TWI582182B - A photocatalyst-containing coating liquid and a photocatalyst-bearing structure - Google Patents
A photocatalyst-containing coating liquid and a photocatalyst-bearing structure Download PDFInfo
- Publication number
- TWI582182B TWI582182B TW105113156A TW105113156A TWI582182B TW I582182 B TWI582182 B TW I582182B TW 105113156 A TW105113156 A TW 105113156A TW 105113156 A TW105113156 A TW 105113156A TW I582182 B TWI582182 B TW I582182B
- Authority
- TW
- Taiwan
- Prior art keywords
- photocatalyst
- coupling agent
- coating liquid
- decane coupling
- mass
- Prior art date
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- 239000011941 photocatalyst Substances 0.000 title claims description 131
- 239000011248 coating agent Substances 0.000 title claims description 88
- 238000000576 coating method Methods 0.000 title claims description 88
- 239000007788 liquid Substances 0.000 title claims description 71
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 103
- 239000007822 coupling agent Substances 0.000 claims description 101
- 239000002245 particle Substances 0.000 claims description 33
- -1 decane compound Chemical class 0.000 claims description 31
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 25
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 25
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 claims description 14
- 230000007062 hydrolysis Effects 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 239000003999 initiator Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000004645 aluminates Chemical class 0.000 claims description 8
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 229920003002 synthetic resin Polymers 0.000 claims description 5
- 239000000057 synthetic resin Substances 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007787 solid Substances 0.000 description 18
- 229910052719 titanium Inorganic materials 0.000 description 15
- 239000010936 titanium Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000725 suspension Substances 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 8
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000000945 filler Substances 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- 125000000962 organic group Chemical group 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 230000000840 anti-viral effect Effects 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 231100000241 scar Toxicity 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 208000032544 Cicatrix Diseases 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
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- 230000005494 condensation Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
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- 229910010272 inorganic material Inorganic materials 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 230000037387 scars Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical compound C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 2
- OAWZPHCPLADLAD-UHFFFAOYSA-N 4-(trimethoxymethyl)dodecyl prop-2-enoate Chemical compound C(C=C)(=O)OCCCC(C(OC)(OC)OC)CCCCCCCC OAWZPHCPLADLAD-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XVEUJTIZHZIHJM-UHFFFAOYSA-N a828782 Chemical compound CCOC(N)=O.CCOC(N)=O XVEUJTIZHZIHJM-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
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- 239000003822 epoxy resin Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 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
- 230000003647 oxidation Effects 0.000 description 2
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- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
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- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
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- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011135 tin Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- ZOZNCAMOIPYYIK-UHFFFAOYSA-N 1-aminoethylideneazanium;acetate Chemical compound CC(N)=N.CC(O)=O ZOZNCAMOIPYYIK-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
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- MTDLVDBRMBSPBJ-UHFFFAOYSA-N C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC Chemical compound C(C1CO1)OCCCC(C(OCC)(OCC)OCC)CCCCCCCC MTDLVDBRMBSPBJ-UHFFFAOYSA-N 0.000 description 1
- KFKILXQFBVYKNF-UHFFFAOYSA-N CCC=COCCCC(C(C)(C)C)CCCCCCC Chemical compound CCC=COCCCC(C(C)(C)C)CCCCCCC KFKILXQFBVYKNF-UHFFFAOYSA-N 0.000 description 1
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZDQWESQEGGJUCH-UHFFFAOYSA-N Diisopropyl adipate Chemical compound CC(C)OC(=O)CCCCC(=O)OC(C)C ZDQWESQEGGJUCH-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
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- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
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- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
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- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
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- KWWBHCXWSVLTBF-UHFFFAOYSA-N decane;prop-2-enoic acid Chemical compound OC(=O)C=C.CCCCCCCCCC KWWBHCXWSVLTBF-UHFFFAOYSA-N 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WPCPXPTZTOMGRF-UHFFFAOYSA-K di(butanoyloxy)alumanyl butanoate Chemical compound [Al+3].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O WPCPXPTZTOMGRF-UHFFFAOYSA-K 0.000 description 1
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- IRPMZRADZZGAMU-UHFFFAOYSA-N ethyl acetate;zirconium Chemical compound [Zr].CCOC(C)=O IRPMZRADZZGAMU-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical class CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- SGNLDVYVSFANHW-UHFFFAOYSA-N pentane-2,4-dione;zirconium Chemical compound [Zr].CC(=O)CC(C)=O SGNLDVYVSFANHW-UHFFFAOYSA-N 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000006748 scratching Methods 0.000 description 1
- 230000002393 scratching effect Effects 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- GPMKKHIGAJLBMZ-UHFFFAOYSA-J titanium(4+);tetraacetate Chemical compound [Ti+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O GPMKKHIGAJLBMZ-UHFFFAOYSA-J 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Description
本發明係關於一種光觸媒承載構造體及用於形成其之含有光觸媒之塗布液，詳細而言，本發明係關於一種將光觸媒層直接設於基材上之光觸媒承載構造體及用於形成其之光觸媒塗布液。 The present invention relates to a photocatalyst-bearing structure and a coating liquid containing the same for forming a photocatalyst. In particular, the present invention relates to a photocatalyst-carrying structure in which a photocatalyst layer is directly provided on a substrate and used for forming the same. Photocatalyst coating solution.
本案係對2015年5月12日提出申請之日本專利申請第2015-97195號主張優先權，將其內容引用於此。 Priority is claimed on Japanese Patent Application No. 2015-97195, filed on May 12, 2015, the content of which is hereby incorporated herein.
於建築材料、內飾材料、器具、包裝材料等用途中，已知大量之使塑膠之表面承載光觸媒而成之材料。 In the use of building materials, interior materials, appliances, packaging materials, etc., a large number of materials are known which allow the surface of the plastic to carry a photocatalyst.
又，對於作為具有光觸媒效果之代表性物質而為人所知之氧化鈦(二氧化鈦)溶膠而言，作為與該效果不同之其他用途，亦被用作用於形成透明之硬塗層之塗布劑成分。 Further, a titanium oxide (titanium dioxide) sol which is known as a representative substance having a photocatalytic effect is used as a coating agent component for forming a transparent hard coat layer as another application different from the effect. .
