monosaccharides have reducibility, they also function as antioxidants. Therefore, the promoter (D) optionally added to the titanium oxide sol in order to improve the photocatalytic action of the titanium oxide particles is prevented or suppressed from being oxidized and deteriorated or discolored.
二糖類にも特に制限はないが、価格や入手の容易性の観点から、ラクトース（乳糖）、スクロース（ショ糖）、マルトース（麦芽糖）、セロビオース及びトレハロースの１種又は２種以上が好ましく、ラクトース（乳糖）、スクロース（ショ糖）及びマルトース（麦芽糖）の１種又は２種以上がより好ましい。ラクトース（乳糖）、マルトース（麦芽糖）、セロビオース及びトレハロースは還元性を有するために酸化防止剤としても機能する。したがって、酸化チタン粒子の光触媒作用を向上させるために酸化チタンゾル中に任意に添加される助触媒（Ｄ）が、酸化して劣化したり変色したりすることが防止又は抑制される。スクロース（ショ糖）は、安価で、人体に無害であるという優れた特徴を有し、また、還元性を有しないため、助触媒中の金属原子の価数変化を起こさないという優れた効果を有する。
単糖類と二糖類は組み合わせて使用することも出来る。
There are no particular restrictions on disaccharides, but from the viewpoint of price and availability, lactose (lactose), sucrose (sucrose), maltose (maltose), cellobiose and trehalose are preferred, and lactose is preferred. One or more of (lactose), sucrose (sucrose) and maltose (maltose) are more preferred. Lactose (lactose), maltose (maltose), cellobiose, and trehalose function as antioxidants because they have reducing properties. Therefore, the promoter (D) optionally added to the titanium oxide sol in order to improve the photocatalytic action of the titanium oxide particles is prevented or suppressed from being oxidized and deteriorated or discolored. Sucrose (sucrose) is inexpensive and has an excellent feature that it is harmless to the human body, and since it does not have a reducing property, it has an excellent effect of not causing a change in the valence of metal atoms in the promoter. Have.
Monosaccharides and disaccharides can also be used in combination.
酸化チタン粒子（Ａ）１００質量部に対する糖類（Ｃ）の割合は、その合計量が好ましくは５〜５０質量部である。５質量部以上であると、酸化チタンゾルが十分に分散し、５０質量部以下であると経済的である。この観点から、糖類（Ｃ）の割合は、より好ましくは７〜４０質量部であり、更に好ましくは１０〜３０質量部である。 The total amount of the saccharide (C) is preferably 5 to 50 parts by mass with respect to 100 parts by mass of the titanium oxide particles (A). When it is 5 parts by mass or more, the titanium oxide sol is sufficiently dispersed, and when it is 50 parts by mass or less, it is economical. In this respect, the proportion of saccharide (C) is more preferably 7 to 40 parts by mass, and still more preferably 10 to 30 parts by mass.
＜任意成分＞
本発明の酸化チタンゾルは、上記の酸化チタン粒子（Ａ）、水性溶媒（Ｂ）及び糖類（Ｃ）の３成分のみからなっていてもよいが、本発明の効果を阻害しない範囲において、他の任意成分を含有してもよい。この任意成分の含有量は、酸化チタン１００質量部に対して、好ましくは５質量部以下であり、より好ましくは４質量部以下であり、更に好ましくは３質量部以下である。
次に、任意成分の具体例について説明する。
<Optional component>
The titanium oxide sol of the present invention may be composed of only the three components of the titanium oxide particles (A), the aqueous solvent (B) and the saccharide (C), but within the range not inhibiting the effects of the present invention, An optional component may be contained. The content of this optional component is preferably 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less with respect to 100 parts by mass of titanium oxide.
Next, specific examples of arbitrary components will be described.
（助触媒（Ｄ））
酸化チタンゾルは、主触媒である酸化チタン粒子（Ａ）の光触媒作用を向上させる助触媒（Ｄ）を含んでいてもよい。
(Cocatalyst (D))
The titanium oxide sol may contain a promoter (D) that improves the photocatalytic action of the titanium oxide particles (A) as the main catalyst.
助触媒（Ｄ）としては、クロム、マンガン、鉄、コバルト、ニッケル、銅、亜鉛、ガリウム、ゲルマニウム、ルテニウム、ロジウム、パラジウム、銀、インジウム、スズ、イリジウム、白金、金、ビスマス等の金属、これらの金属イオン、これらの金属化合物等が挙げられ、これらは、１種で用いても２種以上で用いてもよい。金属化合物としては、金属酸化物、金属水酸化物、金属ハロゲン化物等が挙げられる。
金属化合物としては、具体的には、酸化クロム、水酸化クロム、塩化クロム、硫化クロム、硫酸クロム、硝酸クロム、炭酸クロム、ヨウ化クロム、臭化クロム、酸化マンガン、水酸化マンガン、塩化マンガン、硫化マンガン、硫酸マンガン、硝酸マンガン、炭酸マンガン、ヨウ化マンガン、臭化マンガン、酸化鉄、水酸化鉄、塩化鉄、硫化鉄、硫酸鉄、硝酸鉄、炭酸鉄、フッ化鉄、臭化鉄、酸化コバルト、水酸化コバルト、塩化コバルト、硫化コバルト、硫酸コバルト、硝酸コバルト、炭酸コバルト、ヨウ化コバルト、臭化コバルト、酸化ニッケル、水酸化ニッケル、塩化ニッケル、硫化ニッケル、硫酸ニッケル、硝酸ニッケル、炭酸ニッケル、ヨウ化ニッケル、臭化ニッケル、酸化銅、亜酸化銅、水酸化銅、塩化銅、硫化銅、硫酸銅、硝酸銅、炭酸銅、ヨウ化銅、臭化銅、酸化亜鉛、水酸化亜鉛、塩化亜鉛、硫化亜鉛、硫酸亜鉛、硝酸亜鉛、炭酸亜鉛、フッ化亜鉛、臭化亜鉛、酸化ルテニウム、水酸化ルテニウム、塩化ルテニウム、硫化ルテニウム、硫酸ルテニウム、硝酸ルテニウム、ヨウ化ルテニウム、臭化ルテニウム、酸化ロジウム、水酸化ロジウム、塩化ロジウム、硫化ロジウム、硫酸ロジウム、硝酸ロジウム、ヨウ化ロジウム、臭化ロジウム、酸化パラジウム、水酸化パラジウム、塩化パラジウム、硫化パラジウム、硫酸パラジウム、硝酸パラジウム、ヨウ化パラジウム、臭化パラジウム、酸化銀、塩化銀、硫化銀、硫酸銀、硝酸銀、炭酸銀、ヨウ化銀、臭化銀、酸化スズ、水酸化スズ、塩化スズ、硫化スズ、硫酸スズ、硝酸スズ、炭酸スズ、ヨウ化スズ、臭化スズ、酸化イリジウム、水酸化イリジウム、塩化イリジウム、硫化イリジウム、硫酸イリジウム、硝酸イリジウム、ヨウ化イリジウム、臭化イリジウムの少なくとも１種が好ましいが、酸化銅、水酸化銅、塩化銅、硫化銅、硫酸銅、ヨウ化銅、臭化銅がより好ましい。上記記載の金属化合物無水物であっても水和物であってもよく、また各金属イオンは任意の価数状態とすることができる。
本発明の酸化チタンゾルは、糖類（Ｃ）を含むため、酸化チタン粒子（Ａ）のみならず上記助触媒（Ｄ）の高分散化にも寄与する。その理由は、前述のとおりであると推測される。
Cocatalyst (D) includes chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, ruthenium, rhodium, palladium, silver, indium, tin, iridium, platinum, gold, bismuth, and other metals. These metal ions, these metal compounds, etc. are mentioned, These may be used by 1 type or may be used by 2 or more types. Examples of the metal compound include metal oxides, metal hydroxides, metal halides, and the like.
