JP2009120767A - Aqueous paint containing photocatalyst - Google Patents
Aqueous paint containing photocatalyst Download PDFInfo
- Publication number
- JP2009120767A JP2009120767A JP2007298268A JP2007298268A JP2009120767A JP 2009120767 A JP2009120767 A JP 2009120767A JP 2007298268 A JP2007298268 A JP 2007298268A JP 2007298268 A JP2007298268 A JP 2007298268A JP 2009120767 A JP2009120767 A JP 2009120767A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- water
- substrate
- based paint
- acetylene glycol
- 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.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 115
- 239000003973 paint Substances 0.000 title claims abstract description 53
- 239000000758 substrate Substances 0.000 claims abstract description 61
- -1 acetylene glycol Chemical compound 0.000 claims abstract description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 35
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000004094 surface-active agent Substances 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 58
- 239000011248 coating agent Substances 0.000 claims description 35
- 238000000576 coating method Methods 0.000 claims description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 21
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 150000003755 zirconium compounds Chemical group 0.000 claims description 10
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 239000002736 nonionic surfactant Substances 0.000 claims description 5
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 4
- 239000011787 zinc oxide Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 description 24
- 239000007788 liquid Substances 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 238000010304 firing Methods 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000002738 chelating agent Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000005215 alkyl ethers Chemical class 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 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
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000011163 secondary particle Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- OEERILNPOAIBKF-UHFFFAOYSA-J zirconium(4+);tetraformate Chemical class [Zr+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O OEERILNPOAIBKF-UHFFFAOYSA-J 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N 3-hydroxybutanal Chemical compound CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 2
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 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
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000004166 Lanolin Substances 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000008119 colloidal silica Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229940039717 lanolin Drugs 0.000 description 2
- 235000019388 lanolin Nutrition 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052762 osmium Inorganic materials 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
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
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- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- 229910052702 rhenium Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
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- 229910052713 technetium Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
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- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001371 alpha-amino acids Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
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- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
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- 150000003863 ammonium salts Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WOWBFOBYOAGEEA-UHFFFAOYSA-N diafenthiuron Chemical compound CC(C)C1=C(NC(=S)NC(C)(C)C)C(C(C)C)=CC(OC=2C=CC=CC=2)=C1 WOWBFOBYOAGEEA-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- GFAZHVHNLUBROE-UHFFFAOYSA-N hydroxymethyl propionaldehyde Natural products CCC(=O)CO GFAZHVHNLUBROE-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 229940107700 pyruvic acid Drugs 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 150000003628 tricarboxylic acids Chemical class 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Abstract
Description
本発明は、ガラス、プラスチック、金属、及びセラミックスなどの基板の表面に光触媒活性を有する被膜を形成するための光触媒体水系塗料、及び該光触媒体水系塗料を用いた光触媒被膜付き樹脂基板の製造方法に関する。 The present invention relates to a photocatalyst water-based paint for forming a film having photocatalytic activity on the surface of a substrate such as glass, plastic, metal, and ceramic, and a method for producing a resin substrate with a photocatalyst film using the photocatalyst water-based paint About.
近年、建築材料、家電製品、事務用品、及び車両等の構成材料について、防臭性、防汚性、防カビ性、及び抗菌性等が求められている。これらの特性を付与する方法として、構成材料の表面に光触媒活性を有する被膜を形成する方法が提案されている。具体的には、以下の方法が提案されている。 In recent years, building materials, home appliances, office supplies, vehicles, and other constituent materials have been required to have deodorizing properties, antifouling properties, antifungal properties, antibacterial properties, and the like. As a method for imparting these characteristics, a method of forming a film having photocatalytic activity on the surface of a constituent material has been proposed. Specifically, the following methods have been proposed.
ＴｉＯ２に代表される半導体光触媒物質からなる被膜を、基材表面に形成する方法が提案されている（特許文献１）。 There has been proposed a method of forming a film made of a semiconductor photocatalytic substance typified by TiO 2 on the surface of a substrate (Patent Document 1).
また、光触媒体、シリコンアルコキシド類、ジルコニウム化合物、及びコロイダルシリカを含有する光触媒体コーティング液を用いて基材表面に光触媒体膜を形成する方法が提案されている（特許文献２）。 In addition, a method for forming a photocatalyst film on the surface of a substrate using a photocatalyst coating liquid containing a photocatalyst, a silicon alkoxide, a zirconium compound, and colloidal silica has been proposed (Patent Document 2).
しかし、従来の光触媒体コーティング液は、基板に対して濡れ性が悪く、塗膜を均一に形成することが困難であった。特に、樹脂基板に対して濡れ性が非常に悪く、塗膜を均一に形成することが非常に困難であった。また、従来の光触媒体コーティング液により形成された被膜は、基板への密着強度が低いという問題もあった。特に、樹脂基板を用いた場合には、樹脂基板の変質及び変形を防ぐために塗膜を低温で乾燥処理して被膜を形成する必要があるが、低温で乾燥処理すると前記問題が顕在化していた。 However, the conventional photocatalyst coating liquid has poor wettability with respect to the substrate, and it has been difficult to form a coating film uniformly. In particular, the wettability with respect to the resin substrate was very poor, and it was very difficult to form a coating film uniformly. Moreover, the film formed with the conventional photocatalyst body coating liquid also had the problem that the adhesive strength to a board | substrate was low. In particular, in the case of using a resin substrate, it is necessary to form a coating film by drying the coating film at a low temperature in order to prevent the deterioration and deformation of the resin substrate. .
本発明は、基板に対して濡れ性が良好であり、かつ基板への密着強度が高い被膜を形成できる光触媒体水系塗料、及び該光触媒体水系塗料を用いた光触媒被膜付き基板の製造方法を提供することを目的とする。 The present invention provides a photocatalyst water-based paint capable of forming a film having good wettability to the substrate and high adhesion strength to the substrate, and a method for producing a substrate with a photocatalyst film using the photocatalyst water-based paint The purpose is to do.
本発明者は、上述のような現状に鑑み鋭意研究を重ねた結果、下記方法により、上記課題を解決できることを見出した。 As a result of intensive studies in view of the above situation, the present inventor has found that the above problem can be solved by the following method.
すなわち、本発明は、光触媒体、無機バインダー、及びアセチレングリコール系界面活性剤を含有する光触媒体水系塗料、に関する。 That is, the present invention relates to a photocatalyst water-based paint containing a photocatalyst, an inorganic binder, and an acetylene glycol surfactant.
光触媒体水系塗料にアセチレングリコール系界面活性剤を添加することにより、基板に対する濡れ性を向上させることができ、また基板への密着強度が高い被膜を形成することができる。 By adding an acetylene glycol surfactant to the photocatalyst water-based paint, the wettability with respect to the substrate can be improved, and a film having high adhesion strength to the substrate can be formed.
本発明の光触媒体水系塗料は、樹脂基板に対しても濡れ性が良好であり、均一な塗膜を形成することができる。また、本発明の光触媒体水系塗料を用いることにより、低温で乾燥処理しても樹脂基板への密着強度が高い被膜を形成することができる。 The photocatalyst water-based paint of the present invention has good wettability with respect to a resin substrate and can form a uniform coating film. Further, by using the photocatalyst water-based paint of the present invention, it is possible to form a film having high adhesion strength to a resin substrate even if it is dried at a low temperature.
前記光触媒体は、酸化チタン、酸化タングステン、及び酸化亜鉛からなる群より選択される少なくとも１種の金属酸化物であることが好ましい。これら金属酸化物は、光触媒活性に優れるため光触媒体水系塗料の光触媒体として有用である。 The photocatalyst is preferably at least one metal oxide selected from the group consisting of titanium oxide, tungsten oxide, and zinc oxide. Since these metal oxides are excellent in photocatalytic activity, they are useful as photocatalysts for photocatalyst water-based paints.
前記無機バインダーは、ジルコニウム化合物であることが好ましい。無機バインダーとしてジルコニウム化合物を用いることにより、得られる被膜の基板への密着強度がより高くなる。 The inorganic binder is preferably a zirconium compound. By using a zirconium compound as the inorganic binder, the adhesion strength of the resulting coating to the substrate is further increased.
前記アセチレングリコール系界面活性剤は、アセチレングリコール、非イオン性界面活性剤及び水溶性有機溶媒を含有することが好ましい。また、前記アセチレングリコールは、下記一般式（１）で表される化合物であることが好ましい。
（式中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ独立に炭素数１〜５のアルキル基であり、ｍ及びｎは０≦ｍ＋ｎ≦５０を満たす整数である。）
前記アセチレングリコール系界面活性剤を使用することで、アセチレングリコールが光触媒体水系塗料に溶解しやすくなり、基板に塗工する際に優れた濡れ性を示し、それにより得られる被膜の基板への密着強度がより高くなる。
The acetylene glycol-based surfactant preferably contains acetylene glycol, a nonionic surfactant, and a water-soluble organic solvent. Moreover, it is preferable that the said acetylene glycol is a compound represented by following General formula (1).
(In the formula, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, and m and n are integers satisfying 0 ≦ m + n ≦ 50.)
By using the acetylene glycol-based surfactant, the acetylene glycol is easily dissolved in the photocatalyst water-based paint and exhibits excellent wettability when applied to the substrate, and the resulting coating adheres to the substrate. Strength becomes higher.
また本発明は、前記光触媒体水系塗料を基板上に塗布し、得られた塗膜を乾燥する工程を含む光触媒被膜付き基板の製造方法、に関する。本発明の製造方法は、特に、樹脂基板を用いた場合に有効である。 Moreover, this invention relates to the manufacturing method of the board | substrate with a photocatalyst film including the process of apply | coating the said photocatalyst body aqueous coating material on a board | substrate, and drying the obtained coating film. The production method of the present invention is particularly effective when a resin substrate is used.
本発明の光触媒体水系塗料は、アセチレングリコール系界面活性剤を含有しているため、基板に対する濡れ性が優れており、また基板への密着強度が高い被膜を形成することができる。特に、本発明の光触媒体水系塗料は、基板が樹脂基板の場合にも前記特性に優れている。 Since the photocatalyst water-based paint of the present invention contains an acetylene glycol surfactant, it has excellent wettability with respect to the substrate and can form a film with high adhesion strength to the substrate. In particular, the photocatalyst water-based paint of the present invention is excellent in the above characteristics even when the substrate is a resin substrate.
本発明の光触媒体水系塗料に含まれる光触媒体とは、例えば紫外線や可視光線の照射により光触媒活性を発現する物質であり、具体的には、Ｘ線回折で求められる結晶構造を示し、金属元素と酸素、窒素、イオウ及び弗素との化合物の粉末が挙げられる。例えばＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅのような金属元素の１種または２種以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物などが挙げられる。これらのうち、Ｔｉ、ＷまたはＺｎの酸化物が好ましく、特にアナターゼ型酸化チタン、ブルッカイト型酸化チタン、ルチル型酸化チタン〔ＴｉＯ２〕が好ましい。また、当該技術分野において公知の光触媒体を特に制限することなく使用可能である。これらの光触媒体は、単独で又は２種以上を組み合わせて用いられる。 The photocatalyst contained in the photocatalyst water-based paint of the present invention is a substance that exhibits photocatalytic activity, for example, by irradiation with ultraviolet rays or visible light, and specifically shows a crystal structure obtained by X-ray diffraction, and is a metal element And a powder of a compound of oxygen, nitrogen, sulfur and fluorine. For example, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn One or more of metal elements such as Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce, nitride, sulfide, oxynitride, oxysulfide, Nitrogen fluoride, oxyfluoride, oxynitride fluoride and the like can be mentioned. Of these, oxides of Ti, W, or Zn are preferable, and anatase type titanium oxide, brookite type titanium oxide, and rutile type titanium oxide [TiO 2 ] are particularly preferable. In addition, a photocatalyst known in the art can be used without any particular limitation. These photocatalysts are used alone or in combination of two or more.
光触媒体として使用しうる酸化チタンは、例えば「酸化チタン」（清野学著、技報堂出版）に記載されている硫酸法や塩素法により製造することができる。また、チタン化合物と塩基を反応させ、生成物にアンモニアを添加し、熟成した後、固液分離し、ついで固形分を焼成する方法などで製造することができる。この方法では、チタン化合物として、例えば三塩化チタン〔ＴｉＣｌ３〕、四塩化チタン〔ＴｉＣｌ４〕、硫酸チタン〔Ｔｉ（ＳＯ４）２・ｍＨ２Ｏ、０≦ｍ≦２０〕、オキシ硫酸チタン〔ＴｉＯＳＯ４・ｎＨ２Ｏ、０≦ｎ≦２０〕、オキシ塩化チタン〔ＴｉＯＣｌ２〕を用いることができる。チタン化合物と反応させる塩基としては、例えば水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア、ヒドラジン、ヒドロキシルアミン、モノエタノールアミン、非環式アミン化合物、環式脂肪族アミン化合物を用いることができる。チタン化合物と塩基の反応は、ｐＨ２以上、好ましくは３以上、また７以下、好ましくはｐＨ５以下で行われ、そのときの温度は、通常９０℃以下、好ましくは７０℃以下、さらに好ましくは５５℃以下である。 Titanium oxide that can be used as a photocatalyst can be produced, for example, by the sulfuric acid method or the chlorine method described in “Titanium oxide” (Kyoto Seino, Gihodo Publishing). Further, it can be produced by a method of reacting a titanium compound with a base, adding ammonia to the product, aging, solid-liquid separation, and then baking the solid content. In this method, examples of titanium compounds include titanium trichloride [TiCl 3 ], titanium tetrachloride [TiCl 4 ], titanium sulfate [Ti (SO 4 ) 2 .mH 2 O, 0 ≦ m ≦ 20], titanium oxysulfate [ TiOSO 4 · nH 2 O, 0 ≦ n ≦ 20], titanium oxychloride [TiOCl 2 ] can be used. As the base to be reacted with the titanium compound, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, hydrazine, hydroxylamine, monoethanolamine, acyclic amine compound, or cyclic aliphatic amine compound should be used. Can do. The reaction between the titanium compound and the base is carried out at a pH of 2 or more, preferably 3 or more, and 7 or less, preferably pH 5 or less. The temperature at that time is usually 90 ° C. or less, preferably 70 ° C. or less, more preferably 55 ° C. It is as follows.