於專利文獻1中記載有一種光觸媒承載構造體，其係將含有分散於有機溶劑中之二氧化鈦溶膠、丙烯酸矽樹脂或環氧矽樹脂、及四烷氧基矽烷之部分水解產物的塗布液直接塗布於玻璃等基材上而成。 Patent Document 1 discloses a photocatalyst-bearing structure in which a coating liquid containing a titanium oxide sol, an acrylic resin, an epoxy resin, and a partial hydrolyzate of tetraalkoxysilane dispersed in an organic solvent is directly coated. It is made on a substrate such as glass.
然而，塑膠基材為有機材料，故若使氧化鈦等光觸媒直接承載於其表面上，則存在因紫外線照射導致基材發生分解、引起白化(chalking)等劣化之問題。由此，亦大量地提出有於基材與光觸媒層之間設置中間層之方法。例如於專利文獻2等中記載有如下例子：為了改良光觸媒層與中間層之接著，而使光觸媒層中含有環氧矽烷偶合劑。 However, since the plastic base material is an organic material, when a photocatalyst such as titanium oxide is directly supported on the surface thereof, there is a problem that the base material is decomposed by ultraviolet irradiation, causing deterioration such as chalking. Thus, a method of providing an intermediate layer between a substrate and a photocatalyst layer has also been proposed in large numbers. For example, Patent Document 2 and the like describe an example in which an epoxy decane coupling agent is contained in a photocatalyst layer in order to improve the photocatalyst layer and the intermediate layer.
於專利文獻3中記載有一種硬化物，其係將含有光觸媒、光酸產生劑及γ-縮水甘油氧基丙基三甲氧基矽烷之光硬化性組合物進行光硬化而成。 Patent Document 3 describes a cured product obtained by photocuring a photocurable composition containing a photocatalyst, a photoacid generator, and γ-glycidoxypropyltrimethoxydecane.
於專利文獻4中記載有一種光觸媒塗膜形成用塗料，其含有具有紫外線聚合性官能基之矽烷偶合劑、及光聚合起始劑。 Patent Document 4 describes a coating material for forming a photocatalyst coating film, which comprises a decane coupling agent having an ultraviolet polymerizable functional group and a photopolymerization initiator.
於專利文獻5中記載有一種有機無機複合體，其含有氧化鈦奈米粒子、包含3-甲基丙烯醯基氧丙基三甲基矽烷或3-縮水甘油氧基丙基三甲氧基矽烷等之矽烷化合物之縮合物、以及其他功能性物質(光觸媒性氧化鈦等)。 Patent Document 5 describes an organic-inorganic composite containing titanium oxide nanoparticles, including 3-methylpropenyloxypropyltrimethylnonane or 3-glycidoxypropyltrimethoxydecane. a condensate of a decane compound, and other functional substances (photocatalytic titanium oxide, etc.).
於專利文獻6中記載有一種塗膜，其係塗布塗膜形成劑並藉由紫外線使其硬化而成，上述塗膜形成劑含有包含氧化鈦之光觸媒、四官能性矽烷化合物，以及進而視情形之環氧系或丙烯酸系矽烷偶合劑，且記載有：若塗膜形成劑進而含有金屬烷氧化物，則可抑制由撥水性粒子之凝縮所引起的塗膜之白濁。 Patent Document 6 discloses a coating film which is obtained by applying a coating film forming agent and curing it by ultraviolet rays, and the coating film forming agent contains a photocatalyst containing titanium oxide, a tetrafunctional decane compound, and, as the case may be, In the epoxy-based or acryl-based decane coupling agent, it is described that when the coating film forming agent further contains a metal alkoxide, white turbidity of the coating film due to condensation of the water-repellent particles can be suppressed.
[專利文獻1]日本專利特開2004-67947號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-67947
[專利文獻2]日本專利特開2000-225663號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2000-225663
[專利文獻3]日本專利特開2000-169755號公報 [Patent Document 3] Japanese Patent Laid-Open Publication No. 2000-169755
[專利文獻4]日本專利特開2010-43188號公報 [Patent Document 4] Japanese Patent Laid-Open Publication No. 2010-43188
[專利文獻5]日本專利特開2007-332262號公報 [Patent Document 5] Japanese Patent Laid-Open Publication No. 2007-332262
[專利文獻6]日本專利特開2014-237120號公報 [Patent Document 6] Japanese Patent Laid-Open Publication No. 2014-237120
對於藉由專利文獻3~6之各方法直接塗布於基材上而獲得之塗膜而言，雖可獲得某種程度之強度，但對有機基材引起由紫外線照射 所致之白化的情況作為問題而遺留，尤其兼顧光觸媒活性與防止白化被視為課題。本案發明之目的在於提供一種發揮充分之光觸媒活性、且不對基材引起劣化之光觸媒承載構造體。 The coating film obtained by directly applying to the substrate by each of the methods of Patent Documents 3 to 6 can obtain a certain degree of strength, but causes ultraviolet irradiation on the organic substrate. The whitening caused by the problem remains, especially considering the photocatalytic activity and preventing whitening. An object of the present invention is to provide a photocatalyst-carrying structure which exhibits sufficient photocatalytic activity and which does not deteriorate the substrate.
本發明者等人發現，藉由使用如下塗布液作為含有光觸媒之塗布液而直接塗布於基材上，可獲得解決上述問題之光觸媒承載構造體，進而為了解決上述問題而進行銳意研究，結果完成了本發明，上述塗布液含有作為環氧矽烷偶合劑或丙烯酸矽烷偶合劑之矽烷偶合劑、以及不具有矽作為中心金屬之金屬偶合劑，且不含有上述矽烷偶合劑以外之矽烷化合物。 The inventors of the present invention have found that a photocatalyst-bearing structure for solving the above problems can be obtained by directly applying the coating liquid as a coating liquid containing a photocatalyst to a substrate, and further research is carried out to solve the above problems, and the result is completed. In the present invention, the coating liquid contains a decane coupling agent as an epoxy decane coupling agent or a decane coupling agent, and a metal coupling agent having no ruthenium as a center metal, and does not contain a decane compound other than the decane coupling agent.