Specific examples of the metal compound include chromium oxide, chromium hydroxide, chromium chloride, chromium sulfide, chromium sulfate, chromium nitrate, chromium carbonate, chromium iodide, chromium bromide, manganese oxide, manganese hydroxide, manganese chloride, Manganese sulfide, manganese sulfate, manganese nitrate, manganese carbonate, manganese iodide, manganese bromide, iron oxide, iron hydroxide, iron chloride, iron sulfide, iron sulfate, iron nitrate, iron carbonate, iron fluoride, iron bromide, Cobalt oxide, cobalt hydroxide, cobalt chloride, cobalt sulfide, cobalt sulfate, cobalt nitrate, cobalt carbonate, cobalt iodide, cobalt bromide, nickel oxide, nickel hydroxide, nickel chloride, nickel sulfide, nickel sulfate, nickel nitrate, carbonic acid Nickel, nickel iodide, nickel bromide, copper oxide, cuprous oxide, copper hydroxide, copper chloride, copper sulfide, copper sulfate, nitric acid , Copper carbonate, copper iodide, copper bromide, zinc oxide, zinc hydroxide, zinc chloride, zinc sulfide, zinc sulfate, zinc nitrate, zinc carbonate, zinc fluoride, zinc bromide, ruthenium oxide, ruthenium hydroxide, chloride Ruthenium, ruthenium sulfide, ruthenium sulfate, ruthenium nitrate, ruthenium iodide, ruthenium bromide, rhodium oxide, rhodium hydroxide, rhodium chloride, rhodium sulfide, rhodium sulfate, rhodium nitrate, rhodium iodide, rhodium bromide, palladium oxide, water Palladium oxide, palladium chloride, palladium sulfide, palladium sulfate, palladium nitrate, palladium iodide, palladium bromide, silver oxide, silver chloride, silver sulfide, silver sulfate, silver nitrate, silver carbonate, silver iodide, silver bromide, tin oxide , Tin hydroxide, tin chloride, tin sulfide, tin sulfate, tin nitrate, tin carbonate, tin iodide, tin bromide, acid At least one of iridium, iridium hydroxide, iridium chloride, iridium sulfide, iridium sulfate, iridium nitrate, iridium iodide, and iridium bromide is preferred, but copper oxide, copper hydroxide, copper chloride, copper sulfide, copper sulfate, iodine Copper chloride and copper bromide are more preferable. The metal compound anhydrides or hydrates described above may be used, and each metal ion can be in any valence state.
Since the titanium oxide sol of the present invention contains saccharide (C), it contributes not only to the titanium oxide particles (A) but also to the high dispersion of the promoter (D). The reason is presumed to be as described above.
２価銅化合物は、光照射下での助触媒作用に優れる。また、安定であるために酸化等による変色が防止される。１価銅化合物は、光照射下での助触媒作用に優れると共に光の存在しない暗所下において抗菌性、抗ウイルス性を有する。１価銅化合物を用いる場合には、糖類（Ｃ）として還元性を有するものを用いることが望ましい。これにより、１価銅化合物の酸化が防止又は抑制される。 The divalent copper compound is excellent in the promoter action under light irradiation. Further, since it is stable, discoloration due to oxidation or the like is prevented. The monovalent copper compound is excellent in the co-catalytic action under light irradiation and has antibacterial and antiviral properties in the dark where no light is present. When a monovalent copper compound is used, it is desirable to use a reducing saccharide (C). Thereby, oxidation of a monovalent copper compound is prevented or suppressed.
酸化チタン粒子（Ａ）１００質量部に対する助触媒（Ｄ）の割合は、好ましくは０．０１〜１０質量部である。０．０１質量部以上であると助触媒作用に優れ、１０質量部以下であると分散性に優れ、かつ経済的である。この観点から、助触媒（Ｄ）の割合は、より好ましくは０．１〜８質量部であり、更に好ましくは０．５〜７質量部である。
ここで、例えば、この酸化チタン１００質量部に対する２価銅化合物の銅換算含有量は、２価銅化合物の原料と酸化チタンの原料との仕込み量から算出することができる。また、この銅換算含有量は、後述するＩＣＰ（誘導結合プラズマ）発光分光分析により銅及びチタン含有組成物を測定することで特定することもできる。
The ratio of the promoter (D) to 100 parts by mass of the titanium oxide particles (A) is preferably 0.01 to 10 parts by mass. When the amount is 0.01 parts by mass or more, the cocatalyst action is excellent, and when it is 10 parts by mass or less, the dispersibility is excellent and economical. From this viewpoint, the proportion of the promoter (D) is more preferably 0.1 to 8 parts by mass, and further preferably 0.5 to 7 parts by mass.
Here, for example, the copper equivalent content of the divalent copper compound with respect to 100 parts by mass of titanium oxide can be calculated from the charged amounts of the divalent copper compound raw material and the titanium oxide raw material. Moreover, this copper conversion content can also be specified by measuring a copper and titanium containing composition by ICP (inductively coupled plasma) emission spectral analysis mentioned later.