更に製造された酸化チタンの粉砕性を向上させるために、チタン化合物と塩基の反応を過酸化水素存在下で行ってもよい。熟成は、例えばアンモニアが添加された生成物を、撹拌しながら、０℃以上、好ましくは１０℃以上、また１１０℃以下、好ましくは８０℃以下、より好ましくは５５℃以下の温度範囲に、１分以上、好ましくは１０分以上、また１０時間以内、好ましくは２時間以内の条件で保持する方法で行うことができる。反応と熟成に用いられるアンモニアの総量は、水の存在下でチタン化合物を水酸化チタンに変えるのに必要な塩基の化学量論量を超える量であることが好ましく、例えば１．１モル倍以上であることが好ましい。塩基の量が多いほど、可視光照射によって高い光触媒活性を示す被膜を形成できる光触媒体水系塗料が得られやすいので好ましく、例えば１．５モル倍以上がさらに好ましい。一方、塩基の量があまり多くなっても、量に見合った効果が得られないので、２０モル倍以下、さらには１０モル倍以下が適当である。 Furthermore, in order to improve the grindability of the produced titanium oxide, the reaction between the titanium compound and the base may be performed in the presence of hydrogen peroxide. For aging, for example, a product added with ammonia is stirred at a temperature range of 0 ° C. or higher, preferably 10 ° C. or higher, 110 ° C. or lower, preferably 80 ° C. or lower, more preferably 55 ° C. or lower. It can be carried out by a method of holding for at least 10 minutes, preferably at least 10 minutes, and within 10 hours, preferably within 2 hours. The total amount of ammonia used for the reaction and ripening is preferably an amount exceeding the stoichiometric amount of the base required to convert the titanium compound to titanium hydroxide in the presence of water, for example, 1.1 mol times or more It is preferable that The larger the amount of the base, the easier it is to obtain a photocatalyst water-based paint capable of forming a film exhibiting high photocatalytic activity by irradiation with visible light. For example, 1.5 mole times or more is more preferable. On the other hand, even if the amount of the base is too large, an effect commensurate with the amount cannot be obtained, so 20 mol times or less, further 10 mol times or less is appropriate.
熟成された生成物の固液分離は、加圧濾過、減圧濾過、遠心分離、デカンテーションなどで行うことができる。また固液分離では、得られる固形分を洗浄する操作をあわせて行うことが好ましい。固液分離された固形分または任意の洗浄を行った固形分の焼成は、気流焼成炉、トンネル炉、回転炉などを用いて、通常２５０℃以上、好ましくは２７０℃以上、また６００℃以下、好ましくは５００℃以下、より好ましくは４００℃以下の温度条件で行うことができる。このときの時間は、焼成温度や焼成装置の種類により異なり一義的ではないが、通常１０分以上、好ましくは３０分以上、また３０時間以内、好ましくは５時間以内である。 Solid-liquid separation of the aged product can be performed by pressure filtration, vacuum filtration, centrifugation, decantation, or the like. In the solid-liquid separation, it is preferable to perform an operation for washing the obtained solid content. The solid content separated by solid-liquid separation or the solid content subjected to arbitrary washing is usually 250 ° C or higher, preferably 270 ° C or higher, and 600 ° C or lower, using an airflow firing furnace, a tunnel furnace, a rotary furnace, or the like. Preferably, it can be carried out under a temperature condition of 500 ° C. or lower, more preferably 400 ° C. or lower. The time at this time varies depending on the firing temperature and the type of firing apparatus and is not unambiguous, but is usually 10 minutes or longer, preferably 30 minutes or longer, and 30 hours or shorter, preferably 5 hours or shorter.
焼成して得られる酸化チタンには、必要に応じて、タングステン、ニオブ、鉄、ニッケルの酸化物や水酸化物などのような固体酸性を示す化合物またはランタン、セリウムの酸化物や水酸化物などのような固体塩基性を示す化合物、またインジウム酸化物やビスマス酸化物のような可視光線を吸収する金属化合物を担持してもよい。 If necessary, the titanium oxide obtained by firing includes a compound showing solid acidity such as an oxide or hydroxide of tungsten, niobium, iron, nickel or lanthanum, an oxide or hydroxide of cerium, etc. A compound showing solid basicity such as, or a metal compound that absorbs visible light such as indium oxide or bismuth oxide may be supported.
光触媒体として使用しうる酸化タングステン〔ＷＯ３〕は、例えばメタタングステン酸アンモニウムのようなタングステン化合物を焼成する方法で製造することができる。焼成は、タングステン化合物を酸化タングステンにすることができる条件で行えばよく、例えば２５０℃〜６００℃の空気中で行うことができる。 Tungsten oxide [WO 3 ] that can be used as a photocatalyst can be produced by a method of firing a tungsten compound such as ammonium metatungstate. Firing may be performed under conditions that allow the tungsten compound to be converted to tungsten oxide, and can be performed in air at 250 ° C. to 600 ° C., for example.
光触媒体として使用しうる酸化亜鉛〔ＺｎＯ〕は、例えば硫酸亜鉛水溶液を炭酸ナトリウム水溶液に加えて炭酸亜鉛を得た後、乾燥し、焼成する方法で製造することができる。焼成は、亜鉛化合物を酸化亜鉛にすることができる条件で行えばよく、例えば４００〜７００℃の空気中で行うことができる。 Zinc oxide [ZnO] that can be used as a photocatalyst can be produced, for example, by adding a zinc sulfate aqueous solution to a sodium carbonate aqueous solution to obtain zinc carbonate, followed by drying and firing. Firing may be performed under conditions that allow the zinc compound to be zinc oxide, and can be performed in air at 400 to 700 ° C., for example.
酸化チタン、酸化タングステン、及び酸化亜鉛以外の酸化物を光触媒体として用いる場合、その酸化物は、例えばセラミックスを構成する金属の塩化物、硫酸塩、オキシ硫酸塩もしくはオキシ塩化物とアンモニアを反応させ、この生成物を空気中で焼成する方法、または光触媒体を構成する金属のアンモニウム塩を空気中で焼成する方法などで調製することができる。 When oxides other than titanium oxide, tungsten oxide, and zinc oxide are used as the photocatalyst, the oxide is, for example, a metal chloride, sulfate, oxysulfate, or oxychloride that constitutes ceramics and ammonia. In addition, the product can be prepared by a method of calcining in air or a method of calcining an ammonium salt of a metal constituting the photocatalyst in the air.
光触媒体水系塗料中における光触媒体の含有量は、通常０．１〜３０重量％であり、好ましくは１〜１０重量％である。光触媒体水系塗料中において光触媒体は、通常平均粒子径２００ｎｍ以下の２次粒子を形成している。２次粒子径が小さいほど、水系塗料（分散液）の安定性が向上して光触媒粒子の沈降を抑制することができる。２次粒子径は１５０ｎｍ以下であることが好ましく、より好ましくは１００ｎｍ以下である。 The content of the photocatalyst in the photocatalyst aqueous coating is usually 0.1 to 30% by weight, preferably 1 to 10% by weight. In the photocatalyst water-based paint, the photocatalyst usually forms secondary particles having an average particle diameter of 200 nm or less. As the secondary particle size is smaller, the stability of the water-based paint (dispersion liquid) is improved and the sedimentation of the photocatalyst particles can be suppressed. The secondary particle diameter is preferably 150 nm or less, more preferably 100 nm or less.
本発明で使用する無機バインダーとしては、当該技術分野において公知のものを特に制限することなく使用可能である。具体的には、シリコンアルコキシド類、ジルコニウム化合物、及びコロイダルシリカなどが挙げられる。これらの無機バインダーは、単独で又は２種以上を組み合わせて用いられる。特に、ジルコニウム化合物を用いることが好ましい。 As the inorganic binder used in the present invention, those known in the technical field can be used without any particular limitation. Specific examples include silicon alkoxides, zirconium compounds, and colloidal silica. These inorganic binders are used alone or in combination of two or more. In particular, it is preferable to use a zirconium compound.
シリコンアルコキシド類としては、例えばＳｉ(ＯＲ)４、ＲＳｉ(ＯＲ)３、Ｒ３Ｓｉ(ＯＲ)で示されるシリコンアルコキシドや、その２量体〜６量体などのオリゴマーなどが挙げられる。ここでＲはアルキル基を示す。 Examples of silicon alkoxides include silicon alkoxides represented by Si (OR) 4 , RSi (OR) 3 , and R 3 Si (OR), and oligomers such as dimers to hexamers thereof. Here, R represents an alkyl group.
ジルコニウム化合物としては、例えばＺｒＣｌ４、ＺｒＯＣｌ２、ＺｒＯ（ＯＨ）Ｃｌ、Ｚｒ(ＮＯ３)４、ＺｒＯ(ＮＯ３)２、Ｚｒ(ＣＨ３ＣＯＯ)４、ＺｒＯ(ＣＨ３ＣＯＯ)２、Ｚｒ(ＣＨ３ＣＨ２ＣＯＯ)４、Ｚｒ(ＳＯ４)２、ＺｒＯＳＯ４、Ｎａ２Ｚｒ（ＰＯ４）２、（ＮＨ４）２ＺｒＯ（ＣＯ３）２、Ｋ２ＺｒＯ（ＣＯ３）２、及び蟻酸ジルコニウムなどのジルコニウム塩、ジルコニウムのエトキシド、プロポキシド、ブトキシドなどのジルコニウムアルコキシド、ジルコニウムアルコキシドの部分加水分解物などが挙げられる。これらのうち、ＺｒＯＣｌ２、ＺｒＯ（ＯＨ）Ｃｌ、ＺｒＯ(ＮＯ３)２、（ＮＨ４）２ＺｒＯ（ＣＯ３）２、及び蟻酸ジルコニウムなどの水溶性ジルコニウム化合物は、有機溶剤を使用せずに水系塗料を調製できるため作業環境の観点から好ましく用いられる。 Examples of the zirconium compound include ZrCl 4 , ZrOCl 2 , ZrO (OH) Cl, Zr (NO 3 ) 4 , ZrO (NO 3 ) 2 , Zr (CH 3 COO) 4 , ZrO (CH 3 COO) 2 , Zr ( CH 3 CH 2 COO) 4 , Zr (SO 4 ) 2 , ZrOSO 4 , Na 2 Zr (PO 4 ) 2 , (NH 4 ) 2 ZrO (CO 3 ) 2 , K 2 ZrO (CO 3 ) 2 , and formic acid Zirconium salts such as zirconium, zirconium alkoxides such as ethoxide of zirconium, propoxide and butoxide, partial hydrolysates of zirconium alkoxide, and the like. Among these, water-soluble zirconium compounds such as ZrOCl 2 , ZrO (OH) Cl, ZrO (NO 3 ) 2 , (NH 4 ) 2 ZrO (CO 3 ) 2 , and zirconium formate can be used without using an organic solvent. Since a water-based paint can be prepared, it is preferably used from the viewpoint of the working environment.
無機バインダーの添加量は酸化物換算で、光触媒体１００重量部に対して通常５〜２００重量部であり、好ましくは１０〜７０重量部である。５重量部未満の場合には被膜の基板に対する密着力が低下する傾向にあり、２００重量部を超える場合には光触媒体が無機バインダー中に埋没してしまい、十分な光触媒活性を有する被膜を得にくくなる。 The addition amount of the inorganic binder is usually 5 to 200 parts by weight, preferably 10 to 70 parts by weight, based on 100 parts by weight of the photocatalyst, in terms of oxide. When the amount is less than 5 parts by weight, the adhesion of the coating to the substrate tends to be reduced. When the amount exceeds 200 parts by weight, the photocatalyst is buried in the inorganic binder, thereby obtaining a coating having sufficient photocatalytic activity. It becomes difficult.
本発明で使用するアセチレングリコール系界面活性剤は、少なくともアセチレングリコールを含有するものであれば特に制限されない。アセチレングリコールとしては、例えば、前記一般式（１）で表される化合物が挙げられ、特に２，４，７，９−テトラメチル−５−デシン−４，７−ジオール、及びそのエチレンオキサイド付加体を用いることが好ましい。前記化合物を含むアセチレングリコール系界面活性剤の市販品としては、日信化学製のオレフィンＥＸＰ．４０３６、オレフィンＰＤ−００２Ｗなどが挙げられる。 The acetylene glycol surfactant used in the present invention is not particularly limited as long as it contains at least acetylene glycol. Examples of the acetylene glycol include compounds represented by the general formula (1), and particularly 2,4,7,9-tetramethyl-5-decyne-4,7-diol and its ethylene oxide adducts. Is preferably used. Examples of commercially available acetylene glycol surfactants containing the above compounds include olefin EXP. Manufactured by Nisshin Chemical. 4036, olefin PD-002W and the like.
アセチレングリコール系界面活性剤は、アセチレングリコールの他に非イオン性界面活性剤、及び水溶性有機溶媒を含んでいてもよい。 The acetylene glycol-based surfactant may contain a nonionic surfactant and a water-soluble organic solvent in addition to acetylene glycol.
非イオン性界面活性剤としては、例えば、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリエチレングリコール脂肪酸エステル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンラノリン、ポリオキシエチレンラノリンアルコールなどが挙げられる。これらは１種又は２種以上含まれていてもよい。 Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene alkyl ether Examples thereof include oxyethylene sorbit fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyethylene glycol fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol and the like. These may be contained alone or in combination of two or more.
水溶性有機溶媒としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ポリエチレングリコール、プロプレングリコール、ジプロピレングリコール、１，３−プロパンジオール、１，４−ブタンジオール、及びグリセリンなどが挙げられる。これらは１種又は２種以上含まれていてもよい。 Examples of the water-soluble organic solvent include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,4-butanediol, and glycerin. Is mentioned. These may be contained alone or in combination of two or more.
アセチレングリコール系界面活性剤が混合物の場合、アセチレングリコールは、アセチレングリコール系界面活性剤中に２０重量％以上含有していることが好ましく、より好ましくは４０重量％以上である。アセチレングリコールの含有量が２０重量％未満の場合には、光触媒体水系塗料の基板に対する濡れ性が不十分になり、また基板への密着強度が高い被膜を形成しにくくなる。特に、樹脂基板に対して前記効果が発現しにくくなる。また、アセチレングリコール以外の非イオン性界面活性剤の含有量は、アセチレングリコール系界面活性剤中に、通常０．５〜５０重量％程度である。 When the acetylene glycol surfactant is a mixture, the acetylene glycol is preferably contained in the acetylene glycol surfactant in an amount of 20% by weight or more, more preferably 40% by weight or more. When the content of acetylene glycol is less than 20% by weight, the wettability of the photocatalyst water-based paint to the substrate becomes insufficient, and it becomes difficult to form a film having high adhesion strength to the substrate. In particular, the effect is less likely to appear on the resin substrate. Moreover, content of nonionic surfactants other than acetylene glycol is about 0.5 to 50 weight% normally in an acetylene glycol type surfactant.
アセチレングリコール系界面活性剤の添加量は、光触媒体水系塗料中の水１００重量部に対して０．００５〜５重量部であることが好ましく、より好ましくは０．０１〜１重量部である。０．００５重量部未満の場合には、光触媒体水系塗料の基板に対する濡れ性が不十分になり、また基板への密着強度が高い被膜を形成しにくくなる。特に、樹脂基板に対して前記効果が発現しにくくなる。一方、５重量部を超える場合には十分な光触媒活性を有する被膜を得にくくなる。 The addition amount of the acetylene glycol-based surfactant is preferably 0.005 to 5 parts by weight, more preferably 0.01 to 1 part by weight with respect to 100 parts by weight of water in the photocatalyst aqueous coating material. When the amount is less than 0.005 parts by weight, the wettability of the photocatalyst aqueous paint to the substrate becomes insufficient, and it becomes difficult to form a film having high adhesion strength to the substrate. In particular, the effect is less likely to appear on the resin substrate. On the other hand, when it exceeds 5 parts by weight, it is difficult to obtain a film having sufficient photocatalytic activity.
本発明の光触媒体水系塗料は、分散溶媒として水単独、又は水と有機溶媒の混合溶媒を含む。水の添加量は、光触媒体、無機バインダー、及びアセチレングリコール系界面活性剤が均一分散するのに要する量以上であればよいが、作業環境面及びコスト等を考慮すると分散溶媒全体に対して水を５０重量％以上用いることが好ましく、より好ましくは８５重量％以上である。有機溶媒としては、メタノール、エタノール、ｎ−プロパノール、ｉ−プロパノール、ｎ−ブタノール、ｉ−ブタノール、及びｔ−ブタノールなどのアルコール類が通常用いられるが、これらに限定されない。 The photocatalyst water-based paint of the present invention contains water alone or a mixed solvent of water and an organic solvent as a dispersion solvent. The amount of water added may be more than the amount required to uniformly disperse the photocatalyst, the inorganic binder, and the acetylene glycol surfactant, but considering the working environment and costs, Is preferably used in an amount of 50% by weight or more, more preferably 85% by weight or more. As the organic solvent, alcohols such as methanol, ethanol, n-propanol, i-propanol, n-butanol, i-butanol, and t-butanol are usually used, but are not limited thereto.
本発明の光触媒体水系塗料は、揮発成分を揮発させて得られる固形分の量が通常０．５〜５０重量％、好ましくは１〜３０重量％、より好ましくは２〜１５重量％となるように分散溶媒で希釈される。固形分量が０．５重量％未満の場合には、十分な厚さの被膜を形成しにくくなり、固形分量が５０重量％を超える場合には、得られる被膜の透明性が損なわれる傾向にある。 In the photocatalyst water-based paint of the present invention, the amount of solid content obtained by volatilizing volatile components is usually 0.5 to 50% by weight, preferably 1 to 30% by weight, more preferably 2 to 15% by weight. Diluted with a dispersion solvent. When the solid content is less than 0.5% by weight, it becomes difficult to form a sufficiently thick film, and when the solid content exceeds 50% by weight, the transparency of the resulting film tends to be impaired. .
本発明の光触媒体水系塗料の製造方法は特に制限されず、例えば、光触媒体を単独で溶媒に分散させた光触媒体分散液と、無機バインダー及びアセチレングリコール系界面活性剤を溶媒と混合したバインダー液とを混合する方法で製造することができる。また、光触媒体分散液に無機バインダー及びアセチレングリコール系界面活性剤を順次添加して混合してもよい。また、光触媒体分散液を調製する際に無機バインダー及びアセチレングリコール系界面活性剤を添加してもよい。 The production method of the photocatalyst water-based paint of the present invention is not particularly limited. For example, a photocatalyst dispersion liquid in which a photocatalyst body is dispersed alone in a solvent, and a binder liquid in which an inorganic binder and an acetylene glycol surfactant are mixed with a solvent. And can be produced by mixing them. Further, an inorganic binder and an acetylene glycol surfactant may be sequentially added to and mixed with the photocatalyst dispersion liquid. Moreover, when preparing a photocatalyst dispersion liquid, an inorganic binder and an acetylene glycol surfactant may be added.
光触媒体分散液は、例えば、硝酸等の酸中で解膠する方法、湿式ミルにより分散させる方法、超音波照射により分散させる方法、混合物を急激に減圧したり、高速回転する羽根で撹拌して液中に空洞（キャビティ）を発生させ、その空洞が消滅するときに生じる圧力変化を利用して分散させる方法、撹拌羽根やスクリューなどの回転により発生するせん断力で分散させる方法などにより、光触媒体を溶媒に分散させる分散処理を行うことで得ることができる。これらの方法は、単独で行うこともできるし、２以上組合せて行うこともできる。分散処理は、光触媒体の主成分の結晶構造を実質的に変えることなく、すなわち光触媒体の主成分について、Ｘ線回折スペクトルから求められる結晶構造の主成分を保持することができる条件で行うことが好ましく、例えば９０℃未満の温度で行うことが推奨される。光触媒体の結晶構造の主成分を保持する観点からは、低温で分散処理を行うことが好ましく、８０℃以下、さらには７５℃以下で行うことがより好ましい。一方、分散処理の温度があまり低くなると、得られる光触媒体水系塗料の安定性が低下することがあるので、１０℃以上、さらには２０℃以上が適当である。分散処理の時間は、分散処理の温度、使用する装置の種類に応じて適宜選択すればよく、通常１分以上、好ましくは１時間以上、また５０時間以下、好ましくは２４時間以下である。また分散処理は、複数回に分けて行ってもよい。 The photocatalyst dispersion liquid is, for example, a method of peptizing in an acid such as nitric acid, a method of dispersing by a wet mill, a method of dispersing by ultrasonic irradiation, a pressure of the mixture is rapidly reduced, or stirring is performed with a blade rotating at high speed. A photocatalyst is produced by a method in which a cavity (cavity) is generated in the liquid and dispersed by utilizing the pressure change generated when the cavity disappears, or by a method in which the dispersion is performed by a shearing force generated by rotation of a stirring blade or a screw. Can be obtained by carrying out a dispersion treatment in which is dispersed in a solvent. These methods can be performed alone or in combination of two or more. The dispersion treatment is performed without substantially changing the crystal structure of the main component of the photocatalyst, that is, under the condition that the main component of the photocatalyst can hold the main component of the crystal structure obtained from the X-ray diffraction spectrum. For example, it is recommended to carry out at a temperature below 90 ° C. From the viewpoint of maintaining the main component of the crystal structure of the photocatalyst, it is preferable to carry out the dispersion treatment at a low temperature, more preferably at 80 ° C. or lower, more preferably at 75 ° C. or lower. On the other hand, if the temperature of the dispersion treatment is too low, the stability of the resulting photocatalyst water-based paint may be lowered, so 10 ° C. or higher, more preferably 20 ° C. or higher is appropriate. The time for the dispersion treatment may be appropriately selected according to the temperature of the dispersion treatment and the type of apparatus used, and is usually 1 minute or longer, preferably 1 hour or longer, 50 hours or shorter, preferably 24 hours or shorter. Further, the distributed processing may be performed in a plurality of times.
分散処理したのち、必要に応じて、遠心分離による粗大粒子を除去する操作、又は希釈による光触媒体の含有量を調整する操作を行ってもよい。また、所望する分散剤の含有量に対して過剰の分散剤を用いて分散処理された混合物には、分散剤の一部を除去する操作を行って所定の濃度に調整する。分散剤の除去は、例えば、光照射、加熱、酸化剤もしくは還元剤の添加、イオン交換膜処理、オゾン処理、水熱処理等により行うことができる。さらに分散処理された後の混合物には、必要に応じて、酸又は塩基を添加することによってｐＨを調整する操作を行ってもよい。このとき用いる酸としては、例えば、塩酸、硝酸、リン酸、及び硫酸等が挙げられ、塩基としては、例えば、アンモニア、尿素、ヒドラジン、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、及び水酸化ルビジウムなどが挙げられる。 After the dispersion treatment, an operation of removing coarse particles by centrifugation or an operation of adjusting the content of the photocatalyst by dilution may be performed as necessary. In addition, an operation for removing a part of the dispersant is performed on the mixture that has been dispersed using an excess of the dispersant with respect to the desired content of the dispersant, and the mixture is adjusted to a predetermined concentration. The removal of the dispersing agent can be performed by, for example, light irradiation, heating, addition of an oxidizing agent or a reducing agent, ion exchange membrane treatment, ozone treatment, hydrothermal treatment, and the like. Furthermore, you may perform operation which adjusts pH by adding an acid or a base to the mixture after a dispersion process as needed. Examples of the acid used at this time include hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid, and examples of the base include ammonia, urea, hydrazine, lithium hydroxide, sodium hydroxide, potassium hydroxide, and cesium hydroxide. , And rubidium hydroxide.
本発明の光触媒体水系塗料は、キレート化剤を含有していることが好ましい。それにより、ジルコニウム化合物の加水分解を防止して、塗料の白濁やゲル化を抑制でき、被膜のヘーズを低くし、被膜の硬度を高くすることができる。 The photocatalyst water-based paint of the present invention preferably contains a chelating agent. Thereby, hydrolysis of the zirconium compound can be prevented, and the cloudiness and gelation of the paint can be suppressed, the haze of the coating can be lowered, and the hardness of the coating can be increased.
キレート化剤としては、例えば、アセチルアセトン、ベンゾイルアセトンなどのβ−ジケトン類、アセト酢酸、プロピオニル酪酸、ベンゾイル酢酸、ピルビン酸、ベンゾイル蟻酸などのα−またはβ−ケトン酸類、該ケトン酸類のメチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチルなどのエステル類、グリコール酸、乳酸、α−オキシ酪酸、ヒドロアクリル酸、サリチル酸などのα−またはβ−オキシ酸類のメチル、エチル、ｎ−プロピル、ｉｓｏ−プロピル、ｎ−ブチル、ｔｅｒｔ−ブチルなどのエステル類、ジアセトンアルコール、アセトインなどのα−またはβ−オキシケトン類、グリコールアルデヒド、アルドールなどのα−またはβ−オキシアルデヒド類、グリシン、アラニンなどのα−アミノ酸類、アミノエチルアルコールなどのα−またはβ−アミノアルコール類、シュウ酸、グルタル酸、コハク酸、マロン酸、マレイン酸、アジピン酸のようなジカルボン酸類、クエン酸のようなトリカルボン酸類など、Ｚｒ原子とキレート化合物を形成しうる化合物が挙げられる。これらのキレート化剤は、単独で、又は２種以上の混合物として使用できる。これらのなかで、アセチルアセトン、アセト酢酸エチルを用いることが好ましい。 Examples of the chelating agent include β-diketones such as acetylacetone and benzoylacetone, α- or β-ketone acids such as acetoacetic acid, propionylbutyric acid, benzoylacetic acid, pyruvic acid, and benzoylformic acid, methyl and ethyl of the ketone acids , Esters such as n-propyl, iso-propyl, n-butyl, tert-butyl, methyl, ethyl of α- or β-oxy acids such as glycolic acid, lactic acid, α-oxybutyric acid, hydroacrylic acid, salicylic acid, esters such as n-propyl, iso-propyl, n-butyl, tert-butyl, α- or β-oxyketones such as diacetone alcohol and acetoin, α- or β-oxyaldehydes such as glycolaldehyde, aldol, Α-amino acids such as glycine and alanine, amino acids Α- or β-aminoalcohols such as noethyl alcohol, oxalic acid, glutaric acid, succinic acid, malonic acid, maleic acid, dicarboxylic acids such as adipic acid, tricarboxylic acids such as citric acid, etc. and chelate with Zr atom The compound which can form a compound is mentioned. These chelating agents can be used alone or as a mixture of two or more. Of these, acetylacetone and ethyl acetoacetate are preferably used.
キレート化剤を用いる場合、その添加量は、Ｚｒ原子換算のジルコニウム化合物の添加量に対して通常は１〜４０モル倍、好ましくは１．５〜２０モル倍、より好ましくは２〜１０モル倍である。１モル倍より少ないと安定化の効果がなく、４０モルを超えてもそれに見合った効果に乏しく、経済的に不利である。 When a chelating agent is used, the addition amount is usually 1 to 40 mol times, preferably 1.5 to 20 mol times, more preferably 2 to 10 mol times with respect to the addition amount of the zirconium compound in terms of Zr atoms. It is. If the amount is less than 1 mol, there is no stabilizing effect, and even if it exceeds 40 mol, the effect corresponding to it is poor, which is economically disadvantageous.
本発明の光触媒体水系塗料には、光触媒体以外の無機化合物を添加することができる。無機化合物としては、例えば、非晶質アルミナ、アルミナゾルのようなアルミニウム(水)酸化物、ゼオライト、カオリナイトのようなアルミノ珪酸塩、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウムおよび水酸化バリウムのようなアルカリ土類金属(水)酸化物、リン酸カルシウム、モレキュラーシーブまたは活性炭、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｂｉ、Ｌａ、及びＣｅのような金属元素の水酸化物、又はこれらの金属元素の非晶質酸化物が挙げられる。これらは１種または２種以上を組み合わせて用いることができる。 An inorganic compound other than the photocatalyst can be added to the photocatalyst water-based paint of the present invention. Examples of the inorganic compound include amorphous alumina, aluminum (water) oxide such as alumina sol, zeolite, aluminosilicate such as kaolinite, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, Alkaline earth metal (hydroxide) oxides such as calcium hydroxide, strontium hydroxide and barium hydroxide, calcium phosphate, molecular sieve or activated carbon, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn , Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, and Examples thereof include hydroxides of metal elements such as Ce, and amorphous oxides of these metal elements. These can be used alone or in combination of two or more.
本発明の光触媒被膜付き基板は、前記光触媒体水系塗料を基板上に塗布し、得られた塗膜を乾燥等することにより作製される。基板としては、例えば、ガラス、プラスチック、金属、セラミック、及びコンクリートなどが挙げられる。塗布方法としては、例えばスピンコート、ディップコート、ドクターブレード、スプレー、及びハケ塗りなどが挙げられる。乾燥工程は、使用する基材によって異なるが、樹脂基板の場合には通常室温〜１２０℃で行われる。乾燥時間は、光触媒体水系塗料の組成、塗布量等により適宜調整されるが、通常０．５〜６０分程度である。その後、使用する基材によっては１５０〜８００℃で焼成してもよい。 The substrate with a photocatalyst coating of the present invention is produced by applying the photocatalyst water-based paint on the substrate and drying the obtained coating. Examples of the substrate include glass, plastic, metal, ceramic, and concrete. Examples of the application method include spin coating, dip coating, doctor blade, spraying, and brush coating. Although a drying process changes with the base materials to be used, in the case of a resin substrate, it is normally performed at room temperature-120 degreeC. The drying time is appropriately adjusted depending on the composition of the photocatalyst water-based paint, the coating amount, etc., but is usually about 0.5 to 60 minutes. Then, depending on the substrate used, it may be fired at 150 to 800 ° C.
本発明の光触媒体水系塗料から得られる被膜は、意匠性の観点からヘーズ（曇り価）が１０％以下であることが好ましく、より好ましくは５％以下、更に好ましくは２％以下である。 The film obtained from the photocatalyst water-based paint of the present invention preferably has a haze (haze value) of 10% or less, more preferably 5% or less, and still more preferably 2% or less from the viewpoint of design.
以下、本発明の構成と効果を具体的に示す実施例等について説明する。なお、実施例等における評価項目は下記のようにして測定した。 Examples and the like specifically showing the configuration and effects of the present invention will be described below. The evaluation items in Examples and the like were measured as follows.
〔被膜の密着性〕
被膜の密着性は、セロファンテープを被膜表面の片端から他端にわたって貼着した後、素早く剥したときに、被膜が同時に剥れるか否かにより評価した。
[Coating adhesion]
The adhesion of the coating was evaluated by whether or not the coating peeled off simultaneously when the cellophane tape was applied from one end to the other end of the coating surface and then quickly peeled off.
実施例１
酸化チタンゾル（商品名：ＴＳ−Ｓ４４２０、住友化学製、酸化チタン濃度：１０重量％）８．５００ｇ、水５．７８９ｇ、及びエタノール１．７００ｇを混合して光触媒体分散液を調製した。該光触媒体分散液に炭酸ジルコニウムアンモニウム（商品名：ＡＣ−２０、第一稀元素製）０．９９４ｇ、及びアセチレングリコール系界面活性剤（商品名：オレフィンＥＸＰ．４０３６、日信化学製）０．０１７ｇを添加し、混合して光触媒体水系塗料を調製した。該光触媒体水系塗料をＭＭＡ基板（商品名：スミペックＥ、住友化学製）上にスピンコート（５００ｒｐｍ×３０ｓ）した後、８０℃で１５分間乾燥処理して光触媒被膜付きＭＭＡ基板を作製した。光触媒体水系塗料はＭＭＡ基板に対して濡れ性がよく、斑なく塗布することができた。得られた光触媒被膜は均一に形成されており、被膜の密着性を評価したところ、剥離は認められなかった。
Example 1
A photocatalyst dispersion liquid was prepared by mixing 8.500 g of titanium oxide sol (trade name: TS-S4420, manufactured by Sumitomo Chemical Co., Ltd., titanium oxide concentration: 10 wt%), 5.789 g of water, and 1.700 g of ethanol. 0.994 g of ammonium zirconium carbonate (trade name: AC-20, manufactured by Daiichi Rare Element) and an acetylene glycol-based surfactant (trade name: Olefin EXP. 4036, manufactured by Nisshin Chemical Co., Ltd.) were added to the photocatalyst dispersion. 017 g was added and mixed to prepare a photocatalyst water-based paint. The photocatalyst-based water-based paint was spin-coated (500 rpm × 30 s) on an MMA substrate (trade name: Sumipec E, manufactured by Sumitomo Chemical Co., Ltd.), and then dried at 80 ° C. for 15 minutes to produce a MMA substrate with a photocatalyst coating. The photocatalyst water-based paint had good wettability to the MMA substrate and could be applied without spots. The obtained photocatalyst film was uniformly formed. When the adhesion of the film was evaluated, no peeling was observed.
実施例２
実施例１において、オレフィンＥＸＰ．４０３６の代わりにアセチレングリコール系界面活性剤（商品名：オレフィンＰＤ−００２Ｗ、日信化学製）を用いた以外は実施例１と同様の方法で光触媒体水系塗料を調製した。該光触媒体水系塗料をＭＭＡ基板（商品名：スミペックＥ、住友化学製）上にスピンコート（５００ｒｐｍ×３０ｓ）した後、８０℃で１５分間乾燥処理して光触媒被膜付きＭＭＡ基板を作製した。光触媒体水系塗料はＭＭＡ基板に対して濡れ性がよく、斑なく塗布することができた。得られた光触媒被膜は均一に形成されており、被膜の密着性を評価したところ、剥離は認められなかった。
Example 2
In Example 1, the olefin EXP. A photocatalyst water-based paint was prepared in the same manner as in Example 1 except that acetylene glycol surfactant (trade name: Olefin PD-002W, manufactured by Nissin Chemical) was used instead of 4036. The photocatalyst-based water-based paint was spin-coated (500 rpm × 30 s) on an MMA substrate (trade name: Sumipec E, manufactured by Sumitomo Chemical Co., Ltd.), and then dried at 80 ° C. for 15 minutes to produce a MMA substrate with a photocatalyst coating. The photocatalyst water-based paint had good wettability to the MMA substrate and could be applied without spots. The obtained photocatalyst film was uniformly formed. When the adhesion of the film was evaluated, no peeling was observed.
実施例３
酸化チタンゾル（商品名：ＴＳ−Ｓ４１１０、住友化学製、酸化チタン濃度：１０重量％）３０．０ｇに純水４１．０ｇ及び蟻酸ジルコニウム水溶液（ＺｒＯ2換算濃度１８．７重量％）４．０ｇを添加して光触媒体分散液を調製した。該光触媒体分散液８．７６ｇを純水１１．２４ｇで希釈した後、アセチレングリコール系界面活性剤（商品名：オレフィンＥＸＰ．４０３６、日信化学製）を純水で希釈して０．３％に調整した希釈液１０ｇと混合して光触媒体水系塗料を調製した。該光触媒体水系塗料をＭＭＡ基板（商品名：スミペックＥ、住友化学製）上にバーコート（番手ＮＯ．３）した後、８０℃で１５分間乾燥処理して光触媒被膜付きＭＭＡ基板を作製する。光触媒体水系塗料はＭＭＡ基板に対して濡れ性がよく、斑なく塗布することができる。得られた光触媒被膜は均一に形成されており、被膜の密着性を評価すると、剥離は認められない。
Example 3
30.0 g of titanium oxide sol (trade name: TS-S4110, manufactured by Sumitomo Chemical Co., Ltd., titanium oxide concentration: 10% by weight) is added with 41.0 g of pure water and 4.0 g of zirconium formate aqueous solution (ZrO 2 equivalent concentration 18.7% by weight). A photocatalyst dispersion liquid was prepared by addition. After diluting 8.76 g of the photocatalyst dispersion with 11.24 g of pure water, acetylene glycol surfactant (trade name: Olefin EXP. 4036, manufactured by Nissin Chemical) was diluted with pure water to obtain 0.3% A photocatalyst-based water-based paint was prepared by mixing with 10 g of the diluted solution adjusted to 1. The photocatalyst water-based paint is bar-coated (count No. 3) on an MMA substrate (trade name: Sumipec E, manufactured by Sumitomo Chemical Co., Ltd.), and then dried at 80 ° C. for 15 minutes to produce a MMA substrate with a photocatalyst coating. The photocatalyst water-based paint has good wettability to the MMA substrate and can be applied without spots. The obtained photocatalyst film was uniformly formed, and peeling was not recognized when the adhesion of the film was evaluated.
比較例１
酸化チタンゾル（商品名：ＴＳ−Ｓ４４２０、住友化学製、酸化チタン濃度：１０重量％）８．０００ｇ、水６．２４９ｇ、及びエタノール１．７００ｇを混合して光触媒体分散液を調製した。該光触媒体分散液に炭酸ジルコニウムアンモニウム（商品名：ＡＣ−２０、第一稀元素製）０．９９４ｇを添加し、混合して光触媒体水系塗料を調製した。該光触媒体水系塗料をＭＭＡ基板上にスピンコート（５００ｒｐｍ×３０ｓ）した後、８０℃で１５分間乾燥処理して光触媒被膜付きＭＭＡ基板を作製した。光触媒体水系塗料はＭＭＡ基板に対して濡れ性が悪く、塗膜に斑が生じた。得られた光触媒被膜は不均一であり、被膜の密着性を評価したところ、剥離が認められた。
Comparative Example 1
A photocatalyst dispersion liquid was prepared by mixing 8.000 g of titanium oxide sol (trade name: TS-S4420, manufactured by Sumitomo Chemical Co., Ltd., titanium oxide concentration: 10% by weight), 6.249 g of water, and 1.700 g of ethanol. To the photocatalyst dispersion liquid, 0.994 g of ammonium zirconium carbonate (trade name: AC-20, manufactured by Daiichi Rare Element) was added and mixed to prepare a photocatalyst water-based paint. The photocatalyst water-based paint was spin-coated (500 rpm × 30 s) on the MMA substrate, and then dried at 80 ° C. for 15 minutes to prepare a MMA substrate with a photocatalyst film. The photocatalyst water-based paint had poor wettability with respect to the MMA substrate, and spots were formed on the coating film. The obtained photocatalyst film was non-uniform, and peeling was recognized when the adhesion of the film was evaluated.
比較例２
酸化チタンゾル（商品名：ＴＳ−Ｓ４４２０、住友化学製、酸化チタン濃度：１０重量％）８．０００ｇ、水６．２４９ｇ、及びエタノール１．７００ｇを混合して光触媒体分散液を調製した。該光触媒体分散液に炭酸ジルコニウムアンモニウム（商品名：ＡＣ−２０、第一稀元素製）０．９９４ｇ、及びポリエーテル変性シリコーンオイル（商品名：ＫＦ−６０１１、信越化学製）０．０５７ｇを添加し、混合して光触媒体水系塗料を調製した。該光触媒体水系塗料をＭＭＡ基板上にスピンコート（５００ｒｐｍ×３０ｓ）した後、８０℃で１５分間乾燥処理して光触媒被膜付きＭＭＡ基板を作製した。光触媒体水系塗料はＭＭＡ基板に対して濡れ性が悪く、塗膜に斑が生じた。得られた光触媒被膜は不均一であり、被膜の密着性を評価したところ、剥離が認められた。
Comparative Example 2
A photocatalyst dispersion liquid was prepared by mixing 8.000 g of titanium oxide sol (trade name: TS-S4420, manufactured by Sumitomo Chemical Co., Ltd., titanium oxide concentration: 10% by weight), 6.249 g of water, and 1.700 g of ethanol. To the photocatalyst dispersion liquid, 0.994 g of ammonium zirconium carbonate (trade name: AC-20, manufactured by 1st rare element) and 0.057 g of polyether-modified silicone oil (trade name: KF-6011, manufactured by Shin-Etsu Chemical Co., Ltd.) were added. And mixed to prepare a photocatalyst water-based paint. The photocatalyst water-based paint was spin-coated (500 rpm × 30 s) on the MMA substrate, and then dried at 80 ° C. for 15 minutes to prepare a MMA substrate with a photocatalyst film. The photocatalyst water-based paint had poor wettability with respect to the MMA substrate, and spots were formed on the coating film. The obtained photocatalyst film was non-uniform, and peeling was recognized when the adhesion of the film was evaluated.
Claims (7)
（式中、Ｒ１、Ｒ２、Ｒ３及びＲ４はそれぞれ独立に炭素数１〜５のアルキル基であり、ｍ及びｎは０≦ｍ＋ｎ≦５０を満たす整数である。） The photocatalyst water-based paint according to claim 4, wherein the acetylene glycol is a compound represented by the following general formula (1).
(In the formula, R 1 , R 2 , R 3 and R 4 are each independently an alkyl group having 1 to 5 carbon atoms, and m and n are integers satisfying 0 ≦ m + n ≦ 50.)
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