即，本發明係關於：(1)一種含有光觸媒之塗布液，其含有光觸媒材料粒子、作為選自環氧矽烷偶合劑及丙烯酸矽烷偶合劑中之至少1種的矽烷偶合劑及/或該矽烷偶合劑之水解縮合物、不具有矽作為金屬元素之金屬偶合劑、以及溶劑，且相對於光觸媒材料粒子100質量份，以300質量份以上之比率合計含有上述矽烷偶合劑及該矽烷偶合劑之水解縮合物；(2)如(1)所記載之含有光觸媒之塗布液，其不含上述矽烷偶合劑以外之矽烷化合物；(3)如(1)或(2)所記載之含有光觸媒之塗布液，其進而含有粒子二氧化矽；(4)如(1)或(2)所記載之含有光觸媒之塗布液，其中不具有矽作為金屬元素之金屬偶合劑係選自鈦酸酯(titanate)系偶合劑、鋁酸酯(aluminate)系偶合劑及鋯酸酯(zirconate)系偶合劑中之至少1種；(5)如(1)或(2)所記載之含有光觸媒之塗布液，其中光觸媒材料含有二氧化鈦；(6)如(1)或(2)所記載之含有光觸媒之塗布液，其含有丙烯酸矽烷 偶合劑作為矽烷偶合劑，進而含有光聚合起始劑；及(7)如(1)或(2)所記載之含有光觸媒之塗布液，其含有環氧矽烷偶合劑之水解縮合物作為矽烷偶合劑之水解縮合物，且金屬偶合劑為鋁酸酯系偶合劑。 That is, the present invention relates to: (1) a photocatalyst-containing coating liquid containing photocatalyst material particles, at least one decane coupling agent selected from the group consisting of an epoxy decane coupling agent and an acrylonitrile coupling agent, and/or the decane a hydrolyzed condensate of a coupling agent, a metal coupling agent which does not have ruthenium as a metal element, and a solvent, and the decane coupling agent and the decane coupling agent are contained in total of 300 parts by mass or more based on 100 parts by mass of the photocatalyst material particles. (2) The photocatalyst-containing coating liquid according to (1), which does not contain a decane compound other than the decane coupling agent; (3) the photocatalyst-containing coating described in (1) or (2) And a coating agent containing a photocatalyst as described in (1) or (2), wherein the metal coupling agent having no antimony as a metal element is selected from the group consisting of titanate. At least one of a coupling agent, an aluminate coupling agent, and a zirconate coupling agent; (5) a photocatalyst-containing coating liquid according to (1) or (2), wherein Photocatalyst material contains titanium dioxide; (6 a coating liquid containing a photocatalyst as described in (1) or (2), which contains decane acrylate The coupling agent as a decane coupling agent further contains a photopolymerization initiator; and (7) the photocatalyst-containing coating liquid according to (1) or (2), which contains a hydrolysis condensate of an epoxy decane coupling agent as a decane coupler A hydrolysis condensate of the mixture, and the metal coupling agent is an aluminate coupling agent.
又，本發明係關於：(8)一種光觸媒承載構造體，其係於基材上塗布如(1)至(7)中任一項所記載之含有光觸媒之塗布液並使其乾燥而成的將光觸媒層直接設於基材上者；(9)如(8)所記載之光觸媒承載構造體，其中基材為有機材料；及(10)如(9)所記載之光觸媒承載構造體，其中有機材料為合成樹脂。 Further, the present invention relates to a (8) photocatalyst-bearing structure which is obtained by applying and drying a coating liquid containing a photocatalyst according to any one of (1) to (7) on a substrate. (10) The photocatalyst-bearing structure according to (8), wherein the substrate is an organic material; and (10) the photocatalyst-bearing structure according to (9), wherein The organic material is a synthetic resin.
進而，本發明係關於：(11)一種形成光觸媒承載構造體之方法，其係將如(1)至(7)中任一項所記載之含有光觸媒之塗布液直接塗布於基材上並使其乾燥，藉此形成光觸媒承載構造體。 Further, the present invention relates to a method of forming a photocatalyst-bearing structure according to any one of (1) to (7), wherein the coating liquid containing a photocatalyst as described in any one of (1) to (7) is directly applied to a substrate. It is dried, thereby forming a photocatalyst-bearing structure.
本發明之光觸媒承載構造體發揮充分之光觸媒活性、且與基材之密接性優異，而且不會對基材引起白化等劣化。 The photocatalyst-carrying structure of the present invention exhibits sufficient photocatalytic activity and is excellent in adhesion to a substrate, and does not cause whitening or the like on the substrate.
圖1係表示使用KBM-403(環氧矽烷偶合劑)之情形的本發明之光觸媒承載構造體之抗病毒性之圖表。 Fig. 1 is a graph showing the antiviral properties of the photocatalyst-loaded structure of the present invention in the case of using KBM-403 (epoxydecane coupling agent).
圖2係表示使用KBM-5103(丙烯酸矽烷偶合劑)之情形的本發明之光觸媒承載構造體之抗病毒性之圖表。 Fig. 2 is a graph showing the antiviral properties of the photocatalyst-carrying structure of the present invention in the case of using KBM-5103 (an decane coupling agent).
本發明之含有光觸媒之塗布液係含有光觸媒材料粒子、溶劑、作為選自環氧矽烷偶合劑及丙烯酸矽烷偶合劑中之至少1種的矽烷偶 合劑及/或該矽烷偶合劑之水解縮合物、不具有矽作為中心金屬元素之金屬偶合劑、以及溶劑之液狀組合物。 The photocatalyst-containing coating liquid of the present invention contains photocatalyst material particles, a solvent, and at least one selected from the group consisting of an epoxy decane coupling agent and an acrylonitrile coupling agent. A mixture and/or a hydrolysis-condensation product of the decane coupling agent, a metal coupling agent having no ruthenium as a central metal element, and a liquid composition of a solvent.
本發明之含有光觸媒之塗布液中所使用之光觸媒材料粒子為包含無機材料之粒子，上述無機材料含有具有光觸媒活性之金屬氧化物等。 The photocatalyst material particles used in the photocatalyst-containing coating liquid of the present invention are particles containing an inorganic material, and the inorganic material contains a metal oxide having photocatalytic activity.