（塩素成分（Ｅ））
酸化チタンゾルは、塩素成分（Ｅ）を含んでいてもよい。この塩素成分（Ｅ）としては、前述の塩素法又は液相法による酸化チタンの製造方法において使用又は生成される塩酸、この塩酸を水酸化ナトリウムで中和して生成される塩化ナトリウム等が挙げられる。
塩素成分（Ｅ）を含む場合、酸化チタンゾル中における塩素成分（Ｅ）の含有量は、塩素元素換算で、５０〜１０，０００質量ｐｐｍが好ましい。５０質量ｐｐｍ以上であると、塩素イオンの作用は明らかではないが、基材に形成した酸化チタン薄膜の基材との密着性が十分となり、特に薄膜を焼成した場合に密着性が良くなる。１０，０００ｐｐｍ以下であると、酸化チタンゾルを塗布する対象物の劣化が防止又は抑制され、また薄膜の透明性に優れる。この観点から、塩素成分（Ｅ）の含有量は、７５〜６，０００質量ｐｐｍがより好ましく、１００〜４，０００質量ｐｐｍが更に好ましい。
(Chlorine component (E))
The titanium oxide sol may contain a chlorine component (E). Examples of the chlorine component (E) include hydrochloric acid used or generated in the above-described chlorine method or liquid phase method for producing titanium oxide, sodium chloride generated by neutralizing this hydrochloric acid with sodium hydroxide, and the like. It is done.
When the chlorine component (E) is included, the content of the chlorine component (E) in the titanium oxide sol is preferably 50 to 10,000 mass ppm in terms of chlorine element. When the content is 50 ppm by mass or more, the action of chlorine ions is not clear, but the adhesion of the titanium oxide thin film formed on the substrate to the substrate is sufficient, and the adhesion is improved particularly when the thin film is baked. When the content is 10,000 ppm or less, deterioration of an object to which the titanium oxide sol is applied is prevented or suppressed, and the transparency of the thin film is excellent. In this respect, the content of the chlorine component (E) is more preferably 75 to 6,000 mass ppm, and further preferably 100 to 4,000 mass ppm.
（還元剤）
酸化チタンゾルは、還元剤を含有してもよい。還元剤により、酸化チタンゾル中に任意に添加される助触媒（Ｄ）を任意の価数状態に調整することができる。
還元剤としては、例えば、低酸化状態の金属塩、硫化水素、硫化物、チオ硫酸塩、シュウ酸、ギ酸、アスコルビン酸、アルデヒド結合を有する物質、及びフェノールを含むアルコール化合物などからなる群より選択される少なくとも１種の物質を用いることができる。
(Reducing agent)
The titanium oxide sol may contain a reducing agent. The cocatalyst (D) optionally added to the titanium oxide sol can be adjusted to an arbitrary valence state by the reducing agent.
The reducing agent is selected from the group consisting of, for example, low oxidation state metal salts, hydrogen sulfide, sulfides, thiosulfates, oxalic acid, formic acid, ascorbic acid, substances having an aldehyde bond, and alcohol compounds including phenol. At least one substance can be used.
＜ｐＨ＞
酸化チタンゾルとしては、用途により、酸性、中性、及びアルカリ性のいずれの領域のものも必要とされており、そのｐＨは１〜１３が望ましい。
本発明の酸化チタンゾルは、糖類（Ｃ）を含むために酸化チタン粒子（Ａ）の分散性に優れ、酸性、中性、及びアルカリ性のいずれの領域においても適用できるが、酸性及びアルカリ性であることが好ましい。
酸性の酸化チタンゾルは、酸性用途としてそのまま使用することができ、また、酸性の状態で保管しておき、アルカリ性用途として使用するときにはアルカリを添加してアルカリ性に調整することもできる。酸性の酸化チタンゾルのｐＨは、１〜５であることが好ましい。１以上であると、酸化チタンゾルを塗布等した対象物の酸による腐食が防止又は抑制される。５以下であると、分散性に優れる。この観点から、酸性の酸化チタンゾルのｐＨは、１．５〜４．５がより好ましく、２〜４が更に好ましい。
アルカリ性の酸化チタンゾルのｐＨは、９〜１３であることが好ましい。９以上であると分散性に優れ、１３以下であると酸化チタンゾルを塗布等した対象物のアルカリによる腐食が防止又は抑制される。この観点から、アルカリ性の酸化チタンゾルのｐＨは、９．５〜１２．５がより好ましく、１０〜１２が更に好ましい。
酸化チタンゾルのｐＨは、ｐＨメーター（株式会社堀場製作所製 Ｄ−５１）を用いて、
２５℃で測定すればよい。
<PH>
As the titanium oxide sol, those in any of acidic, neutral, and alkaline regions are required depending on applications, and the pH is desirably 1 to 13.
Since the titanium oxide sol of the present invention contains saccharide (C), it has excellent dispersibility of the titanium oxide particles (A) and can be applied in any of acidic, neutral, and alkaline regions, but is acidic and alkaline. Is preferred.
The acidic titanium oxide sol can be used as it is for an acidic application, or can be stored in an acidic state and adjusted to be alkaline by adding an alkali when used as an alkaline application. The pH of the acidic titanium oxide sol is preferably 1-5. When it is 1 or more, the corrosion of the object coated with the titanium oxide sol due to acid is prevented or suppressed. When it is 5 or less, the dispersibility is excellent. In this respect, the pH of the acidic titanium oxide sol is more preferably 1.5 to 4.5, and further preferably 2 to 4.
The pH of the alkaline titanium oxide sol is preferably 9-13. When it is 9 or more, the dispersibility is excellent, and when it is 13 or less, corrosion due to alkali of an object coated with titanium oxide sol is prevented or suppressed. In this respect, the pH of the alkaline titanium oxide sol is more preferably 9.5 to 12.5, and further preferably 10 to 12.
The pH of the titanium oxide sol was measured using a pH meter (D-51 manufactured by Horiba, Ltd.)
What is necessary is just to measure at 25 degreeC.
［酸化チタンゾルの製造方法］
本発明の酸化チタンゾルの製造方法は、酸化チタン粒子（Ａ）及び水性溶媒（Ｂ）を含む原料ゾルに、単糖類及び二糖類の少なくとも１種からなる糖類（Ｃ）を添加する糖類添加工程を含むものである。前記糖類添加工程の後に、アルカリを添加してｐＨを調製するｐＨ調整工程を実施してもよい。
[Method for producing titanium oxide sol]
The method for producing a titanium oxide sol of the present invention comprises a saccharide addition step of adding a saccharide (C) comprising at least one monosaccharide and disaccharide to a raw material sol containing titanium oxide particles (A) and an aqueous solvent (B). Is included. After the saccharide addition step, a pH adjustment step of adjusting pH by adding alkali may be performed.
