JP5054031B2 - Photocatalyst carrying structure - Google Patents
Photocatalyst carrying structure Download PDFInfo
- Publication number
- JP5054031B2 JP5054031B2 JP2008552025A JP2008552025A JP5054031B2 JP 5054031 B2 JP5054031 B2 JP 5054031B2 JP 2008552025 A JP2008552025 A JP 2008552025A JP 2008552025 A JP2008552025 A JP 2008552025A JP 5054031 B2 JP5054031 B2 JP 5054031B2
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- intermediate layer
- layer
- resin
- oxide
- 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.)
- Active
Links
- 239000011941 photocatalyst Substances 0.000 title claims description 101
- 229920005989 resin Polymers 0.000 claims description 31
- 239000011347 resin Substances 0.000 claims description 31
- 238000000576 coating method Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 10
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 8
- 230000003595 spectral effect Effects 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229920002050 silicone resin Polymers 0.000 claims 1
- 239000010410 layer Substances 0.000 description 122
- -1 WO 3 Inorganic materials 0.000 description 31
- 230000001699 photocatalysis Effects 0.000 description 23
- 239000010408 film Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 150000003755 zirconium compounds Chemical class 0.000 description 11
- 239000000123 paper Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 229910044991 metal oxide Inorganic materials 0.000 description 9
- 150000004706 metal oxides Chemical class 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 description 8
- 150000004692 metal hydroxides Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000011254 layer-forming composition Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 150000003377 silicon compounds Chemical class 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000006096 absorbing agent Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229920001807 Urea-formaldehyde Polymers 0.000 description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 230000000007 visual effect Effects 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- 239000004640 Melamine resin Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229940081735 acetylcellulose Drugs 0.000 description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 229920001893 acrylonitrile styrene Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000010440 gypsum Substances 0.000 description 2
- 229910052602 gypsum Inorganic materials 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 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 2
- 230000007774 longterm Effects 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- VZXTWGWHSMCWGA-UHFFFAOYSA-N 1,3,5-triazine-2,4-diamine Chemical compound NC1=NC=NC(N)=N1 VZXTWGWHSMCWGA-UHFFFAOYSA-N 0.000 description 1
- UPZFLZYXYGBAPL-UHFFFAOYSA-N 2-ethyl-2-methyl-1,3-dioxolane Chemical compound CCC1(C)OCCO1 UPZFLZYXYGBAPL-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- MLZYAQWUAMPXFU-UHFFFAOYSA-M C(C(O)C)(=O)[O-].[O-]CCCC.[O-]CCCC.[Zr+3] Chemical compound C(C(O)C)(=O)[O-].[O-]CCCC.[O-]CCCC.[Zr+3] MLZYAQWUAMPXFU-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 description 1
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 229920002160 Celluloid Polymers 0.000 description 1
- 239000004709 Chlorinated polyethylene Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910001335 Galvanized steel Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 229910019899 RuO Inorganic materials 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- SMEGJBVQLJJKKX-HOTMZDKISA-N [(2R,3S,4S,5R,6R)-5-acetyloxy-3,4,6-trihydroxyoxan-2-yl]methyl acetate Chemical compound CC(=O)OC[C@@H]1[C@H]([C@@H]([C@H]([C@@H](O1)O)OC(=O)C)O)O SMEGJBVQLJJKKX-HOTMZDKISA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- KGBUQHGXOAESDX-UHFFFAOYSA-N [Zr].OOO Chemical compound [Zr].OOO KGBUQHGXOAESDX-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 235000009120 camo Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920001727 cellulose butyrate Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 235000005607 chanvre indien Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 229910052571 earthenware Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011381 foam concrete Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000008397 galvanized steel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000011086 glassine Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 239000011487 hemp Substances 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000113 methacrylic resin Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 229920000083 poly(allylamine) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000120 polyethyl acrylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000306 polymethylpentene Polymers 0.000 description 1
- 239000011116 polymethylpentene Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Description
本発明は、防汚、防曇、浄水、脱臭、殺菌などに用いられる光触媒を担持した光触媒担持構造体に関し、特に、クラック発生と干渉色が低減された光触媒担持構造体に関する。 The present invention relates to a photocatalyst carrying structure carrying a photocatalyst used for antifouling, antifogging, water purification, deodorization, sterilization, and the like, and more particularly, to a photocatalyst carrying structure with reduced generation of cracks and interference color.
従来から、プラスチックフィルム等の有機物を主体とする担体を用いる光触媒担持構造体が知られているが、このものは、光触媒を担体上に担持すると、その触媒作用により該有機物（担体）が分解されたり、劣化したりすることが報告されており、その耐久性に問題があった。 Conventionally, a photocatalyst-supporting structure using a carrier mainly composed of an organic substance such as a plastic film is known. However, when a photocatalyst is supported on a carrier, the organic substance (carrier) is decomposed by the catalytic action. It has been reported that it has deteriorated in durability.
そこで、かかる問題を解決するために、担体上に中間層を設け、該中間層上に光触媒層を形成してなる光触媒構造体が提案されている（例えば、特許文献１、２、３等参照）。 Therefore, in order to solve such a problem, a photocatalyst structure in which an intermediate layer is provided on a carrier and a photocatalyst layer is formed on the intermediate layer has been proposed (see, for example, Patent Documents 1, 2, and 3). ).
これらは、主に担体と光触媒層との間に特定の接着層を設けることにより、下地の担体を光触媒による劣化から保護する作用と、光触媒層を担体に強固に接着させる作用、及び接着層自身が光触媒作用により劣化を受けにくい光触媒担持構造体としたものである。 These are mainly provided by providing a specific adhesive layer between the carrier and the photocatalyst layer, thereby protecting the underlying carrier from deterioration due to the photocatalyst, the effect of firmly adhering the photocatalyst layer to the carrier, and the adhesive layer itself. Is a photocatalyst-supporting structure that is not easily deteriorated by photocatalysis.
しかしながらこの中間層としてアクリルシリコン樹脂などの層を設けることにより光触媒層にクラックが発生することがある。そのため、無機成分を添加しているが、無機成分比率が大きいほど、クラックが入りにくくなるものの、その一方で密着性が低下するという問題がある。また、シリカ系の成分を添加した場合には、光の干渉による縞状の干渉色が強く出るという問題があった。 However, if a layer such as an acrylic silicon resin is provided as the intermediate layer, cracks may occur in the photocatalyst layer. Therefore, although the inorganic component is added, there is a problem that, as the inorganic component ratio is larger, cracks are less likely to occur, but on the other hand, the adhesion is reduced. In addition, when a silica-based component is added, there is a problem that a stripe-like interference color due to light interference appears strongly.
また、本発明の光触媒担持構造体と類似のものとして、特に干渉色対策を講じている以下のものを挙げることができる。 Further, examples of the similar structure to the photocatalyst-supporting structure of the present invention include the following which are particularly provided with interference color countermeasures.
・特許文献４
この発明は、第１層目として膜厚が５０ｎｍ以上２００ｎｍ以下であるＳｉＯ２薄膜あるいはＳｉＯ２系複合酸化物薄膜を形成し、該第１層目上に第２層目として、膜厚が９０ｎｍ以上１９０ｎｍ以下であるＴｉＯ２薄膜あるいはＴｉＯ２系複合酸化物薄膜であって、かつ微量のＰｔ、Ｐｄ、ＲｈあるいはＩｒを添加した薄膜を被覆形成した積層膜とする。その際、該第１層目の膜にはシリカ単独もしくは酸化チタンや酸化ジルコニウム等の高屈折率酸化物を添加して該膜の屈折率を調節するようにし、かつその光学膜厚が５０ｎｍ〜２００ｎｍの範囲内となるようにするというものである。・ Patent Document 4
In the present invention, a SiO 2 thin film or a SiO 2 -based composite oxide thin film having a thickness of 50 nm to 200 nm is formed as a first layer, and a film thickness of 90 nm is formed as a second layer on the first layer. A laminated film in which a TiO 2 thin film or a TiO 2 composite oxide thin film having a thickness of 190 nm or less and a thin film to which a small amount of Pt, Pd, Rh, or Ir is added is formed. At that time, silica alone or a high refractive index oxide such as titanium oxide or zirconium oxide is added to the film of the first layer to adjust the refractive index of the film, and the optical film thickness is 50 nm to It is intended to be within the range of 200 nm.
・特許文献５
この発明は、光透過性を有し光触媒反応を呈する複数層の光触媒層の間に、該光触媒層と屈折率が異なる材料で構成された光透過性を有する中間層を挟み込んだ積層膜を、基材表面に具備している。これによれば、各光触媒層による光触媒効果を加重した光触媒効果が得られるので、個々の光触媒層は薄くても強い光触媒効果を生じさせることができる。しかも、個々の光触媒層は薄くすることができるので、表面反射や干渉色を抑制することができる。この中間層は、例えばＳｉＯ２，ＷＯ３，Ａｌ２Ｏ３、ＩＴＯ等の無機酸化物、その他の酸化物等で構成することが記載されている。・ Patent Document 5
The present invention provides a laminated film in which a light-transmitting intermediate layer composed of a material having a refractive index different from that of the photocatalyst layer is sandwiched between a plurality of photocatalyst layers having light transmittance and exhibiting a photocatalytic reaction, It is provided on the substrate surface. According to this, a photocatalytic effect obtained by weighting the photocatalytic effect of each photocatalytic layer can be obtained, so that a strong photocatalytic effect can be generated even if each photocatalytic layer is thin. And since each photocatalyst layer can be made thin, surface reflection and interference color can be suppressed. It is described that this intermediate layer is made of, for example, inorganic oxides such as SiO 2 , WO 3 , Al 2 O 3 , ITO, and other oxides.