作為光觸媒材料之主成分，可列舉氧化鈦、氧化鋅、氧化錫、氧化鋯、氧化鎢、氧化鉻、氧化鉬、氧化鐵、氧化鎳、氧化釕、氧化釩、氧化鈮、氧化鉭、氧化銠、氧化錸等。該等中，較佳為氧化鈦、氧化鎢等，尤佳為銳鈦礦型或金紅石型氧化鈦。 Examples of the main component of the photocatalyst material include titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, iron oxide, nickel oxide, cerium oxide, vanadium oxide, cerium oxide, cerium oxide, and cerium oxide. , yttrium oxide, etc. Among these, titanium oxide, tungsten oxide, etc. are preferable, and an anatase type or rutile type titanium oxide is especially preferable.
又，亦可使用於該等中添加有Pt、Rh、Ru、Nb、Cu、Sn、Ni、Fe、Ag等金屬或該等之氧化物者。 Further, a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe, or Ag or an oxide thereof may be added thereto.
尤其是承載有CuO之金紅石型氧化鈦，不僅響應紫外線而且亦響應可見光而發揮光觸媒功能，故而較佳。 In particular, rutile-type titanium oxide carrying CuO is preferred not only in response to ultraviolet rays but also in photocatalytic function in response to visible light.
光觸媒材料粒子之粒徑並無特別限定，尤其於併用二氧化矽等金屬氧化物作為填料之情形時，就發揮充分之光觸媒活性之意義而言，較佳為具有較填料之平均粒徑更大之平均粒徑，更佳為平均粒徑為40~500nm。 The particle diameter of the photocatalyst material particles is not particularly limited, and in particular, when a metal oxide such as cerium oxide is used as a filler in combination, it is preferable to have a larger average particle diameter than the filler in the sense of exhibiting sufficient photocatalytic activity. The average particle diameter is more preferably an average particle diameter of 40 to 500 nm.
作為本發明之含有光觸媒之塗布液中所使用之矽烷偶合劑，可使用通式：R1Si(X)3、R1(R2)Si(X)2、或R1(R2)2SiX(其中於各式中，R1表示具有直接鍵結於Si所表示之矽原子上之碳原子、以及選自環氧基及(甲基)丙烯醯氧基中之至少1種官能基的有機基，R2表示非水解性之有機基，X表示氟原子、氯原子、溴原子、碘原子等鹵素原子、烷氧基、苯氧基、或醯氧基。於R2所表示之基或X所表示之基有2個以上之情形時，R2或X可分別相同亦可互不相同)所表示者。 As the decane coupling agent used in the photocatalyst-containing coating liquid of the present invention, a general formula: R 1 Si(X) 3 , R 1 (R 2 )Si(X) 2 , or R 1 (R 2 ) 2 can be used. SiX (wherein, in each formula, R 1 represents a carbon atom directly bonded to a ruthenium atom represented by Si, and at least one functional group selected from the group consisting of an epoxy group and a (meth) propylene fluorenyloxy group; an organic group, R 2 represents the non-hydrolyzable organic group, X represents a halogen atom such as fluorine atom, chlorine atom, bromine atom, iodine atom, an alkoxy group, a phenoxy group, or acyl group. R 2 in the group represented by Or when the base represented by X has two or more cases, R 2 or X may be the same or different from each other.
此處，將R1具有環氧基之矽烷偶合劑稱為環氧矽烷偶合劑，將R1具有(甲基)丙烯醯氧基之矽烷偶合劑稱為丙烯酸矽烷偶合劑。 Here, the decane coupling agent in which R 1 has an epoxy group is referred to as an epoxy decane coupling agent, and the decane coupling agent in which R 1 has a (meth) acryloxy group is referred to as a decane coupling agent.
上述R1係於可具有取代基及/或-O-基之烷基等有機基上具有環氧基或(甲基)丙烯醯氧基之基，具體而言，可例示γ-縮水甘油氧基丙基、β-(3,4-環氧基環己基)乙基、γ-丙烯醯氧基丙基、γ-甲基丙烯醯氧基丙基等，作為上述R2，可例示甲基、乙基等C1~C5之烷基、以及作為上述R1而例示之有機基等，作為上述X，除氯原子外，可例示甲氧基、乙氧基、β-甲氧基乙氧基等C1~C5之烷氧基，甲醯氧基、乙醯氧基、丙醯氧基等C1~C6之醯氧基等。 R 1 is a group having an epoxy group or a (meth) acryloxy group on an organic group such as an alkyl group which may have a substituent and/or an —O- group, and specifically, γ-glycidyloxy is exemplified. a propyl group, a β-(3,4-epoxycyclohexyl)ethyl group, a γ-propyleneoxypropyl group, a γ-methacryloxypropyl group, etc., as the above R 2 , a methyl group can be exemplified The alkyl group of C1 to C5 such as an ethyl group, and the organic group exemplified as the above R 1 , and the above X, in addition to the chlorine atom, may be exemplified by a methoxy group, an ethoxy group, or a β-methoxyethoxy group. The C1-C5 alkoxy group such as a C1-C5 alkoxy group, a C1-C6 methoxy group such as a methyl methoxy group, an ethoxy group or a propyl oxy group.
本發明之含有光觸媒之塗布液中所使用之矽烷偶合劑尤佳為通式：R1Si(OR3)3(式中，R1表示與上述相同者，R3表示C1~C3烷基，R3可相同亦可互不相同)所表示之化合物。 The decane coupling agent used in the photocatalyst-containing coating liquid of the present invention is preferably a formula: R 1 Si(OR 3 ) 3 (wherein R 1 represents the same as defined above, and R 3 represents a C1 to C3 alkyl group, R 3 may be the same or different from each other).
又，本發明之含有光觸媒之塗布液中，較佳為僅含有至少1種之環氧矽烷偶合劑或其水解縮合物、以及至少1種之丙烯酸矽烷偶合劑或其水解縮合物中之任一方。 Further, in the coating liquid containing a photocatalyst of the present invention, it is preferred to contain at least one of an epoxy decane coupling agent or a hydrolysis-condensation product thereof, and at least one of a decyl coupling agent or a hydrolysis condensate thereof. .
本發明之含有光觸媒之塗布液中，較佳為不含上述矽烷偶合劑以外之矽烷化合物。藉此可進一步提高硬塗性。 In the coating liquid containing a photocatalyst of the present invention, it is preferred that the decane compound other than the above decane coupling agent is not contained. Thereby, the hard coat property can be further improved.