＜糖類添加工程＞
本工程では、酸化チタン粒子（Ａ）及び水性溶媒（Ｂ）を含む原料酸化チタンゾルに、単糖類及び二糖類の少なくとも１種からなる糖類（Ｃ）を添加する。
（原料酸化チタンゾル）
原料酸化チタンゾルとしては、液相法、塩素法、及び硫酸法によって製造された酸化チタンゾルを用いることが好ましい。
液相法により製造された原料酸化チタンゾルの市販品としては、昭和電工株式会社製のブルッカイト型酸化チタン分散液「商品名：ＮＴＢ−１」等が挙げられる。このように、本発明の酸化チタンゾルの製造方法によると、既存の酸化チタンゾルを用いて容易に本発明の酸化チタンゾルを製造することができる。
<Sugar addition process>
In this step, a saccharide (C) composed of at least one monosaccharide and disaccharide is added to a raw material titanium oxide sol containing titanium oxide particles (A) and an aqueous solvent (B).
(Raw material titanium oxide sol)
As the raw material titanium oxide sol, it is preferable to use a titanium oxide sol produced by a liquid phase method, a chlorine method, and a sulfuric acid method.
As a commercial item of the raw material titanium oxide sol manufactured by the liquid phase method, a brookite type titanium oxide dispersion “trade name: NTB-1” manufactured by Showa Denko K.K. Thus, according to the manufacturing method of the titanium oxide sol of this invention, the titanium oxide sol of this invention can be easily manufactured using the existing titanium oxide sol.
（糖類（Ｃ）の添加）
上記の原料酸化チタンゾルに対して、糖類（Ｃ）を添加することにより、酸化チタンゾルを得ることができる。この原料酸化チタンゾルに、更に助触媒（Ｄ）及び還元剤の一方又は双方を添加してもよい。これら助触媒（Ｄ）及び還元剤の詳細は、前述のとおりである。
これら糖類（Ｃ）と、助触媒（Ｄ）又は助触媒（Ｄ）の原料化合物とは、同時に添加してもよく、１種又は２種以上を順次添加してもよい。また、糖類は水溶液で添加しても良い。
糖類（Ｃ）を撹拌しながら添加した後、撹拌することが好ましい。攪拌時間には特に制限はなく、例えば５〜１２０分間、好ましくは１０〜６０分程度である。また、攪拌温度には特に制限はないが、例えば室温〜９０℃程度である。
(Addition of sugar (C))
A titanium oxide sol can be obtained by adding saccharide (C) to the raw material titanium oxide sol. One or both of the promoter (D) and the reducing agent may be further added to this raw material titanium oxide sol. The details of the promoter (D) and the reducing agent are as described above.
These saccharides (C) and the cocatalyst (D) or the raw material compound of the cocatalyst (D) may be added at the same time, or one or more of them may be added sequentially. Moreover, you may add saccharides with aqueous solution.
It is preferable to stir after adding saccharide (C), stirring. There is no restriction | limiting in particular in stirring time, For example, it is 5 to 120 minutes, Preferably it is about 10 to 60 minutes. Moreover, there is no restriction | limiting in particular in stirring temperature, For example, it is room temperature-about 90 degreeC.
＜ｐＨ調整工程＞
前記糖類添加工程の後に、アルカリを添加してｐＨを調製するｐＨ調整工程を実施してもよい。測定は、ｐＨメーターで行う。
例えば、前記原料酸化チタンゾルが、液相法、塩酸法、及び硫酸法によって製造された原料酸化チタンゾルである場合、ｐＨが１〜５程度である。この原料酸化チタンゾルにアルカリを添加して酸化チタンゾルのｐＨを９〜１３に調製してもよい。このｐＨの調整工程において、酸化チタン粒子が等電点を経由することになるが、酸化チタンゾル中において、糖類（Ｃ）が酸化チタン粒子（Ａ）の表面に吸着して水和層を形成し、酸化チタン粒子（Ａ）同士の凝集を防止又は抑制すると考えられ、その結果酸化チタン粒子（Ａ）を良好に分散できる。
また糖類を含むため、酸化チタンの凝集を抑制する以外に、金属化合物も高分散化できる。その反応機構として、糖類と金属イオンとが錯体を形成し、その後金属化合物を加水分解等で酸化チタン上に析出させると、反応が緩やかに進行し又は金属化合物同士の凝集が抑制されることが考えられる。これにより、糖類（Ｃ）は、酸化チタンのみならず金属助触媒の高分散化にも寄与する。
<PH adjustment step>
After the saccharide addition step, a pH adjustment step of adjusting pH by adding alkali may be performed. The measurement is performed with a pH meter.
For example, when the raw material titanium oxide sol is a raw material titanium oxide sol produced by a liquid phase method, a hydrochloric acid method, and a sulfuric acid method, the pH is about 1 to 5. An alkali may be added to the raw material titanium oxide sol to adjust the pH of the titanium oxide sol to 9-13. In this pH adjustment step, the titanium oxide particles pass through the isoelectric point. In the titanium oxide sol, the saccharide (C) is adsorbed on the surface of the titanium oxide particles (A) to form a hydrated layer. It is considered that the aggregation of the titanium oxide particles (A) is prevented or suppressed, and as a result, the titanium oxide particles (A) can be favorably dispersed.
Moreover, since it contains saccharides, the metal compound can be highly dispersed in addition to suppressing aggregation of titanium oxide. As the reaction mechanism, when a saccharide and a metal ion form a complex, and then the metal compound is precipitated on titanium oxide by hydrolysis or the like, the reaction proceeds slowly or aggregation of the metal compounds is suppressed. Conceivable. Thereby, saccharide | sugar (C) contributes also to high dispersion | distribution of not only titanium oxide but a metal promoter.
（アルカリ）
前記ｐＨ調整に用いるアルカリとしては、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムハイドロオキサイド、テトラブチルアンモニウムヒドロキシド、トリエチルアミン、トリメチルアミン、アンモニア、塩基性界面活性剤等が挙げられるが、水酸化ナトリウムが好ましい。
上記のアルカリを含有するアルカリ溶液の濃度は、好ましくは０．０４〜２０質量％、より好ましくは０．１２〜１６質量％、更に好ましくは０．２〜１２質量％である。０．０４質量％以上であるとｐＨ調整効果に優れ、２０質量％以下であると均一にｐＨ調整することができる。
(alkali)
Examples of the alkali used for the pH adjustment include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, a basic surfactant, and the like. preferable.
The concentration of the alkali solution containing the alkali is preferably 0.04 to 20% by mass, more preferably 0.12 to 16% by mass, and still more preferably 0.2 to 12% by mass. When the content is 0.04% by mass or more, the pH adjustment effect is excellent, and when the content is 20% by mass or less, the pH can be uniformly adjusted.