・特許文献６
この発明は、カメラレンズの親水性フィルタとして光触媒を使用するものである。この親水性フィルタは、中間層、光触媒層、及び親水層の順番でレンズ上に順次形成される。中間層は、光触媒層とレンズとの間の屈折率を有する。このように構成することにより、光触媒層の反射率を低減することができ、干渉色の発生を抑えることができる。中間層は、例えば、ＳｎＯ２、ＩＴＯ、Ｔａ２Ｏ５、ＺｒＯ２、Ａｌ２Ｏ３、ＷＯ３等の物質により形成され、所定の組成比を有するＩＴＯにより形成されるのが好ましいと記載されている。・ Patent Document 6
The present invention uses a photocatalyst as a hydrophilic filter of a camera lens. The hydrophilic filter is sequentially formed on the lens in the order of the intermediate layer, the photocatalyst layer, and the hydrophilic layer. The intermediate layer has a refractive index between the photocatalytic layer and the lens. By comprising in this way, the reflectance of a photocatalyst layer can be reduced and generation | occurrence | production of an interference color can be suppressed. It is described that the intermediate layer is preferably formed of, for example, a material such as SnO 2 , ITO, Ta 2 O 5 , ZrO 2 , Al 2 O 3 , WO 3 , and ITO having a predetermined composition ratio. ing.
・特許文献７
この発明は、担体上に中間層と光触媒層とを順次設けてなる光触媒坦持構造体であって、前記中間層の膜厚が３μｍ以上で形成されており、かつ前記光触媒層は膜厚が０．０１μｍ〜０．３μｍで形成されている光触媒坦持構造体を提供する。
担体表面に、屈折率に大きな差がない中間層と光触媒層とを順次形成することにより、また、中間層膜厚と光触媒層の膜厚比を１０倍以上の差を設ける事により、担体と光触媒層との密着性に優れ、担体及び中間層が光触媒により分解され難く、いわゆる干渉色がなく、かつ、表面にひび割れ等の生じない光触媒担持構造体が得られる。・ Patent Document 7
The present invention is a photocatalyst support structure in which an intermediate layer and a photocatalyst layer are sequentially provided on a carrier, wherein the intermediate layer has a thickness of 3 μm or more, and the photocatalyst layer has a thickness of 3 μm or more. Provided is a photocatalyst-supporting structure formed of 0.01 μm to 0.3 μm.
By sequentially forming an intermediate layer and a photocatalyst layer having no significant difference in refractive index on the surface of the carrier, and by providing a difference of 10 times or more in the film thickness ratio of the intermediate layer and the photocatalyst layer, It is possible to obtain a photocatalyst-supporting structure that has excellent adhesion to the photocatalyst layer, the carrier and the intermediate layer are hardly decomposed by the photocatalyst, has no so-called interference color, and does not cause cracks on the surface.
また、中間層にジルコニアを添加するものとして、上記のほかに特許文献８もあるが、これは親水性、表面硬度、耐ベタツキ性、耐ブロッキング性、滑性などを向上させるために添加する。 In addition to the above, Patent Document 8 discloses addition of zirconia to the intermediate layer, which is added to improve hydrophilicity, surface hardness, stickiness resistance, blocking resistance, lubricity and the like.
中間層として樹脂を用いた場合に生じるクラック（ひび割れ）の発生を防止し、かつ干渉色の発現を抑えることのできる添加成分を見出すことを目的とする。 It is an object to find an additive component that can prevent the occurrence of cracks (cracks) that occur when a resin is used as an intermediate layer and can suppress the occurrence of interference colors.
本発明者らは上記課題を解決すべく鋭意検討した結果、中間層にジルコニア成分を添加することにより、干渉色がなく、かつ、表面にクラックの生じない光触媒担持構造体が得られることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that by adding a zirconia component to the intermediate layer, a photocatalyst-supporting structure having no interference color and no cracks on the surface can be obtained. The present invention has been completed.
即ち、本発明は、
（１）担体上に中間層と光触媒層を有する光触媒担持構造体において、中間層が樹脂を主成分とし、ジルコニウム化合物を中間層全体の質量に対して１〜３５質量％含有し、屋外暴露後３ヶ月経過後の塗膜のヘイズ率が３％以下、屋外暴露後３ヶ月経過後の３８０ｎｍから８００ｎｍの光の波長における塗膜の分光反射率の最大値と最小値の差が５％以下であることを特徴とする光触媒担持構造体、
（２）ジルコニウム化合物が平均粒子径１０〜３０ｎｍの非晶質酸化ジルコニウムであることを特徴とする上記（１）記載の光触媒担持構造体、
（３）中間層がアクリルシリコン樹脂を含有することを特徴とする上記（１）又は（２）記載の光触媒担持構造体、及び
（４）樹脂及びジルコニウム化合物を含有することを特徴とする上記（１）乃至（３）のいずれかに記載の中間層に使用するための中間層形成用組成物に関する。That is, the present invention
(1) In a photocatalyst-supporting structure having an intermediate layer and a photocatalyst layer on a carrier, the intermediate layer contains a resin as a main component and a zirconium compound in an amount of 1 to 35% by mass with respect to the total mass of the intermediate layer, after outdoor exposure The haze ratio of the coating after 3 months is 3% or less, and the difference between the maximum and minimum spectral reflectances of the coating at a wavelength of light of 380 nm to 800 nm after 3 months after outdoor exposure is 5% or less. A photocatalyst-supporting structure,
(2) The photocatalyst-supporting structure according to the above (1), wherein the zirconium compound is amorphous zirconium oxide having an average particle size of 10 to 30 nm,
(3) The photocatalyst-supporting structure according to (1) or (2) above, wherein the intermediate layer contains an acrylic silicon resin, and (4) the above characterized in that it contains a resin and a zirconium compound ( The present invention relates to an intermediate layer forming composition for use in the intermediate layer according to any one of (1) to (3).
本発明の光触媒坦持構造体について、以下に詳細に説明する。
（光触媒坦持構造体）
本発明の光触媒坦持構造体は、担体上に中間層と光触媒層を有する光触媒担持構造体において、中間層が樹脂、好ましくは難分解性樹脂を主成分とし、ジルコニウム化合物を中間層全体の質量に対して１〜３５質量％、好ましくは５〜２０質量％含有し、ヘイズ率が３％以下、好ましくは１％以下で、屋外暴露後３ヶ月経過後の３８０ｎｍから８００ｎｍの光の波長における分光反射率の最大値と最小値の差が５％以下、好ましくは３％以下であることを特徴とする。
（担体）
本発明の光触媒担持構造体の担体としては、その表面に中間層を介して光触媒を担持可能なものであれば、その材質、形状等に制限はない。The photocatalyst carrying structure of the present invention will be described in detail below.
(Photocatalyst carrying structure)
The photocatalyst carrying structure of the present invention is a photocatalyst carrying structure having an intermediate layer and a photocatalyst layer on a carrier. The intermediate layer is mainly composed of a resin, preferably a hardly decomposable resin, and a zirconium compound is used as a mass of the entire intermediate layer. 1 to 35% by mass, preferably 5 to 20% by mass, a haze ratio of 3% or less, preferably 1% or less, and a spectrum at a wavelength of light of 380 nm to 800 nm after 3 months after outdoor exposure. The difference between the maximum value and the minimum value of the reflectance is 5% or less, preferably 3% or less.
(Carrier)
The carrier of the photocatalyst carrying structure of the present invention is not limited in its material, shape, etc. as long as the photocatalyst can be carried on the surface via an intermediate layer.
かかる担体の形状としては、光触媒が担持可能であれば特に制限はない。例えばフィルム状、管状、繊維状、網状、板状、曲面板等、どのような形状を有していてもよい。 The shape of the carrier is not particularly limited as long as the photocatalyst can be supported. For example, it may have any shape such as a film shape, a tubular shape, a fiber shape, a net shape, a plate shape, or a curved plate.