作為上述矽烷偶合劑以外之矽烷化合物，可列舉通式：Si(X)4、R4Si(X)3、(R4)2Si(X)2、(R4)3SiX、該等之縮合物、或(R4)4Si(其中於各式中，R4為非水解性，且表示不具有環氧基、丙烯醯氧基及甲基丙烯醯氧基中之任一者之有機基，於R4所表示之基有2個以上之情形時，R4可相同亦可互不相同。X表示與上述相同者)所表示者，更具體而言，可例示不與有機物反應之二烷氧基二烷基矽烷、二烷氧基二苯基矽烷、三烷氧基烷基矽烷、三烷氧基苯基矽烷、四烷氧基矽烷、四苯氧基矽烷等化合物。 Examples of the decane compound other than the above decane coupling agent include Si(X) 4 , R 4 Si(X) 3 , (R 4 ) 2 Si(X) 2 , (R 4 ) 3 SiX, and the like. a condensate or (R 4 ) 4 Si (wherein R 4 is non-hydrolyzable in each formula, and represents an organic group having no epoxy group, acryloxy group, or methacryloxy group) when the group represented by R 4 in the group has two or more of the case, may be identical or different R 4 represents the same as those indicated above) by the same .X, and more specifically, the reaction may be exemplified with no organic A compound such as a dialkoxydialkylnonane, a dialkoxydiphenylnonane, a trialkoxyalkylnonane, a trialkoxyphenylnonane, a tetraalkoxydecane or a tetraphenoxydecane.
本發明之含有光觸媒之塗布液中所含之矽烷偶合劑可藉由水解縮合而提高塗膜之強度。 The decane coupling agent contained in the photocatalyst-containing coating liquid of the present invention can increase the strength of the coating film by hydrolysis condensation.
尤其於使用環氧系矽烷偶合劑作為矽烷偶合劑之情形時，較佳 為將矽烷偶合劑水解縮合後與其他成分混合。於此情形時，作為後述金屬偶合劑，較佳為使用鋁酸酯系偶合劑。於使用鈦酸酯系偶合劑或鋯酸酯系偶合劑之情形時，存在以下情況：若存在水則該等發生水解，反而由金屬偶合劑所得之塗膜強化效果反而受損。 Particularly when an epoxy decane coupling agent is used as the decane coupling agent, it is preferably In order to hydrolyze and condense the decane coupling agent, it is mixed with other components. In this case, as the metal coupling agent to be described later, an aluminate coupling agent is preferably used. When a titanate coupling agent or a zirconate coupling agent is used, there is a case where hydrolysis occurs in the presence of water, and the coating film strengthening effect by the metal coupling agent is adversely affected.
又，本發明之含有光觸媒之塗布液中，於使用丙烯酸矽烷偶合劑作為矽烷偶合劑之情形時，較佳為進而含有光聚合起始劑。光聚合起始劑只要為可於照射紫外線時於(甲基)丙烯醯氧基間引發聚合反應之化合物即可。藉此可促進丙烯酸矽烷偶合劑之聚合，提高塗膜之強度。 Further, in the case where the photocatalyst-containing coating liquid of the present invention is a decane coupling agent as a decane coupling agent, it is preferred to further contain a photopolymerization initiator. The photopolymerization initiator may be any compound which initiates a polymerization reaction between (meth) propylene methoxy groups when irradiated with ultraviolet rays. Thereby, the polymerization of the decane coupling agent can be promoted, and the strength of the coating film can be improved.
作為光聚合起始劑，具體而言可列舉：藉由紫外線之照射而產生自由基，以該自由基作為聚合之契機之安息香衍生物等。尤佳為作為烷基苯酮系光聚合起始劑之Irgacure(註冊商標)651、184、907、369、379(BASF公司製造)等。 Specific examples of the photopolymerization initiator include a radical generated by irradiation of ultraviolet rays, and a benzoin derivative or the like which is a polymerization initiator. In particular, it is Irgacure (registered trademark) 651, 184, 907, 369, 379 (manufactured by BASF Corporation) which is an alkylbenzene ketone photopolymerization initiator.
所謂本發明之光觸媒塗布液中所使用之不含有矽作為金屬元素之金屬偶合劑，係指具有水解性基、藉此進行交聯反應之金屬化合物。更具體而言，可列舉配位基配位於金屬元素上而成之金屬錯合物、烷氧基鍵結於金屬元素而成之金屬醇鹽之任一者(亦包含分類為兩者之化合物)。 The metal coupling agent which does not contain ruthenium as a metal element used for the photocatalyst coating liquid of this invention is a metal compound which has a hydrolysable group and carries out a crosslinking reaction. More specifically, any one of a metal complex formed by a ligand grouped on a metal element and a metal alkoxide in which an alkoxy group is bonded to a metal element (including a compound classified as both) ).
其中，較佳為鈦酸酯系偶合劑、鋁酸酯系偶合劑及鋯酸酯系偶合劑。 Among them, a titanate coupling agent, an aluminate coupling agent, and a zirconate coupling agent are preferable.
作為鈦酸酯系偶合劑，例如有鈦酸四異丙酯、鈦酸四正丁酯、四(2-乙基己氧基)鈦、異丙氧基丁二醇鈦等烷氧化鈦；乙醯丙酮鈦、四乙醯丙酮鈦、二-異丙氧基-雙(乙醯丙酮)鈦、二-正丙氧基-雙(乙醯丙酮)鈦、二-正丁氧基-雙(乙醯丙酮)鈦、二乙氧基-雙(乙醯丙酮)鈦、丙烷二氧鈦雙(乙醯乙酸乙酯)等鈦錯合物等。 Examples of the titanate coupling agent include a titanium alkoxide such as tetraisopropyl titanate, tetra-n-butyl titanate, titanium tetrakis(2-ethylhexyloxy), or titanium isopropoxybutylene;醯Acetone titanium, titanium tetraacetate, titanium di-isopropoxy-bis(acetonitrile) titanium, di-n-propoxy-bis(acetonitrile) titanium, di-n-butoxy-double (B Acetone, a titanium complex such as titanium, diethoxy-bis(acetonitrile) titanium, or propane dioxy titanium bis(acetic acid ethyl acetate).
作為鋁酸酯系偶合劑，例如有異丙醇鋁、單-第二丁氧基鋁二異 丙酯、乙醇鋁等鋁醇鹽；乙醯乙酸乙基鋁二異丙酯、雙乙醯乙酸乙基-單乙醯丙酮鋁、三(乙醯乙酸乙酯)鋁、三(乙醯丙酮)鋁、二乙氧基單(乙醯丙酮)鋁、二-異丙氧基單(乙醯丙酮)鋁、二-正丙氧基單(乙醯丙酮)鋁、二-正丁氧基單(乙醯丙酮)鋁、乙氧基雙(乙醯丙酮)鋁、異丙氧基雙(乙醯丙酮)鋁、正丙氧基雙(乙醯丙酮)鋁、正丁氧基雙(乙醯丙酮)鋁等鋁錯合物；環狀鋁低聚物等。 As the aluminate coupling agent, for example, aluminum isopropoxide and mono-second butoxy aluminum diamide Aluminum alkoxides such as propyl ester and aluminum ethoxide; ethyl aluminum diisopropyl ester of acetamidineacetate, ethyl acetoacetate, ethyl acetoacetate, aluminum tris(ethyl acetate), and tris(acetonitrile) Aluminum, diethoxy mono(acetonitrile)aluminum, di-isopropoxy mono(acetonitrile)aluminum, di-n-propoxymono(acetonitrile)aluminum, di-n-butoxy single ( Acetylacetone) aluminum, ethoxybis(acetamidineacetone)aluminum, isopropoxybis(acetonitrile)aluminum, n-propoxybis(acetamidineacetone)aluminum, n-butoxybis(acetamidineacetone) Aluminum complexes such as aluminum; cyclic aluminum oligomers, and the like.
作為鋯酸酯系偶合劑，有四(乙醯丙酮)鋯、二-正丁氧基雙(乙醯丙酮)鋯、四(乙醯乙酸乙酯)鋯、二乙氧基雙乙醯丙酮鋯、二-異丙氧基雙(乙醯丙酮)鋯、二-正丙氧基雙(乙醯丙酮)鋯、三-正丁氧基單乙醯乙酸乙酯鋯、三-正丁氧基單乙醯丙酮鋯等。 As the zirconate coupling agent, there are tetrakis(acetonitrile)zirconium, di-n-butoxybis(acetonitrile)zirconium, tetrakis(acetateacetate)zirconium, diethoxybisacetamidinezincacetate , di-isopropoxy bis(acetonitrile)zirconium, di-n-propoxy bis(acetonitrile)zirconium, tri-n-butoxymonoethyl hydrazide ethyl acetate zirconium, tri-n-butoxy single Acetylacetone zirconium and the like.
作為乙醯丙酮酸鹽系偶合劑，可列舉上述鈦酸酯系偶合劑、鋁酸酯系偶合劑、及鋯酸酯系偶合劑中為乙醯丙酮酸鹽系偶合劑者。 Examples of the acetamyl pyruvate-based coupling agent include those of the above-described titanate coupling agent, aluminate coupling agent, and zirconate coupling agent.
本發明之含有光觸媒之塗布液中含有溶劑。溶劑並無特別限定，例如可列舉：水；甲醇、乙醇、丙醇、異丙醇、丁醇、第三丁醇等醇類；丙酮、甲基乙基酮、甲基異丁基酮、乙醯丙酮、環己酮等酮類；二乙醚、甲基賽路蘇、四氫呋喃等醚類；苯、甲苯、二甲苯等芳香族烴；二氯甲烷、氯仿等鹵化烴；乙酸乙酯、乙酸丙酯、乙酸丁酯等酯類；戊烷、己烷、環己烷等飽和烴等。又，亦可將該等之2種以上混合使用。該等中，特佳為醇類。 The photocatalyst-containing coating liquid of the present invention contains a solvent. The solvent is not particularly limited, and examples thereof include water; alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and butanol; acetone, methyl ethyl ketone, methyl isobutyl ketone, and ethyl Ketones such as acetone and cyclohexanone; ethers such as diethyl ether, methyl sarbuta and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; Esters such as esters and butyl acetate; saturated hydrocarbons such as pentane, hexane and cyclohexane. Further, two or more kinds of these may be used in combination. Among these, it is particularly preferred to be an alcohol.
本發明之含有光觸媒之塗布液中，除上述各成分外，可於不損及本發明之效果之範圍內任意調配成膜助劑、增黏劑、消泡劑、顏料、填料、分散劑、染料、防腐劑等。 In the coating liquid containing a photocatalyst according to the present invention, in addition to the above components, a filming aid, a tackifier, an antifoaming agent, a pigment, a filler, a dispersing agent, and the like may be optionally disposed within a range that does not impair the effects of the present invention. Dyes, preservatives, etc.
尤其藉由使用包含粒子之金屬氧化物作為填料，可獲得提高耐光性等效果。 In particular, by using a metal oxide containing particles as a filler, effects such as improvement in light resistance can be obtained.
作為用作填料之金屬氧化物，可列舉含有鎂、鋁、矽、鈦、釩、鐵、鎳、銅、鋅、釔、鋯、鈮、鉬、釕、銦、錫、銻、鉭、鎢、 鈰等元素之氧化物(其中光觸媒材料除外)。 Examples of the metal oxide used as the filler include magnesium, aluminum, lanthanum, titanium, vanadium, iron, nickel, copper, zinc, lanthanum, zirconium, hafnium, molybdenum, niobium, indium, tin, antimony, bismuth, and tungsten. An oxide of an element such as ruthenium (except photocatalyst material).
本發明之含有光觸媒之塗布液中，尤佳為含有粒子二氧化矽。藉此可提高防白化效果。可認為其原因在於：二氧化矽覆蓋光觸媒粒子表面，光觸媒對有機成分之攻擊得到緩和。作為粒子二氧化矽，較佳為平均粒徑為100nm。又，作為粒子二氧化矽之形狀，較佳為球狀二氧化矽粒子、或球狀二氧化矽粒子結合成細長形狀而成之粒子(其整體之平均粒徑較佳為100nm以下)。此處所述之球狀二氧化矽粒子之平均粒徑較佳為40nm以下，更佳為5~20nm。若平均粒徑大於100nm，則對由鋼絲絨或指甲之摩擦之耐受性欠佳。 In the coating liquid containing a photocatalyst of the present invention, it is particularly preferred to contain particulate cerium oxide. Thereby, the anti-whitening effect can be improved. The reason is considered to be that the cerium oxide covers the surface of the photocatalyst particles, and the attack of the photocatalyst on the organic component is alleviated. As the particulate cerium oxide, the average particle diameter is preferably 100 nm. Moreover, as the shape of the particulate cerium oxide, particles in which spherical cerium oxide particles or spherical cerium oxide particles are combined into an elongated shape (the average particle diameter of the whole is preferably 100 nm or less) is preferable. The spherical cerium oxide particles described herein preferably have an average particle diameter of 40 nm or less, more preferably 5 to 20 nm. If the average particle diameter is more than 100 nm, the resistance to friction by steel wool or nails is poor.