アルカリを添加した後、撹拌することが好ましい。攪拌時間には特に制限はなく、例えば５〜１２０分間、好ましくは１０〜６０分程度である。また、攪拌温度には特に制限はないが、例えば室温〜９０℃程度である。 It is preferable to stir after adding the alkali. There is no restriction | limiting in particular in stirring time, For example, it is 5 to 120 minutes, Preferably it is about 10 to 60 minutes. Moreover, there is no restriction | limiting in particular in stirring temperature, For example, it is room temperature-about 90 degreeC.
［酸化チタンゾルの使用形態］
本発明の酸化チタンゾルを各種の材料、成形体等の基材に塗布し、基材の表面に酸化チタン薄膜を形成することができる。基材としてはセラミックス、ガラス、金属、プラスチック、木材、紙等殆ど制限なく対象とすることができる。基材をアルミナ、ジルコニア等からなる触媒担体とし、これに酸化チタン薄膜の触媒を担持して触媒として使用することもできる。また蛍光ランプ等の照明器具のガラスやそのプラスチックカバー等を基材としてこれに酸化チタン薄膜を形成すれば薄膜は透明であり、かつ光触媒作用を有するので光を遮蔽することなく油煙等の有機物を分解することができ、ガラスやカバーの汚れを防止するのに有効である。また建築用ガラスや壁材に酸化チタン薄膜を形成すれば同様に汚れを防止することが可能になるので、高層ビルなどの窓材や壁材に用いることができ、清掃作業を必要としなくなるためビル管理コスト削減に役立つ。酸化チタンゾルを基材に塗布するには基材をゾル中に浸漬する方法、基材にゾルをスプレーする方法、ゾルを刷毛で基材に塗布する方法などが採用される。ゾルの塗布量は液状の厚さにして０．０１〜０．２ｍｍが適当である。塗布後乾燥して水分を除去すれば薄膜が得られ、このままでも触媒等の用途に供することができる。
[Usage form of titanium oxide sol]
The titanium oxide sol of the present invention can be applied to a substrate such as various materials and molded bodies to form a titanium oxide thin film on the surface of the substrate. As the substrate, ceramics, glass, metal, plastic, wood, paper, etc. can be used without any limitation. The base material may be a catalyst carrier made of alumina, zirconia or the like, and a titanium oxide thin film catalyst may be supported on the base material and used as a catalyst. In addition, if a titanium oxide thin film is formed on a glass or plastic cover of a lighting fixture such as a fluorescent lamp as a base material, the thin film is transparent and has a photocatalytic action, so that organic substances such as oil and smoke can be removed without shielding light. It can be disassembled and is effective in preventing dirt on the glass and cover. In addition, if a titanium oxide thin film is formed on architectural glass or wall materials, it becomes possible to prevent contamination as well, so it can be used for window materials and wall materials for high-rise buildings, etc., and cleaning work is not required. Helps reduce building management costs. In order to apply the titanium oxide sol to the substrate, a method of immersing the substrate in the sol, a method of spraying the sol on the substrate, a method of applying the sol to the substrate with a brush, and the like are employed. The coating amount of the sol is suitably 0.01 to 0.2 mm in terms of liquid thickness. A thin film can be obtained by removing moisture by drying after coating, and it can be used for applications such as a catalyst.
基材が金属やセラミックス、例えばガラス等の耐熱性である場合は酸化チタン薄膜を形成後焼成することができ、これによって薄膜は一層強く基材に密着し、薄膜の硬度も上る。この焼成温度は２００℃以上が好ましい。焼成温度の上限には特に制限はなく、基材の耐熱性に応じて定めればよいが、あまり温度を高くしても薄膜の硬度や基材との密着性は増さないので８００℃位迄が適当である。また、ブルッカイト型酸化チタンの場合は、その結晶形を維持するには７００℃以下の温度で焼成するのがよい。焼成の雰囲気は特に制限されず、大気中でよい。焼成時間は特に制限はなく、例えば１〜６０分の範囲で行えばよい。焼成によって得られる酸化チタン薄膜の厚さは、前記の塗布量の場合０．０５〜１．０μｍ位である。ブルッカイト型酸化チタンは、塗布性、密着性、製膜性等に優れ、また白色度が高いという特徴を有している。
また、本発明の透明薄膜をより強固で基材に対する接着力を高めるために、適当な接着剤（バインダー）を、本発明の酸化チタンゾルに添加することもできる。
例えば、アルキルシリケートなどの有機シリカ化合物が好適である。添加量は、本発明の酸化チタンゾル中の酸化チタンに対しＳｉＯ2換算にして１〜５０質量％が好ましい。添加量が１重量％以上であると、接着剤の添加効果が高い。また、５０質量％以下であると、基材に対する接着強度は非常に強固であると共に、酸化チタン粒子が接着剤に被覆されて光触媒能が低下することが防止又は抑制される。この場合の接着剤は、接着剤の性質により成膜直前に混入するかあらかじめゾルに混合した状態にするか選択すればよく、どちらでも本発明の効果には何ら問題はない。この接着剤を含む薄膜は焼成しなくてもよいが焼成することもできる。
When the base material is heat resistant such as metal or ceramics, for example, glass, it can be fired after forming the titanium oxide thin film, whereby the thin film adheres more strongly to the base material and the hardness of the thin film increases. The firing temperature is preferably 200 ° C. or higher. The upper limit of the firing temperature is not particularly limited and may be determined according to the heat resistance of the substrate. However, even if the temperature is increased too much, the hardness of the thin film and the adhesion to the substrate do not increase, so about 800 ° C. Is suitable. In the case of brookite-type titanium oxide, it is preferable to fire at 700 ° C. or lower in order to maintain the crystal form. The firing atmosphere is not particularly limited and may be in the air. There is no restriction | limiting in particular in baking time, For example, what is necessary is just to carry out in the range of 1 to 60 minutes. The thickness of the titanium oxide thin film obtained by firing is about 0.05 to 1.0 μm in the case of the above coating amount. Brookite-type titanium oxide is characterized by excellent coating properties, adhesion, film-forming properties, etc., and high whiteness.
In addition, in order to make the transparent thin film of the present invention stronger and increase the adhesive force to the substrate, an appropriate adhesive (binder) can be added to the titanium oxide sol of the present invention.
For example, an organic silica compound such as an alkyl silicate is suitable. The addition amount is preferably 1 to 50% by mass in terms of SiO 2 with respect to titanium oxide in the titanium oxide sol of the present invention. When the addition amount is 1% by weight or more, the effect of adding the adhesive is high. Moreover, when it is 50 mass% or less, the adhesive strength with respect to a base material is very strong, and it is prevented or suppressed that a titanium oxide particle is coat | covered with an adhesive agent and photocatalytic capability falls. In this case, the adhesive may be selected to be mixed immediately before film formation or mixed in advance with the sol depending on the nature of the adhesive, and there is no problem with the effect of the present invention. The thin film containing the adhesive does not need to be fired, but can be fired.