担体の材質としては、例えば、ポリエチレン、ポリプロピレン、エチレン−ブテン共重合体、エチレン−酢酸ビニル共重合体、エチレン−ビニルアルコール共重合体等のポリオレフィン樹脂、ポリメタクリル酸メチル、ポリアクリル酸メチル、ポリメタクリル酸エチル、ポリアクリル酸エチル等のアクリル樹脂、ポリ塩化ビニル、ポリスチレン、アクリロニトリル−ブタジエン−スチレン共重合体（ＡＢＳ樹脂）、ポリカーボネート等の熱可塑性樹脂、フェノール樹脂、尿素樹脂、不飽和ポリエステル、ポリウレタン、エポキシ樹脂、メラミン樹脂、ジアリルフタレート樹脂等の熱硬化性樹脂、その他ポリフッ化エチレン、珪素樹脂等の合成樹脂のフィルムや板状体、各種ガラス、陶磁器、土器、ほうろう等のセラミックス板、石膏板、石膏スラグ板、珪酸カルシウム板、軽量発泡コンクリ−ト板、中空押出セメント板、パルプセメント板、石綿セメント板、木片セメント板、硝子繊維強化セメント板、鉄板、アルミニウム板、アルミニウム合金板、亜鉛メッキ鋼板、銅板、銅合金板、ステンレス板等の金属板木材単板、木材合板、パーティクルボード、ＭＤＦ（中密度繊維板）等の木質板、クラフト紙、コート紙、チタン紙、リンター紙、板紙、石膏ボード紙、上質紙、薄葉紙、パラフィン紙、グラシン紙、アート紙、硫酸紙等の紙類、毛、絹、麻等の天然繊維、レーヨン、アセテート等の再生繊維、ナイロン、アクリル、ポリアミド、ポリエステル、ポリアクリロニトリル、ポリ塩化ビニル、ポリ塩化ビニリデン等の合成繊維、アラミド等の耐熱性繊維の単独あるいは混紡繊維からなる織布、不織布、編布等の繊維、硝子繊維、石綿、チタン酸カリウム繊維、シリカ繊維、炭素繊維、アルミナ繊維等の複合強化繊維フェノール樹脂、尿素樹脂、不飽和ポリエステル、ポリウレタン、エポキシ樹脂、メラミン樹脂等の樹脂を、硝子繊維、不織布、布帛、紙、その他各種繊維基材に含浸硬化させて複合化したいわゆるＦＲＰ板等が挙げられる。 Examples of the material of the carrier include polyolefin resins such as polyethylene, polypropylene, ethylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polymethyl methacrylate, polymethyl acrylate, poly Acrylic resin such as ethyl methacrylate and polyethyl acrylate, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer (ABS resin), thermoplastic resin such as polycarbonate, phenol resin, urea resin, unsaturated polyester, polyurethane , Epoxy resins, melamine resins, thermosetting resins such as diallyl phthalate resins, synthetic resin films and plates such as polyfluorinated ethylene and silicon resins, various glass, ceramics, earthenware, enamel ceramic plates, gypsum plates, etc. ,plaster Rug plate, calcium silicate plate, lightweight foamed concrete plate, hollow extruded cement plate, pulp cement plate, asbestos cement plate, wood chip cement plate, glass fiber reinforced cement plate, iron plate, aluminum plate, aluminum alloy plate, galvanized steel plate, Copper plate, copper alloy plate, metal plate such as stainless steel plate, wood single board, wood plywood, particle board, wood board such as MDF (medium density fiber board), kraft paper, coated paper, titanium paper, linter paper, paperboard, gypsum board Paper, fine paper, thin paper, paraffin paper, glassine paper, art paper, sulfate paper, natural fibers such as hair, silk, hemp, etc., recycled fibers such as rayon, acetate, nylon, acrylic, polyamide, polyester, poly Synthetic fibers such as acrylonitrile, polyvinyl chloride, and polyvinylidene chloride, and heat-resistant fibers such as aramid alone or mixed fibers Fibers such as woven fabrics, nonwoven fabrics, knitted fabrics, glass fibers, asbestos, potassium titanate fibers, silica fibers, carbon fibers, alumina fibers, and other composite reinforcing fiber phenol resins, urea resins, unsaturated polyesters, polyurethanes, epoxy resins And so-called FRP plates obtained by impregnating and curing glass fibers, nonwoven fabrics, fabrics, papers, and other various fiber base materials with a resin such as melamine resin.
本発明の光触媒担持構造体は、特に透明担体が好ましい。かかる透明性が高い担体としては、例えばポリエチレンテレフタレート、ポリカーボネート、ポリアクリル酸エステル、ポリメタクリレート、ポリエチレン、ポリプロピレン、ポリアミド、ポリイミド、ポリスチレン、ポリ塩化ビニル、ポリフッ化ビニリデン、ポリ四フッ化エチレン、フッ化エチレン−プロピレン共重合体、フッ化エチレン−エチレン共重合体、エチレン−酢酸ビニル共重合体などのフィルム状に成形加工したときに５５０ｎｍの波長の光の直線透過率が５０％以上である透明性の高い合成樹脂フィルム又はシートを挙げることができる。又、透明な担体を用いる場合には、着色剤等で着色されたものであってもよい。また、上記した各種素材の２種以上、例えば、ガラス板状に透明フィルムを接着剤あるいは熱融着等の公知の手法により積層した複合基材を担体として用いることもできる。さらに本発明の光触媒担持構造体の中間層及び光触媒層は透明性が高いものであるので、表面に絵柄模様が施された担体を用いることもできる。 The photocatalyst carrying structure of the present invention is particularly preferably a transparent carrier. Examples of such highly transparent carriers include polyethylene terephthalate, polycarbonate, polyacrylic acid ester, polymethacrylate, polyethylene, polypropylene, polyamide, polyimide, polystyrene, polyvinyl chloride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene fluoride. -Transparency in which the linear transmittance of light having a wavelength of 550 nm is 50% or more when formed into a film such as propylene copolymer, fluorinated ethylene-ethylene copolymer, ethylene-vinyl acetate copolymer A high synthetic resin film or sheet can be mentioned. When a transparent carrier is used, it may be colored with a colorant or the like. Further, two or more of the various materials described above, for example, a composite base material obtained by laminating a transparent film in a glass plate shape by a known method such as an adhesive or heat fusion can be used as a carrier. Furthermore, since the intermediate layer and the photocatalyst layer of the photocatalyst-supporting structure of the present invention are highly transparent, a carrier having a pattern on the surface can be used.
（中間層）
本発明の光触媒担持構造体は、前記担体表面上に中間層を有する。中間層は、樹脂を主成分としジルコニウム化合物を必須成分とする。ジルコニウム化合物は１〜３５質量％、好ましくは、５〜２０質量％である。中間層の厚みは全体で３μｍ以上であるのが好ましい。(Middle layer)
The photocatalyst carrying structure of the present invention has an intermediate layer on the surface of the carrier. The intermediate layer contains a resin as a main component and a zirconium compound as an essential component. A zirconium compound is 1-35 mass%, Preferably, it is 5-20 mass%. The total thickness of the intermediate layer is preferably 3 μm or more.
中間層を構成する樹脂としては、例えば、酢酸セルロース、酪酸セルロース、セルロイド、セロファン、アセチルセルロース等の天然高分子系プラスチック、フェノール樹脂、尿素樹脂、メラミン樹脂、フラン樹脂、不飽和ポリエステル樹脂、エポキシ樹脂、ジアリルフタレート樹脂、グアナミン樹脂、ケトン樹脂等の熱硬化性樹脂、（超低密度、低密度、中密度、高密度）ポリエチレン、アイオノマー、塩素化ポリエチレン、エチレン−塩化ビニル共重合体、エチレン−酢酸ビニル共重合体、ポリ酢酸ビニル、ポリプロピレン、ポリブテン、エチレン−α−オレフィン共重合体等の熱可塑性樹脂、ポリブタジエン、ポリメチルペンテン、ポリスチレン、ポリ−α−メチルスチレン、ポリパラビニルフェノール、アクリロニトリル−ブタジエン−スチレン共重合体、スチレン−アクリロニトリル共重合体、塩素化ポリエチレン−アクリロニトリル−スチレン共重合体、アクリロニトリル−スチレン共重合体、メタクリル樹脂、ノルボネン樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリアリルアミン、ポリビニルエーテル、ポリビニルアルコール、エチレン−ビニルアルコール共重合体、ポリウレタン樹脂、ポリアクリロニトリル、ポリビニルブチラール、ナイロン、ポリアセタール、ポリカーボネート、変性ポリフェニレンエーテル、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリスルホン、ポリエーテルスルホン、ポリフェニレンスルファイド、ポリアミド、ポリアミドイミド、ポリエーテルイミド、ポリエーテルエーテルケトン、ポリアミノビスマレイミド、超高分子量ポリエチレン、アイソタクチックポリスチレン、ポリテトラフルオロエチレン、テトラフルオロエチレン−パーフルオロアクコキシビニルエーテル共重合体、ポリクロロトリフルオロエチレン、テトラフルオロエチレン−エチレン共重合体、クロロトリフルオロエチレン−エチレン共重合体、ポリビニリデンフロライド、ポリビニルフロライド等の熱可塑性プラスチック、アクリルシリコン樹脂又はエポキシシリコン樹脂等が挙げられる。特に好ましくは、アクリルシリコン樹脂である。また前記中間層は２層以上の積層体からなっていてもよい。 Examples of the resin constituting the intermediate layer include natural polymer plastics such as cellulose acetate, cellulose butyrate, celluloid, cellophane, and acetyl cellulose, phenol resin, urea resin, melamine resin, furan resin, unsaturated polyester resin, and epoxy resin. , Thermosetting resins such as diallyl phthalate resin, guanamine resin, ketone resin, (ultra low density, low density, medium density, high density) polyethylene, ionomer, chlorinated polyethylene, ethylene-vinyl chloride copolymer, ethylene-acetic acid Thermoplastic resins such as vinyl copolymer, polyvinyl acetate, polypropylene, polybutene, ethylene-α-olefin copolymer, polybutadiene, polymethylpentene, polystyrene, poly-α-methylstyrene, polyparavinylphenol, acrylonitrile-butadiene -Styrene copolymer, styrene-acrylonitrile copolymer, chlorinated polyethylene-acrylonitrile-styrene copolymer, acrylonitrile-styrene copolymer, methacrylic resin, norbornene resin, polyvinyl chloride, polyvinylidene chloride, polyallylamine, polyvinyl ether , Polyvinyl alcohol, ethylene-vinyl alcohol copolymer, polyurethane resin, polyacrylonitrile, polyvinyl butyral, nylon, polyacetal, polycarbonate, modified polyphenylene ether, polyethylene terephthalate, polybutylene terephthalate, polysulfone, polyethersulfone, polyphenylene sulfide, polyamide, Polyamideimide, polyetherimide, polyetheretherketone, polyamino bismaleimi , Ultrahigh molecular weight polyethylene, isotactic polystyrene, polytetrafluoroethylene, tetrafluoroethylene-perfluoroacoxy vinyl ether copolymer, polychlorotrifluoroethylene, tetrafluoroethylene-ethylene copolymer, chlorotrifluoroethylene- Examples thereof include thermoplastics such as ethylene copolymer, polyvinylidene fluoride, and polyvinyl fluoride, acrylic silicon resin, and epoxy silicon resin. Particularly preferred is an acrylic silicon resin. The intermediate layer may be a laminate of two or more layers.
本発明において使用するジルコニウム化合物としては、ジルコニウムの酸化物、水酸化物、硝酸塩、オキシ硝酸塩、炭酸塩、オキシ炭酸塩、蓚酸塩、オキシ蓚酸塩、酢酸塩、炭素数１〜６のアルコキシド、該アルコキシドの加水分解生成物などの１種又は２種以上の混合物が挙げられる。
好ましくは、酸化ジルコニウム、オキシ硝酸ジルコニウム、オキシ塩酸ジルコニウム、水和酸化ジルコニウム、オキシ水酸化ジルコニウム、水和硝酸ジルコニウム、水和オキシ塩化ジルコニウム、蓚酸ジルコニウム、酢酸ジルコニウム、ジルコニウムテトライソプロポキシド、ジルコニウムテトラブトキシド、ジルコニウムジブトキシドアセチルアセトナート、ジルコニウムジブトキシドラクテート、ジルコニウムブトキシドの加水分解生成物、ジルコニウムイソプロポキシドの加水分解生成物を挙げることができる。特に好ましくは、平均粒子径は１０〜３０ｎｍの非晶質の酸化ジルコニウムである。ここで、平均粒子径とは、一次粒子径の平均値を意味する。Zirconium compounds used in the present invention include zirconium oxide, hydroxide, nitrate, oxynitrate, carbonate, oxycarbonate, oxalate, oxysuccinate, acetate, C 1-6 alkoxide, 1 type, or 2 or more types of mixtures, such as a hydrolysis product of an alkoxide, is mentioned.
Preferably, zirconium oxide, zirconium oxynitrate, zirconium oxyhydrochloride, hydrated zirconium oxide, zirconium oxyhydroxide, hydrated zirconium nitrate, hydrated zirconium oxychloride, zirconium oxalate, zirconium acetate, zirconium tetraisopropoxide, zirconium tetrabutoxide Zirconium dibutoxide acetylacetonate, zirconium dibutoxide lactate, hydrolysis product of zirconium butoxide, and hydrolysis product of zirconium isopropoxide. Particularly preferred is amorphous zirconium oxide having an average particle size of 10 to 30 nm. Here, the average particle diameter means an average value of primary particle diameters.
またこの層は、厚み（２層以上の場合には合計の厚み）が１μｍ以上で形成するのが好ましい。厚みが１μｍ未満の場合には、担体と光触媒層側の層との層間密着性に乏しくなり、光干渉により、光触媒担持構造体の表面が金色あるいは玉虫色に見える場合がある。 This layer is preferably formed with a thickness (total thickness in the case of two or more layers) of 1 μm or more. When the thickness is less than 1 μm, the interlayer adhesion between the carrier and the layer on the photocatalyst layer side is poor, and the surface of the photocatalyst carrying structure may appear golden or iridescent due to light interference.
また、中間層中には、所望により各種添加剤、補強材、充填剤、例えば、紫外線吸収剤、光安定剤、酸化防止剤、耐電防止剤、難燃剤、耐熱安定剤等を添加することもできる。 In addition, various additives, reinforcing materials, fillers, for example, UV absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, heat stabilizers, etc. may be added to the intermediate layer as desired. it can.
紫外線吸収剤や光安定剤は、樹脂により良好な耐光性（耐候性）を付与する目的で添加される。紫外線吸収剤としては、例えば、ベンゾトリアゾール系紫外線吸収剤、ベンゾフェノン系紫外線吸収剤、サリチル酸エステル系紫外線吸収剤等の有機物、微粒子状の酸化亜鉛、酸化セリウム、酸化チタニウム等の無機物を挙げることができる。 An ultraviolet absorber and a light stabilizer are added for the purpose of imparting good light resistance (weather resistance) to the resin. Examples of ultraviolet absorbers include organic substances such as benzotriazole ultraviolet absorbers, benzophenone ultraviolet absorbers, and salicylic acid ester ultraviolet absorbers, and inorganic substances such as particulate zinc oxide, cerium oxide, and titanium oxide. .
光安定剤としては、例えば、ビス−（２，２，６，６−テトラメチル−４−ピペリジニル）セバケート等のヒンダードアミン系ラジカル捕捉剤、ピペリジン系ラジカル捕捉剤等が挙げられる。 Examples of the light stabilizer include hindered amine radical scavengers such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, piperidine radical scavengers, and the like.
また酸化防止剤は、プラスチックの熱酸化劣化を防止するために添加される物質であり、例えば、フェノール系酸化防止剤やイオウ系酸化防止剤、リン系酸化防止剤等が挙げられる。これらの添加量は、通常、後述する中間層全体に対して０．００５質量％〜１０質量％、好ましくは０．０１質量％〜５質量％である。 Antioxidants are substances added to prevent thermal oxidative degradation of plastics, and examples thereof include phenol-based antioxidants, sulfur-based antioxidants, and phosphorus-based antioxidants. These addition amounts are usually 0.005% by mass to 10% by mass, preferably 0.01% by mass to 5% by mass with respect to the entire intermediate layer described later.
（光触媒層）
光触媒層の厚みは厚い方が光触媒活性は向上するが、０．０１μｍ〜１０μｍが好ましい。より好ましくは、０．０１μｍ〜０．３μｍが良い。厚みが０．０１μｍ未満では光透過性に優れるものの光触媒が利用する紫外線をも透過してしまうため、十分な光触媒活性が得られない。一方、１０μｍを越えると光触媒活性向上の効果が飽和する一方、光触媒層の透明性が低下する。０．０１μｍ〜０．３μｍにすると、長期耐候性試験後にも膜がひび割れたり、剥離しにくくなる。
光触媒は粉末状、ゾル状、溶液状等、光触媒層の乾燥温度で乾燥した時に、中間層と固着して光触媒活性を示すものであればいずれも使用することができる。(Photocatalyst layer)
The photocatalytic activity is improved when the thickness of the photocatalyst layer is thick, but is preferably 0.01 μm to 10 μm. More preferably, 0.01 micrometer-0.3 micrometer are good. When the thickness is less than 0.01 μm, although the light transmittance is excellent, since the ultraviolet light used by the photocatalyst is transmitted, sufficient photocatalytic activity cannot be obtained. On the other hand, if it exceeds 10 μm, the effect of improving the photocatalytic activity is saturated, while the transparency of the photocatalytic layer is lowered. When the thickness is 0.01 μm to 0.3 μm, the film is cracked or hardly peeled even after the long-term weather resistance test.
Any photocatalyst can be used as long as it is fixed to the intermediate layer and exhibits photocatalytic activity when dried at the drying temperature of the photocatalyst layer, such as powder, sol, or solution.
ゾル状の光触媒を使用する場合、粒子径が２０ｎｍ以下、好ましくは１０ｎｍ以下のものを使用すると、光触媒層透明性が向上し、直線透過率が高くなるため、透明性が要求されるガラス基板やプラスチック成形体に塗布する場合に特に好ましい。また、下地の担体に色や模様が印刷されている場合には、下地の色や柄を損なうことなく、透明な光触媒層を形成することができる。 When using a sol-like photocatalyst, if a particle diameter of 20 nm or less, preferably 10 nm or less is used, the photocatalyst layer transparency is improved and the linear transmittance is increased. It is particularly preferable when applied to a plastic molded body. Further, when a color or pattern is printed on the base carrier, a transparent photocatalytic layer can be formed without impairing the base color or pattern.
かかる光触媒としては、例えば、酸化チタン、酸化亜鉛、酸化錫、酸化ジルコニウム、酸化タングステン、酸化クロム、酸化モリブデン、酸化鉄、酸化ニッケル、酸化ルテニウム、酸化コバルト、酸化銅、酸化マンガン、酸化ゲルマニウム、酸化鉛、酸化カドミウム、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化ロジウム、酸化レニウム等の酸化物が挙げられる。これらの中でも、酸化チタン、酸化亜鉛、酸化錫、酸化ジルコニウム、酸化タングステン、酸化鉄、酸化ニオブ、特にアナターゼ型二酸化チタンが、１００℃以下の低温で加熱硬化を行った場合でも優れた光触媒活性を示す点から好ましい。 Examples of such photocatalysts include titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, iron oxide, nickel oxide, ruthenium oxide, cobalt oxide, copper oxide, manganese oxide, germanium oxide, and oxide. Examples thereof include oxides such as lead, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, rhodium oxide, and rhenium oxide. Among these, titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, iron oxide, niobium oxide, especially anatase-type titanium dioxide, have excellent photocatalytic activity even when heat-cured at a low temperature of 100 ° C. or less. It is preferable from the point shown.
