JP3385243B2 - Method for producing titanium oxide sol - Google Patents
Method for producing titanium oxide solInfo
- Publication number
- JP3385243B2 JP3385243B2 JP27309499A JP27309499A JP3385243B2 JP 3385243 B2 JP3385243 B2 JP 3385243B2 JP 27309499 A JP27309499 A JP 27309499A JP 27309499 A JP27309499 A JP 27309499A JP 3385243 B2 JP3385243 B2 JP 3385243B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- sol
- oxide sol
- producing
- titanium
- 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.)
- Expired - Fee Related
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 133
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 93
- 238000004519 manufacturing process Methods 0.000 title claims description 24
- 239000002245 particle Substances 0.000 claims description 39
- 239000008139 complexing agent Substances 0.000 claims description 34
- 230000002378 acidificating effect Effects 0.000 claims description 22
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 14
- -1 amine compound Chemical class 0.000 claims description 14
- 238000002242 deionisation method Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002738 chelating agent Substances 0.000 claims description 7
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 229960001231 choline Drugs 0.000 claims description 5
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 4
- 150000003868 ammonium compounds Chemical class 0.000 claims description 4
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 20
- 239000000243 solution Substances 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 19
- 239000004408 titanium dioxide Substances 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 239000000084 colloidal system Substances 0.000 description 15
- 230000007935 neutral effect Effects 0.000 description 12
- 239000010936 titanium Substances 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229910052719 titanium Inorganic materials 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 6
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000000908 ammonium hydroxide Substances 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 229940005657 pyrophosphoric acid Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000174 gluconic acid Substances 0.000 description 3
- 235000012208 gluconic acid Nutrition 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000004310 lactic acid Substances 0.000 description 3
- 235000014655 lactic acid Nutrition 0.000 description 3
- 239000001630 malic acid Substances 0.000 description 3
- 235000011090 malic acid Nutrition 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000004893 oxazines Chemical class 0.000 description 3
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 229910000348 titanium sulfate Inorganic materials 0.000 description 3
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 3
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910001335 Galvanized steel Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005524 ceramic coating Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 239000008397 galvanized steel Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- 235000011044 succinic acid Nutrition 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- RYSXWUYLAWPLES-MTOQALJVSA-N (Z)-4-hydroxypent-3-en-2-one titanium Chemical compound [Ti].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O RYSXWUYLAWPLES-MTOQALJVSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- QWJSAWXRUVVRLH-LREBCSMRSA-M 2-hydroxyethyl(trimethyl)azanium;(2r,3r)-2,3,4-trihydroxy-4-oxobutanoate Chemical compound C[N+](C)(C)CCO.OC(=O)[C@H](O)[C@@H](O)C([O-])=O QWJSAWXRUVVRLH-LREBCSMRSA-M 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 239000004251 Ammonium lactate Substances 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229940059265 ammonium lactate Drugs 0.000 description 1
- 235000019286 ammonium lactate Nutrition 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- AWXXNBQGZBENFO-UHFFFAOYSA-N morpholine Chemical compound C1COCCN1.C1COCCN1 AWXXNBQGZBENFO-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006267 polyester film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- VKFFEYLSKIYTSJ-UHFFFAOYSA-N tetraazanium;phosphonato phosphate Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[O-]P([O-])(=O)OP([O-])([O-])=O VKFFEYLSKIYTSJ-UHFFFAOYSA-N 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
- C23C18/1208—Oxides, e.g. ceramics
- C23C18/1216—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1262—Process of deposition of the inorganic material involving particles, e.g. carbon nanotubes [CNT], flakes
- C23C18/127—Preformed particles
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Thermal Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Nanotechnology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Colloid Chemistry (AREA)
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、酸化チタンゾルの
製造方法に関するものである。更に詳しく述べるなら
ば、本発明は、主として半導体光触媒として利用される
二酸化チタンのコロイドゾルの製造方法に関するもので
ある。本発明方法により得られる酸化チタンゾルは、主
として紫外線吸収、汚れ防止、親水、防曇、抗菌、など
の各種機能性コーティング剤原料として利用することが
できる。TECHNICAL FIELD The present invention relates to a method for producing a titanium oxide sol. More specifically, the present invention relates to a method for producing a colloidal sol of titanium dioxide mainly used as a semiconductor photocatalyst. The titanium oxide sol obtained by the method of the present invention can be mainly used as a raw material for various functional coating agents such as ultraviolet ray absorption, stain prevention, hydrophilicity, antifogging and antibacterial.
【０００２】[0002]
【従来の技術】従来より、有機系塗料に比較して、耐熱
性、耐摩耗性などにおいて優れているセラミック塗料と
しては、アルカリ金属けい酸塩系、りん酸塩系、シリカ
ゾル系、金属酸化物系などの塗料が知られている。2. Description of the Related Art Conventionally, alkali metal silicate type, phosphate type, silica sol type, metal oxide type ceramic coatings are superior in heat resistance and abrasion resistance as compared with organic coatings. A paint such as a system is known.
【０００３】これらの塗料は、耐熱性、耐摩耗性に優れ
ているなどの無機系塗料の特徴を有しているが、近年、
セラミック皮膜に、さらに新しい機能を具備させようと
する試みが、金属酸化物系を中心になされている。These paints have the characteristics of inorganic paints such as excellent heat resistance and abrasion resistance.
Attempts to provide ceramic coatings with new functions are centered on metal oxide systems.
【０００４】各種セラミックスの中でも酸化チタンは、
優れた光触媒効果を示すことが可能であり、これに紫外
線を照射すると高い酸化力を発揮する。Among various ceramics, titanium oxide is
It is possible to show an excellent photocatalytic effect, and when it is irradiated with ultraviolet rays, it exhibits a high oxidizing power.
【０００５】このため、光触媒活性に優れている酸化チ
タンを、金属、ガラス、セラミックなどの被塗物表面に
存在させることにより、汚れの付着防止、悪臭成分の分
解、水質の浄化、防錆、抗菌、藻類の繁殖防止、難分解
性廃棄物の分解の促進などに有効であることが知られて
いる。Therefore, the presence of titanium oxide, which has excellent photocatalytic activity, on the surface of an object to be coated, such as metal, glass, or ceramic, prevents dirt from adhering, decomposes malodorous components, purifies water, and prevents rust. It is known to be effective in antibacterial, prevention of algae reproduction, and promotion of decomposition of hardly decomposable waste.
【０００６】上記の特性を有する酸化チタン皮膜を素材
表面に形成することを目的とする各種の酸化チタン塗料
及びその製造方法が、これまでにいくつか提案されてき
た。Various titanium oxide paints and methods for producing the same have been proposed so far for the purpose of forming a titanium oxide film having the above characteristics on the surface of a material.