以下、本発明を実施例、比較例、及び参考例により具体的に説明するが、本発明はこれらの例に限定されるものではない。
なお、諸特性は以下に示す方法に従って求めた。
EXAMPLES Hereinafter, although an Example, a comparative example, and a reference example demonstrate this invention concretely, this invention is not limited to these examples.
Various characteristics were determined according to the following methods.
（１）平均粒径（散乱強度分布における５０％通過粒子径：Ｄ５０）の測定
大塚電子（株）製のゼータ電位・粒径測定システム（機種名「ＥＬＳＺ−２」）を用い、レーザードップラー法によりＤ５０を測定した。その際、試料（酸化チタンゾル）は、固形分濃度を０．１質量％にイオン交換水で調整したものを用い、超音波振動による撹拌を行うことなく、ハンドシェイクのみを行った後に、当該装置を用いて平均粒径（散乱強度分布における５０％通過粒子径：Ｄ５０）の測定を行った。
（２）同定
Ｘ線回折測定により、試料の同定を行った。測定装置としてＰＡＮａｌｙｔｉｃａｌ社製「Ｘ’ｐｅｒｔＰＲＯ」を用い、銅ターゲットを用い、Ｃｕ−Ｋα１線を用いて、管電圧４５ｋＶ、管電流４０ｍＡ、測定範囲２θ＝２０〜１００ｄｅｇ、サンプリング幅０．０１６７ｄｅｇ、走査速度３．３ｄｅｇ／ｍｉｎの条件でＸ線回折測定を行った。
ルチル型結晶に対応する最大ピークのピーク高さ（Ｈｒ）、ブルッカイト型結晶に対応する最大ピークのピーク高さ（Ｈｂ）、及びアナターゼ型結晶に対応する最大ピークのピーク高さ（Ｈａ）を求め、以下の計算式により、酸化チタン中におけるブルッカイト型酸化チタンの含有量（ブルッカイト含有量）を求めた。
ブルッカイト含有量（モル％）＝｛Ｈｂ／（Ｈａ＋Ｈｂ＋Ｈｒ））｝×１００
ブルッカイト含有量が、５０％以上のものが好ましく、６０％以上がより好ましく
７０％以上が更に好ましい。
(1) Measurement of average particle size (50% passing particle size in scattering intensity distribution: D50) Laser Doppler method using zeta potential / particle size measurement system (model name “ELSZ-2”) manufactured by Otsuka Electronics Co., Ltd. Was used to measure D50. At that time, the sample (titanium oxide sol) was prepared by adjusting the solid content concentration to 0.1% by mass with ion-exchanged water, and after performing handshake without stirring by ultrasonic vibration, Was used to measure the average particle size (50% passing particle size in scattering intensity distribution: D50).
(2) Identification The sample was identified by X-ray diffraction measurement. Using “X'pertPRO” manufactured by PANalytical as a measuring device, using a copper target, using a Cu-Kα1 line, tube voltage 45 kV, tube current 40 mA, measurement range 2θ = 20 to 100 deg, sampling width 0.0167 deg, scanning X-ray diffraction measurement was performed at a speed of 3.3 deg / min.
Obtain the peak height (Hr) of the maximum peak corresponding to the rutile crystal, the peak height (Hb) of the maximum peak corresponding to the brookite crystal, and the peak height (Ha) of the maximum peak corresponding to the anatase crystal. The brookite-type titanium oxide content (brookite content) in titanium oxide was determined by the following calculation formula.
Brookite content (mol%) = {Hb / (Ha + Hb + Hr))} × 100
The brookite content is preferably 50% or more, more preferably 60% or more, and still more preferably 70% or more.
＜実施例１＞
原料酸化チタンゾルとして、液相法によって製造された市販のブルッカイト型酸化チタンゾル（昭和電工（株）製、商品名「ＮＴＢ−１」、酸化チタン濃度：２０質量％、酸化チタン粒子の平均粒径（Ｄ５０）：５０ｎｍ、ブルッカイト含有率６０％、ｐＨ：３、分散媒：水、塩素元素濃度：０．１２６質量％）を用いた。
この原料酸化チタンゾル２５ｇに、糖類としてスクロース１ｇを添加し、その後７４ｇの水を投入し、酸化チタン粒子１００質量部に対する糖類の割合が２０質量部の酸性酸化チタンゾルを得た。この酸性酸化チタンゾル１００ｇに、アルカリとして４質量％濃度の水酸化ナトリウム水溶液４ｇを１分間かけて撹拌しながら滴下し、ｐＨを１２に調整して、アルカリ性酸化チタンゾルを得た。得られたアルカリ性酸化チタンゾルの諸特性の測定結果を表１に示す。
<Example 1>
As a raw material titanium oxide sol, a commercially available brookite-type titanium oxide sol manufactured by a liquid phase method (manufactured by Showa Denko KK, trade name “NTB-1”, titanium oxide concentration: 20 mass%, average particle diameter of titanium oxide particles ( D50): 50 nm, brookite content 60%, pH: 3, dispersion medium: water, chlorine element concentration: 0.126% by mass).
To 25 g of this raw material titanium oxide sol, 1 g of sucrose was added as a saccharide, and then 74 g of water was added to obtain an acidic titanium oxide sol having a saccharide ratio of 20 parts by mass with respect to 100 parts by mass of titanium oxide particles. To 100 g of this acidic titanium oxide sol, 4 g of a 4% by weight aqueous sodium hydroxide solution as an alkali was added dropwise with stirring over 1 minute, and the pH was adjusted to 12 to obtain an alkaline titanium oxide sol. Table 1 shows the measurement results of various properties of the obtained alkaline titanium oxide sol.
＜実施例２＞
原料酸化チタンゾルとして、液相法によって製造されたアナターゼ型酸化チタンゾル（酸化チタン濃度：２０質量％、酸化チタン粒子の平均粒径（Ｄ５０）：５１ｎｍ、ｐＨ：２、分散媒：水、塩素元素濃度：０．０４０質量％）を用いた。
この原料酸化チタンゾル２５ｇに、糖類としてスクロース１ｇを添加し、その後７４ｇの水を投入し、酸化チタン粒子１００質量部に対する糖類の割合が２０質量部の酸性酸化チタンゾルを得た。この酸性酸化チタンゾル１００ｇに、アルカリとして４質量％濃度の水酸化ナトリウム水溶液６ｇを１分間かけて撹拌しながら滴下し、ｐＨを１２に調整して、アルカリ性酸化チタンゾルを得た。得られたアルカリ性酸化チタンゾルの諸特性の測定結果を表１に示す。
<Example 2>
Anatase-type titanium oxide sol produced by a liquid phase method as a raw material titanium oxide sol (titanium oxide concentration: 20% by mass, average particle diameter of titanium oxide particles (D50): 51 nm, pH: 2, dispersion medium: water, chlorine element concentration : 0.040% by mass).