對於本發明之含有光觸媒之塗布液而言，相對於光觸媒材料粒子100質量份，以300質量份以上之比率合計含有上述矽烷偶合劑及該矽烷偶合劑之水解縮合物。更佳為以300~1000質量份之比率合計含有上述矽烷偶合劑及該矽烷偶合劑之水解縮合物。 In the coating liquid containing the photocatalyst of the present invention, the decane coupling agent and the hydrolysis condensate of the decane coupling agent are added in total at a ratio of 300 parts by mass or more based on 100 parts by mass of the photocatalyst material particles. More preferably, the hydrolyzed condensate containing the above decane coupling agent and the decane coupling agent is added in a total amount of 300 to 1000 parts by mass.
又，較佳為相對於光觸媒100質量份，以下述比率含有其他成分。 Moreover, it is preferable to contain other components in the following ratio with respect to 100 mass parts of photocatalyst.
金屬偶合劑：20質量份以上，更佳為50~300質量份。 Metal coupling agent: 20 parts by mass or more, more preferably 50 to 300 parts by mass.
包含金屬氧化物之填料、較佳為粒子二氧化矽：0~400質量份，更佳為50~400質量份。 The filler containing a metal oxide, preferably particulate cerium oxide: 0 to 400 parts by mass, more preferably 50 to 400 parts by mass.
又，本發明之含有光觸媒之塗布液較佳為以固形物成分中之質量%計而含有以下成分：0.5~20質量%之光觸媒；合計為5~80質量%、更佳為20~80質量%之矽烷偶合劑及/或矽烷偶合劑之水解縮合物；2~60質量%、更佳為2~30質量%之金屬偶合劑；0~40質量%、更佳為1~20質量%之包含金屬氧化物之填料、較佳為粒子二氧化矽。 Further, the photocatalyst-containing coating liquid of the present invention preferably contains the following components: 0.5 to 20% by mass of the photocatalyst in terms of % by mass of the solid content; a total of 5 to 80% by mass, more preferably 20 to 80% by mass Hydrolysis condensate of % decane coupling agent and/or decane coupling agent; metal coupling agent of 2 to 60% by mass, more preferably 2 to 30% by mass; 0 to 40% by mass, more preferably 1 to 20% by mass A filler comprising a metal oxide, preferably particulate cerium oxide.
本發明之光觸媒承載構造體係將本發明之含有光觸媒之塗布液塗布於基材上並進行乾燥而成之光觸媒層直接接觸於基材之光觸媒承 載構造體。 In the photocatalyst-bearing structure system of the present invention, the photocatalyst-containing coating liquid of the present invention is coated on a substrate and dried to form a photocatalyst layer directly contacting the photocatalyst carrier of the substrate. Carrier structure.
基材並無特別限定，作為無機材料，可例示金屬、玻璃、陶瓷、水泥等，作為有機材料，可例示：木材；紙；天然纖維；橡膠；皮革；聚乙烯、聚丙烯、丙烯酸系樹脂、聚對苯二甲酸乙二酯、聚氯乙烯、聚偏二氯乙烯、聚碳酸酯、聚苯乙烯、丙烯腈-丁二烯-苯乙烯樹脂、酚樹脂、尿素樹脂、聚胺基甲酸酯、環氧樹脂、三聚氰胺樹脂等合成樹脂等。 The substrate is not particularly limited, and examples of the inorganic material include metal, glass, ceramics, and cement. Examples of the organic material include wood; paper; natural fiber; rubber; leather; polyethylene, polypropylene, and acrylic resin. Polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, polycarbonate, polystyrene, acrylonitrile-butadiene-styrene resin, phenol resin, urea resin, polyurethane , synthetic resins such as epoxy resin and melamine resin.
其中，較佳為先前難以直接設置光觸媒層之有機材料，其中亦較佳為合成樹脂。 Among them, an organic material which is previously difficult to directly provide a photocatalyst layer is preferable, and a synthetic resin is also preferable.
較佳為對於合成樹脂之光觸媒層接觸之表面，於塗布含有光觸媒之塗布液之前實施易接著處理。作為該易接著處理，例如可列舉對表面實施電暈放電處理、或UV-臭氧處理之方法。 It is preferred that the surface which is in contact with the photocatalyst layer of the synthetic resin is subjected to an easy subsequent treatment before application of the coating liquid containing the photocatalyst. As the easy-to-treat treatment, for example, a method of performing corona discharge treatment or UV-ozone treatment on the surface can be mentioned.
將本發明之含有光觸媒之塗布液塗布於基材上之方法並無特別限定，只要藉由噴塗法、流塗法、旋轉塗布法、絲棒法、浸塗法、輥塗法等公知之方法以特定之塗布量塗布後進行乾燥，以特定之厚度形成光觸媒層即可。 The method of applying the photocatalyst-containing coating liquid of the present invention to a substrate is not particularly limited, and may be any known method such as a spray coating method, a flow coating method, a spin coating method, a wire bar method, a dip coating method, or a roll coating method. After coating with a specific coating amount, it is dried to form a photocatalyst layer with a specific thickness.
本發明之光觸媒承載構造體中之光觸媒層之厚度並無特別限定，乾燥後之厚度通常為0.01~10μm，更佳為0.5~5.0μm。 The thickness of the photocatalyst layer in the photocatalyst-bearing structure of the present invention is not particularly limited, and the thickness after drying is usually 0.01 to 10 μm, more preferably 0.5 to 5.0 μm.
於本發明之含有光觸媒之塗布液含有丙烯酸矽烷偶合劑及光聚合起始劑之情形時，較佳為於上述乾燥步驟後進而照射紫外線，更佳為該紫外線包含350nm以下之波長。 In the case where the photocatalyst-containing coating liquid of the present invention contains a decane coupling agent and a photopolymerization initiator, it is preferred to further irradiate ultraviolet rays after the drying step, and it is more preferable that the ultraviolet rays have a wavelength of 350 nm or less.