【０００７】酸化チタン皮膜の形成方法としては、チタ
ンのアルコキシドを加水分解したものを塗布する方法、
すなわちゾル−ゲル法が最も一般的であり、これに類す
る技術としては、例えば特開平４−８３５３７号公報に
示されているように、チタンアルコキシドにアミド又は
グリコールを添加する方法、及び特開平７−１００３７
８号公報に示されているように、チタンアルコキシドに
アルコールアミン類を添加する方法などが知られてい
る。The titanium oxide film is formed by applying a hydrolyzed titanium alkoxide,
That is, the sol-gel method is the most general method, and as a technique similar to this, for example, a method of adding an amide or glycol to a titanium alkoxide, as disclosed in JP-A-4-83537, and JP-A- -10037
As disclosed in Japanese Patent No. 8, a method of adding alcohol amines to titanium alkoxide is known.
【０００８】また、上記方法の他に、酸化チタンゾルを
製造する方法としては、特開平６−２９３５１９号公報
に示されているように、水熱処理により結晶化させた酸
化チタン微粒子を、pH３以下の酸溶液中に分散させ、こ
の分散液を塗布する方法が知られている。In addition to the above method, as a method for producing a titanium oxide sol, as disclosed in JP-A-6-293519, fine particles of titanium oxide crystallized by hydrothermal treatment have a pH of 3 or less. A method of dispersing in an acid solution and applying the dispersion is known.
【０００９】しかし、上記のゾル−ゲル法及び酸で解膠
又は分散させる方法は、コロイド溶液が酸性であるた
め、金属や紙などの表面に塗布すると、これらの素材を
腐食又は劣化させるという大きな問題点があった。ま
た、樹脂、セラミック又はガラスなど耐酸性の良好な素
材に塗布する場合でも、コーター、印刷機やスプレーガ
ンなど塗装機器に腐食を生じ、また作業員に対する塗布
作業環境の悪化が問題となっていた。However, in the sol-gel method and the method of deflocculating or dispersing with an acid, the colloidal solution is acidic, and therefore, when applied to the surface of metal or paper, these materials corrode or deteriorate. There was a problem. Further, even when it is applied to a material having good acid resistance such as resin, ceramics or glass, the coating equipment such as a coater, a printing machine and a spray gun is corroded, and the deterioration of the application work environment for workers has been a problem. .
【００１０】これらの問題点を解決するための手段とし
ては、特開平９−７１４１８号公報に開示されているよ
うに、過酸化水素水と酸化チタンとを含むゾル液、及び
その製造方法が知られている。このゾル液は中性とする
ことが可能であるという利点を有しているが、しかし酸
化剤を含んでいるために、金属の腐食の防止には効果が
小さいこと、及びゾル液が黄色に着色しており、加熱乾
燥しないと無色の皮膜が得られにくいことなどの問題点
があった。As means for solving these problems, as disclosed in Japanese Patent Laid-Open No. 9-71418, a sol liquid containing hydrogen peroxide solution and titanium oxide, and a method for producing the same are known. Has been. This sol solution has the advantage that it can be neutral, but it is less effective in preventing metal corrosion because it contains an oxidizing agent, and the sol solution becomes yellow. There is a problem in that it is colored and it is difficult to obtain a colorless film unless it is dried by heating.
【００１１】[0011]
【発明が解決しようとする課題】本発明は、これらの従
来あった光触媒酸化チタン溶液が抱えていた問題点を解
決し、中性でも安定であって、安全にコーティング作業
を行うことができ、常温乾燥でも無色透明の皮膜を得る
ことができる酸化チタンコロイドゾルの製造方法を提供
しようとするものである。DISCLOSURE OF THE INVENTION The present invention solves the problems of these conventional photocatalytic titanium oxide solutions, is stable even at neutrality, and enables safe coating work. An object of the present invention is to provide a method for producing a titanium oxide colloidal sol that can obtain a colorless and transparent film even when dried at room temperature.
【００１２】[0012]
【課題を解決するための手段】本発明者らは、上記の課
題を解決するため、まず塩化チタン及び硫酸チタンなど
の無機チタン塩又はチタンアルコキシドを、酸性で水と
反応させて加水分解し、二酸化チタンコロイド溶液を調
製した。さらに発明者らは、この酸化チタンの酸性コロ
イドゾルについて分析し、酸化チタン粒子が酸性におい
ては安定な正電荷を帯びているが、これをアルカリ溶液
で中和してゆくと、pHが３〜５の範囲内ではほぼ電荷を
失い、コロイドが著しく不安定となり、強く凝集して再
分散し難くなり、さらにアルカリ性を強くすると凝集し
た粒子は負帯電することを確認した。In order to solve the above problems, the present inventors firstly hydrolyze an inorganic titanium salt such as titanium chloride and titanium sulfate or a titanium alkoxide by reacting with water in an acidic manner, A titanium dioxide colloidal solution was prepared. Furthermore, the inventors analyzed the acidic colloidal sol of titanium oxide and found that the titanium oxide particles had a stable positive charge in an acidic condition, but when neutralized with an alkaline solution, the pH was 3 to 5 It was confirmed that within the range of 1, the charge was almost lost, the colloid became extremely unstable, strongly aggregated and became difficult to redisperse, and when the alkalinity was increased, the aggregated particles were negatively charged.
【００１３】そこで発明者らは、酸化チタンコロイド粒
子に中性領域でも安定な電荷と良好な分散性とを具備さ
せる方法について検討を重ねた。その結果、酸化チタン
酸性コロイドゾル液に、アルカリ金属の水酸化物、又は
アンモニア水溶液を添加して、ゾル液のpHをアルカリ性
領域にしても、コロイドは再分散せず、強く凝集したス
ラリー状の懸濁液となってしまう現象の原因が、ゾル液
中に存在するＴｉ4+イオンが膠状の水酸化チタンとな
り、これが二酸化チタン粒子どうしを結合させること、
及び中性付近におけるコロイド粒子の負帯電が弱いた
め、粒子間の反発力が小さいことにあることを見出し
た。Therefore, the inventors have conducted extensive studies on a method for providing titanium oxide colloidal particles with stable electric charge and good dispersibility even in a neutral region. As a result, even if the alkali metal hydroxide or aqueous ammonia solution was added to the titanium oxide acidic colloid sol solution to bring the pH of the sol solution to the alkaline range, the colloid did not redisperse, but a strongly aggregated slurry-like suspension. The cause of the phenomenon of becoming a turbid liquid is that Ti 4+ ions present in the sol liquid become colloidal titanium hydroxide, which binds the titanium dioxide particles together,
It was also found that the repulsive force between particles is small because the negative charge of colloidal particles in the vicinity of neutral is weak.
【００１４】そして、あらかじめ酸性酸化チタンコロイ
ドゾルに、Ｔｉ4+イオンと錯体を形成可能な多価カルボ
ン酸、ヒドロキシカルボン酸、及びピロリン酸などの縮
合リン酸などから選ばれた錯化剤を添加して酸化チタン
コロイド粒子表面を表面改質した後、アンモニア水、モ
ルホリン等のアルカリ成分により、ゾル液のpHを上昇さ
せてpH値を所望値に調整することにより、中性〜アルカ
リ性のpH領域において、負電荷により安定に分散した酸
化チタンコロイドゾルが得られ、このゾルを被処理物に
塗布することにより、無色透明で優れた密着性を有する
二酸化チタン皮膜が得られることが見出された。Then, a complexing agent selected from polyvalent carboxylic acids capable of forming a complex with Ti 4+ ions, hydroxycarboxylic acid, condensed phosphoric acid such as pyrophosphoric acid, etc. is added to the acidic titanium oxide colloid sol in advance. After surface-modifying the surface of titanium oxide colloidal particles, the pH of the sol solution is adjusted to a desired value by increasing the pH of the sol solution with an alkaline component such as aqueous ammonia or morpholine, thereby adjusting the pH value in the neutral to alkaline range. It was found that a titanium oxide colloidal sol stably dispersed by a negative charge was obtained, and a colorless and transparent titanium dioxide film having excellent adhesion was obtained by applying this sol to an object to be treated. .
【００１５】また、酸化チタンゾルの組成として、負帯
電の酸化チタンコロイド粒子成分と、前記錯化剤と、ア
ルカリ性成分とを含む中性ゾルが、良好な安定性と分散
性を有し、上記の性能を満足することが見出された。ま
た、上記組成の酸化チタンゾルの製造方法についてさら
に検討された結果、酸化チタンコロイド粒子成分と錯化
剤成分とを含むゾルに、アルカリ性成分を加えてゾル液
を中性〜アルカリ性とし、さらにこの液を透析やイオン
交換樹脂処理などの脱イオン処理に供することにより、
不純物のより少ない酸化チタンゾルが得られることが見
出され、それに基いて本発明が完成された。Further, as the composition of the titanium oxide sol, a neutral sol containing a negatively charged titanium oxide colloidal particle component, the complexing agent and an alkaline component has good stability and dispersibility, It was found that the performance was satisfied. Further, as a result of further examination of a method for producing a titanium oxide sol having the above composition, a sol containing a titanium oxide colloidal particle component and a complexing agent component was added with an alkaline component to make the sol liquid neutral to alkaline. Is subjected to deionization treatment such as dialysis or ion exchange resin treatment,
It was found that a titanium oxide sol with less impurities was obtained, on which the invention was completed.
【００１６】本発明の酸化チタンゾルの製造方法は、酸
化チタンコロイド粒子成分５０〜１００重量部と、錯化
剤成分５〜５０重量部とを含む酸性酸化チタンゾルに、
アルカリ性成分を添加してゾル液のpHを６〜１２に調整
し、さらにこのゾル液に脱イオン処理を施して、酸化チ
タンコロイドゾル粒子を負に帯電させることを特徴とす
るものである。本発明の酸化チタンコロイドゾルにおい
て、錯化剤としては、カルボキシル基を有する少なくと
も１種のキレート性化合物を含むものが好ましく、また
縮合リン酸または縮合リン酸塩が錯化剤として最も好ま
しく使用される。また、本発明の酸化チタンゾルに含ま
れるアルカリ性成分としては、アンモニウム化合物、ア
ルカリ金属化合物、及びアミン類から選ばれてもよく、
また、モルホリンなどのオキサジン類やピペリジン、コ
リンなどの有機アルカリ化合物から選ばれてもよい。本
発明方法において、前記脱イオン処理により得られる酸
化チタンゾルは、負帯電の酸化チタンコロイド粒子成分
５０〜１００重量部と、錯化剤５〜５０重量部と、アル
カリ性成分１〜５０重量部とを含むことが好ましい。本
発明方法において、前記脱イオン処理により得られる酸
化チタンゾルのpHは５〜１０であることが好ましい。The method for producing a titanium oxide sol of the present invention comprises adding an acidic titanium oxide sol containing 50 to 100 parts by weight of a titanium oxide colloidal particle component and 5 to 50 parts by weight of a complexing agent component,
The pH of the sol liquid is adjusted to 6 to 12 by adding an alkaline component, and the sol liquid is subjected to deionization treatment to negatively charge the titanium oxide colloid sol particles. In the titanium oxide colloid sol of the present invention, the complexing agent preferably contains at least one chelating compound having a carboxyl group, and condensed phosphoric acid or condensed phosphate is most preferably used as the complexing agent. It The alkaline component contained in the titanium oxide sol of the present invention may be selected from ammonium compounds, alkali metal compounds, and amines,
Further, it may be selected from oxazines such as morpholine and organic alkaline compounds such as piperidine and choline. In the method of the present invention, the titanium oxide sol obtained by the deionization treatment contains 50 to 100 parts by weight of a negatively charged titanium oxide colloidal particle component, 5 to 50 parts by weight of a complexing agent, and 1 to 50 parts by weight of an alkaline component. It is preferable to include. In the method of the present invention, the titanium oxide sol obtained by the deionization treatment preferably has a pH of 5-10.
【００１７】[0017]
【発明の実施の形態】本発明の酸化チタンゾルの製造方
法は、酸化チタンコロイド粒子成分５０〜１００重量部
と、錯化剤成分５〜５０重量部とを含む酸性酸化チタン
ゾルに、アルカリ成分を添加してゾル液のpHを６〜１２
に調整し、さらにこのゾル液に脱イオン処理を施して、
酸化チタンコロイドゾル粒子を負に帯電させることを特
徴とするものである。本発明方法により得られる酸化チ
タンゾルは、酸化チタンコロイド粒子成分５〜１００重
量部を含有するものであり、かつこの酸化チタンコロイ
ド粒子は中性ゾル溶液中において負に帯電している。中
性領域で酸化チタン粒子が正に帯電していると、コロイ
ドの分散が不安定となるため好ましくない。粒子の帯電
の正負は、ゼータ電位測定装置等によって容易に知るこ
とができる。BEST MODE FOR CARRYING OUT THE INVENTION The method for producing a titanium oxide sol of the present invention comprises adding an alkaline component to an acidic titanium oxide sol containing 50 to 100 parts by weight of a titanium oxide colloidal particle component and 5 to 50 parts by weight of a complexing agent component. Then adjust the pH of the sol to 6-12
And then deionizing this sol,
It is characterized in that the titanium oxide colloid sol particles are negatively charged. The titanium oxide sol obtained by the method of the present invention contains 5 to 100 parts by weight of the titanium oxide colloid particle component, and the titanium oxide colloid particles are negatively charged in the neutral sol solution. If the titanium oxide particles are positively charged in the neutral region, the dispersion of the colloid becomes unstable, which is not preferable. The positive / negative of the charge of the particles can be easily known by a zeta potential measuring device or the like.