To 25 g of this raw material titanium oxide sol, 1 g of sucrose was added as a saccharide, and then 74 g of water was added to obtain an acidic titanium oxide sol having a saccharide ratio of 20 parts by mass with respect to 100 parts by mass of titanium oxide particles. To 100 g of this acidic titanium oxide sol, 6 g of a 4% by weight aqueous sodium hydroxide solution as an alkali was added dropwise with stirring over 1 minute, and the pH was adjusted to 12, whereby an alkaline titanium oxide sol was obtained. Table 1 shows the measurement results of various properties of the obtained alkaline titanium oxide sol.
＜実施例３＞
糖類として、スクロースに代えてグルコースを用いたこと以外は実施例１と同様の操作を行い、アルカリ性酸化チタンゾルを得た。得られたアルカリ性酸化チタンゾルの諸特性の測定結果を表１に示す。
<Example 3>
The same operation as in Example 1 was performed except that glucose was used in place of sucrose as a saccharide to obtain an alkaline titanium oxide sol. Table 1 shows the measurement results of various properties of the obtained alkaline titanium oxide sol.
＜実施例４＞
糖類としてグルコースを１ｇ添加し、助触媒成分の原料として、ＣｕＣｌ2・２Ｈ2Ｏ（関東化学製）を０．１３４ｇ（酸化チタンゾル中の酸化チタン粒子１００質量部に対するＣｕＣｌ2・２Ｈ2Ｏの銅金属換算割合：１質量部）を添加し、アルカリとして４質量％濃度の水酸化ナトリウム水溶液５．５ｇを１分間かけて撹拌しながら滴下し、ｐＨを１２に調整し、ＣｕＣｌ2・２Ｈ2Ｏ：Ｎ2Ｈ4のモル比が１：０．２５となるように０．０１ｍｏｌ／Ｌ、７９μｌヒドラジン（関東化学株式会社製）水溶液を加え、３０分間攪拌混合を行ったこと以外は実施例１と同様の操作を行い、亜酸化銅担持アルカリ性酸化チタンゾルを得た。得られた亜酸化銅担持アルカリ性酸化チタンゾルの諸特性の測定結果を表１に示す。
<Example 4>
1 g of glucose was added as a saccharide, and 0.134 g of CuCl 2 .2H 2 O (manufactured by Kanto Chemical) as a raw material for the promoter component (CuCl 2 .2H 2 O copper based on 100 parts by mass of titanium oxide particles in the titanium oxide sol) Metal conversion ratio: 1 part by mass), 5.5 g of 4% strength by weight sodium hydroxide aqueous solution as an alkali was added dropwise with stirring over 1 minute, the pH was adjusted to 12, and CuCl 2 .2H 2 O was added. Example 1 except that 0.01 mol / L, 79 μl hydrazine (manufactured by Kanto Chemical Co., Inc.) aqueous solution was added so that the molar ratio of N 2 H 4 was 1: 0.25, and the mixture was stirred and mixed for 30 minutes. The same operation as in Example 1 was performed to obtain a cuprous oxide-supported alkaline titanium oxide sol. Table 1 shows the measurement results of various properties of the obtained cuprous oxide-supported alkaline titanium oxide sol.
＜比較例１＞
糖類を添加しなかったこと以外は実施例１と同様の操作を行い、アルカリ性酸化チタンゾルを得た。得られたアルカリ性酸化チタンゾルの諸特性の測定結果を表１に示す。
<Comparative Example 1>
An alkaline titanium oxide sol was obtained by performing the same operation as in Example 1 except that no saccharide was added. Table 1 shows the measurement results of various properties of the obtained alkaline titanium oxide sol.
＜比較例２＞
糖類を添加しなかったこと以外は実施例２と同様の操作を行い、アルカリ性酸化チタンゾルを得た。得られたアルカリ性酸化チタンゾルの諸特性の測定結果を表１に示す。
＜比較例３＞
糖類を添加しなかったこと以外は実施例４と同様の操作を行い、亜酸化銅担持アルカリ性酸化チタンゾルを得た。得られた亜酸化銅担持アルカリ性酸化チタンゾルの諸特性の測定結果を表１に示す。
<Comparative example 2>
Except that no saccharide was added, the same operation as in Example 2 was performed to obtain an alkaline titanium oxide sol. Table 1 shows the measurement results of various properties of the obtained alkaline titanium oxide sol.
<Comparative Example 3>
A cuprous oxide-supported alkaline titanium oxide sol was obtained in the same manner as in Example 4 except that no saccharide was added. Table 1 shows the measurement results of various properties of the obtained cuprous oxide-supported alkaline titanium oxide sol.
表１に示すとおり、実施例１〜４のアルカリ性酸化チタンゾルは、糖類を含むために、平均粒径が小さく、分散性に優れている。一方、比較例１及び２のアルカリ性酸化チタンゾルは、糖類を含まないために、平均粒径が大きく、酸化チタン粒子が凝集して凝集粒子を形成しており、分散性が悪い。
また、実施例４及び比較例３では、共に助触媒（Ｃｕ2Ｏ）を用いているが、糖類を含む実施例４の方が糖類を含まない比較例３と比べて、平均粒径が著しく小さく、分散性が著しく優れている。その理由は次のとおりであると推測される。
すなわち、実施例４では、糖類を含むため、酸化チタンの凝集を抑制する以外に、Ｃｕ2Ｏも高分散化したものと考えられる。その反応機構として、原料（ＣｕＣｌ2・２Ｈ2Ｏ）投入時（ｐＨ＝３）において糖類と銅イオンが錯体を形成し、その後水酸化ナトリウムを加えることにより（ｐＨ＝１２）、加水分解が緩やかに進行し又は銅化合物の凝集が抑制される。その結果として、比較例３に比べ実施例４の方が圧倒的に平均粒径が小さくなったものと推測される。このように糖類は、酸化チタンのみならず金属助触媒の高分散化にも寄与する。
As shown in Table 1, since the alkaline titanium oxide sols of Examples 1 to 4 contain saccharides, the average particle size is small and the dispersibility is excellent. On the other hand, since the alkaline titanium oxide sols of Comparative Examples 1 and 2 do not contain saccharides, the average particle size is large, the titanium oxide particles are aggregated to form aggregated particles, and the dispersibility is poor.