また、これらに光触媒の光触媒還元作用を利用して、Ｐｔ，Ｒｈ，Ｒｕ，ＲｕＯ２，Ｎｂ，Ｃｕ，Ｓｎ，Ｎｉ，Ｆｅ，Ａｇ等の金属もしくはこれらの金属酸化物を添加したものを用いることもできる。In addition to these, a metal such as Pt, Rh, Ru, RuO 2 , Nb, Cu, Sn, Ni, Fe, Ag, or a metal oxide thereof is used by utilizing the photocatalytic reduction action of the photocatalyst. You can also.
光触媒層は、後述するように、中間層表面に光触媒層形成用組成物を塗工することにより形成することができるが、光触媒層中の光触媒の含有量は、接着性の点から、光触媒層の全体に対しに対して７５質量％以下が好ましい。 As will be described later, the photocatalyst layer can be formed by applying a composition for forming a photocatalyst layer on the surface of the intermediate layer. However, the content of the photocatalyst in the photocatalyst layer is determined from the viewpoint of adhesiveness. 75 mass% or less is preferable with respect to the whole.
前記光触媒層中には、光触媒の他にシリコン化合物を含有するのが好ましい。該シリコン化合物は、光触媒層の耐摩耗性を向上させ、光触媒層形成用組成物の経時変化による粘度増加や粒子沈降が生じるのを抑制する役割を果たす。 The photocatalyst layer preferably contains a silicon compound in addition to the photocatalyst. The silicon compound plays a role of improving the abrasion resistance of the photocatalyst layer and suppressing an increase in viscosity and particle sedimentation due to a change with time of the composition for forming the photocatalyst layer.
かかるシリコン化合物としては、例えば、一般式：ＳｉＲ３ｎ５（ＯＲ４）４−ｎ５〔式中、Ｒ３はアミノ基、塩素原子又はカルボキシル基で置換されていてもよい炭素数１〜８のアルキル基を表し、Ｒ４はアルコキシ基で置換されていてもよい炭素数１〜８のアルキル基を表し、ｎ５は０，１，２又は３のいずれかを表す。〕で表されるアルコキシシラン類又はそれらの加水分解性生物の１種又は２種以上の混合物を用いることができる。Examples of such silicon compounds include, for example, the general formula: SiR 3 n 5 (OR 4 ) 4- n 5 [wherein R 3 is an optionally substituted amino group, chlorine atom, or carboxyl group having 1 to 8 carbon atoms. R 4 represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group, and n 5 represents any of 0, 1, 2, or 3. Or a mixture of two or more of these hydrolyzable organisms can be used.
前記Ｒ３としては、メチル基、エチル基、ビニル基、γ−グリシドキシプロピル基、γ−メタクリロキシプロピル基、γ−（２−アミノエチル）アミノプロピル基、γ−クロロプロピル基、γ−メルカプトプロピル基、γ−アミノプロピル基、１−アクロキシプロピル基等が挙げられる。Examples of R 3 include methyl group, ethyl group, vinyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) aminopropyl group, γ-chloropropyl group, γ- Examples include a mercaptopropyl group, a γ-aminopropyl group, and a 1-acryloxypropyl group.
また、ＯＲ４で表される基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、β−メトキシエトキシ基、２−エチルヘキシロキシ基等を例示することができる。Examples of the group represented by OR 4 include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a β-methoxyethoxy group, and a 2-ethylhexyloxy group. Can do.
前記一般式：ＳｉＲ３ｎ５（ＯＲ４）４−ｎ５で表されるシリコン化合物の具体例としては、テトラメトキシシラン、テトラエトキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、及びこれらの加水分解物の１種又は２種以上の混合物を好ましく挙げることができる。Specific examples of the silicon compound represented by the general formula: SiR 3 n 5 (OR 4 ) 4 -n 5 include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, and hydrates thereof. One or a mixture of two or more decomposition products can be preferably exemplified.
前記シリコン化合物の後述する光触媒層形成用組成物中の含有量は０．００１〜５質量％であるのが好ましい。０．００１質量％未満では、光触媒層形成用組成物の長期保存安定性が低下し、５質量％を越えると、光触媒の触媒活性の低下が著しい。 It is preferable that content in the composition for photocatalyst layer formation mentioned later of the said silicon compound is 0.001-5 mass%. If it is less than 0.001% by mass, the long-term storage stability of the composition for forming a photocatalyst layer is lowered, and if it exceeds 5% by mass, the catalytic activity of the photocatalyst is remarkably lowered.
前記光触媒層は、前記光触媒及びシリコン化合物に加えて、金属酸化物ゲル又は金属水酸化物ゲルを更に含有してなるのが好ましい。金属酸化物ゲル又は金属水酸化物ゲルは、光触媒粉末を固着し、中間層と強固に接着させる効果を有する。また、この金属酸化物ゲル又は金属水酸化物ゲルは、多孔質であることから吸着性を有しており、光触媒活性を高める効果もある。これらの光触媒層中の含有量は、固形分として２５〜９５質量％が好ましい。２５質量％未満では、中間層との密着性に乏しくなり、９５質量％を越えると光触媒活性が不十分となる。 The photocatalyst layer preferably further contains a metal oxide gel or a metal hydroxide gel in addition to the photocatalyst and the silicon compound. The metal oxide gel or metal hydroxide gel has an effect of fixing the photocatalyst powder and firmly bonding it to the intermediate layer. Moreover, since this metal oxide gel or metal hydroxide gel is porous, it has adsorptivity and has an effect of enhancing photocatalytic activity. The content in these photocatalyst layers is preferably 25 to 95% by mass as a solid content. If it is less than 25% by mass, the adhesion to the intermediate layer is poor, and if it exceeds 95% by mass, the photocatalytic activity becomes insufficient.
また、金属酸化物ゲル又は金属水酸化物ゲルの比表面積は、好ましくは１５０℃で乾燥後５０ｍ２／ｇ以上、より好ましくは１００ｍ２／ｇ以上であると、接着性は強固となり、光触媒活性も向上し、また、沸騰水中に浸漬した後でも優れた接着性を有している。Further, the specific surface area of the metal oxide gel or metal hydroxide gel is preferably 50 m 2 / g or more after drying at 150 ° C., more preferably 100 m 2 / g or more, and the adhesiveness becomes strong and the photocatalytic activity. In addition, it has excellent adhesion even after being immersed in boiling water.
前記金属酸化物又は金属水酸化物としては、金属成分として、Ｓｉ、Ａｌ、Ｔｉ、Ｚｒ、Ｍｇ、Ｎｂ、Ｔａ、Ｗ、Ｓｎ等を例示することができる。 Examples of the metal oxide or metal hydroxide include Si, Al, Ti, Zr, Mg, Nb, Ta, W, and Sn as metal components.
又、Ｓｉ、Ａｌ、Ｔｉ、Ｚｒ、Ｍｇ、Ｎｂの中から選ばれた２種以上の金属を含有する酸化物ゲルもしくは水酸化物ゲルを使用することにより、沸騰水に浸漬した後の光触媒層の付着性を高めることが可能である。 Moreover, the photocatalyst layer after being immersed in boiling water by using an oxide gel or a hydroxide gel containing two or more metals selected from Si, Al, Ti, Zr, Mg, and Nb Can be improved.
また、光触媒層中にシリコン変性樹脂あるいはシランカップリング剤を光触媒層全体に対して３０重量％以下加えることによっても、高い触媒活性を維持しつつ、沸騰水中へ１５分間浸漬した後でＪＩＳ Ｋ５４００に規定された碁盤目テープ法による付着性試験で評価点数が６点以上の優れた付着性（接着性）を有する光触媒層を得ることができる。 In addition, by adding a silicon-modified resin or a silane coupling agent to the photocatalyst layer in an amount of 30% by weight or less based on the entire photocatalyst layer, it is immersed in boiling water for 15 minutes while maintaining high catalytic activity, and then added to JIS K5400. It is possible to obtain a photocatalyst layer having excellent adhesion (adhesiveness) having an evaluation score of 6 or more in an adhesion test by a specified cross-cut tape method.
（光触媒担持構造体の製造）
本発明の光触媒担持構造体は、例えば、（１）先ず、担体表面に中間層形成用組成物を塗工形成することにより中間層を形成し、（２）次いで、該中間層表面に光触媒層形成用組成物を塗工・形成することにより光触媒層を形成することにより製造することができる。(Manufacture of photocatalyst carrying structure)
The photocatalyst-supporting structure of the present invention has, for example, (1) an intermediate layer is first formed by coating and forming an intermediate layer-forming composition on the surface of the carrier, and (2) a photocatalyst layer is then formed on the surface of the intermediate layer. It can manufacture by forming a photocatalyst layer by applying and forming the composition for formation.
（Ａ）中間層の形成
中間層を形成する方法としては、特に制限はないが、例えば、前記中間層を構成するものとして列記した樹脂、中間層形成用組成物の有機溶媒溶液、有機溶媒縣濁液、水分散エマルジョン等を、担体表面に印刷法、シート形成法、スプレー吹きつけ法、ディップコーティング法、メイヤバー工法、スピンコーティング法、フローコーティング法等でコートし、乾燥させる方法を用いることができる。中間層形成時の乾燥温度は、通常室温から２００℃程度である。(A) Formation of Intermediate Layer The method for forming the intermediate layer is not particularly limited. For example, the resins listed as constituting the intermediate layer, the organic solvent solution of the intermediate layer forming composition, It is possible to use a method in which a suspension, a water-dispersed emulsion or the like is coated on the carrier surface by a printing method, sheet forming method, spray spraying method, dip coating method, Mayer bar method, spin coating method, flow coating method, etc. and dried. it can. The drying temperature when forming the intermediate layer is usually from room temperature to about 200 ° C.
中間層形成用組成物は、前記中間層を構成するものとして列記した樹脂（又は樹脂のモノマーもしくはオリゴマー）の１種又は２種以上と、所望により、金属酸化物ゾル、金属水酸化物ゾル及びその他の添加物を添加した溶液あるいはエマルジョンの形で調製することができる。この場合、樹脂のモノマーあるいはオリゴマーで用いる場合には、硬化触媒（重合触媒）を添加することもできる。 The intermediate layer forming composition comprises one or more of the resins (or resin monomers or oligomers) listed as constituting the intermediate layer, and optionally a metal oxide sol, a metal hydroxide sol, and It can be prepared in the form of a solution or emulsion to which other additives are added. In this case, when used as a resin monomer or oligomer, a curing catalyst (polymerization catalyst) may be added.
用いられる溶媒としては、低沸点のものが好ましいが、例えば、水、メチルアルコール、エチルアルコール、イソプロピルアルコール、ブタノール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチルなどのエステル類、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ペンタン、ヘキサン、ヘプタン、シクロヘキサン等の脂肪族炭化水素等、及びこれらの２種以上の混合溶媒が挙げられる。 As the solvent to be used, those having a low boiling point are preferable. For example, water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as acetylacetone and cyclohexanone, acetic acid Examples thereof include esters such as ethyl and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and a mixed solvent of two or more of these.
又、２種類以上の組成からなる中間層形成用組成物の溶液あるいはエマルジョンをそれぞれ調製し、上記の操作を繰り返すことによって、２層以上の積層体からなる中間層を所定の厚みで形成することができる。 Further, an intermediate layer composed of two or more layers is formed with a predetermined thickness by preparing a solution or emulsion of an intermediate layer forming composition having two or more types of compositions and repeating the above operation. Can do.
（Ｂ）光触媒層の形成
光触媒層は、光触媒層形成用組成物を、前記中間層表面にスプレーコーティング法、フローコーティング法、スピンコーティング法、メイヤバー工法、ディップコーティング法、ロールコーティング法等の公知のコーティング方法により、所定の塗工量で塗工し、乾燥させることにより、所定の厚みで形成することができる。(B) Formation of photocatalyst layer The photocatalyst layer is a known composition such as a spray coating method, a flow coating method, a spin coating method, a Meyer bar method, a dip coating method, or a roll coating method. By coating with a predetermined coating amount by a coating method and drying, it can be formed with a predetermined thickness.
光触媒層形成用組成物は、少なくとも光触媒と、所望により金属酸化物ゾル、金属水酸化物ゾルあるいはシラン化合物を添加したものを、適当な溶媒に溶解ないしは縣濁させて調製することができる。 The composition for forming a photocatalyst layer can be prepared by dissolving or suspending in a suitable solvent at least a photocatalyst and optionally adding a metal oxide sol, a metal hydroxide sol or a silane compound.
用いられる溶媒としては、低沸点のものが好ましいが、例えば、水、メチルアルコール、エチルアルコール、イソプロピルアルコール、ブタノール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類、酢酸エチル、酢酸ブチルなどのエステル類、ベンゼン、トルエン、キシレン等の芳香族炭化水素、ペンタン、ヘキサン、ヘプタン、シクロヘキサン等の脂肪族炭化水素等、及びこれらの２種以上の混合溶媒が挙げられる。 As the solvent to be used, those having a low boiling point are preferable. For example, water, alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol and butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as acetylacetone and cyclohexanone, acetic acid Examples thereof include esters such as ethyl and butyl acetate, aromatic hydrocarbons such as benzene, toluene and xylene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, and a mixed solvent of two or more of these.
又、光触媒層を中間層上に形成する際に、金属酸化物ゾルあるいは金属水酸化物ゾルの前駆体溶液の状態で光触媒を分散し、コート時に加水分解あるいは中和分解してゾル化もしくはゲル化させてもよい。 In addition, when the photocatalyst layer is formed on the intermediate layer, the photocatalyst is dispersed in the state of a precursor solution of a metal oxide sol or metal hydroxide sol, and hydrolyzed or neutralized and decomposed during coating to form a sol or gel. You may make it.
かかるゾルを使用する場合には、安定化のために、酸やアルカリの解膠剤等が添加されていてもよい。光触媒層形成時の乾燥は、担体材質及び中間層中の樹脂材質によっても異なるが、常温で行っても良いし、また、加熱してもよい。 When such a sol is used, an acid or alkali peptizer may be added for stabilization. Drying during the formation of the photocatalyst layer may be performed at room temperature or may be heated, although it varies depending on the support material and the resin material in the intermediate layer.
又、光触媒層を形成する前に、中間層表面に易接着処理を施すことも好ましい。中間層表面に易接着処理を施すことにより、中間層と光触媒層との層間密着性が著しく高められ、中間層表面に光触媒層を形成した場合に、光触媒層表面が見る角度によって金色や玉虫色に見える、いわゆる干渉色が生じるのを効果的に防止することができる。
かかる易接着処理としては、例えば、中間層表面をコロナ放電処理やＵＶ−オゾン処理を施す方法が挙げられる。It is also preferable to subject the intermediate layer surface to an easy adhesion treatment before forming the photocatalytic layer. By applying an easy adhesion treatment to the surface of the intermediate layer, the interlayer adhesion between the intermediate layer and the photocatalyst layer is remarkably enhanced. It is possible to effectively prevent the appearance of so-called interference color.
Examples of such easy adhesion treatment include a method of subjecting the intermediate layer surface to corona discharge treatment or UV-ozone treatment.
本発明の光触媒担持構造体がプラスチックフィルム状の場合には、その防汚、抗菌、脱臭機能を活かして、光触媒を担持していない担体の裏面に、アクリル系あるいはシリコン系粘着剤を塗布したフィルムとすることで、自動車や各種輸送機器、建築物等の窓ガラス、冷凍・冷蔵ショーケースや温室等の内面に貼り付けることができる。
そして、内部空間の微量有機物質の分解と、ガラス表面の汚染防止と破損時の飛散防止に有効な透視性の高いフィルムとすることが可能となる。When the photocatalyst-supporting structure of the present invention is in the form of a plastic film, an anti-fouling, antibacterial, and deodorizing function is utilized, and a film in which an acrylic or silicon-based adhesive is applied to the back surface of a carrier not supporting a photocatalyst By doing so, it can be affixed to the inner surfaces of automobiles, various transport equipment, window glass of buildings, refrigerated / refrigerated showcases, greenhouses, and the like.
And it becomes possible to set it as a highly transparent film effective in decomposition | disassembly of the trace amount organic substance of internal space, prevention of the contamination of the glass surface, and scattering prevention at the time of a failure | damage.
本発明の光触媒担持構造体を少なくとも一部に有した物品としては、例えば、壁紙、壁面材、窓ガラス、サッシ、窓枠類等の建築物の内外装材、ブラインド、カーテン、カーペット、ショーケース等の各種インテリア製品、眼鏡、ガラスレンズ、フロントガラス、ドアミラー、鏡等の各種ガラス製品、照明器具、照明灯、ブラックライト、テレビ、冷蔵庫、オーディオ機器、コンピュータ、パソコン、プリンタ、ファクシミリ等の電気機器、テント、傘、テーブルクロス等の日用品、箪笥、本棚、机、テーブル等の家具類、自動車、電車、飛行機、船舶等の車両の内外装材、農業用フィルム、防草シート、育苗シート等の農園芸用シート類や食品包装材料等が挙げられる。 Examples of the article having the photocatalyst carrying structure of the present invention at least in part include interior and exterior materials for buildings such as wallpaper, wall materials, window glass, sashes, and window frames, blinds, curtains, carpets, and showcases. Various interior products such as glasses, glass lenses, windshields, door mirrors, various glass products such as mirrors, lighting equipment, lighting lamps, black lights, televisions, refrigerators, audio equipment, computers, personal computers, printers, facsimiles, and other electrical equipment Daily goods such as tents, umbrellas, tablecloths, furniture such as bags, bookshelves, desks, tables, etc., interior and exterior materials for vehicles such as automobiles, trains, airplanes, ships, etc., agricultural films, herbicidal sheets, seedling sheets, etc. Agricultural and horticultural sheets, food packaging materials and the like can be mentioned.
以下に、本発明の実施例について説明するが、本発明はこれらに限定されるものではない。 Examples of the present invention will be described below, but the present invention is not limited thereto.
（Ｉ）光触媒担持構造体の製造
（１）担体
担体は以下のものを用いた。
黒色ウレタン塗装板（Ｔ−１）
ソーダライムガラス板（Ｔ−２）(I) Production of photocatalyst carrying structure (1) Carrier The following were used as the carrier.
Black urethane coating board (T-1)
Soda lime glass plate (T-2)
（２）中間層塗布液
シリコン含有量１０重量％のアクリルシリコン樹脂のキシレン溶液（Ｊ）に、以下に示すジルコニウム化合物（Ａ及びＢ）又はコロイダルシリカ（Ｃ）を含有させたものを用いた。
ジルコニアゾル（Ａ）（第一稀元素化学工業（株）製、ＺＳＬ−１０Ｔ 平均粒子径１５ｎｍ）
ジルコニアゾル（Ｂ）（第一稀元素化学工業（株）製、ＺＳＬ−１０Ａ 平均粒子径７０ｎｍ）
コロイダルシリカ（Ｃ）（日産化学（株）製、スノーテックスＸＳ 平均粒子径６ｎｍ）
中間層は担体（Ｔ−１及びＴ−２）上に中間層塗布液をディッピング法で塗布し、常温で乾燥することにより膜厚１〜２μｍで形成した。(2) Intermediate layer coating solution A solution containing the following zirconium compound (A and B) or colloidal silica (C) in a xylene solution (J) of an acrylic silicon resin having a silicon content of 10% by weight was used.
Zirconia sol (A) (Daiichi Rare Element Chemical Co., Ltd., ZSL-10T average particle size 15 nm)
Zirconia sol (B) (Daiichi Rare Element Chemical Co., Ltd., ZSL-10A average particle size 70 nm)
Colloidal silica (C) (manufactured by Nissan Chemical Co., Ltd., Snowtex XS average particle size 6 nm)
The intermediate layer was formed with a film thickness of 1 to 2 μm by applying an intermediate layer coating solution on the carrier (T-1 and T-2) by dipping and drying at room temperature.
（３）光触媒層塗布液
光触媒は次のものを使用した。
硝酸酸性酸化チタンゾル（Ｄ）（結晶粒子径８ｎｍ）
シリカゾルは次のものを使用した。
コロイダルシリカ（Ｃ）（日産化学（株）製 スノーテックスＸＳ）
アルミニウム化合物は次のものを使用した。
１０％ベーマイトアルミナコロイド水溶液（Ｅ）（川研ファインケミカル（株）アルミゾル１０）
ジルコニウム化合物は次のものを使用した。
オキシ硝酸ジルコニウム６水和物（和光純薬（株）製、試薬特級）を水に溶解して１０％水溶液とした後、１２時間加熱して半量の水を常圧で留去して得られた液をオキシ硝酸ジルコニウム液（Ｆ）として使用した。(3) Photocatalyst layer coating solution The photocatalyst used was as follows.
Nitric acid acidic titanium oxide sol (D) (crystal particle size 8nm)
The following silica sol was used.
Colloidal silica (C) (Snowtex XS, manufactured by Nissan Chemical Co., Ltd.)
The following aluminum compounds were used.
10% boehmite alumina colloidal aqueous solution (E) (Kawaken Fine Chemical Co., Ltd. Aluminum Sol 10)
The following zirconium compounds were used.
Zirconium oxynitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) is dissolved in water to make a 10% aqueous solution, and then heated for 12 hours to distill off half of the water at normal pressure. The solution was used as the zirconium oxynitrate solution (F).
上記光触媒、シリカゾル、アルミニウム化合物及びジルコニウム化合物をｐＨ１．５〜９の適当な範囲に調整して混合し、所定量の界面活性剤を加えて光触媒複合体溶液（光触媒層形成組成物）を得た。
得られた光触媒複合体溶液をディッピング法で、上記担体（Ｔ−１及びＴ−２）に形成した中間層上に塗工形成した。光触媒層は、常温で乾燥して膜厚０．０５〜１μｍで形成した。The photocatalyst, silica sol, aluminum compound and zirconium compound were adjusted to an appropriate range of pH 1.5 to 9 and mixed, and a predetermined amount of surfactant was added to obtain a photocatalyst complex solution (photocatalyst layer forming composition). .
The obtained photocatalyst complex solution was applied and formed on the intermediate layer formed on the carrier (T-1 and T-2) by dipping. The photocatalyst layer was dried at room temperature and formed with a film thickness of 0.05 to 1 μm.
表中、担体が「Ｔ−１／Ｔ−２」とは、担体としてＴ−１及びＴ−２をそれぞれ試験したことを意味する。 In the table, the carrier “T-1 / T-2” means that T-1 and T-2 were tested as carriers.
（ＩＩ）光触媒担持構造体の性能試験
上記で得られた光触媒担持構造体を用いて以下の性能試験を行った。
（１）光触媒活性の評価試験
上記で得られた光触媒担持構造体（担体：Ｔ−２）を用いて、大きさ７０ｍｍ×７０ｍｍの試験体を切り出し、容量４Ｌのパイレックス（登録商標）製ガラス容器中に設置した。この容器中に空気とアルデヒドの混合ガスをアルデヒド濃度１００ｐｐｍに調整し、次いで該試料に紫外線強度２ｍＷ／ｃｍ２のブラックライト（ＦＬ１５ＢＬＢ、東芝ライテック製）の光を３時間照射後、容器内部のアルデヒドガス濃度をガスクロマトグラフィーにより測定し、その減少量により光触媒活性を評価した。
その結果、実施例１〜４及び比較例１〜３の光触媒担持構造体は３時間で検出限界以下まで分解したことから、いずれの光触媒担持構造体も優れた光触媒活性を示すことが分かった。(II) Performance test of photocatalyst carrying structure The following performance test was conducted using the photocatalyst carrying structure obtained above.
(1) Evaluation test of photocatalytic activity Using the photocatalyst carrying structure (carrier: T-2) obtained above, a test piece having a size of 70 mm x 70 mm was cut out and a 4 L capacity Pyrex (registered trademark) glass container Installed inside. The mixed gas of air and aldehyde was adjusted to 100 ppm in this container, and then the sample was irradiated with black light (FL15BLB, manufactured by Toshiba Lighting & Technology) with an ultraviolet intensity of 2 mW / cm 2 for 3 hours, and then the aldehyde inside the container The gas concentration was measured by gas chromatography, and the photocatalytic activity was evaluated by the amount of decrease.
As a result, since the photocatalyst carrying structures of Examples 1 to 4 and Comparative Examples 1 to 3 were decomposed to the detection limit or less in 3 hours, it was found that any photocatalyst carrying structure exhibited excellent photocatalytic activity.
（２）ヘイズ率の測定（担体Ｔ−２）
ヘイズ率の測定を濁度計（日本電色工業製 ＮＤＨ３００Ａ）で測定した。空気をリファレンスとして測定した。ヘイズ率（％）は「（全光線透過率−平行光線透過率）×１００／全光線透過率」の数式より算出した。測定結果を下記の表２に示す。(2) Measurement of haze ratio (carrier T-2)
The haze ratio was measured with a turbidimeter (NDH300A, manufactured by Nippon Denshoku Industries Co., Ltd.). Air was measured as a reference. The haze ratio (%) was calculated from the formula “(total light transmittance−parallel light transmittance) × 100 / total light transmittance”. The measurement results are shown in Table 2 below.
（３）テープ剥離試験
各試料表面に、切り傷によって２ｍｍの間隔で２５個のマス目を形成し、ＪＩＳＫ５４００に規定する基板目テープ法試験により付着性の評価を行った。剥離しなかったものを○、少しでも剥離したものを×として評価した。結果を下記の表２に示す。(3) Tape peeling test On the surface of each sample, 25 squares were formed at intervals of 2 mm by cuts, and the adhesion was evaluated by the substrate tape method test defined in JISK5400. Evaluation was made as ○ for those that did not peel, and × for those that did not peel. The results are shown in Table 2 below.
（４）指摩擦試験
試料表面を指で摩擦し、剥離しなかったものを○、少しでも剥離したものを×として評価した。結果を下記の表２に示す。(4) Finger Friction Test A sample surface was rubbed with a finger, and the sample that was not peeled off was evaluated as ○, and the sample that was peeled off was evaluated as ×. The results are shown in Table 2 below.
（５）促進耐候性試験
試料表面に、キセノンランプで紫外線強度１８０Ｗ／ｍ２の光を、温度４０℃、相対湿度９０％の恒温恒湿槽内で１０００時間照射後、ヘイズ率、テープ剥離試験及び指摩擦試験をして耐候性の評価とした。結果を下記の表２に示す。(5) Accelerated weather resistance test The sample surface was irradiated with light of UV intensity 180 W / m 2 with a xenon lamp in a constant temperature and humidity chamber with a temperature of 40 ° C. and a relative humidity of 90% for 1000 hours, and then a haze rate and a tape peeling test. In addition, a finger friction test was performed to evaluate weather resistance. The results are shown in Table 2 below.
表中、「Ｔ−１／Ｔ−２」とは、担体としてＴ−１、Ｔ−２をそれぞれ試験したことを示す。また、テープ剥離及び指摩擦の結果は、Ｔ−１及びＴ−２の両方の結果を示す。 In the table, “T-1 / T-2” indicates that T-1 and T-2 were tested as carriers. Moreover, the result of tape peeling and finger | toe friction shows the result of both T-1 and T-2.
表２より、実施例１〜４及び比較例３の光触媒担持構造体は担体Ｔ−１、Ｔ−２に対して優れた透明性、密着性を有し、耐候性試験１０００時間後においても維持されている。それに比して比較例１、２は、初期のヘイズ率が１％以上であり透明性が劣る結果になっている。 From Table 2, the photocatalyst carrying structures of Examples 1 to 4 and Comparative Example 3 have excellent transparency and adhesion to the carriers T-1 and T-2, and are maintained even after 1000 hours of the weather resistance test. Has been. In contrast, Comparative Examples 1 and 2 have an initial haze ratio of 1% or more, which is inferior in transparency.
（６）干渉色の評価方法
（５）と同様に促進耐候性試験を行って以下の方法により測定した。
１）分光色彩計（日本電色工業製、ＳＤ−５０００）で分光反射率曲線（３８０ｎｍ〜７８０ｎｍ）を求めた。反射率曲線における反射率の最大値と最小値の差を求め、差が３％以上の場合を強い干渉色の基準とした。結果を下記の表３に示す。
２）光触媒担持構造体の外観を目視により下記の基準で判断した。
○：担体Ｔ−１の質感を損なわない透明感がある。干渉色が目立たない。△：担体Ｔ−１の質感をほとんど損なわないが透明感が低下している。干渉色はあるが均一でムラがなく、あまり目立たない。×：透明感が低下して担体Ｔ−１の質感が損なわれている。干渉色が非常に強く、ギラギラしている。結果を下記の表３に示す。(6) Interference color evaluation method An accelerated weather resistance test was conducted in the same manner as in (5), and the interference color was measured by the following method.
1) A spectral reflectance curve (380 nm to 780 nm) was obtained with a spectral colorimeter (Nippon Denshoku Industries, SD-5000). The difference between the maximum value and the minimum value of the reflectance in the reflectance curve was determined, and the case where the difference was 3% or more was used as a strong interference color reference. The results are shown in Table 3 below.
2) The appearance of the photocatalyst-supporting structure was judged visually according to the following criteria.
○: There is a transparent feeling that does not impair the texture of the carrier T-1. The interference color is inconspicuous. (Triangle | delta): Although the texture of the support | carrier T-1 is hardly impaired, transparency is falling. Although there is an interference color, it is uniform, non-uniform and not very noticeable. X: Transparency is lowered and the texture of the carrier T-1 is impaired. The interference color is very strong and glaring. The results are shown in Table 3 below.
表３より、実施例１〜４の光触媒担持構造体は分光色彩計による評価で干渉色が弱い範囲内であり、目視評価でも干渉色が目立っていない。耐候性試験１０００時間後においても外観が維持されている。比較例１は分光色彩計による評価で干渉色が弱い範囲であるが、耐候性試験１０００時間後には目視評価で表面の凹凸による散乱光が増えて透明性の低下した状態が観察されている。比較例２は耐候性試験後に分光色彩計による評価で干渉色が強く、目視評価でも透明感はあるものの干渉色が目立っている。比較例３は分光色彩計による評価及び目視評価で極めて強い干渉色が確認されている。
本発明の光触媒担持構造体は光触媒活性が高く透明性に優れている。また、長時間の光照射、高温多湿、屋外環境下でも高い透明性が維持されるだけではなく干渉色によって外観が損なわれることがない。From Table 3, the photocatalyst carrying structures of Examples 1 to 4 are in a range where the interference color is weak in the evaluation by the spectrocolorimeter, and the interference color is not conspicuous even in the visual evaluation. The appearance is maintained even after 1000 hours of the weather resistance test. Comparative Example 1 is a range in which the interference color is weak in the evaluation by the spectrocolorimeter, but after 1000 hours of the weather resistance test, a state in which the scattered light due to the unevenness on the surface is increased and the transparency is lowered is visually observed. In Comparative Example 2, the interference color was strong in the evaluation by the spectrocolorimeter after the weather resistance test, and the interference color was conspicuous in the visual evaluation although there was a sense of transparency. In Comparative Example 3, an extremely strong interference color was confirmed by evaluation using a spectral colorimeter and visual evaluation.
The photocatalyst carrying structure of the present invention has high photocatalytic activity and excellent transparency. Further, not only high transparency is maintained even under long-time light irradiation, high temperature and high humidity, and outdoor environment, but the appearance is not impaired by the interference color.
本発明の光触媒担持構造体は、担体と光触媒層との間に中間層を設けた光触媒担持構造体であり、中間層にジルコニウム化合物を添加することにより、透明性に優れ、干渉色がなく、かつ、表面にクラック等の生じない光触媒担持構造体を提供することができる。 The photocatalyst carrying structure of the present invention is a photocatalyst carrying structure in which an intermediate layer is provided between a carrier and a photocatalyst layer, and by adding a zirconium compound to the intermediate layer, it is excellent in transparency and has no interference color. And the photocatalyst carrying structure which does not produce a crack etc. on the surface can be provided.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008552025A JP5054031B2 (en) | 2006-12-28 | 2007-12-27 | Photocatalyst carrying structure |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006354874 | 2006-12-28 | ||
| JP2006354874 | 2006-12-28 | ||
| JP2008552025A JP5054031B2 (en) | 2006-12-28 | 2007-12-27 | Photocatalyst carrying structure |
| PCT/JP2007/001476 WO2008081589A1 (en) | 2006-12-28 | 2007-12-27 | Photocatalyst-supporting structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPWO2008081589A1 JPWO2008081589A1 (en) | 2010-04-30 |
| JP5054031B2 true JP5054031B2 (en) | 2012-10-24 |
Family
ID=39588278
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008552025A Active JP5054031B2 (en) | 2006-12-28 | 2007-12-27 | Photocatalyst carrying structure |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP5054031B2 (en) |
| WO (1) | WO2008081589A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010032445A1 (en) * | 2008-09-16 | 2010-03-25 | 株式会社 東芝 | Hydrophilic films and components and structures using same |
| JP5429042B2 (en) * | 2010-03-09 | 2014-02-26 | 信越化学工業株式会社 | Hydrophilic film-forming coating solution and hydrophilic film using the same |
| JP5835219B2 (en) * | 2010-07-29 | 2015-12-24 | Toto株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| CN113058648B (en) * | 2021-03-19 | 2022-07-05 | 江南大学 | Organic composite photocatalyst for degrading drugs and pathogenic bacteria and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001137711A (en) * | 1999-11-10 | 2001-05-22 | Yamaha Livingtec Corp | Method for forming photocatalyst layer |
| JP2001286766A (en) * | 2000-04-11 | 2001-10-16 | Nippon Soda Co Ltd | Photocatalyst-bearing structure body, production method of the same, composition for intermediate layer |
| JP2005212446A (en) * | 2004-02-02 | 2005-08-11 | Mitsubishi Kagaku Sanshi Corp | Manufacturing process for metal resin composite board having photocatalytic function |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3759651B2 (en) * | 1996-05-28 | 2006-03-29 | 日本パーカライジング株式会社 | Resin or resin coating material having photocatalytic surface and method for producing the same |
| JP4026042B2 (en) * | 1999-04-28 | 2007-12-26 | 東芝ライテック株式会社 | Photocatalyst, lamp and lighting fixture |
| JP4509286B2 (en) * | 2000-03-17 | 2010-07-21 | 日本曹達株式会社 | Photocatalyst carrying structure |
-
2007
- 2007-12-27 WO PCT/JP2007/001476 patent/WO2008081589A1/en active Application Filing
- 2007-12-27 JP JP2008552025A patent/JP5054031B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001137711A (en) * | 1999-11-10 | 2001-05-22 | Yamaha Livingtec Corp | Method for forming photocatalyst layer |
| JP2001286766A (en) * | 2000-04-11 | 2001-10-16 | Nippon Soda Co Ltd | Photocatalyst-bearing structure body, production method of the same, composition for intermediate layer |
| JP2005212446A (en) * | 2004-02-02 | 2005-08-11 | Mitsubishi Kagaku Sanshi Corp | Manufacturing process for metal resin composite board having photocatalytic function |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2008081589A1 (en) | 2010-04-30 |
| WO2008081589A1 (en) | 2008-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6228480B1 (en) | Photocatalyst-carrying structure and photocatalyst coating material | |
| EP0866101B1 (en) | Photocatalytic coating composition and photocatalyst-bearing structure | |
| JP5766778B2 (en) | refrigerator | |
| US10201809B2 (en) | Photocatalyst sheet | |
| JP4526153B2 (en) | Photocatalyst carrying structure, process for producing the same, and composition for forming an intermediate layer | |
| JP2003025478A (en) | Hard coating film | |
| JP5054031B2 (en) | Photocatalyst carrying structure | |
| JP4319275B2 (en) | Metal plate made by laminating a photocatalyst-carrying film | |
| WO2015133316A1 (en) | Photocatalyst coating liquid and photocatalyst film using same | |
| JP2005036550A (en) | Wall paper with photocatalyst provided with uneven pattern | |
| EP1029659B1 (en) | Metallic plate or resin structure having photocatalyst-supporting film laminated thereto | |
| JP2002346393A (en) | Photocatalyst and method for manufacturing the same | |
| JP4295037B2 (en) | Film or sheet with photocatalyst for wallpaper | |
| JP4693965B2 (en) | Photocatalyst carrying structure and photocatalyst layer forming composition | |
| JP4868636B2 (en) | Structure comprising a photocatalyst | |
| JP2009039687A (en) | Composition for forming photocatalyst layer | |
| KR100280910B1 (en) | Photocatalyst-carrying structure and photocatalyst coating material | |
| JPWO2003033144A1 (en) | Photocatalyst composite, coating solution for forming photocatalyst layer, and photocatalyst carrying structure | |
| JP4884646B2 (en) | Adhesive layer forming composition and photocatalyst carrying structure | |
| JP4693949B2 (en) | Photocatalyst layer forming coating solution, photocatalyst complex, and photocatalyst structure | |
| JP2006028470A (en) | Antistaining paint, antistaining sheet, and method for producing the same | |
| JP4509286B2 (en) | Photocatalyst carrying structure | |
| JPH11138686A (en) | Resin structural body formed of laminated photocatalyst carrying film | |
| JP4553439B2 (en) | Application method | |
| WO2012009552A1 (en) | Photocatalytic properties and applications of polylactic acid films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20111018 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20111209 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20120724 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120726 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5054031 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150803 Year of fee payment: 3 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |