JP4523344B2 - Method for producing titanium oxide dispersion - Google Patents
Method for producing titanium oxide dispersion Download PDFInfo
- Publication number
- JP4523344B2 JP4523344B2 JP2004178433A JP2004178433A JP4523344B2 JP 4523344 B2 JP4523344 B2 JP 4523344B2 JP 2004178433 A JP2004178433 A JP 2004178433A JP 2004178433 A JP2004178433 A JP 2004178433A JP 4523344 B2 JP4523344 B2 JP 4523344B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium oxide
- sulfur
- titanium
- oxide dispersion
- oxide powder
- 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
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims description 76
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 206
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 191
- 229910052717 sulfur Inorganic materials 0.000 claims description 119
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 116
- 239000011593 sulfur Substances 0.000 claims description 116
- 239000000843 powder Substances 0.000 claims description 98
- 238000000034 method Methods 0.000 claims description 47
- 239000002253 acid Substances 0.000 claims description 40
- 239000002270 dispersing agent Substances 0.000 claims description 39
- 239000010936 titanium Substances 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 21
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- 238000011282 treatment Methods 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 12
- 238000002835 absorbance Methods 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003125 aqueous solvent Substances 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000001228 spectrum Methods 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- 125000003158 alcohol group Chemical group 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 description 44
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 37
- 239000011941 photocatalyst Substances 0.000 description 34
- 239000002245 particle Substances 0.000 description 30
- 150000001875 compounds Chemical class 0.000 description 29
- -1 titanium ions Chemical class 0.000 description 28
- 230000001699 photocatalysis Effects 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- 239000002002 slurry Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000010304 firing Methods 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 125000004434 sulfur atom Chemical group 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 12
- 125000004433 nitrogen atom Chemical group N* 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 239000010408 film Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 11
- 238000006460 hydrolysis reaction Methods 0.000 description 11
- 238000006386 neutralization reaction Methods 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- 238000004220 aggregation Methods 0.000 description 10
- 230000002776 aggregation Effects 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000003513 alkali Substances 0.000 description 8
- 230000031700 light absorption Effects 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 230000003301 hydrolyzing effect Effects 0.000 description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002356 laser light scattering Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 229920000058 polyacrylate Polymers 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 150000001768 cations Chemical group 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 235000014113 dietary fatty acids Nutrition 0.000 description 5
- 238000002050 diffraction method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000194 fatty acid Substances 0.000 description 5
- 229930195729 fatty acid Natural products 0.000 description 5
- 230000003472 neutralizing effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000002612 dispersion medium Substances 0.000 description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- MSXVEPNJUHWQHW-UHFFFAOYSA-N 2-methylbutan-2-ol Chemical compound CCC(C)(C)O MSXVEPNJUHWQHW-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- FRDAATYAJDYRNW-UHFFFAOYSA-N 3-methyl-3-pentanol Chemical compound CCC(C)(O)CC FRDAATYAJDYRNW-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004332 deodorization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- GOQYKNQRPGWPLP-UHFFFAOYSA-N heptadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 125000001297 nitrogen containing inorganic group Chemical group 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- IYVLHQRADFNKAU-UHFFFAOYSA-N oxygen(2-);titanium(4+);hydrate Chemical compound O.[O-2].[O-2].[Ti+4] IYVLHQRADFNKAU-UHFFFAOYSA-N 0.000 description 2
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 229940116411 terpineol Drugs 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 150000003609 titanium compounds Chemical class 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- PVPBBTJXIKFICP-UHFFFAOYSA-N (7-aminophenothiazin-3-ylidene)azanium;chloride Chemical compound [Cl-].C1=CC(=[NH2+])C=C2SC3=CC(N)=CC=C3N=C21 PVPBBTJXIKFICP-UHFFFAOYSA-N 0.000 description 1
- XLSXKCPCBOMHON-UHFFFAOYSA-N 1,1-dimethoxypropan-1-ol Chemical compound CCC(O)(OC)OC XLSXKCPCBOMHON-UHFFFAOYSA-N 0.000 description 1
- PRAYXKGWSGUXQK-UHFFFAOYSA-N 1,1-dimethoxypropan-2-ol Chemical compound COC(OC)C(C)O PRAYXKGWSGUXQK-UHFFFAOYSA-N 0.000 description 1
- KOUJXMCSGVVSRF-UHFFFAOYSA-N 1,2-diphenylethane-1,1-diol Chemical compound C=1C=CC=CC=1C(O)(O)CC1=CC=CC=C1 KOUJXMCSGVVSRF-UHFFFAOYSA-N 0.000 description 1
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- 239000005968 1-Decanol Substances 0.000 description 1
- ULZRKSDAMUWQEZ-UHFFFAOYSA-N 1-anilinoethanol Chemical compound CC(O)NC1=CC=CC=C1 ULZRKSDAMUWQEZ-UHFFFAOYSA-N 0.000 description 1
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 1
- JSPNRYDMYDINGQ-UHFFFAOYSA-N 1-butoxypropane-1,1-diol Chemical compound CCCCOC(O)(O)CC JSPNRYDMYDINGQ-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- OHZAHWOAMVVGEL-UHFFFAOYSA-N 2,2'-bithiophene Chemical compound C1=CSC(C=2SC=CC=2)=C1 OHZAHWOAMVVGEL-UHFFFAOYSA-N 0.000 description 1
- SXSWMAUXEHKFGX-UHFFFAOYSA-N 2,3-dimethylbutan-1-ol Chemical compound CC(C)C(C)CO SXSWMAUXEHKFGX-UHFFFAOYSA-N 0.000 description 1
- BAYAKMPRFGNNFW-UHFFFAOYSA-N 2,4-dimethylpentan-3-ol Chemical compound CC(C)C(O)C(C)C BAYAKMPRFGNNFW-UHFFFAOYSA-N 0.000 description 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- LJDSTRZHPWMDPG-UHFFFAOYSA-N 2-(butylamino)ethanol Chemical compound CCCCNCCO LJDSTRZHPWMDPG-UHFFFAOYSA-N 0.000 description 1
- INFFATMFXZFLAO-UHFFFAOYSA-N 2-(methoxymethoxy)ethanol Chemical compound COCOCCO INFFATMFXZFLAO-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 2-Aminopropanol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- RWLALWYNXFYRGW-UHFFFAOYSA-N 2-Ethyl-1,3-hexanediol Chemical compound CCCC(O)C(CC)CO RWLALWYNXFYRGW-UHFFFAOYSA-N 0.000 description 1
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- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- JCBPETKZIGVZRE-UHFFFAOYSA-N 2-aminobutan-1-ol Chemical compound CCC(N)CO JCBPETKZIGVZRE-UHFFFAOYSA-N 0.000 description 1
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- NECRQCBKTGZNMH-UHFFFAOYSA-N 3,5-dimethylhex-1-yn-3-ol Chemical compound CC(C)CC(C)(O)C#C NECRQCBKTGZNMH-UHFFFAOYSA-N 0.000 description 1
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- 125000002947 alkylene group Chemical group 0.000 description 1
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- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
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- 235000019257 ammonium acetate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- PFURGBBHAOXLIO-OLQVQODUSA-N cis-cyclohexane-1,2-diol Chemical compound O[C@H]1CCCC[C@H]1O PFURGBBHAOXLIO-OLQVQODUSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- VKONPUDBRVKQLM-UHFFFAOYSA-N cyclohexane-1,4-diol Chemical compound OC1CCC(O)CC1 VKONPUDBRVKQLM-UHFFFAOYSA-N 0.000 description 1
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- 238000000151 deposition Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
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- 239000010419 fine particle Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- BTCSSZJGUNDROE-UHFFFAOYSA-N gamma-aminobutyric acid Chemical compound NCCCC(O)=O BTCSSZJGUNDROE-UHFFFAOYSA-N 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- MWCGLTCRJJFXKR-UHFFFAOYSA-N n-phenylethanethioamide Chemical compound CC(=S)NC1=CC=CC=C1 MWCGLTCRJJFXKR-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
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- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001444 polymaleic acid Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
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- 239000004576 sand Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- AGGIJOLULBJGTQ-UHFFFAOYSA-N sulfoacetic acid Chemical compound OC(=O)CS(O)(=O)=O AGGIJOLULBJGTQ-UHFFFAOYSA-N 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 125000002153 sulfur containing inorganic group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- WFRBDWRZVBPBDO-UHFFFAOYSA-N tert-hexyl alcohol Natural products CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- GVIJJXMXTUZIOD-UHFFFAOYSA-N thianthrene Chemical compound C1=CC=C2SC3=CC=CC=C3SC2=C1 GVIJJXMXTUZIOD-UHFFFAOYSA-N 0.000 description 1
- CBDKQYKMCICBOF-UHFFFAOYSA-N thiazoline Chemical compound C1CN=CS1 CBDKQYKMCICBOF-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- XDDVRYDDMGRFAZ-UHFFFAOYSA-N thiobenzophenone Chemical compound C=1C=CC=CC=1C(=S)C1=CC=CC=C1 XDDVRYDDMGRFAZ-UHFFFAOYSA-N 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229940045136 urea Drugs 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
- Crushing And Grinding (AREA)
- Disintegrating Or Milling (AREA)
- Colloid Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
本発明は、湿式太陽電池用電極材料及び光触媒などに使用することが可能であり、分散性に優れた酸化チタン分散体におよびこれを工業的に効率よく製造する方法に関するものである。 The present invention relates to a titanium oxide dispersion that can be used for electrode materials for wet solar cells, photocatalysts, and the like, and is excellent in dispersibility, and to a method for industrially producing the same.
酸化チタン粉末は、白色顔料として古くから利用されており、近年は化粧品などの紫外線遮蔽材料、光触媒、コンデンサ、サーミスタの構成材料あるいはチタン酸バリウムの原料等電子材料に用いられる焼結材料に広く利用されている。特にここ数年、光触媒としての利用が盛んに試みられており、酸化チタンに、そのバンドギャップ以上のエネルギーを持つ光を照射することによって酸化チタンが励起されて、伝導帯に電子が生じ、価電帯に正孔が生じるが、この電子による還元力または正孔による酸化力を利用した光触媒反応の用途開発が盛んに行われている。この酸化チタン光触媒の用途は非常に多岐に渡っており、水の分解による水素の発生、酸化還元反応を利用した有機化合物の合成、排ガス処理、空気清浄、防臭、殺菌、抗菌、水処理、照明機器等の汚れ防止等、数多くの用途開発が行われている。 Titanium oxide powder has long been used as a white pigment, and in recent years, it has been widely used in sintered materials used in electronic materials such as UV shielding materials for cosmetics, photocatalysts, capacitors, thermistors, and barium titanate materials. Has been. In particular, there have been many attempts to use it as a photocatalyst for several years. Titanium oxide is excited by irradiating titanium oxide with light having energy higher than its band gap, and electrons are generated in the conduction band. Holes are generated in the electric band, and development of applications for photocatalytic reactions using the reducing power of electrons or the oxidizing power of holes has been actively conducted. This titanium oxide photocatalyst has a wide variety of uses, including generation of hydrogen by water decomposition, synthesis of organic compounds using redox reactions, exhaust gas treatment, air purification, deodorization, sterilization, antibacterial, water treatment, lighting Numerous applications have been developed, such as preventing contamination of equipment.
しかしながら、酸化チタンは可視光付近の波長領域において大きな屈折率を示すため、可視光領域では殆ど光吸収は起こらない。これは、アナターゼ型二酸化チタンは３．２ｅＶ、ルチル型二酸化チタンは３．０ｅＶというバンドギャップを有することに起因しており、酸化チタンの吸収可能な光の波長は、アナターゼ型酸化チタンで３８５ｎｍ以下、ルチル型酸化チタンで４１５ｎｍ以下である。これらの波長の光は大部分が紫外線領域に該当し、地球上に無限にある太陽光にはごく一部しか含まれておらず、従来知られている酸化チタン光触媒は、紫外線照射下では光触媒特性を発現するものの、太陽光のもとでは、そのエネルギーのうちごく一部しか活用できずに、光触媒として十分な活性は期待できない。また、屋内での蛍光灯などの下での利用を考えると、蛍光灯のスペクトルは殆どが４００ｎｍ以上であるため、光触媒として十分な特性を発現することはできない。そこで可視光領域での触媒活性を発現させより利用性の高く高活性の光触媒の開発が行なわれている。 However, since titanium oxide exhibits a large refractive index in the wavelength region near visible light, light absorption hardly occurs in the visible light region. This is because anatase-type titanium dioxide has a band gap of 3.2 eV and rutile-type titanium dioxide has a band gap of 3.0 eV. The wavelength of light that can be absorbed by titanium oxide is 385 nm or less for anatase-type titanium oxide. The rutile type titanium oxide has a thickness of 415 nm or less. Most of the light of these wavelengths falls in the ultraviolet region, and only a small portion is contained in infinite sunlight on the earth. Conventionally known titanium oxide photocatalysts are photocatalysts under ultraviolet irradiation. Although it exhibits the characteristics, only a part of its energy can be used under sunlight, and sufficient activity as a photocatalyst cannot be expected. Also, considering the use under fluorescent lamps indoors, since the spectrum of fluorescent lamps is almost 400 nm or more, sufficient characteristics as a photocatalyst cannot be expressed. Therefore, development of highly active and highly active photocatalysts has been carried out by exhibiting catalytic activity in the visible light region.
例えば、特許文献１（特開平９−２６２４８２号公報）では、Ｃｒ、Ｖ、Ｃｕ、Ｆｅ、Ｍｇ、Ａｇ、Ｐｄ、Ｎｉ、ＭｎおよびＰｔからなる群から選択される１種以上の金属のイオンが１×１０15イオン／ｇ−ＴｉＯ2以上の割合で酸化チタンの表面から内部に含有させた光触媒が開示されており、これらの金属のイオンを３０ＫｅＶ以上の高エネルギーに加速して、酸化チタンに照射し、該金属イオンを酸化チタンに導入する。また、特許文献２（特開平１１−２９０６９７号公報）では、真空槽内に遷移金属を含む固体と前記遷移金属がドーピングされる酸化チタンとを保持する工程と、前記真空槽内の内部に金属プラズマを発生させ、発生した前記金属プラズマを照射することにより前記遷移金属をドーピングした光触媒酸化チタンが開示されている。しかしながら、これらの発明は、酸化チタンに金属イオンをドーピングするために金属イオンを高エネルギーに加速したり、また金属プラズマを発生させるなど非常に特別な装置を用いなければならず、工業的規模での製造には適していない。 For example, in Patent Document 1 (Japanese Patent Laid-Open No. 9-262482), one or more kinds of metal ions selected from the group consisting of Cr, V, Cu, Fe, Mg, Ag, Pd, Ni, Mn, and Pt are included. A photocatalyst containing titanium oxide from the surface at a rate of 1 × 10 15 ions / g-TiO 2 or more is disclosed, and ions of these metals are accelerated to a high energy of 30 KeV or more to form titanium oxide. Irradiation introduces the metal ions into titanium oxide. Moreover, in patent document 2 (Unexamined-Japanese-Patent No. 11-290697), the process which hold | maintains the solid containing a transition metal and the titanium oxide by which the said transition metal is doped in a vacuum chamber, and a metal inside the said vacuum chamber A photocatalytic titanium oxide doped with the transition metal by generating plasma and irradiating the generated metal plasma is disclosed. However, these inventions must use a very special apparatus such as accelerating metal ions to high energy and generating metal plasma in order to dope metal ions into titanium oxide. Not suitable for manufacturing.
このような問題を解決するために、特許文献３（特開平１２−２３７５９８号公報）には、酸化チタンなどの半導体の表面に、前記半導体の構成成分とは異なる成分であるＢ, Ｐ, Ｔｉ, Ｖ, Ｃｒ, Ｍｎ, Ｆｅ, Ｃｏ, Ｎｉ, Ｃｕ, Ｚｎ, Ｇａ, Ｚｒ, Ｎｂ, Ｍｏ, Ｐｄ, Ａｇ, Ｃｄ, Ｓｎ, Ｓｂ, Ｈｆ, Ｔａ, Ｗ, Ｐｔ, Ｈｇ, Ｐｂ, Ｂｉ, Ｐｒ, Ｎｄ, Ｐｍ, Ｓｍ, Ｅｕ, Ｇｄ,Ｔｂ, Ｄｙ, Ｈｏ, Ｅｒ, Ｔｍ, ＹｂおよびＬｕからなる群から選ばれる少なくとも１種である陽イオンを含む媒体を接触させることにより、前記半導体に前記陽イオンを含有させる第１の工程と、前記陽イオンを含有する前記半導体を還元雰囲気において加熱する第２の工程とを含むことを特徴とする可視光応答型光触媒の製造方法が開示されている。しかしながら、このような方法により金属イオンを酸化チタンにドープした光触媒は必ずしも触媒活性が十分ではなく、さらなる改良が望まれていた。 In order to solve such a problem, Patent Document 3 (Japanese Patent Laid-Open No. 12-237598) discloses that B, P, Ti, which are components different from the constituent components of the semiconductor, on the surface of the semiconductor such as titanium oxide. , V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Zr, Nb, Mo, Pd, Ag, Cd, Sn, Sb, Hf, Ta, W, Pt, Hg, Pb, Bi, Pr , Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and a medium containing at least one cation selected from the group consisting of Lu, and contacting the semiconductor A method for producing a visible light responsive photocatalyst comprising a first step of containing a cation and a second step of heating the semiconductor containing the cation in a reducing atmosphere is disclosed. . However, the photocatalyst doped with metal ions in titanium oxide by such a method does not necessarily have sufficient catalytic activity, and further improvement has been desired.
上記のように遷移金属などの金属イオンを酸化チタンにドープし可視光領域での触媒活性を発現させた光触媒の他、特許文献４（ＷＯ ０１／０１０５５２号公報）では、酸化チタン結晶の酸素サイトの一部を窒素原子で置換すること、または酸化チタン結晶の格子間に窒素原子をドーピングすること、または酸化チタンの結晶粒界に窒素原子をドーピングすることのいずれかまたはこれらの組み合わせにより酸化チタン結晶に窒素原子を含有させた光触媒物質であり、酸化チタン結晶に窒素を含有させたＴｉ−Ｏ−Ｎ構成を有した、可視光領域において光触媒作用を発現する光触媒物質が開示されている。このような光触媒物質を得る方法として、窒素ガス雰囲気中での酸化チタンのスパッタリングが挙げられているが、製造コストが高く工業的規模での製造は困難である。また、酸化チタンをアンモニア雰囲気で焼成するという簡便な方法の開示もあるが、酸化チタン中に十分に窒素原子がドーピングされず、結果として得られる光触媒は触媒活性が十分ではなかった。 In addition to the photocatalyst in which titanium ions are doped with metal ions such as transition metals as described above to exhibit catalytic activity in the visible light region, in Patent Document 4 (WO 01/010552), oxygen sites of titanium oxide crystals are disclosed. Titanium oxide by either substituting part of it with nitrogen atoms, doping nitrogen atoms between the lattices of titanium oxide crystals, or doping nitrogen atoms into the crystal grain boundaries of titanium oxide, or a combination thereof A photocatalytic substance containing a nitrogen atom in a crystal and a photocatalytic substance exhibiting a photocatalytic action in the visible light region having a Ti—O—N structure in which a titanium oxide crystal contains nitrogen is disclosed. As a method for obtaining such a photocatalytic substance, sputtering of titanium oxide in a nitrogen gas atmosphere is mentioned. However, the production cost is high and it is difficult to produce on an industrial scale. Moreover, although there is also a disclosure of a simple method of firing titanium oxide in an ammonia atmosphere, nitrogen atoms are not sufficiently doped in titanium oxide, and the resulting photocatalyst is not sufficiently catalytic.
上記のように酸化チタンを光触媒として用いる場合、水あるいは有機溶剤等に懸濁し分散させてコーティング剤や塗料として基材に酸化チタン被膜あるいは塗膜を形成して使用する場合が多く、その場合酸化チタン粉末の溶媒への分散性が問題となる。具体的には、酸化チタン粉末を溶媒に分散させた後、酸化チタン粉末が凝集して沈殿してしまう。特に1μｍ以下の超微粉酸化チタンを分散させた場合、含有する酸化チタンの濃度を高めると、その分散体の粘度が高くなってしまうという問題があった。 When titanium oxide is used as a photocatalyst as described above, it is often used by suspending and dispersing in water or an organic solvent to form a titanium oxide film or coating on a substrate as a coating agent or paint. Dispersibility of the titanium powder in the solvent becomes a problem. Specifically, after the titanium oxide powder is dispersed in the solvent, the titanium oxide powder aggregates and precipitates. In particular, when ultrafine powdered titanium oxide of 1 μm or less is dispersed, there is a problem that when the concentration of the titanium oxide contained is increased, the viscosity of the dispersion increases.
光触媒、色素増感型太陽電池用電極などの用途で酸化チタン膜を形成する場合、酸化チタン膜の表面は凹凸が少なく平滑であることが要求されるため、酸化チタンの凝集を防止する必要がある。このため、ｐＨが中性領域である酸化チタンゾルあるいは水溶液を酸化チタン膜形成用として使用することができず、そのｐＨを酸性側に調整しなければならず、酸化チタン膜を形成する際の基材または用途に制限があった。紫外線遮断材料として酸化チタン分散体を使用する場合、酸化チタン粒子の凝集により紫外線遮断特性が低下するという問題もあった。 When forming a titanium oxide film for applications such as photocatalysts and dye-sensitized solar cell electrodes, the surface of the titanium oxide film is required to be smooth with few irregularities, so it is necessary to prevent aggregation of titanium oxide. is there. For this reason, it is not possible to use a titanium oxide sol or an aqueous solution having a pH in a neutral region for forming a titanium oxide film, and the pH must be adjusted to the acidic side. There were restrictions on materials or applications. When the titanium oxide dispersion is used as the ultraviolet blocking material, there is a problem that the ultraviolet blocking property is deteriorated due to aggregation of the titanium oxide particles.
上記のような酸化チタン粉末の分散性に関する問題を解決するために、シリカ、アルミナ等の元来分散性の高い疎水性物質を酸化チタン粉末表面にコーティングすることが試みられており、例えば特許文献５（特開平５−２８１７２６号公報）では、アルミニウム塩基性塩水溶液を酸でｐＨを１０．５〜１２．０に調節し、これに二酸化チタンスラリーを混合し、次いでこれを酸で中和して二酸化チタン粉末表面に酸化アルミニウム水和物を均一に析出させる方法が開示されている。また、異物質によるコーティングをすることなく、高濃度に添加しても均一分散が可能な酸化チタン分散体として、例えば特許文献６（特開２００１−２２０１４１号公報）、特許文献７（特開２００１−２６２００５号公報）では、ペルオクソチタン酸含有分散媒に酸化チタン粉末を均一分散してなることを特徴とする酸化チタン分散体が開示されている。これらの分散体は、酸化チタン粉末の分散性は改善されているものの、光触媒として用いた場合の特性が十分ではなく、また従来の酸化チタン分散体を保存し時間が経過すると、劣化等により分散体の粘度が上昇してしまうという問題があった。
従って、本発明の課題は、可視光領域で光触媒活性が発現し、光触媒、色素増感型太陽電池用電極などの光触媒機能を有する酸化チタン膜形成に用いることができる酸化チタン分散体であって、優れた光触媒特性および優れた分散性を有し、ｐＨが中性領域の酸化チタン分散体およびこれを効率よく工業的規模で製造する方法を提供することにある。 Accordingly, an object of the present invention is a titanium oxide dispersion that can be used for forming a titanium oxide film that exhibits photocatalytic activity in the visible light region and has a photocatalytic function such as a photocatalyst or a dye-sensitized solar cell electrode. Another object of the present invention is to provide a titanium oxide dispersion having excellent photocatalytic properties and excellent dispersibility, and having a pH in a neutral range, and a method for efficiently producing the titanium oxide dispersion on an industrial scale.
かかる実情において、本発明者らは鋭意検討を行った結果、硫黄含有酸化チタン粉末と分散剤とを用いて調製した分散体が、優れた分散性を有し、これを用いて光触媒を形成した際に優れた光触媒特性、特に可視光領域において、高い光吸収特性を発現することを見出し、本発明を完成するに至った。 Under such circumstances, the present inventors have conducted intensive studies. As a result, the dispersion prepared using the sulfur-containing titanium oxide powder and the dispersant has excellent dispersibility, and a photocatalyst was formed using the dispersion. In particular, the inventors have found that excellent photocatalytic properties, particularly high light absorption properties are exhibited in the visible light region, and have completed the present invention.
すなわち本発明は、硫黄含有酸化チタン粉末と、アミン系分散剤及び／又はカルボキシル基含有高分子分散剤と、水溶媒又は有機溶媒とからなる酸化チタン分散体前駆体をボールミルにより分散処理し、さらに湿式解砕処理した後、ぺルオクソチタン酸含有溶液と混合することを特徴とする酸化チタン分散体の製造方法を提供するものである。 That is, the present invention disperses a titanium oxide dispersion precursor comprising a sulfur-containing titanium oxide powder, an amine-based dispersant and / or a carboxyl group-containing polymer dispersant, and an aqueous solvent or an organic solvent with a ball mill, The present invention provides a method for producing a titanium oxide dispersion characterized by mixing with a peroxotitanic acid-containing solution after wet crushing treatment .
本発明の酸化チタン分散体は、高分散性、低粘度で、かつ中性であるため、光触媒や色素増感型太陽電池用電極などの光触媒機能を有する酸化チタン膜形成用として有効であり、特に、紫外線領域だけではなく可視光領域の光触媒活性が高いことから、太陽光の当たらない蛍光灯などの室内においても十分に光触媒作用を発揮することができ、今まで紫外線領域に止まっていた光触媒の用途を拡大することが可能となる。 Since the titanium oxide dispersion of the present invention is highly dispersible, low viscosity, and neutral, it is effective for forming a titanium oxide film having a photocatalytic function such as a photocatalyst or a dye-sensitized solar cell electrode, In particular, it has high photocatalytic activity not only in the ultraviolet region but also in the visible light region, so it can fully exert its photocatalytic action even in rooms such as fluorescent lamps that are not exposed to sunlight. Can be expanded.
硫黄含有酸化チタン粉末は以下の種々の方法により調製できる。
（１）四塩化チタンと酸素また必要に応じて燃焼して水を生成する水素ガスなどの可燃性ガスや水蒸気を気相で反応させて得られたルチル型またはアナターゼ型酸化チタンと硫黄または含硫黄化合物を混合し焼成する方法。
（２）硫酸チタニル、硫酸チタン、硫酸チタンアンモニウムを焼成する方法。
（３）硫酸チタニル、硫酸チタン、硫酸チタンアンモニウムなどの含チタン水溶 液を加水分解させ得られた酸化チタンと硫黄または含硫黄化合物を混合し 焼成する方法。
（４）テトライソプロポキシチタンなどのチタンアルコキシドなどの有機チタン 化合物を加水分解させ得られた酸化チタンと硫黄または含硫黄化合物を混 合し焼成する方法。
（５）三塩化チタンあるいは四塩化チタンなどのハロゲン化チタン水溶液を中和 又は加水分解させ得られた酸化チタンと硫黄または含硫黄化合物を混合し 焼成する方法。
The sulfur-containing titanium oxide powder can be prepared by the following various methods.
(1) Rutile-type or anatase-type titanium oxide obtained by reacting titanium tetrachloride and oxygen in a gas phase with a combustible gas such as hydrogen gas that burns as necessary to produce water, or water vapor, and sulfur or A method of mixing and baking sulfur compounds.
(2) A method of firing titanyl sulfate, titanium sulfate, or ammonium ammonium sulfate.
(3) A method in which titanium oxide obtained by hydrolyzing a titanium-containing aqueous solution such as titanyl sulfate, titanium sulfate, or titanium ammonium sulfate is mixed and calcined with sulfur or a sulfur-containing compound.
(4) A method in which titanium oxide obtained by hydrolyzing an organic titanium compound such as titanium alkoxide such as tetraisopropoxytitanium and sulfur or a sulfur-containing compound are mixed and calcined.
(5) A method in which titanium oxide obtained by neutralizing or hydrolyzing a titanium halide aqueous solution such as titanium trichloride or titanium tetrachloride is mixed and calcined with sulfur or a sulfur-containing compound.
上記のうち、得られる酸化チタン光触媒の特性と製造コストを考慮すると（５）のハロゲン化チタン水溶液を原料とする方法が好ましい。以下この方法について詳述する。 Among the above, considering the characteristics and production cost of the resulting titanium oxide photocatalyst, the method (5) using a titanium halide aqueous solution as a raw material is preferable. This method will be described in detail below.
ハロゲン化チタン水溶液としては、三塩化チタン水溶液または四塩化チタン水溶液である。三塩化チタン水溶液は、例えば塩酸に金属チタンを溶解することで得ることができる。金属チタンとしてはチタン粉末やスポンジ状チタン、または切粉などのチタンスクラップなどが用いられる。四塩化チタン水溶液は、四塩化チタンを水または塩酸に溶解させて得ることができる。塩化チタン水溶液中のチタン濃度は任意であるが、製造効率また得られる酸化チタン粉末の粒径などを考慮するとチタン含有量が１〜２０質量％、好ましくは１〜１０質量％、特に好ましくは２〜５質量％である。また塩化チタン水溶液は不純物成分が少なく純度が高いことが望ましく、具体的にはアルミニウム、鉄、及びバナジウムがそれぞれ１ｐｐｍ以下、ケイ素及びスズがそれぞれ１０ｐｐｍ以下である。 The titanium halide aqueous solution is a titanium trichloride aqueous solution or a titanium tetrachloride aqueous solution. The aqueous titanium trichloride solution can be obtained, for example, by dissolving titanium metal in hydrochloric acid. As the metal titanium, titanium powder, sponge-like titanium, or titanium scrap such as chips are used. The titanium tetrachloride aqueous solution can be obtained by dissolving titanium tetrachloride in water or hydrochloric acid. The titanium concentration in the aqueous titanium chloride solution is arbitrary, but considering the production efficiency and the particle size of the resulting titanium oxide powder, the titanium content is 1 to 20% by mass, preferably 1 to 10% by mass, particularly preferably 2 ˜5 mass%. In addition, it is desirable that the aqueous solution of titanium chloride has few impurity components and high purity. Specifically, aluminum, iron, and vanadium are each 1 ppm or less, and silicon and tin are each 10 ppm or less.
該塩化チタン水溶液の加水分解方法は、該塩化チタン水溶液を加熱下、攪拌することにより行なわれる。加水分解温度は、２０℃〜水溶液の沸点、好ましくは３０℃〜水溶液の沸点、特に好ましくは４０℃〜８０℃である。該加水分解温度が、２０℃未満だと加水分解が起こり難くなる。また、加水分解時間は、通常５分〜１０時間、好ましくは１０分〜５時間、特に好ましくは１０分〜１時間である。 The method for hydrolyzing the titanium chloride aqueous solution is carried out by stirring the titanium chloride aqueous solution under heating. The hydrolysis temperature is 20 ° C to the boiling point of the aqueous solution, preferably 30 ° C to the boiling point of the aqueous solution, particularly preferably 40 ° C to 80 ° C. If the hydrolysis temperature is less than 20 ° C., hydrolysis is difficult to occur. The hydrolysis time is usually 5 minutes to 10 hours, preferably 10 minutes to 5 hours, particularly preferably 10 minutes to 1 hour.
また、該塩化チタン水溶液の加水分解方法、特に、水溶液の沸点下で行なう場合、塩化水素が反応槽から排出され反応系のｐＨが上昇するため、水溶液の沸点下加水分解を行なう際は、反応槽に還流装置等を用いること等により、該塩酸が塩酸ガスとして反応系外へ放出されることを抑えることが、低ｐＨ領域で加水分解が行えるので、粒径が小さい酸化チタンを得ることができる点で好ましい。 In addition, when the hydrolysis method of the aqueous solution of titanium chloride is carried out under the boiling point of the aqueous solution, particularly when hydrogen chloride is discharged from the reaction tank and the pH of the reaction system rises, It is possible to obtain a titanium oxide having a small particle size because it is possible to suppress the release of hydrochloric acid as hydrochloric acid gas from the reaction system by using a reflux apparatus or the like in the tank, so that hydrolysis can be performed in a low pH region. It is preferable in that it can be performed.
該塩化チタン水溶液の中和方法において、該塩化チタン水溶液と接触させるアルカリとしては、特に制限されず、例えば、アンモニア；アンモニア水；水酸化ナトリウム、水酸化カリウム、水酸化カルシウム等の金属の水酸化物；炭酸ナトリウム、炭酸カリウム、炭酸カルシウム等の炭酸塩等が挙げられる。これらのうち、アンモニア又はアンモニア水が、酸化チタン光触媒中に金属成分が含有されないので、該触媒の触媒活性が高まる点で好ましい。 In the neutralization method of the aqueous titanium chloride solution, the alkali to be brought into contact with the aqueous titanium chloride solution is not particularly limited. For example, ammonia; aqueous ammonia; hydroxylation of a metal such as sodium hydroxide, potassium hydroxide, calcium hydroxide Products; carbonates such as sodium carbonate, potassium carbonate and calcium carbonate; Among these, ammonia or aqueous ammonia is preferable because the titanium oxide photocatalyst does not contain a metal component, so that the catalytic activity of the catalyst is increased.
また、アルカリ金属又はアルカリ土類金属は、該酸化チタン光触媒中に含まれていても、該触媒の光触媒活性に与える影響が少ないので、該塩化チタン水溶液の中和方法におけるアルカリとして、アルカリ金属又はアルカリ土類金属の水酸化物を、好適に用いることができる。一般的な塩化チタンの工業的排水処理においては、水酸化カルシウム水溶液（消石灰溶液）等のアルカリ金属又はアルカリ土類金属の水酸化物を、該排水に加え中和し、酸化チタン水和物を析出させ、析出した該酸化チタン水和物の懸濁液に、ポリ塩化アルミニウムのような凝集剤を添加して固形物を沈降分離させることにより、排水中からチタン化合物を除去することが行われている。そして、このような方法は、非常に効率が良く、該酸化チタンの製造に応用可能である。従って、アルカリ金属又はアルカリ土類金属の水酸化物を用いることが、工業的に効率よく該酸化チタンを製造できる点で好ましい。 In addition, even if the alkali metal or alkaline earth metal is contained in the titanium oxide photocatalyst, it has little influence on the photocatalytic activity of the catalyst. Alkaline earth metal hydroxides can be suitably used. In general industrial wastewater treatment of titanium chloride, alkali metal or alkaline earth metal hydroxide such as calcium hydroxide aqueous solution (slaked lime solution) is added to the wastewater to neutralize it, and titanium oxide hydrate is added. The titanium compound is removed from the waste water by precipitating and adding a flocculant such as polyaluminum chloride to the suspension of the precipitated titanium oxide hydrate to precipitate and separate the solid. ing. Such a method is very efficient and can be applied to the production of the titanium oxide. Therefore, it is preferable to use an alkali metal or alkaline earth metal hydroxide in terms of industrially efficient production of the titanium oxide.
該塩化チタン水溶液の中和方法の反応温度は、１０〜８０℃、好ましくは３０ 〜８０℃、特に好ましくは４０〜７０℃である。該反応温度が、１０℃未満だと中和反応が起こり難く、また、８０℃を超えると発熱が激しく、塩化水素の発生が著しくなり、微粒で比表面積の大きい酸化チタンが得られない。また、該中和反応の反応時間は、通常５分〜１０時間、好ましくは１０〜５時間、特に好ましくは３０〜３時間である。 The reaction temperature of the neutralizing method of the titanium chloride aqueous solution is 10 to 80 ° C, preferably 30 to 80 ° C, particularly preferably 40 to 70 ° C. When the reaction temperature is less than 10 ° C., the neutralization reaction hardly occurs. When the reaction temperature exceeds 80 ° C., heat generation is severe, hydrogen chloride is generated remarkably, and titanium oxide having fine particles and a large specific surface area cannot be obtained. The reaction time for the neutralization reaction is usually 5 minutes to 10 hours, preferably 10 to 5 hours, particularly preferably 30 to 3 hours.
また、該塩化チタン水溶液の加水分解方法又は該塩化チタン水溶液の中和方法は、硫黄又は含硫黄化合物が反応系中に存在していても、特に該化合物の影響を受けない。従って、例えば、塩化チタン水溶液と、該化合物の混合物を用いて、該塩化チタン水溶液の加水分解方法又は塩化チタン水溶液の中和方法を行うことができる。 Further, the hydrolysis method of the titanium chloride aqueous solution or the neutralization method of the titanium chloride aqueous solution is not particularly affected by the compound even if sulfur or a sulfur-containing compound is present in the reaction system. Therefore, for example, a titanium chloride aqueous solution and a mixture of the compounds can be used to hydrolyze the titanium chloride aqueous solution or neutralize the titanium chloride aqueous solution.
該塩化チタン水溶液の加水分解方法又は塩化チタン水溶液の中和方法により得られる該酸化チタンは、オルトチタン酸又はメタチタン酸であるが、メタチタン酸であることが、光触媒活性が高まる点で好ましい。該塩化チタン水溶液の加水分解方法又は塩化チタン水溶液の中和方法において、該メタチタン酸が生成し易い条件とは、塩化チタン水溶液を予め４０〜７０℃程度に加熱し、その後アンモニアなどのアルカリを添加して中和する。 The titanium oxide obtained by the hydrolysis method of the aqueous titanium chloride solution or the neutralization method of the aqueous titanium chloride solution is orthotitanic acid or metatitanic acid, and is preferably metatitanic acid from the viewpoint of increasing the photocatalytic activity. In the method of hydrolyzing the titanium chloride aqueous solution or the method of neutralizing the titanium chloride aqueous solution, the conditions under which the metatitanic acid is likely to be generated include heating the titanium chloride aqueous solution to about 40 to 70 ° C. in advance and then adding an alkali such as ammonia. To neutralize.
該酸化チタン（Ａ）の比表面積は、特に制限されないが、ＢＥＴ比表面積で５０ｍ2／ｇ以上、好ましくは１００ｍ2／ｇ以上、特に好ましくは１５０〜２５０ｍ2／ｇである。該比表面積が、５０ｍ2／ｇ以上であると、酸化チタン光触媒の光触媒活性が高くなる。また、該酸化チタンの平均粒径は、特に制限されないが、０．１μｍ以下、好ましくは０．０５μｍ以下、特に好ましくは０．０３μｍ以下である。このように平均粒径は小さいほうが比表面積が大きくなり、光触媒として活性が向上する。該平均粒子径が０．１μｍを超えると比表面積が小さくなり、光触媒活性が十分に発現しない。また、該酸化チタンの結晶形は、ルチル型又はアナターゼ型のいずれであってもよいが、好ましくはルチル型単独結晶、又はルチル型及びアナターゼ型の混合結晶である。 The specific surface area of titanium oxide (A) is not particularly limited, 50 m 2 / g or more in BET specific surface area is preferably 100 m 2 / g or more, particularly preferably 150 to 250 2 / g. When the specific surface area is 50 m 2 / g or more, the photocatalytic activity of the titanium oxide photocatalyst increases. The average particle diameter of the titanium oxide is not particularly limited, but is 0.1 μm or less, preferably 0.05 μm or less, and particularly preferably 0.03 μm or less. Thus, the smaller the average particle size, the larger the specific surface area, and the activity as a photocatalyst is improved. When the average particle diameter exceeds 0.1 μm, the specific surface area becomes small and the photocatalytic activity is not sufficiently exhibited. The crystal form of the titanium oxide may be either a rutile type or an anatase type, but is preferably a rutile type single crystal or a mixed crystal of a rutile type and an anatase type.
該酸化チタンの比表面積、平均粒径又は結晶形は、該塩化チタン水溶液の加水分解方法又は塩化チタン水溶液の中和方法の条件を調整することにより、制御することができる。その条件は、例えば塩化チタン水溶液を加熱し加水分解する方法では、反応中に塩化水素が発生し、反応系より排出されｐＨが上昇するが、この塩化水素の排出を制御し反応系のｐＨを低く保持することによって、得られる酸化チタンの平均粒径を小さくでき、また酸化チタン生成後に塩酸酸性雰囲気などの低ｐＨ領域で酸化チタンを熟成することにより、平均粒径の小さいルチル型の酸化チタンを得ることができる。 The specific surface area, average particle diameter or crystal form of the titanium oxide can be controlled by adjusting the conditions of the hydrolysis method of the titanium chloride aqueous solution or the neutralization method of the titanium chloride aqueous solution. For example, in the method of heating and hydrolyzing a titanium chloride aqueous solution, hydrogen chloride is generated during the reaction and discharged from the reaction system to raise the pH. However, the pH of the reaction system is controlled by controlling the discharge of this hydrogen chloride. By keeping low, the average particle size of the resulting titanium oxide can be reduced, and by aging titanium oxide in a low pH region such as an acidic atmosphere of hydrochloric acid after the formation of titanium oxide, a rutile type titanium oxide having a small average particle size Can be obtained.
また、該酸化チタンは、該塩化チタンの加水分解方法又は塩化チタン水溶液の中和方法を行って得られる酸化チタンを含有する反応液、又は該反応液から該酸化チタンをろ過等により取り出し、必要に応じ塩酸分やアルカリ成分等の不純物の除去のための洗浄、乾燥等を行ない得られる酸化チタンの粉末のいずれであってもよい。 In addition, the titanium oxide is required by taking out the titanium oxide by filtration or the like from the reaction liquid containing titanium oxide obtained by performing the method of hydrolyzing the titanium chloride or the method of neutralizing the aqueous solution of titanium chloride. Depending on the above, any of titanium oxide powders obtained by washing, drying, etc. for removing impurities such as hydrochloric acid and alkali components may be used.
また、該酸化チタンの粉末を用いる場合、該酸化チタンの粉末は、水分や塩素分の含有量が少ないことが、光触媒活性を向上させる点で好ましい。従って、該酸化チタンの粉末中の水分を除去するために、該粉末を焼成することが好ましく、焼成温度は、２００〜８００℃、好ましくは３００〜６００℃である。 Further, when the titanium oxide powder is used, it is preferable that the titanium oxide powder has a low content of moisture and chlorine in terms of improving the photocatalytic activity. Therefore, in order to remove moisture in the titanium oxide powder, the powder is preferably fired, and the firing temperature is 200 to 800 ° C, preferably 300 to 600 ° C.
含硫黄化合物としては、常温で液体あるいは固体の化合物が好ましく、含硫黄無機化合物、含硫黄有機化合物あるいは金属の硫化物などが挙げられる。具体的にはチオエーテル類、チオ尿素類、チオアミド類、チオアルコール類、チオアルデヒド類、チアジル類、メルカプタール類、チオール類、チオシアン酸塩類などであり、具体的な化合物としては、チオ尿素、スルホ酢酸、チオフェノール、チオフェン、ベンゾチオフェン、ジベンゾチオフェン、チオベンゾフェノン、ビチオフェン、フェノチアジン、スルホラン、チアジン、チアゾール、チアジアゾール、チアゾリン、チアゾリジン、チアントレン、チアン、チオアセトアニリド、チオアセトアミド、チオベンズアミド、チオアニソール、チオニン、メチルチオール、チオエーテル、チオシアン、硫酸、スルホン酸類、スルホニウム塩類、スルホンアミド類、スルフィン酸類、スルホキシド類、スルフィン類、スルファン類などが挙げられる。なおこれらの化合物は１種または２種以上組み合わせて用いることができる。 The sulfur-containing compound is preferably a compound that is liquid or solid at room temperature, and examples thereof include sulfur-containing inorganic compounds, sulfur-containing organic compounds, and metal sulfides. Specific examples include thioethers, thioureas, thioamides, thioalcohols, thioaldehydes, thiazyl, mercaptals, thiols, and thiocyanates. Specific compounds include thiourea and sulfoacetic acid. , Thiophenol, thiophene, benzothiophene, dibenzothiophene, thiobenzophenone, bithiophene, phenothiazine, sulfolane, thiazine, thiazole, thiadiazole, thiazoline, thiazolidine, thianthrene, thiane, thioacetanilide, thioacetamide, thiobenzamide, thioanisole, thionine, methyl Thiol, thioether, thiocyan, sulfuric acid, sulfonic acids, sulfonium salts, sulfonamides, sulfinic acids, sulfoxides, sulfines, sulfanes, etc. It is. These compounds can be used alone or in combination of two or more.
上記のなかでも含硫黄有機化合物が好ましく、さらには酸素原子を含まず硫黄原子と窒素原子が混在した有機化合物が特に好ましく、具体的には、チオ尿素が好ましい。 Among these, sulfur-containing organic compounds are preferable, and organic compounds containing no oxygen atom and containing sulfur and nitrogen atoms are particularly preferable, and specifically, thiourea is preferable.
上記のようにして得られる酸化チタン粉末は、加水分解あるいはアルカリでの中和の条件により平均粒径、比表面積また結晶形を制御することができるが、光触媒の活性を向上させるためには、比表面積が大きいほうが好ましい。具体的にはＢＥＴ比表面積で５０ｍ2／ｇ以上、好ましくは１００ｍ2／ｇ以上、特に好ましくは１５０〜２５０ｍ2／ｇである。結晶形としてはルチル型であって、かつ比表面積が５０ｍ2／ｇ以上の微粒酸化チタンが好ましい。 The titanium oxide powder obtained as described above can control the average particle size, specific surface area, and crystal form depending on the conditions of hydrolysis or neutralization with alkali. In order to improve the activity of the photocatalyst, A larger specific surface area is preferred. Specifically 50 m 2 / g or more in BET specific surface area is preferably 100 m 2 / g or more, particularly preferably 150 to 250 2 / g. The crystal form is preferably a rutile type and a fine titanium oxide having a specific surface area of 50 m 2 / g or more.
上記の酸化チタン粉末と硫黄または含硫黄化合物の混合物を形成する。この混合物の形成方法は、
（１）塩化チタン水溶液に硫黄または含硫黄化合物を混合し、次いで加水分解またはアルカリで中和して酸化チタン粉末と硫黄または含硫黄化合物との混合物を得る方法、
（２）塩化チタン水溶液を加水分解またはアルカリで中和して酸化チタン粉末を得、次いで該酸化チタン粉末と硫黄または含硫黄化合物とを混合し混合物を得る方法、
（３）塩化チタン水溶液を加水分解またはアルカリで中和して酸化チタン粉末を得、得られた酸化チタン粉末を仮焼し、次いで該酸化チタン粉末と硫黄または含硫黄化合物とを混合し混合物を得る方法、
（４）塩化チタン水溶液に硫黄または含硫黄化合物を混合し、次いで加水分解またはアルカリで中和して固形物を形成した後、さらに硫黄または含硫黄化合物を混合して酸化チタン粉末と硫黄または含硫黄化合物の混合物を得る方法、
などが挙げられる。
A mixture of the above titanium oxide powder and sulfur or a sulfur-containing compound is formed. The method of forming this mixture is:
(1) A method of obtaining a mixture of titanium oxide powder and sulfur or a sulfur-containing compound by mixing sulfur or a sulfur-containing compound with an aqueous titanium chloride solution and then neutralizing with hydrolysis or alkali.
(2) A method in which an aqueous titanium chloride solution is hydrolyzed or neutralized with an alkali to obtain a titanium oxide powder, and then the titanium oxide powder and sulfur or a sulfur-containing compound are mixed to obtain a mixture;
(3) Titanium chloride aqueous solution is hydrolyzed or neutralized with alkali to obtain titanium oxide powder, the obtained titanium oxide powder is calcined, and then the titanium oxide powder and sulfur or a sulfur-containing compound are mixed to obtain a mixture. How to get,
(4) Sulfur or a sulfur-containing compound is mixed with an aqueous titanium chloride solution, then hydrolyzed or neutralized with alkali to form a solid, and further mixed with sulfur or a sulfur-containing compound to form titanium oxide powder and sulfur or a sulfur-containing compound. A method for obtaining a mixture of sulfur compounds,
Etc.
酸化チタン粉末と混合する硫黄または含硫黄化合物の量は、硫黄原子の質量に換算すると、酸化チタンに対し、通常１質量％以上であり、好ましくは５質量％以上、より好ましくは１０〜３０質量％である。硫黄または含硫黄化合物の混合量が少ないと、最終的に光触媒酸化チタンに含まれる硫黄原子量が少なくなり、十分な可視光吸収が起こらなくなる。 The amount of sulfur or sulfur-containing compound to be mixed with the titanium oxide powder is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10 to 30% by mass with respect to titanium oxide when converted to the mass of sulfur atoms. %. If the amount of sulfur or sulfur-containing compound mixed is small, the amount of sulfur atoms contained in the photocatalytic titanium oxide will eventually decrease, and sufficient visible light absorption will not occur.
上記の硫黄含有酸化チタン粉末の調製において、硫黄または硫黄化合物の他に、含窒素化合物又は含炭素化合物を併用して酸化チタンとの混合物を形成してもよい。含窒素化合物又は含炭素化合物を併用することによって、酸化チタン分散体の可視光領域における吸収特性がより向上し活性がより向上する。 In the preparation of the above sulfur-containing titanium oxide powder, in addition to sulfur or a sulfur compound, a nitrogen-containing compound or a carbon-containing compound may be used in combination to form a mixture with titanium oxide. By using a nitrogen-containing compound or a carbon-containing compound in combination, the absorption characteristics in the visible light region of the titanium oxide dispersion are further improved and the activity is further improved.
該含窒素化合物又は含炭素化合物としては、特に制限されず、含窒素無機化合物；アミン類、アミノ酸等の含窒素有機化合物、又は二酸化炭素等の窒素原子を含有しない含炭素化合物が挙げられ、具体的には、含窒素無機化合物としては、アンモニア等が、含窒素有機化合物としては、酢酸アンモニウム、尿素、アミノ酪酸、アミノベンゼン、グリシン、アラニン等が、窒素を含有しない含炭素化合物としては、炭素、一酸化炭素、二酸化炭素、炭化チタン、炭化カルシウム、炭酸等が挙げられる。これらのうち、アンモニア、又は窒素及び炭素を含有する含窒素有機化合物が好ましく、尿素が特に好ましい。また、これらは１種又は２種以上の組合せて用いることができる。 The nitrogen-containing compound or the carbon-containing compound is not particularly limited, and examples thereof include nitrogen-containing inorganic compounds; nitrogen-containing organic compounds such as amines and amino acids, or carbon-containing compounds not containing nitrogen atoms such as carbon dioxide. Specifically, ammonia and the like are used as nitrogen-containing inorganic compounds, and ammonium acetate, urea, aminobutyric acid, aminobenzene, glycine, and alanine are used as nitrogen-containing organic compounds, and carbon-containing compounds that do not contain nitrogen include carbon. , Carbon monoxide, carbon dioxide, titanium carbide, calcium carbide, carbonic acid and the like. Among these, ammonia or nitrogen-containing organic compounds containing nitrogen and carbon are preferable, and urea is particularly preferable. Moreover, these can be used 1 type or in combination of 2 or more types.
次いで、上記で得られた酸化チタン粉末と硫黄または含硫黄化合物（必要に応じて含窒素化合物又は含炭素化合物）の混合物を焼成し硫黄含有酸化チタン粉末を形成するが、焼成温度は２００〜８００℃、好ましくは３００〜６００℃、より好ましくは４００〜５００℃である。含硫黄有機化合物を用いた場合、その化合物が分解し硫黄原子が遊離して酸化チタン中のチタン原子と置換する温度で行なう。また焼成雰囲気は、空気、酸素などの酸化性雰囲気、水素ガスやアンモニアガスなどの還元性雰囲気、窒素ガスやアルゴンガスなどの不活性雰囲気、また真空下などで行なわれる。これらのなかでも水素ガスのような還元性雰囲気で行なうことによって、より可視光領域での光触媒活性が向上し好ましい。水素ガスのような還元性ガスのみでもよいが、水素と酸素の混合ガス、水素と酸素と不活性ガスの混合ガスの雰囲気で焼成することも有効である。さらに焼成時に硫黄が蒸発しまたは含硫黄化合物が分解して硫黄成分が焼成炉から排出しないよう、ある程度硫黄成分の分圧を保持するよう焼成雰囲気を保つことが重要である。炭素原子を有する含硫黄有機化合物など焼成時に分解して炭酸ガスなどの副生ガスを発生する場合は、ある程度焼成雰囲気から排出したほうがよい。従って、焼成する際の容器は、完全にオープンまたは密閉のものではなく、ある程度の圧力がかかりかつ副生ガスを排出し得るような、上部が開放され、この上部に非固定式の蓋体を備えた円筒形、皿状または矩形などの容器が好ましい。 Next, a mixture of the titanium oxide powder obtained above and sulfur or a sulfur-containing compound (a nitrogen-containing compound or a carbon-containing compound as necessary) is fired to form a sulfur-containing titanium oxide powder, but the firing temperature is 200 to 800. ° C, preferably 300-600 ° C, more preferably 400-500 ° C. When a sulfur-containing organic compound is used, the reaction is performed at a temperature at which the compound is decomposed and sulfur atoms are liberated and replaced with titanium atoms in titanium oxide. The firing atmosphere is performed in an oxidizing atmosphere such as air or oxygen, a reducing atmosphere such as hydrogen gas or ammonia gas, an inert atmosphere such as nitrogen gas or argon gas, or under vacuum. Of these, the photocatalytic activity in the visible light region is preferably improved by carrying out in a reducing atmosphere such as hydrogen gas. Although only a reducing gas such as hydrogen gas may be used, firing in an atmosphere of a mixed gas of hydrogen and oxygen or a mixed gas of hydrogen, oxygen and inert gas is also effective. Furthermore, it is important to maintain the firing atmosphere so that the partial pressure of the sulfur component is maintained to some extent so that sulfur does not evaporate during the firing or the sulfur-containing compound decomposes and the sulfur component is not discharged from the firing furnace. When a by-product gas such as carbon dioxide gas is generated by decomposition during firing, such as a sulfur-containing organic compound having a carbon atom, it is better to exhaust from the firing atmosphere to some extent. Therefore, the container for firing is not completely open or sealed, and the upper part is opened so that a certain amount of pressure is applied and the by-product gas can be discharged, and a non-fixed lid is placed on the upper part. A cylindrical, dished or rectangular container provided is preferred.
上記のようにして得られた硫黄含有酸化チタン粉末は、必要に応じて洗浄して遊離の硫黄成分やその他を除去する。また、粒子の分散性を向上させるために界面活性剤などにより表面処理することもできる。 The sulfur-containing titanium oxide powder obtained as described above is washed as necessary to remove free sulfur components and others. Moreover, in order to improve the dispersibility of particle | grains, it can also surface-treat with surfactant etc.
上記のようにして得られた硫黄含有酸化チタン粉末は、淡黄色、黄色または黄橙色の粉末であり、硫黄原子及び炭素原子、また硫黄原子、炭素原子及び窒素原子を含有する。そして、該硫黄含有酸化チタン粉末は、酸化チタン中のチタン原子の一部が、硫黄原子に置換、すなわち、該硫黄原子が、陽イオンとして酸化チタン中にドープされたものも含まれる。具体的に陽イオンとして硫黄原子がドープされた場合、Ｔｉ1-xＳxＯ2の化学式で表すことができ、チタン原子の数及び硫黄原子の数の合計に対する、該硫黄原子の数の割合を示すｘは、０．００１以上、好ましくは０．００２以上、特に好ましくは０．００２〜０．００８である。また、本発明の硫黄含有酸化チタン粉末中に、硫黄原子の他、炭素原子、あるいは炭素原子および窒素原子を含有するものである。本発明に係る硫黄含有酸化チタン粉末中に含有する硫黄原子、炭素原子あるいは窒素原子の含有量は、硫黄原子が０．０１〜５質量％、好ましくは０．０５〜１．０質量％、特に好ましくは０．１〜０．５質量％、炭素原子が０．１〜１０質量％、好ましくは０．５〜５．０質量％、特に好ましくは１．０〜３．０質量％、窒素原子が０〜３質量％、好ましくは０．０１〜１．０質量％、特に好ましくは０．１〜０．５質量％である。また、該含硫黄酸化チタン粉末の平均粒径は、ＳＥＭ写真画像観察による１次粒子の粒径で５〜５０ｎｍ、ＢＥＴ比表面積は１００〜２５０ｍ2／ｇである。 The sulfur-containing titanium oxide powder obtained as described above is a pale yellow, yellow or yellow-orange powder and contains sulfur atoms and carbon atoms, and also sulfur atoms, carbon atoms and nitrogen atoms. The sulfur-containing titanium oxide powder includes those in which some of the titanium atoms in the titanium oxide are substituted with sulfur atoms, that is, the sulfur atoms are doped into the titanium oxide as cations. Specifically, when a sulfur atom is doped as a cation, it can be represented by a chemical formula of Ti 1-x S x O 2 , and the ratio of the number of sulfur atoms to the total number of titanium atoms and the number of sulfur atoms X which represents is 0.001 or more, preferably 0.002 or more, particularly preferably 0.002 to 0.008. In addition, the sulfur-containing titanium oxide powder of the present invention contains carbon atoms or carbon atoms and nitrogen atoms in addition to sulfur atoms. The sulfur atom, carbon atom or nitrogen atom content in the sulfur-containing titanium oxide powder according to the present invention is 0.01 to 5% by mass, preferably 0.05 to 1.0% by mass, especially sulfur atom. Preferably 0.1 to 0.5 mass%, carbon atom 0.1 to 10 mass%, preferably 0.5 to 5.0 mass%, particularly preferably 1.0 to 3.0 mass%, nitrogen atom Is 0 to 3 mass%, preferably 0.01 to 1.0 mass%, particularly preferably 0.1 to 0.5 mass%. The average particle size of the sulfur-containing titanium oxide powder is 5 to 50 nm in terms of the particle size of primary particles observed by SEM photographic image, and the BET specific surface area is 100 to 250 m 2 / g.
上記のようにして得られた硫黄含有酸化チタン粉末を水溶媒または有機溶媒の分散媒に分散剤とともに分散させて混合し、本発明の酸化チタン分散体を製造する。 The sulfur-containing titanium oxide powder obtained as described above is dispersed in an aqueous solvent or an organic solvent dispersion medium together with a dispersing agent and mixed to produce the titanium oxide dispersion of the present invention.
分散媒は水、あるいは有機溶媒を使用することができる。有機溶媒としては、アルコール類、エーテル類、アセトン類が好ましい。具体的には、メタノール、エタノール、１−メトキシ−２−プロパノール、ジメトキシ−２−プロパノール、ブタノール、イソプロピルアルコール、ヘキサノール、２−エチルヘキサノール、２−メチル−１−プロパノール、イソブタノール、２−（エチルアミノ）エタノール、２−エチル−１−ブタノール、３−エチル−３−ペンタノール、２−イソプロポキシエタノール、２−エトキシエタノール、２−プロポキシエタノール、２−メトキシエタノール、２−メトキシメトキシエタノール、１−オクタデカノール、ｎ−オクタノール、２，３−エポキシ−１−プロパノール、シクロヘキサノール、ジメチルブタノール、ジメチルプロパノール、２，６−ジメチル−４−ヘプタノール、２，４−ジメチル−３−ペンタノール、１，３−ジメトキシ−２−プロパノール、ジメトキシプロパノール、１−デカノール、１−ドデカノール、トリメチルブタノール、３，５，５−トリメチルヘキサノール、ノナノール、フェニルエタノール、２−メチル−２−プロパノール、ｔ−ブタノール、メチルプロパノール、１−エトキシ−２−プロパノール、１−ブトキシ−２−プロパノール、ヘキサデカノール、ヘプタデカノール、ｔ−ペンチルアルコール、メチルシクロヘキサノール、２−メチル−１−ブタノール、３−メチル−１−ブタノール、３−メチル−３−ペンタノール、３−メトキシブタノール、２−（２−ブトキシエトキシ）エタノール、アニリノエタノール、アミノエタノール、アミノプロパノール、アミノブタノール、２−（ブチルアミノ）エタノール、２−（メチルアミノ）エタノール、２−アミノ−２−エチル−１，３−プロパンジオール、２−アミノ−２−メチル−１，３−プロパンジオール、ジフェニルエタンジオール、エチレングリコール、グリセリン、２−エチル−１，３−ヘキサンジオール、２−クロロ−１，３−プロパンジオール、ｃｉｓ−１，２−シクロヘキサンジオール、ｃｉｓ−１，４−シクロヘキサンジオール、３，５−ジメチル−１−ヘキシン−３−オール、テルピネオール、ブタンジオール、ブテンオール、ブトキシプロパンジオール、プロパンジオール、ヘキサンジオール、ヘキシレングリコール、ペンタンジオール、テルピネオール、ジエチルエーテル、アセトン、重合度２のポリオキシエチレングリコール、ポリオキシプロピレングルコール、ポリオキシエチレングリコールモノエステルなどが挙げられる。アルコール類が好ましく、エタノール系のアルコール類が特に好ましい。 As the dispersion medium, water or an organic solvent can be used. As the organic solvent, alcohols, ethers and acetones are preferable. Specifically, methanol, ethanol, 1-methoxy-2-propanol, dimethoxy-2-propanol, butanol, isopropyl alcohol, hexanol, 2-ethylhexanol, 2-methyl-1-propanol, isobutanol, 2- (ethyl) Amino) ethanol, 2-ethyl-1-butanol, 3-ethyl-3-pentanol, 2-isopropoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-methoxyethanol, 2-methoxymethoxyethanol, 1- Octadecanol, n-octanol, 2,3-epoxy-1-propanol, cyclohexanol, dimethylbutanol, dimethylpropanol, 2,6-dimethyl-4-heptanol, 2,4-dimethyl-3-pentanol, 1, 3-jime Xyl-2-propanol, dimethoxypropanol, 1-decanol, 1-dodecanol, trimethylbutanol, 3,5,5-trimethylhexanol, nonanol, phenylethanol, 2-methyl-2-propanol, t-butanol, methylpropanol, 1 -Ethoxy-2-propanol, 1-butoxy-2-propanol, hexadecanol, heptadecanol, t-pentyl alcohol, methylcyclohexanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3- Methyl-3-pentanol, 3-methoxybutanol, 2- (2-butoxyethoxy) ethanol, anilinoethanol, aminoethanol, aminopropanol, aminobutanol, 2- (butylamino) ethanol, 2- (methylamino) Ethanol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol, diphenylethanediol, ethylene glycol, glycerin, 2-ethyl-1,3-hexane Diol, 2-chloro-1,3-propanediol, cis-1,2-cyclohexanediol, cis-1,4-cyclohexanediol, 3,5-dimethyl-1-hexyn-3-ol, terpineol, butanediol, Buteneol, butoxypropanediol, propanediol, hexanediol, hexylene glycol, pentanediol, terpineol, diethyl ether, acetone, polyoxyethylene glycol with a polymerization degree of 2, polyoxypropylene glycol, polyoxyethylene glycol mono Examples include esters. Alcohols are preferred, and ethanol-based alcohols are particularly preferred.
硫黄含有酸化チタン粉末の分散量は、その用途に応じて適宜調製すればよいが、１〜６０質量％であることが好ましい。 The dispersion amount of the sulfur-containing titanium oxide powder may be appropriately adjusted depending on the application, but is preferably 1 to 60% by mass.
分散剤としては、公知のものが用いられるが、特にアミン系分散剤及び／又はカルボキシル基含有高分子分散剤が好ましく、これらの１種もしくは２種以上が用いられる。またチタン系の分散剤としてペルオクソチタン酸またはその塩も好ましく用いられる。特にはアミン系分散剤及び／又はカルボキシル基含有高分子分散剤とペルオクソチタン酸を併用することが望ましい。ペルオクソチタン酸を分散剤に用いることによって硫黄含有酸化チタン粉末の分散性がより向上するばかりでなく、酸化チタン分散体中にペルオクソチタン酸が含有されているため、この酸化チタン分散体を用いて基材に酸化チタンの薄膜あるいは塗膜を形成した際、基材と光触媒作用を持つ硫黄含有酸化チタン粉末との間にアモルファスの酸化チタンが形成され、樹脂など光触媒作用劣化してしまう基材を用いた場合、基材を劣化させることを防止することが可能となる。さらには金属やセラミックスなどの光触媒作用により劣化しない無機材料の表面に酸化チタンの薄膜あるいは塗膜を形成する場合、さらに基材を加熱処理することによってペルオクソチタン酸によって生じたアモルファス酸化チタンが結晶性となり、新たな光触媒酸化チタンが形成され、より光触媒特性が向上する、 As the dispersant, known ones are used, but amine-based dispersants and / or carboxyl group-containing polymer dispersants are particularly preferable, and one or more of these are used. Further, peroxotitanic acid or a salt thereof is preferably used as a titanium-based dispersant. In particular, it is desirable to use an amine dispersant and / or a carboxyl group-containing polymer dispersant in combination with peroxotitanic acid. By using peroxotitanic acid as a dispersant, not only the dispersibility of the sulfur-containing titanium oxide powder is further improved, but also peroxotitanic acid is contained in the titanium oxide dispersion. When a thin film or coating film of titanium oxide is formed on the base material, amorphous titanium oxide is formed between the base material and the sulfur-containing titanium oxide powder having a photocatalytic action, and the photocatalytic action of the resin is deteriorated. When the material is used, it is possible to prevent the base material from being deteriorated. Furthermore, when a titanium oxide thin film or coating film is formed on the surface of an inorganic material that does not deteriorate due to photocatalytic action such as metal or ceramics, amorphous titanium oxide produced by peroxotitanic acid is further crystallized by heating the substrate. New photocatalytic titanium oxide is formed, and the photocatalytic properties are improved.
アミン系分散剤としては、アルキルアミンおよびポリカルボン酸のアミン塩のうち少なくとも１種の分散剤が好ましい。例えば、ポリエステル酸、脂肪酸、脂肪酸アミド、ポリカルボン酸、アルキレンオキサイド、ポリアルキレンオキサイド、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、およびこれらの誘導体等をアミン化したものが挙げられる。アミン塩としては、アミドアミン塩、脂肪族アミン塩、芳香族アミン塩、アルカノールアミン塩、多価アミン塩等がある。具体的には、ポリオキシエチレン脂肪酸アミド、ポリオキシエチレンアルキルアミン、トリプロピルアミン、ジエチルアミノエチルアミン、ジメチルアミノプロピルアミン、ジエチルアミノプロピルアミン等が挙げられる。 As the amine-based dispersant, at least one dispersant among alkylamine and amine salt of polycarboxylic acid is preferable. For example, polyester acids, fatty acids, fatty acid amides, polycarboxylic acids, alkylene oxides, polyalkylene oxides, polyoxyethylene fatty acid esters, polyoxyethylene glycerin fatty acid esters, and derivatives thereof are exemplified. Examples of amine salts include amidoamine salts, aliphatic amine salts, aromatic amine salts, alkanolamine salts, and polyvalent amine salts. Specific examples include polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, tripropylamine, diethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine and the like.
カルボキシル基含有高分子分散剤としては、ポリカルボン酸及びその塩の少なくとも１種の分散剤が好ましい。例えば、ポリカルボン酸、ポリカルボン酸アンモニウム、ポリカルボン酸ナトリウムなどが挙げられる。具体的には、ポリアクリル酸、ポリアクリル酸アンモニウム、ポリアクリル酸ナトリウム、ポリアクリル酸アンモニウム共重合体、ポリマレイン酸、ポリマレイン酸アンモニウム、ポリマレイン酸ナトリウム等が挙げられる。 As the carboxyl group-containing polymer dispersant, at least one dispersant of polycarboxylic acid and a salt thereof is preferable. Examples thereof include polycarboxylic acid, ammonium polycarboxylate, sodium polycarboxylate and the like. Specific examples include polyacrylic acid, ammonium polyacrylate, sodium polyacrylate, ammonium polyacrylate copolymer, polymaleic acid, ammonium polymaleate, and sodium polymaleate.
これらアミン系分散剤やカルボキシル基含有高分子分散剤は、溶剤成分に溶解させた溶液状態のものを使用することもでき、また市販されているものも使用することができる。また、これらアミン系分散剤及び／又はカルボキシル基含有高分子分散剤は、分散体中の硫黄含有酸化チタン粉末に対し０．２〜２０質量％、好ましくは０．５〜１０質量％、より好ましくは１〜１０質量％となるように添加する。分散剤の添加量が硫黄含有酸化チタン粉末に対し０．２質量％未満の場合、硫黄含有酸化チタン分散体の分散性を向上させるのに充分な効果が得られない。また、分散剤の添加量が多すぎる場合は、硫黄含有酸化チタンの特性を低下させるため好ましくない。 As these amine-based dispersants and carboxyl group-containing polymer dispersants, those in a solution state dissolved in a solvent component can be used, and commercially available ones can also be used. Further, these amine dispersants and / or carboxyl group-containing polymer dispersants are 0.2 to 20% by mass, preferably 0.5 to 10% by mass, more preferably, based on the sulfur-containing titanium oxide powder in the dispersion. Is added so as to be 1 to 10% by mass. When the addition amount of the dispersant is less than 0.2% by mass with respect to the sulfur-containing titanium oxide powder, an effect sufficient to improve the dispersibility of the sulfur-containing titanium oxide dispersion cannot be obtained. Moreover, when there is too much addition amount of a dispersing agent, since the characteristic of sulfur-containing titanium oxide is reduced, it is unpreferable.
ペルオクソチタン酸は、ペルオキシチタン酸又は過酸化チタンともいわれるもので、その構造はＨ4ＴｉＯ5、Ｔｉ（ＯＯＨ）（ＯＨ）3またはＴｉＯ3・２Ｈ2Ｏで表される。ペルオクソチタン酸は、通常、黄色、黄褐色または赤褐色の透明粘性水溶液（ゾル溶液）で取り扱われ、水溶液の場合、そのｐＨは５〜８でありほぼ中性領域にある。ペルオクソチタン酸は市販されているものを使用することができ、例えば「ＰＴＡ−８５」、「ＰＴＡ−１７０」（いずれも（株）田中転写製のペルオクソチタン酸水溶液）が挙げられる。また、公知の方法によって調製することも可能であり、例えば、四塩化チタン水溶液をアンモニア水で加水分解し、水酸化チタンを含むスラリーを生成し、これを洗浄した後、過酸化水素を加えてペルオキシチタン酸水溶液を得ることができる。ペルオクソチタン酸溶液の溶媒としては特に制限されないが、例えば水及びエタノール、メタノールなどのアルコール類が挙げられ、このうち、水が好ましい。ペルオクソチタン酸水溶液を使用する場合は、市販のペルオクソチタン酸水溶液をそのまま使用することができる。使用するペルオクソチタン酸溶液の濃度は、硫黄含有酸化チタン粉末の添加濃度、酸化チタンスラリーの用途等によって適宜決定される。また、酸化チタン分散体とペルオクソチタン酸溶液の配合比率も、酸化チタン粉末の添加濃度や、酸化チタンスラリーの用途によって適宜決定すればよい。ペルオクソチタン酸の塩としては、ペルオクソチタン酸アンモニウム、ペルオクソチタン酸ナトリウム、ペルオクソチタン酸カリウム、ペルオクソチタン酸マグネシウム、ペルオクソチタン酸カルシウムなどが用いられる。また、上記ペルオクソチタン酸の塩と酒石酸、クエン酸などのキレート剤との錯体なども用いられ、具体的には、チタンペルオクソクエン酸アンモニウムなどが挙げられる。 Peroxotitanic acid is also called peroxytitanic acid or titanium peroxide, and its structure is represented by H 4 TiO 5 , Ti (OOH) (OH) 3 or TiO 3 .2H 2 O. Peroxotitanic acid is usually handled as a yellow, yellow-brown or red-brown transparent viscous aqueous solution (sol solution), and in the case of an aqueous solution, its pH is 5 to 8 and is almost in the neutral region. As the peroxotitanic acid, commercially available ones can be used, and examples thereof include “PTA-85” and “PTA-170” (both are peroxotitanic acid aqueous solutions manufactured by Tanaka Transfer Co., Ltd.). It can also be prepared by a known method. For example, an aqueous solution of titanium tetrachloride is hydrolyzed with ammonia water to produce a slurry containing titanium hydroxide, which is washed and then added with hydrogen peroxide. A peroxytitanic acid aqueous solution can be obtained. Although it does not restrict | limit especially as a solvent of a peroxotitanic acid solution, For example, water and alcohols, such as ethanol and methanol, are mentioned, Among these, water is preferable. When using a peroxotitanic acid aqueous solution, a commercially available peroxotitanic acid aqueous solution can be used as it is. The concentration of the peroxotitanic acid solution to be used is appropriately determined depending on the addition concentration of the sulfur-containing titanium oxide powder, the use of the titanium oxide slurry, and the like. Moreover, what is necessary is just to determine suitably the mixture ratio of a titanium oxide dispersion and a peroxotitanic acid solution with the addition density | concentration of a titanium oxide powder, and the use of a titanium oxide slurry. As the salt of peroxotitanate, ammonium peroxotitanate, sodium peroxotitanate, potassium peroxotitanate, magnesium peroxotitanate, calcium peroxotitanate and the like are used. In addition, complexes of the above peroxotitanic acid salts with chelating agents such as tartaric acid and citric acid are also used, and specific examples include titanium peroxocitrate ammonium.
上記のように分散剤を添加した酸化チタン分散体は、より高い分散性を得るために、酸化チタン分散体中に存在する硫黄含有酸化チタン粉末の凝集を緩和することを目的として湿式解砕処理を行うことが望ましい。この湿式解砕処理は、酸化チタン分散体中の硫黄含有酸化チタン粉末の凝集を緩和することができるものであれば、せん断作用や摩砕作用を利用した解砕装置、攪拌式の解砕装置などの公知の湿式解砕装置を使用することができる。具体的には、ジェットミル、ビーズミル、ロールミル、ハンマーミル、振動ミル、流星型ボールミル、サンドミル、三本ロールミル等の解砕装置を使用することができる。本発明における解砕処理をより効果的かつ効率的に行うためには、ジェットミル解砕機又はビーズミル解砕機を使用することが好ましく、特にジェットミルを使用して湿式解砕処理すると、より効率的に解砕処理することができる。また、湿式解砕処理に先立って、酸化チタン分散体をボールミルにより予備解砕処理することにより、硫黄含有酸化チタン粉末の凝集をより緩和することができ、酸化チタン分散体の分散性をより高めることができる。 In order to obtain higher dispersibility, the titanium oxide dispersion to which a dispersant is added as described above is a wet crushing treatment for the purpose of relaxing the aggregation of the sulfur-containing titanium oxide powder present in the titanium oxide dispersion. It is desirable to do. As long as this wet crushing treatment can alleviate the aggregation of the sulfur-containing titanium oxide powder in the titanium oxide dispersion, a crushing apparatus utilizing a shearing action or a grinding action, a stirring type crushing apparatus A known wet crushing apparatus such as can be used. Specifically, crushing apparatuses such as a jet mill, a bead mill, a roll mill, a hammer mill, a vibration mill, a meteor type ball mill, a sand mill, and a three-roll mill can be used. In order to perform the crushing treatment in the present invention more effectively and efficiently, it is preferable to use a jet mill crusher or a bead mill crusher, and in particular, a wet crushing treatment using a jet mill is more efficient. Can be crushed. Prior to the wet pulverization treatment, the titanium oxide dispersion is preliminarily pulverized with a ball mill, so that the aggregation of the sulfur-containing titanium oxide powder can be further relaxed and the dispersibility of the titanium oxide dispersion is further improved. be able to.
また本発明において、分散剤としてアミン系分散剤及び／又はカルボキシル基含有高分子分散剤とペルオクソチタン酸を併用する場合、硫黄含有酸化チタン粉末の分散性をより向上させるために、硫黄含有酸化チタン粉末と、アミン系分散剤及び／又はカルボキシル基含有高分子分散剤から選ばれる１種もしくは２種以上の分散剤と、水溶媒又は有機溶媒とからなる酸化チタンスラリーを湿式解砕処理した後、ペルオクソチタン酸含有溶液と混合して酸化チタン分散体を製造することが望ましい。 Further, in the present invention, when an amine-based dispersant and / or a carboxyl group-containing polymer dispersant and peroxotitanic acid are used in combination as a dispersant, in order to improve the dispersibility of the sulfur-containing titanium oxide powder, After wet crushing a titanium oxide slurry comprising titanium powder, one or more dispersants selected from amine dispersants and / or carboxyl group-containing polymer dispersants, and an aqueous solvent or an organic solvent It is desirable to produce a titanium oxide dispersion by mixing with a peroxotitanic acid-containing solution.
硫黄含有酸化チタン粉末と、アミン系分散剤及び／又はカルボキシル基含有高分子分散剤から選ばれる１種もしくは２種以上の分散剤と、水溶媒又は有機溶媒とからなる酸化チタンスラリーを湿式解砕処理した後、ペルオクソチタン酸含有溶液と混合して硫黄含有酸化チタン粉末をペルオクソチタン酸含有溶液中に均一分散させる方法としては、一般的な方法を使用することができる。例えば、ホモジナイザー、ヘンシェルミキサー、スーパーミキサー等の高速攪拌、振とう等の手段を使用して分散する方法、又は振動ミル、ボールミル等の解砕機を使用して湿式解砕する方法等が挙げられる。このうち、１０００〜１５００回転／分の高速攪拌による方法が短時間で効率的に均一分散できる点で好ましい。また、酸化チタン分散体とペルオクソチタン酸溶液を混合し分散させる際の分散効率を高めるため、ペルオクソチタン酸溶液を、室温〜１００℃、好ましくは３０〜８０℃に加熱して行ってもよい。このとき酸化チタン分散体中のペルオクソチタン酸の比率は、硫黄含有酸化チタン粉末に対して１〜１０質量％、好ましくは５〜８０質量％、より好ましくは１０〜５０質量％である。 Wet crushing of titanium oxide slurry comprising sulfur-containing titanium oxide powder, one or more dispersants selected from amine-based dispersants and / or carboxyl group-containing polymer dispersants, and water or organic solvents After the treatment, a general method can be used as a method of mixing with the peroxotitanic acid-containing solution and uniformly dispersing the sulfur-containing titanium oxide powder in the peroxotitanic acid-containing solution. Examples thereof include a method of dispersing using a means such as high-speed stirring and shaking such as a homogenizer, a Henschel mixer, and a super mixer, or a method of wet crushing using a crusher such as a vibration mill and a ball mill. Among these, the method using high-speed stirring at 1000 to 1500 revolutions / minute is preferable in that it can be uniformly dispersed efficiently in a short time. Further, in order to increase the dispersion efficiency when mixing and dispersing the titanium oxide dispersion and the peroxotitanic acid solution, the peroxotitanic acid solution may be heated to room temperature to 100 ° C, preferably 30 to 80 ° C. Good. At this time, the ratio of peroxotitanic acid in the titanium oxide dispersion is 1 to 10% by mass, preferably 5 to 80% by mass, and more preferably 10 to 50% by mass with respect to the sulfur-containing titanium oxide powder.
また、本発明の酸化チタン分散体中の硫黄含有酸化チタン粉末の濃度は、酸化チタン分散体の用途により適宜設定すればよいが、好ましくは０．５〜６０質量％、好ましくは１〜５０質量％、より好ましくは５〜４０質量％になるように調製すればよい。本発明の酸化チタン分散体は、硫黄含有酸化チタン粉末の濃度を上げても分散体自体の粘度が上昇しないため、従来では達成出来なかった高濃度の酸化チタン分散体を得ることが可能である。 The concentration of the sulfur-containing titanium oxide powder in the titanium oxide dispersion of the present invention may be appropriately set depending on the use of the titanium oxide dispersion, but is preferably 0.5 to 60% by mass, preferably 1 to 50% by mass. %, More preferably 5 to 40% by mass. The titanium oxide dispersion of the present invention does not increase the viscosity of the dispersion itself even when the concentration of the sulfur-containing titanium oxide powder is increased, and therefore it is possible to obtain a high concentration titanium oxide dispersion that could not be achieved conventionally. .
本発明の酸化チタン分散体は、分散媒が水である場合、そのｐＨは用途によって任意に調整することができるが、本発明ではｐＨ５〜１０、好ましくはｐＨ６〜８、より好ましくは６．５〜７．５である。元来酸化チタン粒子表面は水酸基を含有しているため、中性領域での分散性は低い。そのため、前述したように従来の酸化チタンゾルは、ｐＨを酸性に調整して分散性を改善している。したがって、従来の酸化チタンゾルを基材に塗布して酸化チタン膜を形成し、光触媒や紫外線遮蔽材料を製造するような場合、酸性で腐食するような基材を使用することはできず、その用途に制限があった。本発明の酸化チタン分散体は、中性領域においても極めて高い分散性を示すため、光触媒や色素増感型太陽電池用電極材料用途として極めて有効である。 In the titanium oxide dispersion of the present invention, when the dispersion medium is water, the pH can be arbitrarily adjusted according to the use, but in the present invention, the pH is 5 to 10, preferably 6 to 8, and more preferably 6.5. -7.5. Since the surface of the titanium oxide particles originally contains a hydroxyl group, the dispersibility in the neutral region is low. Therefore, as described above, the conventional titanium oxide sol improves the dispersibility by adjusting the pH to acidic. Therefore, when a conventional titanium oxide sol is applied to a base material to form a titanium oxide film to produce a photocatalyst or an ultraviolet shielding material, it is not possible to use a base material that is acidic and corroded. There was a limit. Since the titanium oxide dispersion of the present invention exhibits extremely high dispersibility even in the neutral region, it is extremely effective as a photocatalyst or dye-sensitized solar cell electrode material application.
以上のように、本発明の酸化チタン分散体は、光触媒として活性の高い硫黄含有酸化チタン粉末が高濃度でかつ高分散しているので、光触媒や色素増感型太陽電池用電極料などの酸化チタン膜形成用として利用可能である。本発明の酸化チタン分散体から酸化チタン膜を形成するには、公知の方法で行えばよく、例えば、該酸化チタン分散体を充填した噴霧器で基材に所望の量となるように吹き付け、その後常温で乾燥、あるいは加熱処理する方法が使用できる。 As described above, the titanium oxide dispersion of the present invention has a high concentration and high dispersion of a sulfur-containing titanium oxide powder that is highly active as a photocatalyst. Therefore, oxidation of photocatalysts, dye-sensitized solar cell electrode materials, etc. It can be used for forming a titanium film. In order to form a titanium oxide film from the titanium oxide dispersion of the present invention, a known method may be used. For example, the substrate is sprayed to a desired amount with a sprayer filled with the titanium oxide dispersion, and thereafter A method of drying at room temperature or heat treatment can be used.
以下、本発明の酸化チタン分散体を製造する具体的なプロセスの一例を示す。 Hereinafter, an example of a specific process for producing the titanium oxide dispersion of the present invention will be shown.
硫黄含有酸化チタン粉末を、アミン系分散剤及び／またはカルボキシル基含有高分子分散剤の１種もしくは２種以上とともに、水あるいはアルコール等の有機溶媒に分散させる。分散は、ボールミルにより１〜１５時間予備分散した後、湿式ジェットミルを使用して解砕処理する。ジェットミル解砕条件は、硫黄含有酸化チタン粉末分散体の凝集状態に応じて、凝集が充分に緩和されるよう適宜設定することができる。具体的には、ジェットミルに投入する酸化チタン分散体の温度は、０〜５０℃であることが好ましく、より好ましくは１０〜３０℃である。また、酸化チタン分散体は、供給圧力１００〜２５０ＭＰａ、好ましくは１００〜１５０ＭＰａに設定し、流速１００〜５００ｍ／ｓ、好ましくは２００〜３００ｍ／ｓで供給すればよい。また、ジェットミルによる解砕処理回数は、硫黄含有酸化チタン分散体の凝集状態に応じ、凝集を充分緩和できるよう設定すればよい。具体的には、１〜５回解砕処理を行うことによって、充分凝集を緩和することができる。こうして得られた硫黄含有酸化チタンスラリーを、硫黄含有酸化チタン粉末濃度を０．５〜６０質量％になるようにペルオクソチタン酸水溶液に混合、分散させて本発明の酸化チタン分散体を得ることができる。 The sulfur-containing titanium oxide powder is dispersed in an organic solvent such as water or alcohol together with one or more amine-based dispersant and / or carboxyl group-containing polymer dispersant. The dispersion is preliminarily dispersed for 1 to 15 hours by a ball mill and then pulverized using a wet jet mill. Jet mill crushing conditions can be appropriately set according to the aggregation state of the sulfur-containing titanium oxide powder dispersion so that the aggregation is sufficiently relaxed. Specifically, the temperature of the titanium oxide dispersion charged into the jet mill is preferably 0 to 50 ° C, more preferably 10 to 30 ° C. The titanium oxide dispersion may be supplied at a supply pressure of 100 to 250 MPa, preferably 100 to 150 MPa, and a flow rate of 100 to 500 m / s, preferably 200 to 300 m / s. Moreover, what is necessary is just to set the frequency | count of the crushing process by a jet mill so that aggregation can fully be eased according to the aggregation state of a sulfur containing titanium oxide dispersion. Specifically, aggregation can be sufficiently relaxed by performing the crushing treatment 1 to 5 times. The sulfur-containing titanium oxide slurry thus obtained is mixed and dispersed in a peroxotitanic acid aqueous solution so that the concentration of the sulfur-containing titanium oxide powder is 0.5 to 60% by mass to obtain the titanium oxide dispersion of the present invention. Can do.
また、前記酸化チタン分散体中の硫黄含有酸化チタン粉末は、可視光の光吸収特性に優れており、紫外可視拡散反射スペクトルを測定して、波長３００〜３５０ｎｍの吸光度の積分値を１として、通常、波長３５０〜４００ｎｍの吸光度の積分値が０．３〜０．９であり、且つ波長４００〜５００ｎｍの吸光度の積分値が０．３〜０．９であり、好ましくは波長３５０〜４００ｎｍの吸光度の積分値が０．４〜０．８であり、且つ波長４００〜５００ｎｍの吸光度の積分値が０．４〜０．８であり、さらに好ましくは、波長３５０〜４００ｎｍの吸光度の積分値が０．５〜０．７であり、且つ波長４００〜５００ｎｍの吸光度の積分値が０．５〜０．７５である。 Moreover, the sulfur-containing titanium oxide powder in the titanium oxide dispersion is excellent in visible light absorption characteristics, and an ultraviolet-visible diffuse reflection spectrum is measured, and an integrated value of absorbance at a wavelength of 300 to 350 nm is set to 1. Usually, the integrated value of absorbance at a wavelength of 350 to 400 nm is 0.3 to 0.9, and the integrated value of absorbance at a wavelength of 400 to 500 nm is 0.3 to 0.9, preferably a wavelength of 350 to 400 nm. The integrated value of absorbance is 0.4 to 0.8, and the integrated value of absorbance at a wavelength of 400 to 500 nm is 0.4 to 0.8, and more preferably, the integrated value of absorbance at a wavelength of 350 to 400 nm is The integrated value of the absorbance at a wavelength of 400 to 500 nm is 0.5 to 0.75.
上記のようにして得られる本発明の酸化チタン分散体は、酸化チタン光触媒として用いた際、可視光領域での吸収特性に優れているため、ブラックライトなど特に紫外光の光源がなくとも、太陽光や室内における蛍光灯による光源で十分に光触媒活性が発現する。また、酸化チタンに窒素原子をドープしたものなど従来の可視光応答型光触媒に比べて、効率的にかつ低コストで製造できるため工業的に非常に有利であり、排ガス処理、空気清浄、防臭、殺菌、抗菌、水処理、照明機器等の汚れ防止、酸化作用による有害物の分解作用を利用した光触媒装置などを目的とした光触媒塗料や光触媒コーティング材などに広く適用できる。 The titanium oxide dispersion of the present invention obtained as described above has excellent absorption characteristics in the visible light region when used as a titanium oxide photocatalyst. The photocatalytic activity is sufficiently manifested by light or a light source using a fluorescent lamp in the room. In addition, compared to conventional visible light responsive photocatalysts such as titanium oxide doped with nitrogen atoms, it is industrially very advantageous because it can be produced efficiently and at low cost, exhaust gas treatment, air purification, deodorization, It can be widely applied to photocatalyst paints and photocatalyst coating materials for the purpose of sterilization, antibacterial, water treatment, prevention of soiling of lighting equipment, etc., and photocatalytic devices utilizing the action of decomposing harmful substances due to oxidation.
次に、実施例を挙げて本発明を更に具体的に説明するが、これは単に例示であって、本発明を制限するものではない。 EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.
実施例
実施例および比較例において硫黄含有酸化チタン粉末、酸化チタン粉末及び酸化チタン分散体の評価は以下のように実施した。
（１）硫黄含有酸化チタン粉末中の硫黄含有量の測定
エネルギー分散型蛍光Ｘ線分析装置（ＥＤＸ）を付帯した電界放出型走査型電子顕微鏡（Field Emission-SEM:FE-SEM）（日立電子走査顕微鏡Ｓ−４７００）にて硫黄含有酸化チタン粉末中の硫黄原子の定量分析を行なった。
（２）可視光吸収特性の測定
積分球付き紫外可視分光光度計（日本分光株式会社製Ｖ−５５０−ＤＳ）により酸化チタン分散体中の硫黄含有酸化チタン粉末又は酸化チタン粉末の拡散反射吸収スペクトルを測定した。
（３）ＳＥＭによる平均粒径（ＳＥＭ径）の測定
電子顕微鏡（ＳＥＭ）により酸化チタン分散体を観察し、インターセプト法により測定した。（解析数２００個）
（４）レーザー光散乱回折法による粒度分布
レーザー光散乱回折法粒度測定機（ＬＡ−７００：堀場製作所製）を用い、酸化チタン分散体に超音波をかけて３分間分散させ、粒度を測定し体積統計値の粒度分布を求めた。なお、なお、粒度分布はＤ９０（積算粒度９０％の粒径（μｍ））、Ｄ５０（積算粒度５０％の粒径（μｍ））、Ｄ１０（積算粒度１０％の粒径（μｍ））を求めた。
Examples In the examples and comparative examples, the evaluation of the sulfur-containing titanium oxide powder, the titanium oxide powder and the titanium oxide dispersion was carried out as follows.
(1) Measurement of sulfur content in sulfur-containing titanium oxide powder Field Emission-SEM (FE-SEM) with energy dispersive X-ray fluorescence spectrometer (EDX) (Hitachi Electronic Scan) Quantitative analysis of sulfur atoms in the sulfur-containing titanium oxide powder was performed with a microscope S-4700).
(2) Measurement of visible light absorption characteristics Diffuse reflection absorption spectrum of sulfur-containing titanium oxide powder or titanium oxide powder in titanium oxide dispersion by UV-visible spectrophotometer with integrating sphere (JASCO Corporation V-550-DS) Was measured.
(3) Measurement of average particle diameter (SEM diameter) by SEM The titanium oxide dispersion was observed by an electron microscope (SEM) and measured by an intercept method. (200 analyzes)
(4) Particle size distribution by laser light scattering diffraction method Using a laser light scattering diffraction particle size analyzer (LA-700: manufactured by HORIBA, Ltd.), an ultrasonic wave is applied to the titanium oxide dispersion for 3 minutes to measure the particle size. The particle size distribution of volume statistics was determined. In addition, the particle size distribution is determined by obtaining D90 (particle size with integrated particle size of 90% (μm)), D50 (particle size with integrated particle size of 50% (μm)), and D10 (particle size with integrated particle size of 10% (μm)). It was.
（硫黄含有酸化チタン粉末の調製）
攪拌器を具備した容量１０００ミリリッターの丸底フラスコにチタン濃度４質量％の四塩化チタン水溶液２９７ｇ挿入し、次いで６０℃に加熱した。次いで反応系のｐＨが７．４に維持させるようにアンモニア水を添加して、６０℃で１時間中和処理を行なった。中和処理後、生成した固形物をろ過し、更に純水で洗浄して、酸化チタン粉末を得た。得た酸化チタン粉末を５００℃で３時間焼成し、次いで、焼成した酸化チタン粉末を、１００ｍｌの純水に溶解させたチオ尿素９．７ｇを添加し３０分攪拌した。その後、固形物を６０℃で乾燥して、ボールミルにて粉砕して酸化チタン粉末とチオ尿素の混合物を得た。この混合物を焼成炉に装入し４００℃で３時間焼成した。その後ボールミルにて粉砕して、純水で洗浄した後、６０℃で乾燥して淡黄色の硫黄含有酸化チタン粉末を得た。得られた硫黄含有酸化チタン粉末中の硫黄含有量を測定したところ０．２５質量％、比表面積は１８０ｍ2／ｇであった。
(Preparation of sulfur-containing titanium oxide powder)
297 g of a titanium tetrachloride aqueous solution having a titanium concentration of 4 mass% was inserted into a 1000-ml round bottom flask equipped with a stirrer, and then heated to 60 ° C. Next, ammonia water was added so that the pH of the reaction system was maintained at 7.4, and neutralization was performed at 60 ° C. for 1 hour. After the neutralization treatment, the produced solid was filtered and further washed with pure water to obtain a titanium oxide powder. The obtained titanium oxide powder was calcined at 500 ° C. for 3 hours, and then 9.7 g of thiourea obtained by dissolving the calcined titanium oxide powder in 100 ml of pure water was added and stirred for 30 minutes. Thereafter, the solid was dried at 60 ° C. and pulverized with a ball mill to obtain a mixture of titanium oxide powder and thiourea. This mixture was placed in a firing furnace and fired at 400 ° C. for 3 hours. Thereafter, it was pulverized by a ball mill, washed with pure water, and then dried at 60 ° C. to obtain a pale yellow sulfur-containing titanium oxide powder. When the sulfur content in the obtained sulfur-containing titanium oxide powder was measured, it was 0.25% by mass and the specific surface area was 180 m 2 / g.
（酸化チタン分散体の調製）
上記のようにして得た硫黄含有酸化チタン粉末を、分散剤としてポリアクリル酸アンモニウムとともに純水中に添加し、攪拌して分散させ、ボールミル解砕機を用いて常温で８時間予備解砕処理し、硫黄含有酸化チタンスラリーを得た。得られた硫黄含有酸化チタンスラリーは硫黄含有酸化チタン濃度２０質量％であり、ポリアクリル酸アンモニウムは硫黄含有酸化チタン分散量に対し５質量％になるように調製した。このようにして得られた硫黄含有酸化チタンスラリーを、湿式ジェットミルを用いて解砕処理した。湿式ジェットミル解砕機は、吉田機械興業株式会社製のナノマイザーを使用し、常温で、硫黄含有酸化チタンスラリーの供給圧力１５０ＰＭａ、供給速度２５０ｍ／ｓで行った。このジェットミル解砕処理を５回繰り返して得られた酸化チタン分散体に、０．８５質量％のペルオクソチタン酸水溶液を添加して攪拌し、酸化チタン粉末濃度１０質量％の酸化チタン分散体を得た。
(Preparation of titanium oxide dispersion)
The sulfur-containing titanium oxide powder obtained as described above is added to pure water together with ammonium polyacrylate as a dispersant, stirred and dispersed, and pre-pulverized at room temperature for 8 hours using a ball mill pulverizer. A sulfur-containing titanium oxide slurry was obtained. The obtained sulfur-containing titanium oxide slurry had a sulfur-containing titanium oxide concentration of 20% by mass, and ammonium polyacrylate was prepared so as to be 5% by mass with respect to the sulfur-containing titanium oxide dispersion amount. The sulfur-containing titanium oxide slurry thus obtained was pulverized using a wet jet mill. The wet jet mill crusher was a nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd., and performed at room temperature at a supply pressure of 150 PMa and a supply speed of 250 m / s for the sulfur-containing titanium oxide slurry. To the titanium oxide dispersion obtained by repeating this jet mill crushing process 5 times, 0.85 mass% peroxotitanic acid aqueous solution was added and stirred, and the titanium oxide dispersion having a titanium oxide powder concentration of 10 mass%. Got.
この酸化チタン分散体のＳＥＭ径およびレーザー光散乱回折法による粒度分布を表１に示した。またこの酸化チタン分散体中の硫黄含有酸化チタン粉末の可視光吸収特性を図１に示した。 Table 1 shows the SEM diameter of this titanium oxide dispersion and the particle size distribution by the laser light scattering diffraction method. The visible light absorption characteristics of the sulfur-containing titanium oxide powder in the titanium oxide dispersion are shown in FIG.
（硫黄含有酸化チタン粉末の調製）
攪拌器を具備した容量１０００ミリリッターの丸底フラスコにチタン濃度４質量％の四塩化チタン水溶液２９７ｇ挿入し、次いで１００ｍｌの純水に溶解させたチオ尿素９．７ｇを添加して６０℃に加熱した。次いで反応系のｐＨが７．４に維持させるようにアンモニア水を添加して、６０℃で１時間中和処理を行なった。得られた固形物を濾過し純水で洗浄し３０分攪拌した。その後、固形物を６０℃で乾燥して、ボールミルにて粉砕して酸化チタン粉末とチオ尿素の混合物を得た。この混合物を焼成炉に装入し４００℃で３時間焼成した。その後ボールミルにて粉砕して、純水で洗浄した後、６０℃で乾燥して淡黄色の硫黄含有酸化チタン粉末を得た。得られた硫黄含有チタン粉末中の硫黄含有量を測定したところ０．２７質量％、比表面積は１７０ｍ2／ｇであった。
(Preparation of sulfur-containing titanium oxide powder)
297 g of titanium tetrachloride aqueous solution having a titanium concentration of 4% by mass was inserted into a 1000-ml round bottom flask equipped with a stirrer, and then 9.7 g of thiourea dissolved in 100 ml of pure water was added and heated to 60 ° C. did. Next, ammonia water was added so that the pH of the reaction system was maintained at 7.4, and neutralization was performed at 60 ° C. for 1 hour. The obtained solid was filtered, washed with pure water, and stirred for 30 minutes. Thereafter, the solid was dried at 60 ° C. and pulverized with a ball mill to obtain a mixture of titanium oxide powder and thiourea. This mixture was placed in a firing furnace and fired at 400 ° C. for 3 hours. Thereafter, it was pulverized by a ball mill, washed with pure water, and then dried at 60 ° C. to obtain a pale yellow sulfur-containing titanium oxide powder. When the sulfur content in the obtained sulfur-containing titanium powder was measured, it was 0.27% by mass and the specific surface area was 170 m 2 / g.
（酸化チタン分散体の調製）
上記のようにして得られた硫黄含有酸化チタン粉末をもちいた以外は実施例１と同様に酸化チタン分散体を調製した。この酸化チタン分散体のＳＥＭ径およびレーザー光散乱回折法による粒度分布を表１に示した。また酸化チタン分散体中の硫黄含有酸化チタン粉末の可視光吸収特性を図１に示した。
(Preparation of titanium oxide dispersion)
A titanium oxide dispersion was prepared in the same manner as in Example 1 except that the sulfur-containing titanium oxide powder obtained as described above was used. Table 1 shows the SEM diameter of this titanium oxide dispersion and the particle size distribution by the laser light scattering diffraction method. The visible light absorption characteristics of the sulfur-containing titanium oxide powder in the titanium oxide dispersion are shown in FIG.
（酸化チタン分散体の調製）
実施例１で調製した硫黄含有酸化チタン粉末を、ポリアクリル酸アンモニウムと伴にエタノール中に添加し、攪拌して分散させ、ボールミル解砕機を用いて常温で８時間予備解砕処理し、硫黄含有酸化チタン粉末濃度３０質量％の硫黄含有酸化チタン粉末エタノールスラリーを得た。ポリアクリル酸アンモニウムは、硫黄含有酸化チタン粉末に対し５質量％添加した。
(Preparation of titanium oxide dispersion)
The sulfur-containing titanium oxide powder prepared in Example 1 was added to ethanol together with ammonium polyacrylate, stirred and dispersed, and pre-pulverized at room temperature for 8 hours using a ball mill pulverizer. A sulfur-containing titanium oxide powder ethanol slurry having a titanium oxide powder concentration of 30% by mass was obtained. The ammonium polyacrylate was added in an amount of 5% by mass with respect to the sulfur-containing titanium oxide powder.
このようにして得られた硫黄含有酸化チタン粉末エタノールスラリーを、実施例１同様に湿式ジェットミル解砕処理し、さらに実施例１と同様にペルオクソチタン酸水溶液を添加して酸化チタン分散体を得た。酸化チタン分散体の硫黄含有酸化チタン濃度は１５質量％であった。得られた結果を表１に示した。 The sulfur-containing titanium oxide powder ethanol slurry thus obtained was subjected to wet jet mill crushing treatment in the same manner as in Example 1, and further a peroxotitanic acid aqueous solution was added in the same manner as in Example 1 to obtain a titanium oxide dispersion. Obtained. The concentration of sulfur-containing titanium oxide in the titanium oxide dispersion was 15% by mass. The obtained results are shown in Table 1.
比較例１
（酸化チタン粉末の調製）
攪拌器を具備した容量１０００ミリリッターの丸底フラスコにチタン濃度４質量％の四塩化チタン水溶液２９７ｇ挿入し、次いで６０℃に加熱した。次いで反応系のｐＨが７．４に維持させるようにアンモニア水を添加して、６０℃で１時間中和処理を行なった。得られた固形物を濾過し純水で洗浄した。その後、固形物を６０℃で乾燥して、ボールミルにて粉砕して粉末を得た。この粉末を焼成炉に装入し４００℃で３時間焼成した。その後ボールミルにて粉砕して、純水で洗浄した後、６０℃で乾燥して酸化チタン粉末を得た。得られた酸化チタン粉末の比表面積は１７０ｍ2／ｇであった。
Comparative Example 1
(Preparation of titanium oxide powder)
297 g of a titanium tetrachloride aqueous solution having a titanium concentration of 4 mass% was inserted into a 1000-ml round bottom flask equipped with a stirrer, and then heated to 60 ° C. Next, ammonia water was added so that the pH of the reaction system was maintained at 7.4, and neutralization was performed at 60 ° C. for 1 hour. The obtained solid was filtered and washed with pure water. Thereafter, the solid was dried at 60 ° C. and pulverized with a ball mill to obtain a powder. This powder was placed in a firing furnace and fired at 400 ° C. for 3 hours. Thereafter, it was pulverized by a ball mill, washed with pure water, and dried at 60 ° C. to obtain a titanium oxide powder. The specific surface area of the obtained titanium oxide powder was 170 m 2 / g.
（酸化チタン分散体の調製）
上記のようにして得られた酸化チタン粉末をもちいた以外は実施例１と同様に酸化チタン分散体を調製した。この酸化チタン分散体のＳＥＭ径およびレーザー光散乱回折法による粒度分布を表１に示した。また酸化チタン分散体中の酸化チタン粉末の可視光吸収特性を図１に示した。
(Preparation of titanium oxide dispersion)
A titanium oxide dispersion was prepared in the same manner as in Example 1 except that the titanium oxide powder obtained as described above was used. Table 1 shows the SEM diameter of this titanium oxide dispersion and the particle size distribution by the laser light scattering diffraction method. The visible light absorption characteristics of the titanium oxide powder in the titanium oxide dispersion are shown in FIG.
比較例２
（酸化チタン分散体の調製）
実施例１で調製した硫黄含有酸化チタン粉末を、分散剤を用いることなしに純水中に添加し、攪拌して分散させ、ボールミル解砕機を用いて常温で８時間予備解砕処理し、硫黄含有酸化チタンスラリーを得た。得られた硫黄含有酸化チタンスラリーは硫黄含有酸化チタン濃度１０質量％になるように調製した。このようにして得られた酸化チタンスラリーを、湿式ジェットミルを用いて解砕処理した。湿式ジェットミル解砕機は、吉田機械興業株式会社製のナノマイザーを使用し、常温で、硫黄含有酸化チタンスラリーの供給圧力１５０ＰＭａ、供給速度２５０ｍ／ｓで行った。このジェットミル解砕処理を５回繰り返して酸化チタン分散体を得た。この酸化チタン分散体のＳＥＭ径およびレーザー光散乱回折法による粒度分布を表１に示した。
Comparative Example 2
(Preparation of titanium oxide dispersion)
The sulfur-containing titanium oxide powder prepared in Example 1 was added to pure water without using a dispersant, dispersed by stirring, and preliminarily pulverized at room temperature for 8 hours using a ball mill pulverizer. A titanium oxide slurry was obtained. The obtained sulfur-containing titanium oxide slurry was prepared so as to have a sulfur-containing titanium oxide concentration of 10% by mass. The titanium oxide slurry thus obtained was pulverized using a wet jet mill. The wet jet mill crusher was a nanomizer manufactured by Yoshida Kikai Kogyo Co., Ltd., and performed at room temperature at a supply pressure of 150 PMa and a supply speed of 250 m / s for the sulfur-containing titanium oxide slurry. This jet mill crushing treatment was repeated 5 times to obtain a titanium oxide dispersion. Table 1 shows the SEM diameter of this titanium oxide dispersion and the particle size distribution by the laser light scattering diffraction method.
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| WO2019142695A1 (en) * | 2018-01-16 | 2019-07-25 | 昭和電工株式会社 | Oxygen reduction catalyst |
| JP7294644B2 (en) * | 2019-05-21 | 2023-06-20 | 国立研究開発法人物質・材料研究機構 | Composition, laminate, body cosmetic sheet, beauty method, beauty device, and method for preventing leaf scorch |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2781433B2 (en) * | 1988-12-16 | 1998-07-30 | チオクサイド グループ ピーエルシー | Aqueous dispersion system of titanium dioxide and method for producing the same |
| JP2001220141A (en) * | 2000-02-03 | 2001-08-14 | Toho Titanium Co Ltd | Titanium oxide dispersion |
| JP2001262005A (en) * | 2000-03-16 | 2001-09-26 | Toho Titanium Co Ltd | Coating-film-forming composition, coating film, and coated article for photocatalyst |
| JP2003138162A (en) * | 2001-10-30 | 2003-05-14 | Amuzu:Kk | Coating agent |
| JP2004143032A (en) * | 2002-08-26 | 2004-05-20 | Tokuyama Corp | Sulfur-containing metal oxide |
| JP2004322002A (en) * | 2003-04-25 | 2004-11-18 | Sumitomo Metal Ind Ltd | Photocatalytic ceramic dispersion and coating liquid |
-
2004
- 2004-06-16 JP JP2004178433A patent/JP4523344B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2781433B2 (en) * | 1988-12-16 | 1998-07-30 | チオクサイド グループ ピーエルシー | Aqueous dispersion system of titanium dioxide and method for producing the same |
| JP2001220141A (en) * | 2000-02-03 | 2001-08-14 | Toho Titanium Co Ltd | Titanium oxide dispersion |
| JP2001262005A (en) * | 2000-03-16 | 2001-09-26 | Toho Titanium Co Ltd | Coating-film-forming composition, coating film, and coated article for photocatalyst |
| JP2003138162A (en) * | 2001-10-30 | 2003-05-14 | Amuzu:Kk | Coating agent |
| JP2004143032A (en) * | 2002-08-26 | 2004-05-20 | Tokuyama Corp | Sulfur-containing metal oxide |
| JP2004322002A (en) * | 2003-04-25 | 2004-11-18 | Sumitomo Metal Ind Ltd | Photocatalytic ceramic dispersion and coating liquid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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