【００１８】本発明方法に用いられる酸化チタンの種類
としてはアナターゼ型二酸化チタン（メタチタン酸を含
む）及びオルソチタン酸が最も好ましく、次にルチル型
など他の二酸化チタンを用いることが好ましい。The types of titanium oxide used in the method of the present invention are most preferably anatase type titanium dioxide (including metatitanic acid) and orthotitanic acid, and then it is preferable to use other titanium dioxide such as rutile type.
【００１９】酸化チタンコロイド粒子の粒径には特に限
定はないが、一般に１nm〜５００nmであることが好まし
く、３〜１２０nmであることがより好ましい。The particle size of the titanium oxide colloidal particles is not particularly limited, but is generally preferably 1 nm to 500 nm, more preferably 3 to 120 nm.
【００２０】これらの二酸化チタンコロイド粒子は、塩
化チタン、オキシ塩化チタン、硫酸チタン及び硫酸チタ
ニルなどの無機チタン化合物を水に溶解し、塩酸や硝酸
などの触媒を必要に応じて添加し、常温または加熱によ
り加水分解することによって得られる。また別の方法と
して、チタニウムアルコキシド、チタニウムアセチルア
セトネートなどの有機チタン化合物の加水分解によって
も得ることができる。これらのように酸性溶液中で得ら
れた酸化チタン粒子は正に帯電しているため、ゾル液に
アルカリ成分を添加して、そのpHを６以上にする際に、
ゾル液中に錯化剤を添加することにより二酸化チタン粒
子の帯電を負にすることが必要である。These titanium dioxide colloidal particles are prepared by dissolving an inorganic titanium compound such as titanium chloride, titanium oxychloride, titanium sulfate and titanyl sulfate in water, and adding a catalyst such as hydrochloric acid or nitric acid as necessary, at room temperature or Obtained by hydrolysis by heating. Alternatively, it can be obtained by hydrolysis of an organic titanium compound such as titanium alkoxide or titanium acetylacetonate. Titanium oxide particles obtained in an acidic solution like these are positively charged, so when adding an alkaline component to the sol liquid to adjust its pH to 6 or more,
It is necessary to add a complexing agent to the sol solution to make the titanium dioxide particles negatively charged.
【００２１】また、本発明方法においては、酸性酸化チ
タンゾル中には、錯化剤が５〜５０重量部の割合で含ま
れる必要がある。また本発明方法で使用できる錯化剤の
うち、キレート性化合物としては、その分子骨格中に少
なくとも１個のカルボキシル基が含まれていることが好
ましく、しかもＴｉ4+イオンに対して強いキレート効果
を有するものが好ましい。好ましいキレート性化合物の
種類としては、多価カルボン酸やヒドロキシカルボン酸
などであり、例えばグルコン酸、グリコール酸、乳酸、
酒石酸、クエン酸、リンゴ酸及びコハク酸などである。
最も好ましい錯化剤はピロリン酸、トリポリリン酸など
の縮合リン酸及びそれらの塩である。In the method of the present invention, the acidic titanium oxide sol should contain the complexing agent in a proportion of 5 to 50 parts by weight. Of the complexing agents that can be used in the method of the present invention, the chelating compound preferably has at least one carboxyl group in its molecular skeleton, and has a strong chelating effect on Ti 4+ ions. Those having are preferred. Preferred chelating compound types include polycarboxylic acids and hydroxycarboxylic acids, such as gluconic acid, glycolic acid, lactic acid,
Examples include tartaric acid, citric acid, malic acid and succinic acid.
The most preferable complexing agents are condensed phosphoric acids such as pyrophosphoric acid and tripolyphosphoric acid, and salts thereof.
【００２２】本発明方法において、酸性酸化チタンゾル
中には、錯化剤の他に、ゾル液中に残存している塩酸イ
オン又は硫酸イオンなどの酸性イオンを中和して、二酸
化チタンコロイド粒子により安定な負電荷を与えるため
に、好ましくは１〜５０重量部のアルカリ性成分が添加
され、それによってゾル液のpHが６〜１２の範囲に調整
される。In the method of the present invention, in the acidic titanium oxide sol, in addition to the complexing agent, acidic ions such as hydrochloric acid ion or sulfuric acid ion remaining in the sol solution are neutralized, and the titanium dioxide colloidal particles are used. In order to give a stable negative charge, preferably 1 to 50 parts by weight of an alkaline component is added, whereby the pH of the sol solution is adjusted to the range of 6 to 12.
【００２３】本発明方法に用いられるアルカリ性成分と
しては、アンモニウム化合物、アルカリ金属化合物、及
びアミン類の中から選ばれた少なくとも１種のアルカリ
性成分を含むことが好ましく、例えば水酸化アンモニウ
ム（アンモニア水）、水酸化ナトリウム、水酸化カリウ
ム、水酸化リチウム、珪酸ナトリウム、並びにエチレン
ジアミン及び、トリエチレンテトラミンなどのポリアミ
ンなどを使用することができる。さらに好ましいアルカ
リ性成分としては、モルホリンなどのオキサジン、ピペ
リジン、及びコリンがある。本発明の二酸化チタンコロ
イドゾルをコーティング剤として使用する場合は、焼成
によって塗膜中から揮発しやすいオキサジン、ピペリジ
ンの他、水酸化アンモニウムやトリエタノールアミンな
どの低分子量アミンを用いることがより好ましい。The alkaline component used in the method of the present invention preferably contains at least one alkaline component selected from ammonium compounds, alkali metal compounds, and amines. For example, ammonium hydroxide (aqueous ammonia). , Sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium silicate, and polyamines such as ethylenediamine and triethylenetetramine can be used. More preferred alkaline components include oxazines such as morpholine, piperidine, and choline. When the titanium dioxide colloid sol of the present invention is used as a coating agent, it is more preferable to use low molecular weight amines such as ammonium hydroxide and triethanolamine in addition to oxazine and piperidine, which are easily volatilized from the coating film by firing.
【００２４】錯化剤とアルカリ性成分とは、例えばピロ
リン酸アンモニウムや乳酸アンモニウム、酒石酸水素コ
リンなどの形で両成分を兼用する化合物を添加すること
もできる。As the complexing agent and the alkaline component, for example, a compound which serves as both components in the form of ammonium pyrophosphate, ammonium lactate, choline hydrogen tartrate or the like can be added.
【００２５】ゾル中に含まれるその他の成分としては、
使用するチタン原料によって、塩素イオン、硫酸イオ
ン、アルコールなどが含まれるが、残余の成分は実質上
水からなるものである。本発明の二酸化チタンコロイド
ゾルをコーティング剤として使用する場合には、補助溶
剤として水の一部をアルコール、グリコール、ケトン等
の水溶性溶剤に置き換えることも好ましい。また、この
場合、シリカゾルやアルキルトリメトキシシランなどの
シラン誘導体などをバインダーとして添加して、塗膜物
性を改善させることも可能である。Other components contained in the sol include:
Depending on the titanium raw material used, chlorine ions, sulfate ions, alcohols, etc. are included, but the remaining components are essentially water. When the titanium dioxide colloid sol of the present invention is used as a coating agent, it is also preferable to replace a part of water as a cosolvent with a water-soluble solvent such as alcohol, glycol or ketone. In this case, it is also possible to add a silica sol or a silane derivative such as alkyltrimethoxysilane as a binder to improve the physical properties of the coating film.
【００２６】本発明方法において、酸化チタンコロイド
粒子成分の重量に対して錯化剤の重量比が過少であると
コロイドの分散が不十分となり、安定なゾルを得ること
ができない。また、錯化剤の重量比が過大であると、得
られる塗膜の硬度が低下するため好ましくない。同様
に、アルカリ性成分の比率が過大であると塗膜硬度が低
下し、或はアルミニウム、亜鉛等の金属に対し腐食性を
示すため好ましくなく、またそれが過小の場合には、ゾ
ル液が酸性になるため好ましくない。In the method of the present invention, if the weight ratio of the complexing agent to the weight of the titanium oxide colloidal particle component is too small, the colloid is insufficiently dispersed, and a stable sol cannot be obtained. On the other hand, if the weight ratio of the complexing agent is too large, the hardness of the coating film obtained will decrease, which is not preferable. Similarly, if the proportion of the alkaline component is too large, the coating film hardness is lowered, or it is corrosive to metals such as aluminum and zinc, which is not preferable, and if it is too small, the sol solution becomes acidic. Is not preferable.
【００２７】また、本発明の酸化チタンコロイドゾルの
製造方法では、酸化チタンコロイド粒子５０〜１００重
量部と、錯化剤５〜５０重量部とを含む酸性酸化チタン
ゾルに、アルカリ性成分を添加して、ゾル液のpHを６〜
１２に調整し、さらにこのゾル液に脱イオン処理を施し
て、酸化チタンコロイド粒子を負に帯電させるものであ
る。In the method for producing a titanium oxide colloidal sol of the present invention, an alkaline component is added to an acidic titanium oxide sol containing 50 to 100 parts by weight of titanium oxide colloidal particles and 5 to 50 parts by weight of a complexing agent. , PH of sol liquid is 6 ~
It is adjusted to 12, and the sol solution is subjected to deionization treatment to negatively charge the titanium oxide colloidal particles.
【００２８】本発明方法において使用される酸性酸化チ
タンゾル成分は、前記塩化チタン、オキシ塩化チタン、
硫酸チタン、硫酸チタニルなどの無機チタン化合物を水
に溶解し、これに塩酸や硝酸などの触媒を必要に応じて
添加し、常温または加熱により加水分解することによっ
て得られ或いは、チタニウムアルコキシド、又はチタニ
ウムアセチルアセトネートなどの有機チタン化合物を加
水分解することによっても得ることができる。本発明方
法に使用される錯化剤としては、好ましくは多価カルボ
ン酸やヒドロキシカルボン酸などのように、分子骨格中
に少なくとも１個のカルボキシル基を有するキレート性
化合物であり、例えばグルコン酸、グリコール酸、乳
酸、酒石酸、クエン酸、リンゴ酸、コハク酸などを包含
するが、最も好ましい錯化剤は、ピロリン酸、トリポリ
リン酸などの縮合リン酸やそれらの塩から選ばれる。The acidic titanium oxide sol component used in the method of the present invention is titanium chloride, titanium oxychloride,
Obtained by dissolving an inorganic titanium compound such as titanium sulfate or titanyl sulfate in water, adding a catalyst such as hydrochloric acid or nitric acid as necessary to this, and hydrolyzing at room temperature or heating, or a titanium alkoxide or titanium. It can also be obtained by hydrolyzing an organic titanium compound such as acetylacetonate. The complexing agent used in the method of the present invention is preferably a chelating compound having at least one carboxyl group in the molecular skeleton, such as polyvalent carboxylic acid or hydroxycarboxylic acid, for example, gluconic acid, Glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, succinic acid and the like are included, but the most preferable complexing agent is selected from condensed phosphoric acid such as pyrophosphoric acid and tripolyphosphoric acid and salts thereof.
【００２９】本発明の酸化チタンゾルの製造方法におい
て使用できるアルカリ成分としては、水酸化アンモニウ
ムなどのアンモニウム化合物、アミン類、モルホリン等
のオキサジン、ピペリジン、及びコリンなどであり、ア
ルカリ金属の水酸化物はコーティング用に使用する場合
には比較的好ましくない。アルカリ性成分の添加量は、
ゾル液のpHが６〜１２の範囲となる量である。Alkali components that can be used in the method for producing a titanium oxide sol of the present invention include ammonium compounds such as ammonium hydroxide, amines, oxazines such as morpholine, piperidine, choline and the like. It is relatively unfavorable when used for coating. The amount of alkaline components added is
The amount is such that the pH of the sol liquid is in the range of 6-12.
【００３０】一方、本発明の製造方法に用いられるアル
カリ性成分としては、前記したものを使用できるが、水
酸化ナトリウム、水酸化カリウム、水酸化リチウム等の
アルカリ金属化合物を併用してもよい。On the other hand, as the alkaline component used in the production method of the present invention, those mentioned above can be used, but an alkali metal compound such as sodium hydroxide, potassium hydroxide or lithium hydroxide may be used in combination.
【００３１】本発明の製造方法において、アルカリ性成
分は、ゾル液のpHを６〜１２、好ましくは７〜９まで上
昇させる量で添加される。アルカリ性成分の添加後のゾ
ル液のpHが６未満では、コロイド粒子の分散が不十分と
なり、またゾル液のpHが１２をこえると、それと接触す
る金属材料に対する腐食性が強くなるため好ましくな
い。In the production method of the present invention, the alkaline component is added in such an amount that the pH of the sol liquid is raised to 6 to 12, preferably 7 to 9. When the pH of the sol solution after addition of the alkaline component is less than 6, the dispersion of the colloidal particles becomes insufficient, and when the pH of the sol solution exceeds 12, the corrosiveness against the metal material in contact with it becomes unfavorable.
【００３２】本発明の製造方法では、アルカリ性成分を
添加した後、さらにこのゾル液に脱イオン処理を施して
ゾル液中の余剰のイオンを除去する。In the manufacturing method of the present invention, after the alkaline component is added, the sol solution is further subjected to deionization treatment to remove excess ions in the sol solution.
【００３３】上記脱イオン処理の方法としては、半透膜
による拡散透析、イオン交換膜による電気透析、または
イオン交換樹脂との接触処理を用いることが好ましく、
この脱イオン処理を施すことにより、酸化チタンゾル中
のアルカリイオン及び酸性アニオンなどの夾雑イオンが
除去され、酸化チタン純度を高め、より実用的で塗膜性
能の高いゾルを得ることができる。脱イオン処理された
酸化チタンゾルのpHは５〜１０であることが好ましく、
６〜８．５とすることがより好ましい。As a method of the above deionization treatment, it is preferable to use diffusion dialysis with a semipermeable membrane, electrodialysis with an ion exchange membrane, or contact treatment with an ion exchange resin.
By performing this deionization treatment, impurities such as alkali ions and acidic anions in the titanium oxide sol are removed, the purity of titanium oxide is increased, and a more practical sol having high coating performance can be obtained. The pH of the deionized titanium oxide sol is preferably 5-10,
It is more preferable to set it to 6 to 8.5.
【００３４】被処理物に本発明の酸化チタンゾルを塗布
する場合、二酸化チタンの付着量として２００〜２００
０mg／ｍ2 となるように調整することが最も好ましい。
乾燥は、加熱乾燥のみでなく室温で乾燥することも可能
であるが、錯化剤としてカルボン酸等の有機化合物を使
用し、かつ１００℃以下の温度で乾燥する場合は、塗布
層の乾燥中または乾燥後に、この塗布層に波長４００nm
未満の紫外線を照射し錯化剤を分解させることが最も好
ましい。When the titanium oxide sol of the present invention is applied to the object to be treated, the amount of titanium dioxide deposited is 200 to 200.
Most preferably, the amount is adjusted to 0 mg / m 2 .
Drying can be performed not only by heat drying but also at room temperature. However, when an organic compound such as a carboxylic acid is used as a complexing agent and drying is performed at a temperature of 100 ° C. or lower, the coating layer is dried. Alternatively, after drying, the coating layer has a wavelength of 400 nm.
Most preferably, the complexing agent is decomposed by irradiating less than ultraviolet rays.
【００３５】本発明の負帯電酸化チタンゾルは、従来の
酸性酸化チタンゾル中に未反応成分として残存していた
４価チタンイオンを、カルボキシル基を有するキレート
性化合物、及び／又は縮合リン酸又はその塩を含む錯化
剤成分によって、マスキングし、それによって中性領域
におけるゲル化析出を防止し、かつ酸化チタンコロイド
粒子に吸着した錯化剤の負帯電が、正帯電酸化チタンコ
ロイド粒子を負帯電させる作用を示し、従って、安定な
中性酸化チタンゾルが得られる。有機キレート剤成分は
塗膜形成後には二酸化チタンの光触媒効果により水と炭
酸ガスに分解されるため害作用を及ぼすことはない。The negatively charged titanium oxide sol of the present invention is a chelating compound having a carboxyl group, and / or condensed phosphoric acid or a salt thereof, which is a tetravalent titanium ion which remains as an unreacted component in a conventional acidic titanium oxide sol. Of the complexing agent component containing a complexing agent to prevent gelation and precipitation in the neutral region, and the negative charge of the complexing agent adsorbed on the titanium oxide colloidal particles causes the positively charged titanium oxide colloidal particles to be negatively charged. A stable neutral titanium oxide sol is obtained. The organic chelating agent component does not have a harmful effect since it is decomposed into water and carbon dioxide gas by the photocatalytic effect of titanium dioxide after the coating film is formed.
【００３６】また、カルボキシル基の酸性、及び二酸化
チタン製造原料に由来するＣｌ- ，ＳＯ4 2- などの夾雑
酸性アニオンは、アンモニウム、アミン類、アルカリ金
属、オキサジン、ピペリジンなどのアルカリ性成分によ
って中和され、完全に中性のゾルとすることができる。Contaminant acidic anions such as Cl − and SO 4 2− derived from the acidity of the carboxyl group and titanium dioxide production raw material are neutralized by alkaline components such as ammonium, amines, alkali metals, oxazine and piperidine. And can be a completely neutral sol.
【００３７】本発明の負帯電酸化チタンコロイドゾル
は、錯化剤を含む酸性酸化チタンゾルに前記のアルカリ
性成分を添加することによって製造可能であるが、これ
にさらに、例えば半透膜による透析などの方法によって
脱イオン処理を施すことにより、さらに良質の酸化チタ
ンゾルを得ることができる。The negatively charged titanium oxide colloidal sol of the present invention can be produced by adding the above-mentioned alkaline component to an acidic titanium oxide sol containing a complexing agent. By performing the deionization treatment by the method, a higher quality titanium oxide sol can be obtained.
【００３８】[0038]
【実施例】本発明を、下記実施例によりさらに説明する
が、本発明はこれら実施例によって何ら制約されるもの
ではない。The present invention will be further described by the following examples, but the present invention is not limited to these examples.
【００３９】実施例１〜８及び比較例１〜４
下記実施例及び比較例には、下記の材料を使用した。
（酸化チタンコロイド）下記の２種類（Ａ，Ｂ）のうち
何れかを使用した。
Ａ）比較例１、比較例２、及び実施例１〜３及び実施例
６〜８において、酸化チタンコロイドとして、下記の方
法により調製したものを使用した。住友シチックス
（株）製塩化チタン水溶液（Ｔｉ：１５〜１６％）を水
で希釈し、イオン交換膜により脱イオン処理してオキシ
塩化チタン水溶液を調製し、これを７０〜８５℃で加熱
加水分解し、pH１〜２の二酸化チタンゾルを得た。透過
型電子顕微鏡により測定された二酸化チタンの結晶粒子
径は、０．００２〜０．０１μｍであった。酸化チタン
コロイド粒子の濃度は、その乾燥重量で５．０％であっ
た。
Ｂ）また、比較例３、比較例４及び実施例４及び５、日
本アエロジル（株）製の二酸化チタン粉体粒子（粒子
径：０．０２μｍ、アナターゼ＋ルチル型）を水中に分
散し、塩酸を添加してpH１．５に調製して得られた二酸
化チタンゾルを使用した。 Examples 1 to 8 and Comparative Examples 1 to 4 The following materials were used in the following Examples and Comparative Examples. (Titanium oxide colloid) One of the following two types (A, B) was used. A) In Comparative Example 1, Comparative Example 2, and Examples 1 to 3 and Examples 6 to 8, the titanium oxide colloids prepared by the following method were used. Sumitomo Sitix Co., Ltd. titanium chloride aqueous solution (Ti: 15 to 16%) is diluted with water and deionized with an ion exchange membrane to prepare a titanium oxychloride aqueous solution, which is heated and hydrolyzed at 70 to 85 ° C. Then, a titanium dioxide sol having a pH of 1 to 2 was obtained. The crystal particle size of titanium dioxide measured by a transmission electron microscope was 0.002 to 0.01 μm. The concentration of titanium oxide colloidal particles was 5.0% by dry weight. B) In addition, Comparative Example 3, Comparative Example 4 and Examples 4 and 5, titanium dioxide powder particles (particle size: 0.02 μm, anatase + rutile type) manufactured by Nippon Aerosil Co., Ltd. were dispersed in water, and hydrochloric acid was added. Was used to prepare a titanium dioxide sol obtained by adjusting the pH to 1.5.
【００４０】（錯化剤）錯化剤としては、グルコン酸、
グリコール酸、乳酸、酒石酸、クエン酸、リンゴ酸、ピ
ロリン酸、及びトリポリリン酸の中から表１，２に示す
ように選択して使用した。これらの薬品は、和光純薬
（株）製試薬１級品を使用した。(Complexing agent) As the complexing agent, gluconic acid,
Glycolic acid, lactic acid, tartaric acid, citric acid, malic acid, pyrophosphoric acid, and tripolyphosphoric acid were selected and used as shown in Tables 1 and 2. As these chemicals, Wako Pure Chemical Industries, Ltd. reagent first-grade products were used.
【００４１】（アルカリ性成分）アンモニア水（水酸化
アンモニウム）（比較例１）、水酸化ナトリウム（比較
例２）、水酸化カリウム（比較例３）、水酸化リチウム
（比較例４、実施例４）、トリエチレンテトラミン（実
施例１）、モルホリン（テトラヒドロ−１，４−オキサ
ジン）（実施例２，３）、ピペリジン（実施例５，６，
７）、及びコリン（実施例８）の中から表１に示すよう
に選択して使用した。これらの薬品は、試薬１級品また
は相当品を使用した。(Alkaline component) Ammonia water (ammonium hydroxide) (Comparative example 1), Sodium hydroxide (Comparative example 2), Potassium hydroxide (Comparative example 3), Lithium hydroxide (Comparative example 4, Example 4) , Triethylenetetramine (Example 1), morpholine (tetrahydro-1,4-oxazine) (Examples 2 and 3), piperidine (Examples 5 and 6).
7) and choline (Example 8) were selected and used as shown in Table 1. As these chemicals, first-class reagents or equivalent products were used.
【００４２】表１に、比較例及び実施例で使用した酸化
チタンゾルの組成を示した。調製したゾルは、ゼータ電
位測定装置によって酸化チタン粒子の荷電の正負を測定
した。また、アルミニウム、酸性紙、亜鉛めっき鋼板ま
たはステンレス板基材表面に、バーコーターで１０ml／
ｍ2 の塗布量で塗布し、８０℃で乾燥し、得られた塗膜
の外観品質及び光触媒活性（脂肪酸分解速度：単位；mg
／ｍ2 ・ｄａｙ）を測定した。Table 1 shows the composition of the titanium oxide sol used in Comparative Examples and Examples. With respect to the prepared sol, the positive and negative charges of titanium oxide particles were measured by a zeta potential measuring device. In addition, aluminum, acid paper, galvanized steel sheet or stainless steel plate substrate surface, 10ml / with a bar coater
It was applied at a coating amount of m 2 and dried at 80 ° C., and the appearance quality and photocatalytic activity (fatty acid decomposition rate: unit; mg) of the obtained coating film
/ M 2 · day) was measured.
【００４３】基材は、比較例１、実施例１、実施例３、
及び実施例７ではアルミニウム合金を使用し、比較例
２、及び実施例２では酸性紙を使用し、比較例３、及び
実施例５では亜鉛めっき鋼板を使用し、比較例４、及び
実施例４では鋼板を使用し、実施例６はステンレス鋼板
（ＳＵＳ３０４）を使用した。また、実施例８ではポリ
エステルフィルムにシリコーン樹脂プライマーを塗布し
たものを基材として使用した。The base materials are Comparative Example 1, Example 1, Example 3,
In Example 7, an aluminum alloy is used, in Comparative Examples 2 and 2, acid paper is used, in Comparative Examples 3 and 5, a galvanized steel sheet is used, and Comparative Examples 4 and 4 are used. Then, a steel plate was used, and in Example 6, a stainless steel plate (SUS304) was used. In Example 8, a polyester film coated with a silicone resin primer was used as a substrate.
【００４４】原料酸化チタンゾルとしては、前記Ａ）ま
たはＢ）の酸性ゾルを使用し、比較例１については錯化
剤を添加せずにアルカリ成分を添加してpH７から８に調
整した。また、比較例２、比較例４においては、酸性ゾ
ルに錯化剤を添加し、次にアルカリ成分を加えて、表１
に示したpH値にそれぞれ調整した。As the raw material titanium oxide sol, the acidic sol of A) or B) was used, and in Comparative Example 1, the pH was adjusted to 7 to 8 by adding the alkali component without adding the complexing agent. Further, in Comparative Examples 2 and 4, the complexing agent was added to the acidic sol, and then the alkaline component was added, and
The pH values shown in Table 1 were adjusted respectively.
【００４５】また、比較例３、実施例１〜８では、同様
にＡ）またはＢ）の酸性ゾルを使用し、これに錯化剤を
添加し、さらにアルカリ性成分を６〜１２のpHとなるま
で添加して酸化チタン粒子を分散させた。次に、実施例
１、実施例２、実施例４、及び実施例６〜７においては
半透膜（セロハン膜）により脱イオン水中で２４時間拡
散透析した。また、実施例３、実施例５、及び実施例８
においては、拡散透析のかわりにアニオン交換樹脂及び
カチオン交換樹脂のはいったカラムを通過させて脱イオ
ン処理を施した。Further, in Comparative Example 3 and Examples 1 to 8, similarly, the acidic sol of A) or B) was used, a complexing agent was added thereto, and the alkaline component was adjusted to a pH of 6 to 12. Was added to disperse the titanium oxide particles. Next, in Example 1, Example 2, Example 4, and Examples 6 to 7, diffusion dialysis was performed for 24 hours in deionized water using a semipermeable membrane (cellophane membrane). Moreover, Example 3, Example 5, and Example 8
In the above, instead of diffusion dialysis, deionization was performed by passing through a column containing an anion exchange resin and a cation exchange resin.
【００４６】塗膜性能の評価は、下記の試験法及び評価
基準により行った。
（塗布外観）錆の発生の有無または変色の有無について
目視で評価した。
（密着性）塗膜の密着性についてＪＩＳ−Ｋ５４００碁
盤目テープ法塗膜付着性試験に準じ塗膜の密着性を判定
した。
（皮膜硬さ）ＪＩＳ−Ｋ５４００鉛筆引っ掻き試験用鉛
筆により塗膜を引っ掻き、硬さを鉛筆硬度で測定した。
（紙以外の基材について評価）
（光触媒活性）試験片上に塗布、乾燥した試験片につい
てステアリン酸をエタノールに希釈して塗布し、２０Ｗ
ブラックライトで紫外線を２４時間照射し、照射前後の
重量差から２４時間あたり脂肪酸分解速度を求めた。The coating film performance was evaluated by the following test methods and evaluation criteria. (Applied appearance) The presence or absence of rust or the presence or absence of discoloration was visually evaluated. (Adhesiveness) Regarding the adhesiveness of the coating film, the adhesiveness of the coating film was determined according to the JIS-K5400 cross-cut tape method coating film adhesion test. (Film hardness) The coating film was scratched with a JIS-K5400 pencil scratch test pencil, and the hardness was measured by pencil hardness.
(Evaluation of base materials other than paper) (Photocatalytic activity) A test piece which had been coated and dried on a test piece was diluted with stearic acid in ethanol and then applied, and 20 W
Ultraviolet rays were irradiated for 24 hours with black light, and the fatty acid decomposition rate per 24 hours was calculated from the weight difference before and after irradiation.
【００４７】[0047]
【表１】 [Table 1]
【００４８】表１から明らかなように、従来の酸化チタ
ンの製造方法による比較例１〜４の酸化チタンゾルで
は、腐食や劣化し易い素材に対して満足できる結果を得
ることができなかった。本発明に係る実施例１〜８の酸
化チタンゾル及び酸化チタンゾルの製造方法によれば、
いずれも良好な性能が得られた。As is clear from Table 1, the titanium oxide sols of Comparative Examples 1 to 4 prepared by the conventional method for producing titanium oxide were not able to obtain satisfactory results with respect to materials that are easily corroded or deteriorated. According to the titanium oxide sol and the method for producing a titanium oxide sol of Examples 1 to 8 according to the present invention,
In all cases, good performance was obtained.
【００４９】[0049]
【発明の効果】上記に詳しく説明したように、本発明の
酸化チタンゾルの製造方法によれば、従来ではその使用
が困難であった腐食しやすい金属素材や劣化しやすい有
機素材に対しても、コーティング剤としての使用が可能
で、安定で良好な分散性を有する中性の光触媒酸化チタ
ンゾルが得られ、この酸化チタンを、汚れ分解、紫外線
吸収、殺菌、ガス分解や水質浄化などの各種目的に応用
する場合、より広い範囲の素材に適用できるようにな
り、作業環境や安全面での問題も解決されることから、
その実用価値は大きい。As described in detail above, according to the method for producing a titanium oxide sol of the present invention, even with respect to a corrosive metal material or an organic material which easily deteriorates, which has been difficult to use conventionally, A neutral photocatalytic titanium oxide sol, which can be used as a coating agent and has stable and good dispersibility, is obtained, and this titanium oxide is used for various purposes such as dirt decomposition, ultraviolet absorption, sterilization, gas decomposition and water purification. When applied, it can be applied to a wider range of materials, and it also solves problems in work environment and safety,
Its practical value is great.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平10−114870（ＪＰ，Ａ) 特開 平７−89722（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C01G 23/053 B01J 35/02 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-10-114870 (JP, A) JP-A-7-89722 (JP, A) (58) Fields investigated (Int.Cl. 7 , DB name) C01G 23/053 B01J 35/02
Claims (7)
０重量部及び錯化剤５〜５０重量部を含む酸性酸化チタ
ンゾルに、アルカリ性成分を添加してゾル液のpHを６〜
１２に調整し、さらにこのゾル液に脱イオン処理を施し
て、前記酸化チタンコロイド粒子を負に帯電させること
を特徴とする酸化チタンゾルの製造方法。1. A titanium oxide colloidal particle component 50 to 10.
To the acidic titanium oxide sol containing 0 parts by weight and 5 to 50 parts by weight of a complexing agent, an alkaline component is added to adjust the pH of the sol solution to 6 to.
12. The method for producing a titanium oxide sol, wherein the sol liquid is adjusted to 12, and the sol solution is subjected to deionization treatment to negatively charge the titanium oxide colloidal particles.
１種以上のキレート性化合物を含む、請求項１に記載の
酸化チタンゾルの製造方法。2. The method for producing a titanium oxide sol according to claim 1, wherein the complexing agent contains at least one chelating compound having a carboxyl group.
塩から選ばれた１種以上を含む、請求項１に記載の酸化
チタンゾルの製造方法。3. The method for producing a titanium oxide sol according to claim 1, wherein the complexing agent contains at least one selected from condensed phosphoric acid and condensed phosphate.
合物、アルカリ金属化合物、及びアミン化合物の中から
選ばれた少なくとも１種を含む、請求項１に記載の酸化
チタンゾルの製造方法。4. The method for producing a titanium oxide sol according to claim 1, wherein the alkaline component contains at least one selected from an ammonium compound, an alkali metal compound, and an amine compound.
ペリジン、及びコリンの中から選ばれた少なくとも１種
を含む、請求項１に記載の酸化チタンゾルの製造方法。5. The method for producing a titanium oxide sol according to claim 1, wherein the alkaline component contains at least one selected from oxazine, piperidine, and choline.
タンゾルが、負帯電の酸化チタンコロイド粒子成分５０
〜１００重量部と、錯化剤５〜５０重量部と、アルカリ
性成分１〜５０重量部とを含む、請求項１に記載の酸化
チタンゾルの製造方法。6. The titanium oxide sol obtained by the deionization treatment is a negatively charged titanium oxide colloidal particle component 50.
-100 parts by weight, a complexing agent 5-50 parts by weight, and an alkaline component 1-50 parts by weight, the method for producing a titanium oxide sol according to claim 1.
タンゾルのpHが５〜１０である、請求項１に記載の酸化
チタンゾルの製造方法。7. The method for producing a titanium oxide sol according to claim 1, wherein the titanium oxide sol obtained by the deionization treatment has a pH of 5 to 10.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27309499A JP3385243B2 (en) | 1998-01-27 | 1999-09-27 | Method for producing titanium oxide sol |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1381198 | 1998-01-27 | ||
| JP10-13811 | 1998-01-27 | ||
| JP27309499A JP3385243B2 (en) | 1998-01-27 | 1999-09-27 | Method for producing titanium oxide sol |
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|---|---|---|---|
| JP10282938A Division JP3080162B2 (en) | 1998-01-27 | 1998-10-05 | Titanium oxide sol and method for producing the same |
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| JP2000119019A JP2000119019A (en) | 2000-04-25 |
| JP3385243B2 true JP3385243B2 (en) | 2003-03-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2002222689A1 (en) * | 2000-12-19 | 2002-07-01 | Idemitsu Kosan Co. Ltd. | Titanium compound, aqueous solution containing titanium, and process for producing the same |
| JP4521801B2 (en) * | 2001-09-25 | 2010-08-11 | 多木化学株式会社 | Organic solvent-dispersed titanium oxide sol and method for producing the same |
| ITFI20040252A1 (en) * | 2004-12-06 | 2005-03-06 | Colorobbia Italiana Spa | PROCESS FOR THE PREPARATION OF TI02 DISPERSIONS IN THE FORM OF NANOPARTICLES, AND DISPERSIONS OBTAINABLE WITH THIS PROCESS |
| JP5113723B2 (en) * | 2008-11-04 | 2013-01-09 | 住友化学株式会社 | Photocatalyst dispersion |
| CN114570297A (en) * | 2021-12-31 | 2022-06-03 | 杭州大岸科技有限公司 | Preparation method and application of titanium oxide modified sol |
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