In Example 4 and Comparative Example 3, co-catalyst (Cu 2 O) is used. However, Example 4 containing saccharide has a significantly larger average particle diameter than Comparative Example 3 containing no saccharide. It is small and has excellent dispersibility. The reason is estimated as follows.
That is, in Example 4, since saccharides were included, it was considered that Cu 2 O was highly dispersed in addition to suppressing aggregation of titanium oxide. As the reaction mechanism, when the raw material (CuCl 2 · 2H 2 O) is charged (pH = 3), saccharides and copper ions form a complex, and then sodium hydroxide is added (pH = 12), so that the hydrolysis is slow. Or aggregation of the copper compound is suppressed. As a result, it is presumed that the average particle size of Example 4 was significantly smaller than that of Comparative Example 3. Thus, the saccharide contributes not only to titanium oxide but also to high dispersion of the metal promoter.
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012212020A JP6034110B2 (en) | 2012-09-26 | 2012-09-26 | Titanium oxide sol and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012212020A JP6034110B2 (en) | 2012-09-26 | 2012-09-26 | Titanium oxide sol and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2014065632A true JP2014065632A (en) | 2014-04-17 |
| JP6034110B2 JP6034110B2 (en) | 2016-11-30 |
Family
ID=50742410
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012212020A Expired - Fee Related JP6034110B2 (en) | 2012-09-26 | 2012-09-26 | Titanium oxide sol and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6034110B2 (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003072661A1 (en) * | 2002-02-27 | 2003-09-04 | Sustainable Titania Technology Incorporated | Solution for forming ultra-hydrophilic photocatalyst film, construct provided with the film and process for producing the same |
| JP2004083376A (en) * | 2002-08-29 | 2004-03-18 | National Institute Of Advanced Industrial & Technology | Ceramic porous membrane with porosity and membrane thickness controlled simultaneously, and its producing method |
| JP2006007119A (en) * | 2004-06-25 | 2006-01-12 | Andes Denki Kk | Photocatalyst material, manufacturing method therefor and synthetic raw material solution |
| JP2010274142A (en) * | 2009-04-30 | 2010-12-09 | Shin-Etsu Chemical Co Ltd | Dispersion of photocatalyst particles, and method of producing the same |
| WO2011049068A1 (en) * | 2009-10-19 | 2011-04-28 | 国立大学法人 東京大学 | Method for inactivating virus and article provided with antiviral properties |
| JP2013082654A (en) * | 2011-10-12 | 2013-05-09 | Showa Denko Kk | Antimicrobial and antiviral composition and method of producing the same |
-
2012
- 2012-09-26 JP JP2012212020A patent/JP6034110B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003072661A1 (en) * | 2002-02-27 | 2003-09-04 | Sustainable Titania Technology Incorporated | Solution for forming ultra-hydrophilic photocatalyst film, construct provided with the film and process for producing the same |
| JP2004083376A (en) * | 2002-08-29 | 2004-03-18 | National Institute Of Advanced Industrial & Technology | Ceramic porous membrane with porosity and membrane thickness controlled simultaneously, and its producing method |
| JP2006007119A (en) * | 2004-06-25 | 2006-01-12 | Andes Denki Kk | Photocatalyst material, manufacturing method therefor and synthetic raw material solution |
| JP2010274142A (en) * | 2009-04-30 | 2010-12-09 | Shin-Etsu Chemical Co Ltd | Dispersion of photocatalyst particles, and method of producing the same |
| WO2011049068A1 (en) * | 2009-10-19 | 2011-04-28 | 国立大学法人 東京大学 | Method for inactivating virus and article provided with antiviral properties |
| JP2013082654A (en) * | 2011-10-12 | 2013-05-09 | Showa Denko Kk | Antimicrobial and antiviral composition and method of producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6034110B2 (en) | 2016-11-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4408702B2 (en) | Superhydrophilic photocatalyst film forming liquid, structure provided with the film, and method for producing the same | |
| JP5812488B2 (en) | Antibacterial antiviral composition and method for producing the same | |
| TWI732752B (en) | Visible light response type photocatalyst titanium oxide microparticle dispersion liquid, its production method, and member having a photocatalyst film on the surface | |
| EP1740660B1 (en) | Coating material and use thereof | |
| JP6040021B2 (en) | Antibacterial antiviral composition and method for producing the same | |
| TWI746633B (en) | Visible light responsive photocatalyst titanium oxide microparticle mixture, its dispersion, method for producing the dispersion, photocatalyst film, and member with photocatalyst film on the surface | |
| JP5447178B2 (en) | Visible light responsive titanium oxide fine particle dispersion and method for producing the same | |
| WO2011145385A1 (en) | Visible-light-responsive titanium oxide microparticle dispersion, and process for production thereof | |
| CN101792618A (en) | The manufacture method of hydrophilic agent, hydrophilic agent and hydrophile function product | |
| KR20090127820A (en) | Zirconium oxalate sol | |
| KR101767528B1 (en) | BiVO₄-CARRIED TITANIUM OXIDE, METHOD FOR MANUFACTURING THE SAME, AND ANTIVIRAL COMPOSITION | |
| CN110354844A (en) | Photocatalyst material | |
| TWI430838B (en) | Visible-light sensitive photocatalyst, method for preparing the same, coating agent and dispersion comprising the same | |
| JP5317432B2 (en) | Deodorant antibacterial composition and method for producing dispersion thereof | |
| JP5447177B2 (en) | Visible light responsive titanium oxide fine particle dispersion and method for producing the same | |
| JP4849778B2 (en) | Antibacterial deodorant and method for producing the same | |
| JP6034110B2 (en) | Titanium oxide sol and method for producing the same | |
| JP7088082B2 (en) | A method for producing a titanium oxide fine particle mixture, a dispersion thereof, a photocatalyst thin film, a member having a photocatalyst thin film on the surface, and a titanium oxide fine particle dispersion. | |
| JP7070474B2 (en) | Titanium oxide fine particles, their dispersion, and a method for producing the dispersion. | |
| JP5313051B2 (en) | Zirconium oxalate sol | |
| CN100450622C (en) | Transparent film-forming composition | |
| JP4964331B2 (en) | Method for producing antibacterial deodorant | |
| JP5113723B2 (en) | Photocatalyst dispersion | |
| JP7074556B2 (en) | Coating film and water-based composition | |
| JP2001029795A (en) | Titanium oxide coating film-formable composition for photocatalyst and production of the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20150619 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20160520 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20160524 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160704 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20161004 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20161027 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6034110 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |