JP3238349B2 - Titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and translucency and method for producing the same - Google Patents
Titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and translucency and method for producing the sameInfo
- Publication number
- JP3238349B2 JP3238349B2 JP12862197A JP12862197A JP3238349B2 JP 3238349 B2 JP3238349 B2 JP 3238349B2 JP 12862197 A JP12862197 A JP 12862197A JP 12862197 A JP12862197 A JP 12862197A JP 3238349 B2 JP3238349 B2 JP 3238349B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- titanium oxide
- aqueous solution
- treatment
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims description 156
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title claims description 136
- 239000011224 oxide ceramic Substances 0.000 title claims description 43
- 239000003973 paint Substances 0.000 title claims description 40
- 230000001699 photocatalysis Effects 0.000 title claims description 39
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- 239000002245 particle Substances 0.000 claims description 72
- 239000007864 aqueous solution Substances 0.000 claims description 67
- 239000011248 coating agent Substances 0.000 claims description 62
- 238000000576 coating method Methods 0.000 claims description 62
- 238000011282 treatment Methods 0.000 claims description 57
- 150000002500 ions Chemical class 0.000 claims description 54
- 238000000034 method Methods 0.000 claims description 52
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 51
- 239000012528 membrane Substances 0.000 claims description 42
- 150000003608 titanium Chemical class 0.000 claims description 36
- 239000010936 titanium Substances 0.000 claims description 35
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 33
- 238000000502 dialysis Methods 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 31
- 229910052719 titanium Inorganic materials 0.000 claims description 29
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 27
- 239000000356 contaminant Substances 0.000 claims description 18
- 239000002244 precipitate Substances 0.000 claims description 18
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims description 17
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 239000000084 colloidal system Substances 0.000 claims description 16
- 238000000909 electrodialysis Methods 0.000 claims description 16
- -1 titanium (IV) ions Chemical class 0.000 claims description 14
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 10
- 238000005342 ion exchange Methods 0.000 claims description 10
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 6
- 238000002834 transmittance Methods 0.000 claims description 6
- 239000002612 dispersion medium Substances 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 description 66
- 239000010408 film Substances 0.000 description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- 238000005524 ceramic coating Methods 0.000 description 22
- 239000002253 acid Substances 0.000 description 20
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- 239000003011 anion exchange membrane Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 17
- 239000007788 liquid Substances 0.000 description 17
- 238000009792 diffusion process Methods 0.000 description 14
- 150000001450 anions Chemical class 0.000 description 13
- 239000011521 glass Substances 0.000 description 11
- 239000003014 ion exchange membrane Substances 0.000 description 10
- 229910000348 titanium sulfate Inorganic materials 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 9
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 8
- 238000005341 cation exchange Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229920000298 Cellophane Polymers 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003957 anion exchange resin Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000005349 anion exchange Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 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 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- 239000012780 transparent material Substances 0.000 description 3
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000195493 Cryptophyta Species 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- MSYNCHLYGJCFFY-UHFFFAOYSA-B 2-hydroxypropane-1,2,3-tricarboxylate;titanium(4+) Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O MSYNCHLYGJCFFY-UHFFFAOYSA-B 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
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 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 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- UHWHMHPXHWHWPX-UHFFFAOYSA-J dipotassium;oxalate;oxotitanium(2+) Chemical compound [K+].[K+].[Ti+2]=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UHWHMHPXHWHWPX-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000011034 membrane dialysis Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ガラス、金属、セ
ラミック、プラスチック等の素材に塗布するに好適な酸
化チタンセラミック塗料およびその製造方法に関するも
のである。さらに詳しく述べるならば、本発明は、良好
な親水性、光触媒性および光透過性を有する塗膜形成用
酸化チタンセラミック塗料、およびその製造方法に関す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanium oxide ceramic paint suitable for coating materials such as glass, metal, ceramic and plastic, and a method for producing the same. More specifically, the present invention relates to a titanium oxide ceramic paint for forming a coating film having good hydrophilicity, photocatalytic property and light transmittance, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来より、有機系塗料に比較して、耐熱
性、耐摩耗性などに優れるセラミック塗料として、アル
カリ金属けい酸塩系、りん酸塩系、シリカゾル系、およ
び金属酸化物系塗料などが知られている。これら従来の
セラミック塗料は、耐熱性、耐摩耗性に優れているなど
の点において、無機系塗料の特徴を有しているが、近
年、セラミック皮膜に対してさらに新しい機能を付与す
る試みが、金属酸化物系を中心に展開されている。2. Description of the Related Art Conventionally, alkali metal silicate-based, phosphate-based, silica sol-based, and metal oxide-based paints have been used as ceramic paints which are more excellent in heat resistance and abrasion resistance than organic paints. Etc. are known. These conventional ceramic paints have the characteristics of inorganic paints in that they are excellent in heat resistance and abrasion resistance, but in recent years, attempts to impart further new functions to ceramic coatings have been made. It is mainly developed for metal oxides.
【０００３】各種セラミック材料の中でも酸化チタン
は、酸化珪素等のセラミックスと同様に、強い親水性を
発揮することが知られている。このような機能は、例え
ば熱交換器用フィン材の表面に酸化チタンセラミック塗
料を塗布する事により、結露水のフィン間でのブリッジ
を低減し、水滴の飛散を防止し、熱交換効率を上昇させ
ることなどに有効である。また、この酸化チタンセラミ
ックス塗料をガラス等の表面に塗布することにより、そ
の曇り防止にも有効である。[0003] Among various ceramic materials, titanium oxide is known to exhibit strong hydrophilicity like ceramics such as silicon oxide. Such a function reduces the bridge between the fins of dew condensation water, prevents water droplets from scattering, and increases the heat exchange efficiency, for example, by applying a titanium oxide ceramic paint to the surface of the heat exchanger fin material. It is effective for things. Further, by applying this titanium oxide ceramic paint to the surface of glass or the like, it is also effective in preventing fogging.
【０００４】各種セラミック材料の中でも酸化チタン
は、塗膜に優れた光触媒効果を付与することができ、ま
た、紫外線の照射により高い酸化力を発揮する。従っ
て、光触媒活性に優れた酸化チタンの皮膜を、金属、ガ
ラス、セラミックなどの被塗物表面上に形成させること
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
解などに有効であることが知られている。そこでこのよ
うな用途のために、酸化チタン皮膜を素材表面上に形成
することを目的とする各種の酸化チタン塗料やその製造
方法がこれまでにいくつか提案されてきた。[0004] Among various ceramic materials, titanium oxide can impart an excellent photocatalytic effect to a coating film and exhibits high oxidizing power when irradiated with ultraviolet rays. Therefore, by forming a film of titanium oxide with excellent photocatalytic activity on the surface of the object to be coated such as metal, glass, ceramic, etc., prevention of adhesion of dirt, decomposition of malodorous components, purification of water quality, rust prevention, antibacterial, It is known that it is effective in preventing the growth of algae and decomposing hard-to-decompose waste. Therefore, for such applications, various titanium oxide paints aiming to form a titanium oxide film on the surface of a material and methods for producing the same have been proposed.
【０００５】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ゾル−
ゲル法が最も一般的に知られており、また、これに類す
る方法としては、例えば特開平４−８３５３７号公報
に、チタンアルコキシドにアミド、グリコールを添加す
る方法が開示されており、また、特開平７−１００３７
８号公報には、チタンアルコキシドにアルコールアミン
類を添加する方法が開示されている。さらに、特開平６
−２９３５１９号公報には、水熱処理により結晶化させ
た酸化チタン微粒子を分散剤を使用して分散させ、この
分散液を塗布する方法、および結晶性酸化チタン粒子
に、水ガラス、コロイダルシリカ、弗素系樹脂などのバ
インダーを混和して塗布する方法が開示されている。[0005] As a method of forming a titanium oxide film, a sol is applied by applying a hydrolyzed titanium alkoxide.
The gel method is most generally known, and as a similar method, for example, JP-A-4-83537 discloses a method in which an amide or glycol is added to a titanium alkoxide. Kaihei 7-10037
No. 8 discloses a method of adding an alcoholamine to a titanium alkoxide. Further, Japanese Unexamined Patent Application Publication No.
JP-A-293519 discloses a method of dispersing titanium oxide fine particles crystallized by hydrothermal treatment using a dispersant and applying this dispersion, and adding water glass, colloidal silica, and fluorine to crystalline titanium oxide particles. A method is disclosed in which a binder such as a system resin is mixed and applied.
【０００６】しかし、上記のゾル−ゲル法には、加水分
解に使用した酸、および添加剤として加えたアミン、グ
リコールなどが皮膜中に残存しやすく、高温で焼成する
必要があること、腐食しやすい素材例えばアルミニウム
製フィン材、銅製フィン材などには使用できないこと、
得られる酸化チタン皮膜中に可燃性有機溶剤が高含有率
で残留することと、水系塗料にすることが困難であるこ
と、および原料が高価であることなどの問題点がある。
また、１００℃以上の温度で結晶成長させた酸化チタン
を塗布する上記方法には、皮膜が十分に透明にならない
ため、ガラスなどの透明素材には適さないこと、および
熱交換器用フィン材に用いたとき、金属素材上の酸化チ
タンの固定率が低いためセラミック材料特有の無機臭が
発生することなどの問題点がある。さらに、酸化チタン
粒子用バインダーとして樹脂を使用する方法には、その
塗工性、密着性および固定率は改善されるが、樹脂が光
触媒によって劣化しやすく、塗膜の耐久性が不十分にな
るなどの問題が発生したり、また皮膜の酸化チタン含有
率が低下するため、親水性および光触媒能が充分に発揮
されないなどの欠点がある。However, in the above-mentioned sol-gel method, the acid used for the hydrolysis and the amines and glycols added as additives tend to remain in the film, necessitating baking at a high temperature, and causing corrosion. It cannot be used for easy materials such as aluminum fin material and copper fin material,
There are problems such as the fact that a high content of the flammable organic solvent remains in the obtained titanium oxide film, that it is difficult to make an aqueous paint, and that the raw materials are expensive.
In addition, the above method of applying titanium oxide grown at a temperature of 100 ° C. or more is not suitable for a transparent material such as glass because the film is not sufficiently transparent. However, there is a problem that the inorganic odor peculiar to the ceramic material is generated due to a low fixing rate of titanium oxide on the metal material. Furthermore, in the method of using a resin as a binder for titanium oxide particles, the coatability, adhesion and fixing rate are improved, but the resin is easily deteriorated by a photocatalyst, and the durability of the coating film becomes insufficient. And the like, and the content of titanium oxide in the film is reduced, so that the hydrophilicity and the photocatalytic ability are not sufficiently exhibited.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、従来技術の
上記問題点を解決するためになされたものであって、酸
化チタンの光触媒活性に有害な不純物や、アルコールな
どの有機物を含まず、良好な親水性および光触媒性を有
し、かつ、透明で密着性に優れた酸化チタンの薄膜を形
成することができる、親水性、光触媒性および透光性
（塗膜の透明性）に優れた酸化チタンセラミック塗料お
よびその製造方法を提供しようとするものである。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and does not contain impurities harmful to the photocatalytic activity of titanium oxide and organic substances such as alcohol. It has good hydrophilicity and photocatalytic properties, and can form a titanium oxide thin film that is transparent and has excellent adhesion, and is excellent in hydrophilicity, photocatalytic properties and translucency (transparency of coating film). An object of the present invention is to provide a titanium oxide ceramic paint and a method for producing the same.
【０００８】[0008]
【課題を解決するための手段】本発明に係る親水性、光
触媒性および透光性に優れた酸化チタンセラミック塗料
は、オルソチタン酸、およびチタン（IV) イオンから選
ばれた少なくとも１種、および平均粒子径が０．００１
〜０．２μｍのアナターゼ型結晶性酸化チタン粒子を、
１：０．１〜１：２００の重量比で含み、実質的に夾雑
イオンを含有しないことを特徴とするものである。塗料
の溶媒としては水が好ましいが、水に可溶なアルコー
ル、グリコール、ケトン類を混合して塗工性を向上させ
ることもできる。Means for Solving the Problems The titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and light transmittance according to the present invention is at least one selected from orthotitanic acid and titanium (IV) ion, and Average particle size 0.001
~ 0.2 μm anatase type crystalline titanium oxide particles,
It is characterized in that it is contained in a weight ratio of 1: 0.1 to 1: 200 and contains substantially no impurity ions. Water is preferred as a solvent for the paint, but water-soluble alcohols, glycols, and ketones may be mixed to improve coatability.
【０００９】上記親水性、光触媒性および透光性に優れ
た酸化チタンセラミック塗料を製造するための本発明方
法（１）は、チタン塩水溶液を、 （Ａ）半透膜を用いる透析処理、 （Ｂ）半透膜を用いる電気透析処理、および （Ｃ）イオン交換体を用いるイオン交換処理 から選ばれた少なくとも１処理に供し、それによって前
記チタン塩の少なくとも１部を加水分解してオルソチタ
ン酸および結晶性酸化チタンコロイド粒子に変化させる
とともに前記水溶液中の夾雑イオンを除去することを特
徴とするものである。上記本発明方法（１）において、
前記処理（Ａ），（Ｂ），（Ｃ）は０〜８０℃の温度で
行われることが好ましい。The method (1) of the present invention for producing the above-mentioned titanium oxide ceramic coating having excellent hydrophilicity, photocatalytic property and translucency comprises: (A) a dialysis treatment using a semipermeable membrane; B) electrodialysis treatment using a semi-permeable membrane, and (C) ion exchange treatment using an ion exchanger, whereby at least one part of the titanium salt is hydrolyzed to obtain orthotitanic acid. And changing to titanium oxide colloidal particles and removing contaminant ions in the aqueous solution. In the above method (1) of the present invention,
The treatments (A), (B) and (C) are preferably performed at a temperature of 0 to 80 ° C.
【００１０】上記親水性、光触媒性および透光性に優れ
た酸化チタンセラミック塗料を製造するための本発明方
法（２）は、チタン塩水溶液を５０℃以上１００℃未満
の温度に加熱し、次にそれを、 （Ａ）半透膜を用いる透析処理、 （Ｂ）半透膜を用いる電気透析処理、および （Ｃ）イオン交換体を用いるイオン交換処理 から選ばれた少なくとも１処理に供して、前記チタン塩
の少なくとも１部分を加水分解してオルソチタン酸およ
び結晶性酸化チタンコロイド粒子に変化させ、かつ、前
記水溶液中の夾雑イオンを除去することを特徴とするも
のである。上記本発明方法（１）および（２）におい
て、前記チタン塩水溶液がオキシ塩化チタンおよびオキ
シ硫酸チタンから選ばれた少なくとも１種を含む水溶液
であることが好ましい。[0010] The method (2) of the present invention for producing a titanium oxide ceramic coating having excellent hydrophilicity, photocatalytic property and light-transmitting property comprises heating an aqueous solution of a titanium salt to a temperature of 50 ° C or more and less than 100 ° C. And subjecting it to at least one treatment selected from the group consisting of (A) a dialysis treatment using a semipermeable membrane, (B) an electrodialysis treatment using a semipermeable membrane, and (C) an ion exchange treatment using an ion exchanger. The method is characterized in that at least a part of the titanium salt is hydrolyzed into orthotitanic acid and colloidal particles of crystalline titanium oxide, and contaminating ions in the aqueous solution are removed. In the above methods (1) and (2) of the present invention, the titanium salt aqueous solution is preferably an aqueous solution containing at least one selected from titanium oxychloride and titanium oxysulfate.
【００１１】上記親水性、光触媒性および透光性に優れ
た酸化チタンセラミック塗料を製造するための本発明方
法（３）は、チタン塩水溶液に、この水溶液中のチタン
量１モルに対し、４モル未満の、アルカリ金属水酸化物
およびアンモニアから選ばれた少なくとも１種を添加
し、この混合水溶液を５０℃以上１００℃未満の温度に
加熱し、さらに、 （Ａ）半透膜を用いる透析処理、 （Ｂ）半透膜を用いる電気透析処理、および （Ｃ）イオン交換体を用いるイオン交換処理 から選ばれた少なくとも１処理に供して、前記チタン塩
の少なくとも１部分を加水分解してオルソチタン酸およ
び結晶性酸化チタンコロイド粒子に変化させ、かつ、前
記水溶液中の夾雑イオンを除去することを特徴とするも
のである。The method (3) of the present invention for producing a titanium oxide ceramic coating excellent in hydrophilicity, photocatalytic property and light transmissivity includes the steps of: Less than one mole of at least one selected from alkali metal hydroxides and ammonia is added, the mixed aqueous solution is heated to a temperature of 50 ° C. or more and less than 100 ° C., and (A) dialysis treatment using a semipermeable membrane And (B) electrodialysis treatment using a semipermeable membrane, and (C) ion exchange treatment using an ion exchanger. It is characterized in that it is changed into an acid and crystalline titanium oxide colloid particles, and that contaminant ions in the aqueous solution are removed.
【００１２】上記親水性、光触媒性および透光性に優れ
た酸化チタンセラミック塗料を製造するための本発明方
法（４）は、チタン塩水溶液に、この水溶液中のチタン
量１モルに対し４モル未満のアルカリ金属水酸化物およ
びアンモニアから選ばれた少なくとも１種を添加し、さ
らにこの混合水溶液を５０℃以上１００℃未満の温度に
加熱して、前記チタン塩の少なくとも１部分を加水分解
してオルソチタン酸および結晶性酸化チタンコロイド粒
子に変化させ、この酸化チタンコロイド含有水溶液にア
ルカリ金属水酸化物およびアンモニアから選ばれた少な
くとも１種を添加して沈殿を生成させ、この沈殿を捕集
して、これを水、過酸化化合物水溶液、および錯化剤水
溶液から選ばれた分散媒中に分散させることを特徴とす
るものである。The method (4) of the present invention for producing a titanium oxide ceramic coating material having excellent hydrophilicity, photocatalytic property and light-transmitting property is characterized in that a titanium salt aqueous solution is used in an amount of 4 mol per 1 mol of titanium in the aqueous solution. At least one selected from the group consisting of an alkali metal hydroxide and ammonia, and further heating the mixed aqueous solution to a temperature of 50 ° C. or more and less than 100 ° C. to hydrolyze at least a portion of the titanium salt. The particles are converted into orthotitanic acid and crystalline titanium oxide colloid particles, and at least one selected from alkali metal hydroxides and ammonia is added to the titanium oxide colloid-containing aqueous solution to form a precipitate, and the precipitate is collected. And dispersing it in a dispersion medium selected from water, an aqueous solution of a peroxide compound, and an aqueous solution of a complexing agent.
【００１３】[0013]
【発明の実施の形態】本発明の親水性、光触媒性および
透光性に優れた酸化チタンセラミック塗料には、チタン
酸、およびチタン（IV) イオンから選ばれた少なくとも
１種、すなわち、その１種、又は２種を含むことが必要
である。本発明において、オルソチタン酸は、酸性水溶
液に易溶性であっても結晶性を殆ど有していないため、
結晶性酸化チタンから容易に区別できる。また、本発明
に用いられる二酸化チタンは、アナターゼ型結晶性二酸
化チタンである。BEST MODE FOR CARRYING OUT THE INVENTION The titanium oxide ceramic coating having excellent hydrophilicity, photocatalytic property and light-transmitting property of the present invention contains at least one kind selected from titanic acid and titanium (IV) ion. It is necessary to include the species, or two. In the present invention, orthotitanic acid has little crystallinity even though it is easily soluble in an acidic aqueous solution,
It can be easily distinguished from crystalline titanium oxide. The titanium dioxide used in the present invention is an anatase type crystalline titanium dioxide.
【００１４】本発明において、オルソチタン酸は、塩化
チタン、硫酸チタン、オキシ塩化チタン、又はオキシ硫
酸チタンなどのチタン化合物溶液に水酸化ナトリウム、
アンモニア水などを添加して沈澱として生成させること
ができる。生成したオルソチタン酸は濾過、水洗したも
のを塗料原料として使用することができる。また、本発
明の塗料に含まれるチタン（IV) イオン（Ｔｉ+4イオ
ン）は、水溶液チタン塩の水溶液により生成供給され
る。特にpH３以下の酸性水溶液中において安定に存在で
きるが、チタン（IV) イオンは、その有機又は無機錯体
として存在することが好ましい。In the present invention, orthotitanic acid is obtained by adding sodium hydroxide, titanium hydroxide, or the like to a titanium compound solution such as titanium chloride, titanium sulfate, titanium oxychloride, or titanium oxysulfate.
It can be formed as a precipitate by adding aqueous ammonia or the like. The generated orthotitanic acid can be filtered and washed with water and used as a coating material. The titanium (IV) ions (Ti +4 ions) contained in the paint of the present invention are produced and supplied by an aqueous solution of an aqueous titanium salt. In particular, titanium (IV) ions can exist stably in an acidic aqueous solution having a pH of 3 or less, but titanium (IV) ions preferably exist as an organic or inorganic complex thereof.
【００１５】本発明の酸化チタンセラミック塗料には、
前記オルソチタン酸、及び／又はチタン（IV) イオンに
加えて、さらに結晶性酸化チタン粒子を含むことが必要
で、その結晶形はアナターゼ型である。この結晶性酸化
チタン粒子は平均粒子径が０．００１〜０．２μｍの範
囲にあることが必要で、より好ましい平均粒子径は０．
００２〜０．１μｍであり、さらに好ましくは０．００
２〜０．０７μｍである。平均粒子径が０．００１μｍ
未満では、得られる酸化チタン塗膜の親水性および光触
媒性が十分でなく、またそれが０．２μｍ以上では、得
られる塗膜の親水性、透光性および密着性が不十分とな
るため好ましくない。特に結晶性酸化チタン粒子の平均
粒子径が０．００２〜０．１μｍの範囲内にあるとき、
得られる本発明の酸化チタンセラミック塗料は、すぐれ
た親水性を示す。The titanium oxide ceramic paint of the present invention includes:
In addition to the orthotitanic acid and / or titanium (IV) ion, it is necessary to further contain crystalline titanium oxide particles, and the crystal form is an anatase type. The crystalline titanium oxide particles need to have an average particle diameter in the range of 0.001 to 0.2 μm, and a more preferable average particle diameter is 0.1 to 0.2 μm.
002 to 0.1 μm, more preferably 0.00
2 to 0.07 μm. Average particle size 0.001μm
If it is less than 1, the hydrophilicity and photocatalytic property of the obtained titanium oxide coating film are not sufficient, and if it is 0.2 μm or more, the hydrophilicity, light transmittance and adhesion of the obtained coating film become insufficient, which is preferable. Absent. Especially when the average particle diameter of the crystalline titanium oxide particles is in the range of 0.002 to 0.1 μm,
The resulting titanium oxide ceramic coating of the present invention exhibits excellent hydrophilicity.
【００１６】本発明の酸化チタンセラミック塗料は、オ
ルソチタン酸、及びチタンIVイオン（Ｔｉ4+)から選ば
れた少なくとも１種と、平均粒子径が０．００１〜０．
２μｍ、好ましくは０．００２〜０．１μｍの結晶性酸
化チタン粒子とを、重量比が１：０．１〜１：２００に
なるように含むものである。この範囲よりもオルソチタ
ン酸、及び／又はチタン（IV) イオンの含有比率が低く
酸化チタン粒子の含有比率が高い場合には、得られる塗
膜の親水性、密着性および透明性が不十分となり、ま
た、酸化チタン粒子の含有比率が過少であると、得られ
る塗膜の親水性および光触媒性が低下するため好ましく
ない。The titanium oxide ceramic coating of the present invention has at least one selected from orthotitanic acid and titanium IV ion (Ti 4+ ), and has an average particle size of 0.001 to 0.1.
It contains crystalline titanium oxide particles of 2 μm, preferably 0.002 to 0.1 μm, in a weight ratio of 1: 0.1 to 1: 200. If the content of orthotitanic acid and / or titanium (IV) ions is lower than this range and the content of titanium oxide particles is higher, the resulting coating film becomes insufficient in hydrophilicity, adhesion and transparency. Further, if the content ratio of the titanium oxide particles is too small, the hydrophilicity and photocatalytic property of the resulting coating film are undesirably reduced.
【００１７】本発明の酸化チタンセラミック塗料は、オ
ルソチタン酸、およびチタン（IV)イオンから選ばれた
１種以上の水溶液に、酸化チタン粒子または酸化チタン
粒子を含むゾル液を混合させるか、またはチタン塩溶液
を原料とし、これを加水分解してオルソチタン酸および
酸化チタン粒子を生成させることによって得ることがで
きる。オルソチタン酸、および／又はチタン（IV) イオ
ンの溶液は、オルソチタン塩の水溶液にアルカリ溶液を
添加してオルソチタン酸の沈澱を生成させ、この沈澱を
捕集し、水、又は錯化剤水溶液中に分散させる前記の方
法によって調製することができる。オルソチタン酸溶液
は、チタン塩溶液に必要に応じてpH調製を施したのち、
イオン交換膜などの半透膜による透析、半透膜による電
気透析又はイオン交換処理等によって夾雑イオン除去を
行うことによっても得る事が可能である。pH値が低い場
合、例えば２以下の場合、オルソチタン酸の１部がチタ
ン（IV) イオンになるが、錯化剤を添加して、Ｔｉ（I
V) 錯体とすることにより安定な溶液を得ることができ
る。４価チタン錯体を形成するための錯化剤としては、
乳酸、シュウ酸、ギ酸、およびアセチルアセトンを用い
ることが好ましいが、その他に、グルコン酸、酒石酸、
酢酸、リンゴ酸、ラク酸、ＥＤＴＡ、などを用いること
ができる。The titanium oxide ceramic coating of the present invention is obtained by mixing titanium oxide particles or a sol containing titanium oxide particles with one or more aqueous solutions selected from orthotitanic acid and titanium (IV) ions, or It can be obtained by using a titanium salt solution as a raw material and hydrolyzing it to generate orthotitanic acid and titanium oxide particles. The solution of orthotitanic acid and / or titanium (IV) ions is formed by adding an alkaline solution to an aqueous solution of orthotitanium salt to form a precipitate of orthotitanic acid, collecting the precipitate, and adding water or complexing agent. It can be prepared by the above-mentioned method of dispersing in an aqueous solution. Orthotitanic acid solution, after subjecting the titanium salt solution to pH adjustment as needed,
It can also be obtained by removing contaminating ions by dialysis using a semipermeable membrane such as an ion exchange membrane, electrodialysis using a semipermeable membrane, or ion exchange treatment. When the pH value is low, for example, 2 or less, part of the orthotitanic acid becomes titanium (IV) ion.
V) By forming a complex, a stable solution can be obtained. As a complexing agent for forming a tetravalent titanium complex,
It is preferable to use lactic acid, oxalic acid, formic acid, and acetylacetone, but in addition, gluconic acid, tartaric acid,
Acetic acid, malic acid, lactic acid, EDTA, and the like can be used.
【００１８】前記オルソチタン酸、及び／又はチタン
（IV) イオンを含有する分散液に混合する酸化チタン
は、粉体粒子であってもゾル溶液であってもかまわない
が、粉体を添加する場合、特に均一に分散させるため、
ホモミキサーなどで十分に攪拌し、凝集粒子が生成しな
いようにすることが好ましい。また、界面活性剤などの
分散剤を少量添加して分散しやすくすることも許容され
る。The titanium oxide to be mixed with the dispersion containing the orthotitanic acid and / or titanium (IV) ion may be a powder particle or a sol solution. In particular, to distribute evenly,
It is preferable that the mixture is sufficiently stirred with a homomixer or the like so that aggregated particles are not generated. It is also acceptable that a small amount of a dispersant such as a surfactant is added to facilitate dispersion.
【００１９】本発明の酸化チタンセラミック塗料の製造
方法において、原料として、用いられるチタン塩は、塩
化チタン、硫酸チタン、オキシ硫酸チタン、およびオキ
シ塩化チタンなどから選ばれることが好ましいが、その
他の水溶性無機チタン化合物やしゅう酸チタンカリウ
ム、クエン酸チタンなどの水溶性有機チタン塩も使用す
ることができる。これらのチタン塩水溶液は、上記の化
合物を水中に溶解して調製したものか、又は市販の希釈
液であってもよい。無水塩化チタンを出発原料として使
用する場合は、無水塩化チタンを氷冷しながら徐々に純
水に溶解することにより塩化チタン水溶液を調製するこ
とができる。また、三塩化チタンを原料として使用する
場合は、あらかじめ過酸化水素などの酸化剤で４価チタ
ンに酸化したのち、得られた四塩化チタンを原料として
用いる。硫酸チタンは３０％程度の水溶液として市販品
を入手できるため、これを適宜希釈して使用すればよ
い。オキシ硫酸チタン水溶液又はオキシ塩化チタン水溶
液は、硫酸チタン又は塩化チタンの水溶液を、イオン交
換膜、又はイオン交換樹脂による脱アニオン処理に供す
るか、又は硫酸又は塩酸に水和酸化チタンを溶解する方
法などにより調製することができる。In the method for producing a titanium oxide ceramic coating material of the present invention, the titanium salt used as a raw material is preferably selected from titanium chloride, titanium sulfate, titanium oxysulfate, titanium oxychloride and the like. Water-soluble organic titanium salts such as a water-soluble inorganic titanium compound, potassium titanium oxalate, and titanium citrate can also be used. These titanium salt aqueous solutions may be prepared by dissolving the above compounds in water, or may be commercially available diluents. When anhydrous titanium chloride is used as a starting material, an aqueous titanium chloride solution can be prepared by gradually dissolving anhydrous titanium chloride in pure water while cooling with ice. When titanium trichloride is used as a raw material, it is oxidized to tetravalent titanium with an oxidizing agent such as hydrogen peroxide in advance, and the obtained titanium tetrachloride is used as a raw material. Since commercially available titanium sulfate can be obtained as an aqueous solution of about 30%, it may be appropriately diluted and used. Titanium oxysulfate aqueous solution or titanium oxychloride aqueous solution is prepared by subjecting an aqueous solution of titanium sulfate or titanium chloride to anion exchange treatment with an ion exchange membrane or an ion exchange resin, or dissolving hydrated titanium oxide in sulfuric acid or hydrochloric acid. Can be prepared.
【００２０】本発明方法（１）（２）および（３）にお
いて、加水分解処理に供されるチタン塩水溶液中のチタ
ン濃度は、０．１〜１０重量％であることが好ましく、
０．５〜４重量％がより好ましい。この濃度が０．１重
量％未満では得られる塗料から十分な塗膜厚さが得られ
ないことがあり、またそれが１０重量％を超えると、夾
雑イオンの除去を行う際に液がゲル化することがあるの
で、好ましくない。In the methods (1), (2) and (3) of the present invention, the titanium concentration in the aqueous titanium salt solution subjected to the hydrolysis treatment is preferably 0.1 to 10% by weight,
0.5-4% by weight is more preferred. If the concentration is less than 0.1% by weight, a sufficient coating film thickness may not be obtained from the obtained paint, and if it exceeds 10% by weight, the liquid gels when removing contaminating ions. It is not preferable because it may cause
【００２１】本発明方法（１）における半透膜透析処理
（Ａ）、半透膜電気透析処理（Ｂ）およびイオン交換体
によるイオン交換処理（Ｃ）の各々は、０〜８０℃の温
度において行われることが好ましく、１０〜５０℃であ
ることがより好ましい。これらの処理において、チタン
塩の少なくとも一部分は加水分解されてオルソチタン酸
および酸化チタン粒子に変化する。このときの加水分解
（ＴｉＣｌ4 の場合）は下記のように行われる。 （１）ＴｉＣｌ4 ＋４Ｈ2 Ｏ→ＴｉＯ2 ・２Ｈ2 Ｏ＋４ＨＣｌ （オルソチタン酸） （２）ＴｉＣｌ4 ＋２Ｈ2 Ｏ→ＴｉＯ2 ＋４ＨＣｌ 副生したＨＣｌは、その他の夾雑イオンとともに脱イオ
ンされる。このような本発明方法（１）においては、生
成するオルソチタン酸の比率が比較的高く、また酸化チ
タン粒子の粒子径がきわめて小さいものになるので得ら
れる塗膜の機械的強度が向上する。Each of the semipermeable membrane dialysis treatment (A), the semipermeable membrane electrodialysis treatment (B) and the ion exchange treatment (C) in the method (1) of the present invention is carried out at a temperature of 0 to 80 ° C. It is preferably performed, and more preferably 10 to 50 ° C. In these treatments, at least a portion of the titanium salt is hydrolyzed into orthotitanic acid and titanium oxide particles. The hydrolysis (in the case of TiCl 4 ) at this time is performed as follows. (1) TiCl 4 + 4H 2 O → TiO 2 .2H 2 O + 4HCl (ortho titanate) (2) TiCl 4 + 2H 2 O → TiO 2 + 4HCl By-produced HCl is deionized together with other contaminant ions. In the method (1) of the present invention, the ratio of the generated orthotitanic acid is relatively high, and the particle size of the titanium oxide particles is extremely small, so that the mechanical strength of the coating film obtained is improved.
【００２２】本発明方法（２）において、原料となるチ
タン塩水溶液（好ましくは硫酸チタン又は塩化チタン水
溶液）は、夾雑アニオン除去の前に、５０℃以上１００
℃未満の温度で加熱処理される。より好ましい加熱温度
範囲は６０〜９０℃である。このような加熱処理により
生成する酸化チタンの比率が高くなり、かつその粒子径
を適当な値にコントロールすることができる。つまり、
酸化チタン粒子の光触媒活性を所望値にコントロールす
ることが可能になる。この加熱温度が５０℃未満では、
酸化チタン粒子の生成が困難になるため得られる塗膜の
光触媒性が低下し、またそれが１００℃以上では、粗大
な酸化チタン粒子の含有量が多くなり、このため、得ら
れる塗膜の透光性が低下したり、或は酸化チタン粒子が
塗料中で沈降しやすくなるため好ましくない。In the method (2) of the present invention, an aqueous solution of a titanium salt (preferably an aqueous solution of titanium sulfate or titanium chloride) as a raw material is heated to 50 ° C. or higher before removal of contaminating anions.
The heat treatment is performed at a temperature of less than ° C. A more preferred heating temperature range is 60 to 90 ° C. The ratio of titanium oxide generated by such a heat treatment increases, and the particle size can be controlled to an appropriate value. That is,
The photocatalytic activity of the titanium oxide particles can be controlled to a desired value. If the heating temperature is lower than 50 ° C,
Since the formation of titanium oxide particles becomes difficult, the photocatalytic property of the resulting coating film is reduced. When the temperature is 100 ° C. or higher, the content of coarse titanium oxide particles increases, and therefore, the transparency of the resulting coating film increases. It is not preferable because the light property is lowered or the titanium oxide particles are liable to settle in the coating material.
【００２３】また、本発明方法（２），（３）および
（４）における加熱処理は、３〜２４０分間行うことが
好ましいが、処理温度が比較的低く例えば３０〜６０℃
であり、液のpHが比較的高く、例えば３〜７である場合
には２４０分以上の処理時間でも許容される。この加熱
処理は、攪拌しながら温水熱交換器や湯浴等で反応容器
全体を均一に加熱することが好ましく、投げ込みヒータ
等による局部的加熱は避けることが好ましい。また、加
熱処理により酸化チタン粒子の生成および成長を制御す
るために、加熱処理前に、チタン塩水溶液にコロイド粒
子成長の核となる酸化チタン粒子又はその分散液を少量
添加することも好ましい。The heat treatment in the methods (2), (3) and (4) of the present invention is preferably performed for 3 to 240 minutes, but the treatment temperature is relatively low, for example, 30 to 60 ° C.
When the pH of the solution is relatively high, for example, 3 to 7, a processing time of 240 minutes or more is acceptable. In this heat treatment, it is preferable to uniformly heat the entire reaction vessel with a hot water heat exchanger or a hot water bath while stirring, and it is preferable to avoid local heating by a throwing heater or the like. In addition, in order to control the generation and growth of titanium oxide particles by heat treatment, it is preferable to add a small amount of titanium oxide particles serving as nuclei for colloid particle growth or a dispersion thereof to the aqueous titanium salt solution before the heat treatment.
【００２４】加熱処理が終了した液は、好ましくは水冷
等により冷却して４０℃未満に温度を下げたのち、塗料
の安定性や塗膜の光触媒性に有害な夾雑アニオン（Ｃｌ
- ，ＳＯ4 2- などで、Ｔｉ，Ｏ，Ｈ以外の元素からなる
アニオン）の除去処理工程に供される。夾雑アニオンの
除去は、半透膜による透析処理（Ａ）、陰イオン交換膜
などの半透膜による電気透析処理（Ｂ）、又はイオン交
換体との接触によるイオン交換処理（Ｃ）の３つの処理
のうちの１処理以上によって行われる。本発明方法
（１）において、これらの工程によりチタン酸は加水分
解されてオルソチタン酸および酸化チタンコロイド粒子
に変化し、夾雑イオンが除去される。The liquid after the completion of the heat treatment is preferably cooled by water cooling or the like to lower the temperature to less than 40 ° C., and then mixed with an anion (Cl) which is harmful to the stability of the paint and the photocatalytic property of the coating film.
- , SO 4 2-, etc., which are subjected to a step of removing anions comprising elements other than Ti, O and H). The removal of contaminating anions is performed by three treatments: dialysis treatment using a semipermeable membrane (A), electrodialysis treatment using a semipermeable membrane such as an anion exchange membrane (B), or ion exchange treatment (C) by contact with an ion exchanger. It is performed by one or more of the processes. In the method (1) of the present invention, titanic acid is hydrolyzed by these steps to be converted into orthotitanic acid and titanium oxide colloid particles, and contaminant ions are removed.
【００２５】夾雑アニオンの除去を、上記の処理方法に
よらず、加熱処理後の液をそのままミクロフィルターや
ウルトラフィルターを使用して濾過し、沈澱を水洗した
のち乾燥焼成する従来の方法では、本発明の方法によっ
て製造される酸化チタンセラミック塗料中に含まれるオ
ルソチタン酸が除去、又は溶出し、または乾燥焼成時に
酸化チタンに変化し、このため得られる塗膜の透明性や
密着性が損なわれてしまう。Regarding the conventional method of removing contaminating anions, regardless of the treatment method described above, the liquid after the heat treatment is directly filtered using a microfilter or an ultrafilter, and the precipitate is washed with water and then dried and calcined. The orthotitanic acid contained in the titanium oxide ceramic paint produced by the method of the present invention is removed or eluted, or changes to titanium oxide during drying and firing, thereby impairing the transparency and adhesion of the resulting coating film. Would.
【００２６】夾雑アニオン除去の方法（Ａ）は、半透膜
を介する拡散透析処理法であって、水、好ましくは純水
を使用して行われる。この方法において使用される半透
膜としては、陰イオン交換膜が最も適しており、また、
例えばＲＯ膜、セロハン膜、ブレッダー膜及びコロージ
オン膜などのように陰イオン、陽イオンともに透過する
膜も使用できるが、陽イオン交換膜のみを使用すること
は、Ｃｌ- ，ＳＯ4 2- などの夾雑アニオンを除去しにく
いため好ましくない。しかし、陽イオン交換膜を陰イオ
ン交換膜と組合わせて使用することは差し支えない。こ
の拡散透析は好ましくは１時間以上行い、可能であれば
３時間以上行うことがさらに好ましい。透析の進行状態
はpH又は電気電導度で確認することができる。すなわ
ち、透析は、透析液のpHが２〜７の範囲に上昇するか、
又は電気電導度が１mS／cm未満に低下するまで行うこと
が好ましいが、約１ｇ／リットル以下のＣｌ- イオンの
残存はオルソチタン酸、および酸化チタンコロイドの安
定性を高めるため許容される。The method (A) for removing contaminating anions is a diffusion dialysis treatment through a semipermeable membrane, and is carried out using water, preferably pure water. As the semipermeable membrane used in this method, an anion exchange membrane is most suitable,
For example RO membrane, cellophane film, anions such as Buredda film and Korojion film, can be used film which transmits both cation, using only cation exchange membranes, Cl -, SO 4 2- etc. It is not preferable because it is difficult to remove contaminating anions. However, the cation exchange membrane can be used in combination with the anion exchange membrane. The diffusion dialysis is preferably performed for 1 hour or more, and more preferably for 3 hours or more if possible. The progress of dialysis can be confirmed by pH or electric conductivity. That is, dialysis raises the pH of the dialysate to a range of 2 to 7,
Alternatively, the reaction is preferably performed until the electric conductivity is reduced to less than 1 mS / cm, but the remaining Cl - ion of about 1 g / liter or less is acceptable for enhancing the stability of the orthotitanic acid and the titanium oxide colloid.
【００２７】また、夾雑アニオン除去のための方法
（Ｂ）では、半透膜、好ましくは陰イオン交換膜を介し
て電気透析が施される。この方法（Ｂ）は拡散透析によ
る方法（Ａ）よりも処理が短時間で完了するという利点
がある。陰イオン交換膜を使用した電気透析は、電解槽
内を陰極および陽極板に平行に設置された陰イオン交換
膜で仕切り、陰極側の電解室内にチタン塩水溶液を入
れ、陽極側の電解室内に水を入れた状態で行う。この場
合、陽極には白金、白金被覆チタン、又はＤＳＥ（不溶
性陽極）を使用することが好ましく、陰極には白金被覆
チタン、ステンレス鋼などを使用することができる。In the method (B) for removing contaminating anions, electrodialysis is performed through a semipermeable membrane, preferably an anion exchange membrane. This method (B) has an advantage that the treatment is completed in a shorter time than the method (A) by diffusion dialysis. In electrodialysis using an anion exchange membrane, the inside of the electrolytic cell is partitioned by an anion exchange membrane installed in parallel with the cathode and the anode plate, a titanium salt aqueous solution is put into the cathode side electrolytic chamber, and the anode side electrolytic chamber is put into the anode side electrolytic chamber. Perform with water. In this case, platinum, platinum-coated titanium, or DSE (insoluble anode) is preferably used for the anode, and platinum-coated titanium, stainless steel, or the like can be used for the cathode.
【００２８】電気透析処理（Ｂ）において、電流密度は
０．０１〜１０Ａ／dm2 であることが好ましく、電流密
度が１０Ａ／dm2 よりも高過ぎる場合、コロイド粒子が
膜面に付着するなどの弊害を生ずることがあるので好ま
しくない。また、使用する陰イオン交換膜としては、強
塩基性陰イオン交換膜であって、耐酸性の高いものが好
ましい。[0028] In electrodialysis treatment (B), it is preferable that current density is 0.01~10A / dm 2, when the current density is too high than 10A / dm 2, and colloidal particles adhere to the film surface This is not preferred because it may cause adverse effects. The anion exchange membrane to be used is preferably a strongly basic anion exchange membrane having high acid resistance.
【００２９】夾雑アニオン除去の処理方法（Ｃ）におい
ては、陰イオン交換体として陰イオン交換樹脂を使用す
ることが最も好ましい。イオン交換体としては、この他
にも、ゼオライト、塩基性白雲母、水和酸化鉄、水和酸
化ジルコニウムなど陰イオン交換能を持つものを使用す
ることができる。処理方法（Ｃ）において陰イオン交換
体との接触は、加熱処理後のチタン酸含有水溶液中にイ
オン交換体を直接投入して攪拌する方法と、チタン酸含
有水溶液を、イオン交換体が充填されているカラムを通
過させる方法との何れによっても可能である。この場合
も、前記処理方法（Ｂ）と同様に、処理後のチタン酸含
有水溶液のpHが一定値以上に上昇していること、又は電
気電導度が低下していることを確認して、工程を管理す
ることが好ましい。In the treatment method (C) for removing contaminant anions, it is most preferable to use an anion exchange resin as the anion exchanger. In addition, as the ion exchanger, zeolite, basic muscovite, hydrated iron oxide, hydrated zirconium oxide, or the like having an anion exchange ability can be used. In the treatment method (C), the contact with the anion exchanger is carried out by directly charging the ion exchanger into the aqueous solution of titanic acid after the heat treatment and stirring, or by filling the aqueous solution of titanic acid with the ion exchanger. It is possible by any of the methods of passing through a column. In this case as well, as in the treatment method (B), it was confirmed that the pH of the treated aqueous solution of titanic acid had risen to a certain value or higher, or that the electric conductivity had decreased, and the process was repeated. Is preferably managed.
【００３０】また、本発明方法（３）においては、チタ
ン塩水溶液（好ましくは硫酸チタン又は塩化チタン水溶
液）に、これを加熱処理する前に、溶液中のチタン量１
モルにつき４モル未満、好ましくは０．１モル以上４モ
ル未満のアルカリ金属水酸化物および／又はアンモニア
を添加する。この場合のアルカリ金属水酸化物および／
又はアンモニアの添加量は、チタン１モルに対して０．
５モル以上３モル未満であることがより好ましい。上記
アルカリおよび／又はアンモニアの添加量が４モル以上
では、次の加熱工程でも酸化チタン粒子が充分成長しな
いことがあるので好ましくない。また、その添加量が
０．１モル未満のときは加熱処理によって生成する酸化
チタン粒子が粗大化しやすいことがある。また、アルカ
リ金属水酸化物および／又はアンモニアは、２〜１０重
量％程度の濃度に水で希釈したものを添加することがよ
り好ましい。In the method (3) of the present invention, the amount of titanium in the aqueous solution of titanium salt (preferably aqueous solution of titanium sulfate or titanium chloride) is adjusted to 1 before heating.
Less than 4 moles, preferably 0.1 mole or more and less than 4 moles of alkali metal hydroxide and / or ammonia are added per mole. In this case, the alkali metal hydroxide and / or
Alternatively, the amount of ammonia added is 0.1 mol per mol of titanium.
More preferably, the amount is 5 mol or more and less than 3 mol. If the amount of the alkali and / or ammonia is 4 mol or more, the titanium oxide particles may not grow sufficiently even in the next heating step, which is not preferable. When the amount is less than 0.1 mol, the titanium oxide particles generated by the heat treatment may easily become coarse. It is more preferable to add the alkali metal hydroxide and / or ammonia diluted with water to a concentration of about 2 to 10% by weight.
【００３１】また、加熱処理に供するチタン塩水溶液中
のチタンの濃度は、アルカリ金属水酸化物および／又は
アンモニアの添加後において、０．１〜１０重量％であ
ることが好ましく、最も好ましい濃度は０．５〜４重量
％である。チタン濃度が０．１重量％未満では、得られ
る塗料により十分な塗膜厚さを得ることができないこと
があり、またそれが１０重量％を超えると、夾雑イオン
の除去を行う際に、液がゲル化することがあるので好ま
しくない。The concentration of titanium in the aqueous titanium salt solution to be subjected to the heat treatment is preferably 0.1 to 10% by weight after the addition of the alkali metal hydroxide and / or ammonia, and the most preferred concentration is 0.5 to 4% by weight. If the titanium concentration is less than 0.1% by weight, it may not be possible to obtain a sufficient coating film thickness with the obtained paint, and if it exceeds 10% by weight, the removal of contaminant ions may be difficult. Is not preferred because it may gel.
【００３２】アルカリおよび又はアンモニアの添加後
に、得られたチタン酸含有溶液は、夾雑イオン除去処理
の前に、前記本発明方法（２）と同様の条件（５０℃以
上１００℃未満）で加熱処理される。加熱処理が終了し
た後、得られた反応混合液は、好ましくは水冷等により
冷却して４０℃未満に温度を下げたのち、塗料の安定性
や塗膜の光触媒性に有害な夾雑イオン（Ｃｌ- ，Ｎａ
+ ，ＳＯ4 2- など）の除去処理工程に供される。これら
の工程により、チタン塩は加水分解されてオルソチタン
酸および酸化チタンコロイド粒子に変化し、かつ、夾雑
イオンが除去される。本発明方法（３）において、アル
カリ及び／又はアンモニア混合処理および加熱処理の組
み合わせは、チタニウム塩のオルソチタン酸および二酸
化チタン粒への変化を促進し、得られる塗膜の親水性、
光触媒活性及び密着性を向上させるという利点を有す
る。After the addition of the alkali and / or ammonia, the obtained titanic acid-containing solution is subjected to a heat treatment under the same conditions (50 ° C. to less than 100 ° C.) as in the method (2) of the present invention before the impurity ion removal treatment. Is done. After the completion of the heat treatment, the obtained reaction mixture is cooled preferably by water cooling or the like to lower the temperature to less than 40 ° C., and then the contaminant ions (Cl. - , Na
+ , SO 4 2- ). Through these steps, the titanium salt is hydrolyzed into orthotitanic acid and titanium oxide colloidal particles, and contaminant ions are removed. In the method (3) of the present invention, the combination of the alkali and / or ammonia mixing treatment and the heat treatment promotes the conversion of the titanium salt to orthotitanic acid and titanium dioxide particles, and the resulting coating film has hydrophilicity,
It has the advantage of improving photocatalytic activity and adhesion.
【００３３】夾雑イオンの除去は、（Ａ）半透膜による
透析処理、（Ｂ）半透膜（イオン交換膜）による電気透
析処理、又は（Ｃ）イオン交換体との接触によるイオン
交換処理のいずれかの方法によって行われる。The removal of the contaminant ions is carried out by (A) dialysis treatment using a semipermeable membrane, (B) electrodialysis treatment using a semipermeable membrane (ion exchange membrane), or (C) ion exchange treatment by contact with an ion exchanger. This can be done by either method.
【００３４】夾雑イオン除去処理方法（Ａ）は、半透膜
を介した透析による方法で、主として拡散透析によって
行われる。この処理（Ａ）において使用される半透膜
は、イオン交換膜、ＲＯ膜、セロハン膜、ぼうこう膜、
コロジオン膜、パイポーラ膜などでから選ぶことがで
き、コロイド粒子を透過せず、水および夾雑アニオンお
よびカチオンを透過するものであればその種類に制限は
ない。この透析操作は好ましくは１時間以上行い、可能
であれば３時間以上行うことがさらに好ましい。また、
夾雑イオン除去処理（Ｂ）は、半透膜、好ましくはイオ
ン交換膜を介して電気透析を行うものであって、この処
理（Ｂ）は拡散透析による処理（Ａ）よりも処理が短時
間で完了するという利点がある。The contaminant ion removal treatment method (A) is a method by dialysis through a semipermeable membrane, and is mainly performed by diffusion dialysis. The semipermeable membrane used in this treatment (A) is an ion exchange membrane, a RO membrane, a cellophane membrane, a bladder membrane,
The type can be selected from collodion membranes, bipolar membranes and the like, and there is no limitation on the type of the membrane as long as it does not permeate the colloid particles and permeates water and contaminant anions and cations. This dialysis operation is preferably performed for 1 hour or more, and more preferably for 3 hours or more if possible. Also,
The contaminant ion removal treatment (B) performs electrodialysis through a semi-permeable membrane, preferably an ion exchange membrane, and the treatment (B) is performed in a shorter time than the treatment (A) by diffusion dialysis. It has the advantage of being completed.
【００３５】電気透析（Ｂ）は、電解処理槽内を陰極お
よび陽極板に平行に設置された陰イオン交換膜と陽イオ
ン交換膜で交互に仕切り、これらの電解室内に水と加熱
処理後のチタン化合物溶液を交互に入れた状態で行うこ
とが望ましい。また、使用されるイオン交換膜は、陰イ
オン交換膜としては強塩基性陰イオン交換膜が用いら
れ、かつ陽イオン交換膜としては強酸性陽イオン交換膜
で耐酸性を有するものが用いられることが好ましい。In the electrodialysis (B), the inside of the electrolytic treatment tank is alternately partitioned by an anion exchange membrane and a cation exchange membrane installed in parallel to the cathode and anode plates, and water and heat-treated water are placed in these electrolytic chambers. It is desirable to carry out in a state where titanium compound solutions are alternately put. The ion exchange membrane used is a strong basic anion exchange membrane as the anion exchange membrane, and a strongly acidic cation exchange membrane having acid resistance is used as the cation exchange membrane. Is preferred.
【００３６】イオン交換体を用いる夾雑イオン除去処理
（Ｃ）においては、イオン交換体としては陰イオン交換
樹脂、および陽イオン交換樹脂を混合して使用すること
が最も好ましい。In the contaminant ion removal treatment (C) using an ion exchanger, it is most preferable to use a mixture of an anion exchange resin and a cation exchange resin as the ion exchanger.
【００３７】本発明方法（４）においては、前記本発明
方法（３）と同様にチタン酸水溶液に、この水溶液中の
チタン量１モルに対し４モル未満の、好ましくは０．１
モル以上４モル未満の、アルカリ金属水酸化物およびア
ンモニアから選ばれた少なくとも１種を添加する。次に
この液を５０℃以上１００℃未満の温度に加熱したの
ち、さらにアルカリ金属水酸化物またはアンモニアを加
えて、生成した沈澱を捕集し、これを水、過酸化化合物
水溶液、およびチタン（IV) 錯化剤水溶液から選ばれた
分散媒中に分散することによって酸化チタンセラミック
塗料を製造することができる。上記沈澱（オルソチタン
酸）を、分散媒液から捕集（濾過、遠心分離など）する
ことにより、夾雑イオンが除去され、格別の夾雑イオン
除去処理を省略することが可能になる。In the process (4) of the present invention, as in the process (3) of the present invention, the aqueous solution of titanic acid is added to the aqueous solution of titanium in an amount of less than 4 mol, preferably less than 0.1 mol per mol of titanium in the aqueous solution.
At least one selected from an alkali metal hydroxide and ammonia in an amount of at least 4 moles and less than 4 moles is added. Next, the solution is heated to a temperature of 50 ° C. or more and less than 100 ° C., and further, an alkali metal hydroxide or ammonia is added to collect a formed precipitate, which is collected by using water, an aqueous solution of a peroxide compound, and titanium ( IV) A titanium oxide ceramic coating can be produced by dispersing in a dispersion medium selected from aqueous solutions of complexing agents. By collecting (filtration, centrifugation, and the like) the precipitate (orthotitanic acid) from the dispersion medium, contaminant ions are removed, and it becomes possible to omit a special contaminant ion removal treatment.
【００３８】本発明方法（１）〜（４）のいずれかによ
って製造されたセラミック塗料には、さらに光触媒性を
有する酸化チタン粒子または、酸化チタンコロイド（ゾ
ル）を添加してもよい。The titanium oxide particles having photocatalytic properties or titanium oxide colloid (sol) may be further added to the ceramic paint produced by any of the methods (1) to (4) of the present invention.
【００３９】本発明方法（１），（２），（３）又は
（４）の方法によって製造される酸化チタンセラミック
塗料は、結晶性酸化チタンの粒子を多く含み、これにオ
ルソチタン酸および／又はＴｉ（IV）イオンが含まれ
る。塗料中に含まれる結晶性酸化チタンは、主としてア
ナターゼ型の結晶型を有しているが、加熱処理条件によ
っては、ルチル型酸化チタンを含む場合もある。The titanium oxide ceramic coating produced by the method (1), (2), (3) or (4) of the present invention contains a large amount of crystalline titanium oxide particles, and contains orthotitanic acid and / or Or Ti (IV) ions are included. The crystalline titanium oxide contained in the paint mainly has an anatase-type crystal form, but may contain rutile-type titanium oxide depending on heat treatment conditions.
【００４０】本発明の方法（１）〜（４）のいずれかに
よって製造された酸化チタンセラミック塗料中に含まれ
る酸化チタンの粒子は、その粒子径が１０-3〜４×１０
-1μｍの範囲内にあり、またその平均粒子径が０．００
１〜０．２μｍ、好ましくは０．００２〜０．１μｍの
範囲にある。また、本発明の方法によって製造される酸
化チタンセラミック塗料を使用する場合、被塗物に塗布
して乾燥したのち１００〜７００℃で焼成することが好
ましく、２００〜５００℃で焼成することがより好まし
い。尚生成した酸化チタン皮膜中の酸化チタンは主とし
てアナターゼ型であるが７００℃以上の高温で焼成され
た場合、それがルチル型に変化することがあるが、それ
によって皮膜の親水性が失われることはない。The titanium oxide particles contained in the titanium oxide ceramic paint produced by any one of the methods (1) to (4) of the present invention have a particle diameter of 10 −3 to 4 × 10 4.
-1 μm and the average particle size is 0.00
It is in the range of 1 to 0.2 μm, preferably 0.002 to 0.1 μm. When the titanium oxide ceramic paint produced by the method of the present invention is used, it is preferably applied to an object to be coated, dried and then fired at 100 to 700 ° C, more preferably fired at 200 to 500 ° C. preferable. The titanium oxide in the generated titanium oxide film is mainly anatase type, but when baked at a high temperature of 700 ° C. or more, it may change to rutile type, but the film loses hydrophilicity. There is no.
【００４１】尚、本発明の酸化チタンセラミック塗料
に、着色顔料を混合して装飾性を付与したり、各種酸化
物、窒化物、炭化物等の硬質セラミックスを混合して耐
磨耗性を向上させたり、亜鉛末、アルミニウム末などの
金属微粒子を混合させて耐食性を付与するなど、使用目
的に合った塗料を新たに調整することも可能である。The titanium oxide ceramic paint of the present invention is mixed with a coloring pigment to impart decorativeness, or mixed with various kinds of hard ceramics such as oxides, nitrides, carbides, etc. to improve abrasion resistance. It is also possible to newly prepare a paint suitable for the purpose of use, for example, by adding metal particles such as zinc powder and aluminum powder to impart corrosion resistance.
【００４２】本発明の光触媒性および透光性に優れる酸
化チタンセラミック塗料を被塗物表面に塗布、乾燥する
ことにより、被塗物表面には０．０５〜１μｍ程度の皮
膜が形成することができるが、この皮膜中において、平
均粒子径０．００１〜０．２μｍ、好ましくは０．００
２〜０．１μｍの結晶性酸化チタン粒子の間に膠質のオ
ルソチタン酸又はペルオキソチタン酸が充填されてい
る。この皮膜は１００〜２００℃程度の比較的低温で乾
燥するのみで膠質のオルソチタン酸又はペルオキソチタ
ン酸が脱水して表面積が大きく、吸着水の含有量の多い
含水酸化チタン、又は酸化チタンとなり、さらにこれが
酸化チタン粒子同士を結合させ、被塗物表面に強く密着
するとともに親水性を向上させ、粒子表面における光の
散乱を防止するのである。このため非常に透明でかつ親
水性の良好な塗膜が得られ、この塗膜は光触媒性のない
バインダー成分を含んでいないため、良好な光触媒効果
と親水性および透光性とを満足することができるもので
ある。By coating the titanium oxide ceramic paint having excellent photocatalytic properties and light transmittance of the present invention on the surface of the object to be coated and drying, a film of about 0.05 to 1 μm can be formed on the surface of the object to be coated. However, in this film, the average particle diameter is 0.001 to 0.2 μm, preferably 0.001 to 0.2 μm.
Colloidal orthotitanic acid or peroxotitanic acid is filled between crystalline titanium oxide particles of 2 to 0.1 μm. This film is only dried at a relatively low temperature of about 100 to 200 ° C., and the colloidal orthotitanic acid or peroxotitanic acid is dehydrated, the surface area is large, and the hydrated titanium oxide or titanium oxide having a large content of adsorbed water is obtained. Further, this binds the titanium oxide particles to each other, strongly adheres to the surface of the object to be coated, improves the hydrophilicity, and prevents light scattering on the particle surface. As a result, a coating film which is very transparent and has good hydrophilicity is obtained, and since this coating film does not contain a binder component having no photocatalytic property, it satisfies a good photocatalytic effect, hydrophilicity and translucency. Can be done.
【００４３】また、本発明の酸化チタンセラミック塗料
の製造方法（１），（２），（３）および（４）におい
ては、特定の組成のチタン塩水溶液を特定条件で加水分
解することにより、親水性および光触媒性に優れた酸化
チタン微粒子が生成して、最適な粒径にまで成長する。
この場合、加熱処理による加水分解前のチタン塩水溶液
にチタン量１モルに対し４モル未満、好ましくは０．１
モル以上４モル未満の水酸化アルカリ又はアンモニアを
添加することにより、水和酸化チタンの結晶核を生成
し、結晶成長の過程においてこれらのアルカリ性イオン
が結晶相中に取り込まれるため、加熱処理によって酸化
チタン粒子が粗大化するのを防止し、製造後の酸化チタ
ン塗料を塗布した場合の塗膜の透明性および親水性が一
層向上する。しかし、加熱処理を行った後のＴｉＯ2 コ
ロイド粒子を含む溶液は、このままでは、Ｃｌ- ，ＳＯ
4 2- やＮａ+ などの夾雑イオンを多く含むため、この液
をガラス等の上に塗布、乾燥しても透明皮膜は得られ
ず、白色の不均一な塗膜となり、光触媒性も不十分とな
るため、ガラスなどの透明素材における使用には適さな
い。In the production methods (1), (2), (3) and (4) of the titanium oxide ceramic paint of the present invention, a titanium salt aqueous solution having a specific composition is hydrolyzed under specific conditions. Titanium oxide fine particles having excellent hydrophilicity and photocatalytic properties are generated and grow to an optimum particle size.
In this case, less than 4 mol, preferably 0.1 mol, per 1 mol of titanium is added to the aqueous titanium salt solution before hydrolysis by heat treatment.
By adding at least 4 moles and less than 4 moles of alkali hydroxide or ammonia, crystal nuclei of the hydrated titanium oxide are generated, and these alkaline ions are taken into the crystal phase during the crystal growth process. Titanium particles are prevented from becoming coarse, and the transparency and hydrophilicity of the coating film when a titanium oxide paint after production is applied are further improved. However, the solution containing the TiO 2 colloidal particles after the heat treatment is, as it is, Cl − , SO
4 Because it contains a lot of contaminating ions such as 2- and Na + , a transparent film cannot be obtained even if this solution is applied and dried on glass etc., resulting in a white non-uniform film and insufficient photocatalytic properties. Therefore, it is not suitable for use in a transparent material such as glass.
【００４４】このため、本発明においては、塗料液か
ら、透析などの特定のイオン除去手段によって夾雑イオ
ンを取り除くことにより、透明で密着性が良く、優れた
親水性及び光触媒性を示す良好な塗膜が得られるように
なるのである。また、例えば熱交換器用フィン材等のよ
うに親水性機能の付与が必要な材料の場合、光触媒活性
の優れた酸化チタンを、アルミニウム、銅等の被塗物表
面に形成させることにより、汚れの付着防止、悪臭成分
の分解、防錆、抗菌、藻類の繁殖防止などの他に、親水
性の経時劣化、及び結露水に繁殖するバクテリヤ等によ
る異臭を防止することも可能となるのである。なお、ガ
ラス等のように透明な素材に対しても、本発明の酸化チ
タンセラミック塗料から作られる塗膜の透明性が良好で
あるため、高い実用性を有しているのである。For this reason, in the present invention, by removing contaminating ions from the coating liquid by a specific ion removing means such as dialysis, a transparent coating with good adhesion, good hydrophilicity and excellent photocatalytic properties can be obtained. A film can be obtained. In the case of a material that needs to be provided with a hydrophilic function, such as a fin material for a heat exchanger, for example, titanium oxide having excellent photocatalytic activity is formed on the surface of an object to be coated such as aluminum or copper, thereby reducing contamination. In addition to preventing adhesion, decomposing unpleasant odor components, preventing rust, antibacterial activity, and preventing the growth of algae, it also makes it possible to prevent the deterioration of hydrophilicity over time and the unpleasant odor caused by bacteria or the like that propagates in dew condensation water. It should be noted that the coating film made of the titanium oxide ceramic coating of the present invention has high practicability even with a transparent material such as glass, since the coating film has good transparency.
【００４５】[0045]
【実施例】本発明を、下記実施例によりさらに説明す
る。The present invention is further described by the following examples.
【００４６】実施例１及び２ 実施例１及び２の塗料溶液は、５％塩化チタン水溶液に
１０％水酸化ナトリウム溶液を加えてオルソチタン酸か
らなる沈澱を生成させ、この沈澱を濾過により捕集して
水洗し、得られたオルソチタン酸を水に再分散させて得
たオルソチタン酸溶液に、結晶性酸化チタン粒子を加
え、さらにこの液に実施例１、および２においては錯化
剤を、表１に記載の濃度で添加し、上記結晶性酸化チタ
ン粒子として、日本アエロジル（株）製Ｐ−２５酸化チ
タン（アナターゼ又はルチル型）を使用した。錯化剤と
してアセチルアセトン（実施例１）、及び乳酸（実施例
２）を使用した。The coating solution of Example 1 and 2 Examples 1 and 2, addition of 10% sodium hydroxide solution 5% titanium chloride aqueous solution to produce a precipitate consisting of ortho titanate, collecting the precipitate by filtration Then, crystalline titanium oxide particles are added to an orthotitanic acid solution obtained by redispersing the obtained orthotitanic acid in water, and a complexing agent is added to the solution in Examples 1 and 2. And P-25 titanium oxide (anatase or rutile type) manufactured by Nippon Aerosil Co., Ltd. was used as the crystalline titanium oxide particles. Acetylacetone (Example 1) and lactic acid (Example 2) were used as complexing agents.
【００４７】実施例３ 実施例３の塗料溶液は、１０％塩化チタン水溶液にチタ
ン１モルに対し水酸化ナトリウムを１モルの割合で加
え、９０℃で４０分加熱処理し、さらに５％水酸化ナト
リウム溶液を、液が中性となるまで加えて沈澱を生成さ
せ、得られたチタン酸および酸化チタンの沈澱を水に再
分散させ、この液をホモミキサーで十分攪拌混合して調
製した。分析の結果、得られた酸化チタン含有液は平均
粒子径０．０８μｍのアナターゼ型酸化チタン粒子を含
んでいた。The coating solution of Example 3 Example 3, a 10% sodium hydroxide to titanium 1 mole titanium chloride aqueous solution was added at a ratio of 1 mole to 40 minutes heat treatment at 90 ° C., a further 5% aqueous A sodium solution was added until the solution became neutral to form a precipitate. The obtained precipitate of titanic acid and titanium oxide was redispersed in water, and the solution was prepared by sufficiently stirring and mixing with a homomixer. As a result of the analysis, the obtained titanium oxide-containing liquid contained anatase type titanium oxide particles having an average particle diameter of 0.08 μm.
【００４８】実施例４ 実施例４の塗料溶液は、１０％塩化チタン水溶液にチタ
ン１モルに対し水酸化ナトリウムを２モルの割合で加
え、７５℃で２０分加熱処理し、さらに５％水酸化ナト
リウム溶液を、液が中性となるまで加えて沈澱を生成さ
せ、得られたチタン酸および酸化チタンの沈澱を水に再
分散させ、得られた分散液に、実施例４においては錯化
剤としてグルコン酸の表１に記載の濃度で添加し、この
液をホモミキサーで十分攪拌混合して調製した。分析の
結果、得られた酸化チタン含有液は平均粒子径０．００
５μｍのアナターゼ型酸化チタンコロイド粒子を含んで
いた。The coating solution of Example 4 Example 4, the sodium hydroxide to titanium 1 mole to 10% titanium chloride aqueous solution was added at a ratio of 2 moles, and 20 minutes heat treatment at 75 ° C., a further 5% aqueous A sodium solution was added until the solution became neutral to form a precipitate, and the obtained precipitate of titanic acid and titanium oxide was redispersed in water. The obtained dispersion was mixed with a complexing agent in Example 4. Gluconic acid was added at the concentration shown in Table 1, and this solution was prepared by sufficiently stirring and mixing with a homomixer. As a result of the analysis, the obtained titanium oxide-containing liquid had an average particle diameter of 0.00
It contained 5 μm anatase type titanium oxide colloid particles.
【００４９】実施例５ 四塩化チタン水溶液（２０重量％）をビーカーに入れて
水で希釈した溶液を、８０℃の温度で１０分間加熱処理
したのち、水冷して３０℃まで冷却した。この液を陰イ
オン交換膜を介して脱イオン流水で２７℃において拡散
透析を行い、夾雑イオンを除去した。 Example 5 A titanium tetrachloride aqueous solution (20% by weight) was placed in a beaker, and a solution diluted with water was heated at a temperature of 80 ° C. for 10 minutes, and then cooled with water to 30 ° C. This solution was subjected to diffusion dialysis at 27 ° C. with flowing deionized water through an anion exchange membrane to remove contaminating ions.
【００５０】実施例６ 四塩化チタン水溶液（２０重量％）をビーカーに入れて
水で希釈し、攪拌、水冷しながら、１０重量％の水酸化
ナトリウム水溶液を、チタン１モルに対し１モル添加し
た溶液を、５５℃の温度で６０分間加熱処理したのち、
水冷して３０℃まで冷却した。この液を２５℃の温度に
おいてセロハン膜を介して脱イオン流水で拡散透析を行
い、夾雑イオンを除去した。得られた酸化チタンコロイ
ド含有液に０．５重量％の乳酸（錯化剤）を添加した。 Example 6 An aqueous solution of titanium tetrachloride (20% by weight) was placed in a beaker, diluted with water, and 1 mol of a 10% by weight aqueous sodium hydroxide solution was added to 1 mol of titanium while stirring and cooling with water. After heat-treating the solution at a temperature of 55 ° C. for 60 minutes,
It cooled with water and cooled to 30 degreeC. This solution was subjected to diffusion dialysis with flowing deionized water through a cellophane membrane at a temperature of 25 ° C. to remove contaminating ions. 0.5% by weight of lactic acid (complexing agent) was added to the obtained titanium oxide colloid-containing liquid.
【００５１】実施例７ 三塩化チタン水溶液（２０重量％）をビーカーに入れて
水で希釈し、過酸化水素水（３１％）を液中の紫色のチ
タン（III)が無色のチタン（IV）になるまで加えた後、
この四塩化チタン水溶液に１０重量％の水酸化ナトリウ
ム水溶液を、チタン１モルに対し２モル添加した。この
溶液を、７０℃の温度で３０分間加熱処理したのち、水
冷して３０℃まで冷却した。この液をＲＯ膜を介して４
０℃の温度において脱イオン流水で拡散透析を行い、夾
雑イオンを除去した。 Example 7 An aqueous solution of titanium trichloride (20% by weight) was placed in a beaker and diluted with water, and aqueous hydrogen peroxide (31%) was replaced with purple titanium (III) in colorless titanium (IV). After adding until
To this titanium tetrachloride aqueous solution, a 10% by weight aqueous solution of sodium hydroxide was added in an amount of 2 mol per 1 mol of titanium. After heat-treating this solution at a temperature of 70 ° C. for 30 minutes, it was cooled with water to 30 ° C. This solution is passed through the RO membrane
Diffusion dialysis was performed with deionized running water at a temperature of 0 ° C. to remove contaminating ions.
【００５２】実施例８ 三塩化チタン水溶液（２０重量％）をビーカーに入れて
水で希釈し、過酸化水素水（３１％）を液中の紫色のチ
タン（III)が無色のチタン（IV）になるまで加えた後、
攪拌、水冷しながら、この四塩化チタン水溶液に１０重
量％の水酸化ナトリウム水溶液を、チタン１モルに対し
０．２４モル添加した。この溶液を、９５℃の温度で５
分間加熱処理したのち、水冷により３０℃まで冷却し、
この冷却された液に、陰イオン交換膜および陽イオン交
換膜を介して３０℃において脱イオン流水による拡散透
析を施し、夾雑イオンを除去した。得られた酸化チタン
コロイド含有液に１．２重量％のアセチルアセトンから
なる錯化剤を添加した。 Example 8 An aqueous titanium trichloride solution (20% by weight) was placed in a beaker, diluted with water, and aqueous hydrogen peroxide (31%) was replaced with purple titanium (III) in colorless titanium (IV). After adding until
While stirring and cooling with water, an aqueous solution of 10% by weight of sodium hydroxide was added to this aqueous solution of titanium tetrachloride in an amount of 0.24 mol per 1 mol of titanium. This solution is heated at 95 ° C. for 5 hours.
After heat treatment for 30 minutes, it is cooled to 30 ° C by water cooling,
The cooled liquid was subjected to diffusion dialysis with deionized running water at 30 ° C. through an anion exchange membrane and a cation exchange membrane to remove contaminating ions. A complexing agent consisting of 1.2% by weight of acetylacetone was added to the obtained titanium oxide colloid-containing liquid.
【００５３】実施例９ 硫酸チタン溶液（３０重量％）をビーカーに入れて水で
希釈した液を、６５℃の温度で９０分間加熱処理したの
ち、水冷して３０℃まで冷却した。この液を、陰イオン
交換膜（セレミオン ＡＭＶ型：旭硝子（株）製）で槽
内を分割した電解槽中で、１〜５Ａ／dm2 の電流密度
で、４５℃の温度において電気透析した。電極として
は、陰極板、陽極板ともに白金めっきチタン板を使用し
た。また、電極板およびイオン交換膜が、陽極板−陰イ
オン交換膜−陰極板の順に平行になるよう配置して２分
割された電解槽の陰極室に、加熱処理後の酸化チタン含
有液をいれ、陽極室には水をいれて通電を行い、夾雑イ
オンを除去した。 Example 9 A solution obtained by placing a titanium sulfate solution (30% by weight) in a beaker and diluting with water was heated at a temperature of 65 ° C. for 90 minutes, and then cooled with water and cooled to 30 ° C. This solution was electrodialyzed at a current density of 1 to 5 A / dm 2 at a temperature of 45 ° C. in an electrolytic cell having a divided cell with an anion exchange membrane (Selemion AMV type: manufactured by Asahi Glass Co., Ltd.). As the electrode, a platinum-plated titanium plate was used for both the cathode plate and the anode plate. Further, the electrode plate and the ion-exchange membrane are arranged in parallel in the order of anode plate-anion exchange membrane-cathode plate, and the heat-treated titanium oxide-containing liquid is put into the cathode compartment of the electrolytic cell divided into two. Then, electricity was supplied to the anode chamber by pouring water to remove contaminant ions.
【００５４】実施例１０ 硫酸チタン溶液（３０重量％）をビーカーに入れて水で
希釈し、攪拌、水冷しながら、２重量％の水酸化ナトリ
ウム水溶液をチタン１モルに対し０．５モル添加した溶
液を、９０℃の温度で５分間加熱処理したのち、水冷し
て３０℃まで冷却した。この液を、陰イオン交換膜（セ
レミオン ＡＭＶ型：旭硝子（株）製）および陽イオン
交換膜（セレミオン ＣＭＶ型：同社製）で仕切った電
解槽中で、０．２〜０．６Ａ／dm2 の電流密度で３０℃
において電気透析した。電極として、陰極板、陽極板と
もに白金めっきチタン板を使用した。また、電極板およ
びイオン交換膜が、陽極板−陰イオン交換膜−陽イオン
交換膜−陰極板の順に平行になるよう配置して、３分割
された電解槽の中央の電解室に加熱処理後の酸化チタン
含有液をいれ、陰極室および、陽極室には水をいれて通
電を行い、夾雑イオンを除去した。 Example 10 A titanium sulfate solution (30% by weight) was placed in a beaker, diluted with water, and while stirring and cooling with water, a 2% by weight aqueous solution of sodium hydroxide was added in an amount of 0.5 mol per mol of titanium. The solution was heat-treated at a temperature of 90 ° C. for 5 minutes, and then cooled with water to 30 ° C. This solution is placed in an electrolytic cell partitioned by an anion exchange membrane (Selemion AMV type: Asahi Glass Co., Ltd.) and a cation exchange membrane (Selemion CMV type: manufactured by the company) in a concentration of 0.2 to 0.6 A / dm 2. 30 ° C at current density of
Was electrodialyzed. Platinum-plated titanium plates were used for both the cathode plate and the anode plate as electrodes. Further, the electrode plate and the ion exchange membrane are arranged in parallel in the order of anode plate-anion exchange membrane-cation exchange membrane-cathode plate, and after the heat treatment in the central electrolysis chamber of the three-part electrolytic cell. The titanium oxide-containing solution was added, water was poured into the cathode chamber and the anode chamber, and electricity was supplied to remove impurity ions.
【００５５】実施例１１ ８重量％のオキシ硫酸チタンの水溶液をビーカー中で水
で希釈し、６０℃の温度で１８０分間加熱処理したの
ち、水冷して３０℃まで冷却した。この液を、陰イオン
交換樹脂（ダイヤイオン ＳＡ型：三菱化成（株）製）
および陽イオン交換樹脂（ダイヤイオン ＳＫ型：同社
製）を混合して充填したカラムに３０℃において透過さ
せて、夾雑イオンを除去した。 Example 11 An 8% by weight aqueous solution of titanium oxysulfate was diluted with water in a beaker, heat-treated at a temperature of 60 ° C. for 180 minutes, and then cooled with water to 30 ° C. This solution is used as an anion exchange resin (Diaion SA type: manufactured by Mitsubishi Kasei Corporation).
And a cation exchange resin (Diaion SK type: manufactured by the same company) were mixed and permeated at 30 ° C. through a packed column to remove impurity ions.
【００５６】実施例１２ １５重量％のオキシ硫酸チタンの水溶液をビーカー中で
水により希釈し、８０℃の温度で８分間加熱処理したの
ち、水冷して３０℃まで冷却した。この液を、陰イオン
交換樹脂（ダイヤイオン ＳＡ型：三菱化成（株）製）
を充填したカラムに５０℃において透過させて夾雑イオ
ンを除去した。 Example 12 A 15% by weight aqueous solution of titanium oxysulfate was diluted with water in a beaker, heated at a temperature of 80 ° C. for 8 minutes, and then cooled with water to 30 ° C. This solution is used as an anion exchange resin (Diaion SA type: manufactured by Mitsubishi Kasei Corporation).
At 50 ° C. to remove contaminating ions.
【００５７】実施例１３ １０重量％のオキシ塩化チタンの水溶液をビーカー内に
おいて水で希釈し、８５℃の温度で１０分間加熱処理し
たのち、水冷して３０℃まで冷却した。この液を、実施
例１２と同様にイオン交換樹脂を充填したカラムに４０
℃において透過させて夾雑イオンを除去した。 Example 13 A 10% by weight aqueous solution of titanium oxychloride was diluted with water in a beaker, heated at a temperature of 85 ° C. for 10 minutes, and then cooled to 30 ° C. with water. This solution was applied to a column filled with an ion exchange resin in the same manner as in Example 12,
C. to remove contaminating ions.
【００５８】実施例１４ 四塩化チタン水溶液（２０重量％）をビーカー内におい
て水で希釈し、この溶液を２０〜３０℃の室温において
陰イオン交換膜（商標：セレミオン ＤＭＶ：旭硝子
（株）製）を介して脱イオン流水により、溶液中の酸濃
度が透析前の１／１０以下になるまで拡散透析した。 Example 14 An aqueous titanium tetrachloride solution (20% by weight) was diluted with water in a beaker, and this solution was anion-exchange membrane (trade name: Selemion DMV: manufactured by Asahi Glass Co., Ltd.) at room temperature of 20 to 30 ° C. The solution was subjected to diffusion dialysis with deionized flowing water until the acid concentration in the solution became 1/10 or less of that before dialysis.
【００５９】実施例１５ 硫酸チタン溶液（３０重量パーセント）をビーカー内に
おいて水により希釈し、この溶液を、１〜１０℃の温度
に冷却しながら、陰イオン交換膜（セレミオンＤＭＶ）
を介して、脱イオン流水により、溶液の酸濃度が透析前
の１／１０以下になるまで拡散透析した。 Example 15 A titanium sulfate solution (30% by weight) was diluted with water in a beaker, and the solution was cooled to a temperature of 1 to 10 ° C. while anion exchange membrane (Selemion DMV) was used.
The solution was subjected to diffusion dialysis with deionized running water until the acid concentration of the solution became 1/10 or less of that before dialysis.
【００６０】実施例１６ 四塩化チタン水溶液（２０重量％）をビーカー内におい
て水により希釈し、この溶液を攪拌しながら、２０〜３
０℃の室温において、この溶液中に陰イオン交換樹脂
（商標：ダイヤイオン ＳＡ、三菱化成（株）製）を、
溶液中の酸濃度が透析前の１／１０以下になるまでゆっ
くり添加した。上記実施例１４〜１６において、酸濃度
は０．１規定ＮａＯＨ標準液でブロムフェノールブルー
を指示薬として中和滴定法により測定した。 Example 16 An aqueous titanium tetrachloride solution (20% by weight) was diluted with water in a beaker, and the solution was stirred for 20 to 3%.
At room temperature of 0 ° C., an anion exchange resin (trade name: Diaion SA, manufactured by Mitsubishi Kasei Corporation) was added to the solution.
The solution was slowly added until the acid concentration in the solution became 1/10 or less of that before dialysis. In Examples 14 to 16, the acid concentration was measured by a neutralization titration method using a 0.1 N NaOH standard solution and bromophenol blue as an indicator.
【００６１】比較例１〜３ 比較例１〜３の塗料溶液は、５％塩化チタン水溶液に１
０％水溶液ナトリウム溶液を加えて沈澱を生成させ、沈
澱を水洗して得たオルソチタン酸を水に再分散させて得
たオルソチタン酸溶液に、酸化チタン粒子を加え、さら
にこの液に過酸化水素水を表１のペルオキソチタン酸濃
度となるように加え、得られた混合液をホモミキサーで
十分攪拌混合することにより調製した。添加用酸化チタ
ン粒子としては、比較例１では平均粒子径０．５μｍの
ルチル型酸化チタン顔料を用い、比較例２では日本アエ
ロジル（株）製Ｐ−２５酸化チタン（アナターゼ又はル
チル型）を用い、また比較例３では８％オキシ塩化チタ
ン溶液を、７５℃で２０分加熱処理したのち、イオン交
換膜で拡散透析して得た平均粒子径０．０１μｍのアナ
ターゼ型酸化チタン粒子コロイド溶液を使用した。[0061] coating solution of Comparative Examples 1-3 Comparative Examples 1-3, 1 to 5% titanium chloride aqueous solution
A 0% aqueous sodium solution was added to form a precipitate, and the precipitate was washed with water. The titanium oxide particles were added to an orthotitanic acid solution obtained by redispersing orthotitanic acid in water. Hydrogen water was added so as to have the peroxotitanic acid concentration shown in Table 1, and the resulting mixture was prepared by sufficiently stirring and mixing with a homomixer. As the titanium oxide particles for addition, a rutile type titanium oxide pigment having an average particle diameter of 0.5 μm was used in Comparative Example 1, and P-25 titanium oxide (anatase or rutile type) manufactured by Nippon Aerosil Co., Ltd. was used in Comparative Example 2. In Comparative Example 3, an anatase-type titanium oxide particle colloid solution having an average particle diameter of 0.01 μm obtained by subjecting an 8% titanium oxychloride solution to heat treatment at 75 ° C. for 20 minutes and then performing diffusion dialysis with an ion exchange membrane was used. did.
【００６２】比較例４ 四塩化チタン水溶液（１７重量％）をビーカーに入れて
水で希釈し、１００℃で１５分間加熱処理し、冷却後に
この溶液にセロハン膜による拡散透析に供した。 Comparative Example 4 An aqueous solution of titanium tetrachloride (17% by weight) was placed in a beaker, diluted with water, heated at 100 ° C. for 15 minutes, cooled, and then subjected to diffusion dialysis using a cellophane membrane.
【００６３】比較例５ 硫酸チタン水溶液（３０重量％）をビーカーに入れて水
で希釈し、攪拌、水冷しながら、チタン量１モルに対し
水酸化ナトリウム４．５モルとなるように１０重量％の
水酸化ナトリウム溶液を添加し、７０℃で１５分間加熱
処理し、冷却後、この溶液に比較例４と同様の拡散透析
を施した。COMPARATIVE EXAMPLE 5 A titanium sulfate aqueous solution (30% by weight) was put into a beaker, diluted with water, and stirred and cooled with water so that 10% by weight of sodium hydroxide was added to 4.5% by weight of sodium hydroxide. Was heated at 70 ° C. for 15 minutes. After cooling, the solution was subjected to the same diffusion dialysis as in Comparative Example 4.
【００６４】比較例６ オキシ塩化チタン水溶液（５重量％）をビーカーに入
れ、４０℃で３０分間加熱処理し、冷却後にこの溶液は
実施例１３〜１５と同様のイオン交換膜による電気透析
を施した。COMPARATIVE EXAMPLE 6 An aqueous titanium oxychloride solution (5% by weight) was placed in a beaker and heated at 40 ° C. for 30 minutes. After cooling, the solution was subjected to electrodialysis using the same ion exchange membrane as in Examples 13 to 15. did.
【００６５】上記実施例および比較例および下記試験に
おいて用いられた試薬は、和光純薬（株）製一級試薬又
は相当品である。The reagents used in the above Examples and Comparative Examples and the following tests are first-class reagents manufactured by Wako Pure Chemical Industries, Ltd. or equivalents.
【００６６】試験方法 実施例および比較例において作製された酸化チタンセラ
ミック塗料溶液を、下記の方法による分析および試験に
供した。 Test Methods The titanium oxide ceramic coating solutions prepared in Examples and Comparative Examples were subjected to analysis and tests according to the following methods.
【００６７】塗料液中酸化チタン濃度 二酸化チタン酸濃度は、試料溶液２０mlをガラスビーカ
ーにいれて乾燥器中で水分を８０℃で蒸発させ、さらに
５００℃で２時間加熱して固体二酸化チタンとし、測定
前後のビーカーの重量差から求めた。オルソチタン酸、
Ｔｉ（IV) イオン、又はペルオキソチタン酸を含む塗料
液の場合は、オルソチタン酸又はペルオキソチタン酸濃
度の測定値を酸化チタンに換算し、この数値を前記測定
値から差し引いた数値を酸化チタン濃度とした。The concentration of titanium oxide in the coating solution was determined by placing 20 ml of the sample solution in a glass beaker, evaporating the water at 80 ° C. in a drier, and further heating at 500 ° C. for 2 hours to obtain solid titanium dioxide. It was determined from the difference in weight of the beaker before and after the measurement. Orthotitanic acid,
In the case of a coating liquid containing Ti (IV) ions or peroxotitanic acid, the measured value of the concentration of orthotitanic acid or peroxotitanic acid is converted to titanium oxide, and the value obtained by subtracting this value from the measured value is the concentration of titanium oxide. And
【００６８】塗料液中ペルオキソチタン酸濃度 塗料液中のペルオキソチタン酸濃度は、塗料液を水で希
釈し、５Ｃ濾紙で濾過した液に塩酸を加えて酸性とした
のち、分光光度計を使用して波長４３０nmのペルオキソ
チタン酸の吸光度を測定して求めた。The concentration of peroxotitanic acid in the coating liquid is determined by diluting the coating liquid with water, adding hydrochloric acid to the liquid filtered through a 5C filter paper to make it acidic, and then using a spectrophotometer. The absorbance of peroxotitanic acid having a wavelength of 430 nm was measured.
【００６９】塗料液中オルソチタン酸とＴｉ（IV) イオ
ン合計濃度 オルソチタン酸とＴｉ（IV) イオンとの合計濃度は、塗
料液を５Ｃ濾紙で濾過し、塩酸でpHを酸性としたのち、
これに過酸化水素水を加えてペルオキソチタン酸とし、
分光光度計を使用して波長４３０nmのペルオキソチタン
酸の吸光度を測定して求めた。ペルオキソチタン酸を含
む塗料液の場合は、測定値からペルオキソチタン酸濃度
を差し引いて求めた。 Ortho titanic acid and Ti (IV) ion in coating liquid
The total concentration of orthotitanic acid and Ti (IV) ions can be determined by filtering the coating liquid through a 5C filter paper and acidifying the pH with hydrochloric acid.
Hydrogen peroxide solution is added to this to make peroxotitanic acid,
It was determined by measuring the absorbance of peroxotitanic acid at a wavelength of 430 nm using a spectrophotometer. In the case of a coating liquid containing peroxotitanic acid, the value was obtained by subtracting the peroxotitanic acid concentration from the measured value.
【００７０】塗膜性能の評価 調製したセラミック塗料試料液を、７５×２５mmの板ガ
ラス基盤又はアルミニウム（ＪＩＳ Ａ１２００）板上
に約０．５μｍの厚みで塗布し、塗布層を１００℃で乾
燥したのち２８０℃で焼付けた。この試料について塗膜
の親水性、耐食性、透明性、密着性、および光触媒性を
評価した。 Evaluation of coating film performance The prepared ceramic coating sample solution was applied on a 75 x 25 mm plate glass substrate or aluminum (JIS A1200) plate with a thickness of about 0.5 µm, and the coated layer was dried at 100 ° C. Bake at 280 ° C. This sample was evaluated for hydrophilicity, corrosion resistance, transparency, adhesion, and photocatalytic property of the coating film.
【００７１】（ａ）塗膜の親水性 実施例及び比較例の各々において得られた酸化チタンセ
ラミック塗料を用いてアルミニウム又はガラス板上に酸
化チタン皮膜を形成して供試材を作製し、この供試材の
表面に５mlの純水を滴下し、得られた小水滴の接触角を
ＦＡＣＥ接触角計ＣＡ−Ｐ型（協和界面科学（株）製）
を用いて測定した。形成直後の（＝焼き付け直後の）皮
膜、および流水侵漬８時間、および８０℃乾燥１６時間
の処理を１サイクルとして５サイクルの処理が施された
後の皮膜について、上記測定結果を、下記の基準により
判定した。 (A) Hydrophilicity of coating film A titanium oxide film was formed on an aluminum or glass plate using the titanium oxide ceramic paint obtained in each of the examples and comparative examples to prepare a test material. 5 ml of pure water is dropped on the surface of the test material, and the contact angle of the obtained small water droplet is measured with a FACE contact angle meter CA-P type (manufactured by Kyowa Interface Science Co., Ltd.).
It measured using. The measurement results of the film immediately after formation (= immediately after baking) and the film after being subjected to 5 cycles of treatment with 1 hour of treatment with 8 hours of immersion in running water and 16 hours of drying at 80 ° C. The judgment was made based on the standard.
【００７２】（ｂ）塗膜の耐食性 実施例及び比較例の各々において得られた酸化チタンセ
ラミック塗料を用いてアルミニウム板上に酸化チタン皮
膜を形成し、これに塩水噴霧試験をＪＩＳ−Ｚ２３７１
に準じて、２００時間施し、その外観を観察し、下記の
基準で目視判定した。 (B) Corrosion Resistance of Coating Film A titanium oxide coating film was formed on an aluminum plate using the titanium oxide ceramic coating obtained in each of the Examples and Comparative Examples, and subjected to a salt spray test according to JIS-Z2371.
Was applied for 200 hours, and its appearance was observed, and visually judged according to the following criteria.
【００７３】（３）塗膜の透明性 実施例および比較例の各々において得られた酸化チタン
セラミック塗料をガラス板上に塗布、焼付け、得られた
塗膜の透明性を目視により下記の基準で判定した。 ◎ ： 塗膜に濁り、着色が全くなく均一に透明なもの ○ ： 塗膜にわずかな着色があるが均一に透明なもの △ ： 塗膜に明らかな着色がある × ： 塗膜に濁りがあり不透明なもの(3) Transparency of Coating Film The titanium oxide ceramic coating material obtained in each of Examples and Comparative Examples was applied to a glass plate and baked, and the transparency of the obtained coating film was visually observed according to the following criteria. Judged. ◎: The coating film is turbid and has no coloration and is uniformly transparent.: The coating film is slightly colored but is uniformly transparent.: The coating film is clearly colored. X: The coating film is turbid. Opaque things
【００７４】（４）塗膜の密着性 塗膜の密着性は、塗膜上にセロハンテープを貼付け、こ
れを引き剥がして塗膜剥離の有無を確認した。 （５）光触媒性 光触媒性は、２５mm×７５mmのガラス板上の塗膜表面に
試験油としてトリステアリン酸を塗布し、ＵＶライト
（１５Ｗ）で紫外線を７２時間照射した後の塗布油の分
解量（mg／ｍ2 ）を紫外線照射前後の重量差から求め
た。(4) Adhesion of Coating Film The adhesion of the coating film was determined by attaching a cellophane tape to the coating film and peeling it off to determine whether the coating film had peeled off. (5) Photocatalytic property Photocatalytic property is the amount of decomposition of applied oil after applying tristearic acid as a test oil to the surface of a coating film on a 25 mm x 75 mm glass plate and irradiating with UV light (15 W) for 72 hours. (Mg / m 2 ) was determined from the difference in weight before and after irradiation with ultraviolet light.
【００７５】表１に実施例１〜４、比較例１〜３の酸化
チタンセラミック塗料の組成と塗膜性能を示し、表２に
実施例５〜１３、比較例４〜６の酸化チタンセラミック
塗料の製造条件、濃度、および塗膜性能を示し、表３に
実施例１４〜１６の酸化チタンセラミック塗料の組成及
び塗膜性能を示す。Table 1 shows the compositions and coating properties of the titanium oxide ceramic coatings of Examples 1-4 and Comparative Examples 1-3, and Table 2 shows the titanium oxide ceramic coatings of Examples 5-13 and Comparative Examples 4-6. Table 3 shows the compositions and coating film performances of the titanium oxide ceramic paints of Examples 14 to 16 in Table 3.
【００７６】[0076]
【表１】 [Table 1]
【００７７】[0077]
【表２】 [Table 2]
【００７８】[0078]
【表３】 [Table 3]
【００７９】表１、表２および表３から明らかなよう
に、本発明に係る実施例１〜１６の酸化チタンセラミッ
ク塗料により得られた塗膜は、親水性、耐食性、透明
性、密着性、光触媒性ともに優れていた。一方、本発明
の範囲外のセラミック塗料組成又は製造条件を用いた比
較例１〜６の塗料から得られた塗膜においては、これら
の性能のすべてを同時に満足するものは一つもなかっ
た。As is clear from Tables 1, 2 and 3, the coating films obtained by using the titanium oxide ceramic coatings of Examples 1 to 16 according to the present invention exhibited hydrophilicity, corrosion resistance, transparency, adhesion, Both photocatalytic properties were excellent. On the other hand, none of the coating films obtained from the coating materials of Comparative Examples 1 to 6 using ceramic coating compositions or manufacturing conditions outside the scope of the present invention satisfy any of these properties at the same time.
【００８０】[0080]
【発明の効果】本発明の酸化チタンセラミック塗料は、
塗膜の透明性、耐食性および密着性が良好で、かつ優れ
た光触媒性および親水性を有するものである。また、本
発明の酸化チタンセラミック塗料の製造方法は、従来の
ゾル−ゲル法などに比較して原料コストが安価で塗料の
安全性、安定性に優れる利点も併せ有している。このた
め本発明の製造方法によって製造された酸化チタンセラ
ミック塗料は、汚れの付着防止や、悪臭成分の分解、抗
菌、防錆、大気および水質浄化等の各種の用途に有用な
ものであり、その産業上の利用価値はきわめて高いもの
である。The titanium oxide ceramic paint of the present invention
The coating has good transparency, corrosion resistance and adhesion, and has excellent photocatalytic properties and hydrophilicity. In addition, the method for producing a titanium oxide ceramic coating material of the present invention also has the advantage that the raw material cost is low and the coating material is excellent in safety and stability as compared with the conventional sol-gel method. For this reason, the titanium oxide ceramic paint produced by the production method of the present invention is useful for various applications such as adhesion prevention of dirt, decomposition of odorous components, antibacterial, rust prevention, air and water purification, and the like. The industrial utility value is extremely high.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 西澤 嘉彦 東京都中央区日本橋１丁目15番１号 日 本パーカライジング株式会社内 (56)参考文献 特開 平９−71418（ＪＰ，Ａ) 特開 平６−293519（ＪＰ，Ａ) 特開 平９−221324（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C09D 1/00 - 1/12 B01J 21/06 - 21/08 B01J 35/02 - 35/10 C01G 23/04 - 23/08 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshihiko Nishizawa 1-15-1, Nihonbashi, Chuo-ku, Tokyo Inside Japan Parkerizing Co., Ltd. (56) References JP-A-9-71418 (JP, A) JP-A Heisei 6-293519 (JP, A) JP-A-9-221324 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) C09D 1/00-1/12 B01J 21/06-21 / 08 B01J 35/02-35/10 C01G 23/04-23/08
Claims (7)
ンから選ばれた少なくとも１種、および平均粒子径が
０．００１〜０．２μｍのアナターゼ型結晶性酸化チタ
ン粒子を、チタンに換算して１：０．１〜１：２００の
重量比で含み、実質的に夾雑イオンを含有しないことを
特徴とする、親水性、光触媒性および透光性に優れた酸
化チタンセラミック塗料。1. Anatase-type crystalline titanium oxide particles having an average particle diameter of 0.001 to 0.2 μm and at least one selected from orthotitanic acid and titanium (IV) ions. 1. A titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and translucency, comprising a weight ratio of 1: 0.1 to 1: 200 and containing substantially no impurity ions.
記チタン塩の少なくとも１部を加水分解してオルソチタ
ン酸および結晶性酸化チタンコロイド粒子に変化させる
とともに前記水溶液中の夾雑イオンを除去することを特
徴とする、請求項１に記載の親水性、光触媒性および透
光性に優れた酸化チタンセラミック塗料の製造方法。2. An aqueous titanium salt solution comprising at least one selected from the group consisting of (A) a dialysis treatment using a semipermeable membrane, (B) an electrodialysis treatment using a semipermeable membrane, and (C) an ion exchange treatment using an ion exchanger. Subjecting the aqueous solution to a single treatment, whereby at least a part of the titanium salt is hydrolyzed to convert the titanium salt into orthotitanic acid and crystalline titanium oxide colloid particles, and contaminant ions in the aqueous solution are removed. 2. The method for producing a titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and light transmittance according to 1.
８０℃の温度で行われる、請求項２に記載の、親水性、
光触媒性および透光性に優れた酸化チタンセラミック塗
料の製造方法。3. The processing (A), (B), (C) is 0 to
The hydrophilicity according to claim 2, which is performed at a temperature of 80 ° C.
A method for producing a titanium oxide ceramic paint having excellent photocatalytic properties and translucency.
満の温度に加熱し、次にそれを、 （Ａ）半透膜を用いる透析処理、 （Ｂ）半透膜を用いる電気透析処理、および （Ｃ）イオン交換体を用いるイオン交換処理 から選ばれた少なくとも１処理に供して、前記チタン塩
の少なくとも１部分を加水分解してオルソチタン酸およ
び結晶性酸化チタンコロイド粒子に変化させ、かつ、前
記水溶液中の夾雑イオンを除去することを特徴とする、
請求項１に記載の親水性、光触媒性および透光性に優れ
た酸化チタンセラミック塗料の製造方法。4. Heating the aqueous titanium salt solution to a temperature of 50 ° C. or higher and lower than 100 ° C., and then subjecting it to (A) a dialysis treatment using a semipermeable membrane, (B) an electrodialysis treatment using a semipermeable membrane, and (C) an ion exchange treatment using an ion exchanger, which is subjected to at least one treatment selected from the group consisting of: hydrolyzing at least a part of the titanium salt to convert the titanium salt into orthotitanic acid and crystalline titanium oxide colloid particles; and Characterized by removing contaminant ions in the aqueous solution,
The method for producing a titanium oxide ceramic paint according to claim 1, which is excellent in hydrophilicity, photocatalytic property, and translucency.
およびオキシ硫酸チタンから選ばれた少なくとも１種を
含む水溶液である、請求項２又は４に記載の方法。5. The method according to claim 2, wherein the titanium salt aqueous solution is an aqueous solution containing at least one selected from titanium oxychloride and titanium oxysulfate.
ン量１モルに対し、４モル未満の、アルカリ金属水酸化
物およびアンモニアから選ばれた少なくとも１種を添加
し、この混合水溶液を５０℃以上１００℃未満の温度に
加熱し、さらに、 （Ａ）半透膜を用いる透析処理、 （Ｂ）半透膜を用いる電気透析処理、および （Ｃ）イオン交換体を用いるイオン交換処理 から選ばれた少なくとも１処理に供して、前記チタン塩
の少なくとも１部分を加水分解してオルソチタン酸およ
び結晶性酸化チタンコロイド粒子に変化させ、かつ、前
記水溶液中の夾雑イオンを除去することを特徴とする、
請求項１に記載の親水性、光触媒性および透光性に優れ
た酸化チタンセラミック塗料の製造方法。6. To a titanium salt aqueous solution, at least one selected from an alkali metal hydroxide and ammonia is added in an amount of less than 4 mol per 1 mol of titanium in the aqueous solution. Heated to a temperature of at least 100 ° C. and further selected from (A) a dialysis treatment using a semipermeable membrane, (B) an electrodialysis treatment using a semipermeable membrane, and (C) an ion exchange treatment using an ion exchanger. And subjecting the titanium salt to at least one treatment to hydrolyze at least a portion of the titanium salt into orthotitanic acid and crystalline titanium oxide colloid particles, and to remove contaminating ions in the aqueous solution. ,
The method for producing a titanium oxide ceramic paint according to claim 1, which is excellent in hydrophilicity, photocatalytic property, and translucency.
ン量１モルに対し４モル未満のアルカリ金属水酸化物お
よびアンモニアから選ばれた少なくとも１種を添加し、
さらにこの混合水溶液を５０℃以上１００℃未満の温度
に加熱して、前記チタン塩の少なくとも１部分を加水分
解してオルソチタン酸および結晶性酸化チタンコロイド
粒子に変化させ、この酸化チタンコロイド含有水溶液に
アルカリ金属水酸化物およびアンモニアから選ばれた少
なくとも１種を添加して沈殿を生成させ、この沈殿を捕
集して、これを水、および錯化剤水溶液から選ばれた分
散媒中に分散させることを特徴とする、請求項１に記載
の親水性、光触媒性および透光性に優れた酸化チタンセ
ラミック塗料の製造方法。7. An aqueous solution of a titanium salt to which at least one selected from an alkali metal hydroxide and ammonia in an amount of less than 4 moles per 1 mole of titanium in the aqueous solution is added,
Further, the mixed aqueous solution is heated to a temperature of 50 ° C. or higher and lower than 100 ° C. to hydrolyze at least a part of the titanium salt to convert the titanium salt into orthotitanic acid and crystalline titanium oxide colloid particles. At least one selected from an alkali metal hydroxide and ammonia is added to the mixture to form a precipitate, and the precipitate is collected and dispersed in a dispersion medium selected from water and an aqueous solution of a complexing agent. The method for producing a titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and light transmittance according to claim 1, characterized in that the coating is performed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12862197A JP3238349B2 (en) | 1996-05-24 | 1997-05-19 | Titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and translucency and method for producing the same |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13009096 | 1996-05-24 | ||
| JP8-216306 | 1996-08-16 | ||
| JP8-130090 | 1996-08-16 | ||
| JP21630696 | 1996-08-16 | ||
| JP12862197A JP3238349B2 (en) | 1996-05-24 | 1997-05-19 | Titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and translucency and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10114870A JPH10114870A (en) | 1998-05-06 |
| JP3238349B2 true JP3238349B2 (en) | 2001-12-10 |
Family
ID=27315782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12862197A Expired - Fee Related JP3238349B2 (en) | 1996-05-24 | 1997-05-19 | Titanium oxide ceramic paint excellent in hydrophilicity, photocatalytic property and translucency and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3238349B2 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10237352A (en) * | 1997-02-24 | 1998-09-08 | Tao:Kk | Polyfunctional coating agent |
| JP4236769B2 (en) * | 1999-08-02 | 2009-03-11 | 日新製鋼株式会社 | Galvanized steel sheet, surface treatment liquid and surface treatment method with improved corrosion resistance |
| JP4608042B2 (en) * | 1999-09-16 | 2011-01-05 | 関西ペイント株式会社 | Coating agent for forming inorganic film, method for producing the same, and method for forming the inorganic film |
| JP2001220141A (en) * | 2000-02-03 | 2001-08-14 | Toho Titanium Co Ltd | Titanium oxide dispersion |
| JP2002047012A (en) * | 2000-07-31 | 2002-02-12 | Sumitomo Chem Co Ltd | Method of manufacturing titanium oxide |
| AU2002222689A1 (en) * | 2000-12-19 | 2002-07-01 | Idemitsu Kosan Co. Ltd. | Titanium compound, aqueous solution containing titanium, and process for producing the same |
| KR100393733B1 (en) * | 2001-03-28 | 2003-08-06 | 홍국선 | Ceramic Compositions for superhydrophilic coating and its manufacturing method |
| JP4599817B2 (en) * | 2003-08-08 | 2010-12-15 | 株式会社豊田中央研究所 | Method for supporting NOx storage material |
| WO2006123425A1 (en) * | 2005-05-20 | 2006-11-23 | Axtis Company | Process for producing solution for forming titanium oxide film |
| JP4793297B2 (en) * | 2007-03-20 | 2011-10-12 | Ｊｆｅエンジニアリング株式会社 | Manufacturing method of diffuser plate |
| JP4815380B2 (en) * | 2007-03-30 | 2011-11-16 | 花王株式会社 | Method for producing titanic acid nanosheet dispersion |
| JP5410035B2 (en) * | 2008-05-14 | 2014-02-05 | 勝之 中野 | Photocathode anticorrosive and metal material coated with photocathode anticorrosive |
-
1997
- 1997-05-19 JP JP12862197A patent/JP3238349B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| JPH10114870A (en) | 1998-05-06 |
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