該紫外線照射中，可使用超高壓水銀燈、高壓水銀燈、低壓水銀燈、金屬鹵化物燈、準分子燈、碳弧燈、氙弧燈等裝置。又，作為紫外線照射量，較佳為0.1~100J/cm2。 In the ultraviolet irradiation, an apparatus such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an excimer lamp, a carbon arc lamp, a xenon arc lamp, or the like can be used. Further, the amount of ultraviolet irradiation is preferably 0.1 to 100 J/cm 2 .
以下，示出本發明之實施例，但本發明之技術範圍並不限定於 此。 Hereinafter, embodiments of the present invention are shown, but the technical scope of the present invention is not limited to this.
使60g(100質量份)之金紅石型氧化鈦A(昭和電工陶瓷公司製造，金紅石化率95.9莫耳%)懸浮於蒸餾水1000g中，進而添加4.979g(以銅換算計為3.0質量份)之CuCl2‧2H2O(關東化學股份有限公司製造)，攪拌10分鐘。以pH值成為10之方式添加1mol/L之氫氧化鈉(關東化學公司製造)水溶液，進行30分鐘之攪拌混合而獲得漿料。 60 g (100 parts by mass) of rutile-type titanium oxide A (manufactured by Showa Denko Ceramics Co., Ltd., 92.9 mol% of the product) was suspended in 1000 g of distilled water, and 4.979 g (3.0 parts by mass in terms of copper) was further added. CuCl 2 ‧2H 2 O (manufactured by Kanto Chemical Co., Ltd.) was stirred for 10 minutes. An aqueous solution of 1 mol/L sodium hydroxide (manufactured by Kanto Chemical Co., Ltd.) was added thereto at a pH of 10, and the mixture was stirred and mixed for 30 minutes to obtain a slurry.
將該漿料過濾，以純水將所獲得之固形物成分洗淨，於80℃下乾燥，以攪拌器粉碎。將該粉碎物於大氣中於450℃下熱處理3小時，獲得試樣1。 The slurry was filtered, and the obtained solid component was washed with pure water, dried at 80 ° C, and pulverized with a stirrer. The pulverized material was heat-treated at 450 ° C for 3 hours in the atmosphere to obtain Sample 1.
再者，將該試樣1於氫氟酸溶液中進行加熱而使其完全溶解，藉由ICP發射光譜分析(inductively coupled plasma-atomic emission spectrometry，感應耦合電漿發射光譜分析)對萃取液進行定量，結果相對於氧化鈦100質量份，銅離子為3.0質量份。即，所加入之銅離子(來自CuCl2‧2H2O)之總量作為CuO而承載於氧化鈦表面。又，試樣1之平均粒徑為約150nm。 Further, the sample 1 was heated in a hydrofluoric acid solution to be completely dissolved, and the extract was quantified by inductively coupled plasma-atomic emission spectrometry (inductively coupled plasma emission spectrometry). As a result, the copper ion was 3.0 parts by mass based on 100 parts by mass of the titanium oxide. That is, the total amount of copper ions (from CuCl 2 ‧2H 2 O) added is carried as CuO on the surface of the titanium oxide. Further, the average particle diameter of the sample 1 was about 150 nm.
於異丙醇中添加一定量之試樣1使其懸浮，製成固形物成分含量0.25~5.0質量%之光觸媒懸浮液。 A certain amount of the sample 1 was added to isopropyl alcohol to suspend it to prepare a photocatalyst suspension having a solid content of 0.25 to 5.0% by mass.
(金屬偶合劑之效果) (effect of metal coupling agent)
於製造例1中所獲得之固形物成分含量為0.25質量%(實施例1)、0.5質量%(實施例2)、1.0質量%(實施例3)、2.5質量%(實施例4)、或5.0質量%(比較例1)之光觸媒懸浮液21.67g中，添加KBM-5103(γ-丙烯醯氧基丙基三甲氧基矽烷，信越矽酮公司製造)2.27g並攪拌5分鐘，添加T-50(二-異丙氧基-雙(乙醯丙酮)鈦，日本曹達公司製造)0.86g並 攪拌5分鐘，進而添加Irgacure(註冊商標)907(光聚合起始劑2-甲基-1-[4-(甲硫基)苯基]-2-嗎啉基-丙烷-1-酮，BASF公司製造)0.23g並攪拌5分鐘，獲得光觸媒塗布液。 The content of the solid content obtained in Production Example 1 was 0.25 mass% (Example 1), 0.5% by mass (Example 2), 1.0% by mass (Example 3), 2.5% by mass (Example 4), or To 21.67 g of a photocatalyst suspension of 5.0% by mass (Comparative Example 1), 2.27 g of KBM-5103 (γ-acryloxypropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred for 5 minutes, and T- was added. 50 (di-isopropoxy-bis(acetoxime) titanium, manufactured by Japan Soda Co., Ltd.) 0.86g After stirring for 5 minutes, Irgacure (registered trademark) 907 (photopolymerization initiator 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinyl-propan-1-one, BASF, was added. 0.23 g manufactured by the company and stirred for 5 minutes to obtain a photocatalyst coating liquid.
於固形物成分含量為0.25質量%(比較例2)、0.5質量%(比較例3)、1.0質量%(比較例4)、或2.5質量%(比較例5)之光觸媒懸浮液21.67g中，添加KBM-5103(γ-丙烯醯氧基丙基三甲氧基矽烷，信越矽酮公司製造)2.27g並攪拌5分鐘，進而添加Irgacure(註冊商標)907 0.23g並攪拌5分鐘，獲得含有光觸媒之塗布液。 In the photocatalyst suspension of 21.67 g, which has a solid content of 0.25 mass% (Comparative Example 2), 0.5% by mass (Comparative Example 3), 1.0% by mass (Comparative Example 4), or 2.5% by mass (Comparative Example 5), 2.27 g of KBM-5103 (γ-acryloxypropyltrimethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred for 5 minutes, and Irgacure (registered trademark) 907 0.23 g was further added and stirred for 5 minutes to obtain a photocatalyst. Coating solution.
於COSMOSHINE(註冊商標)A4300(經易接著處理之聚對苯二甲酸乙二酯膜，東洋紡公司製造)上，將實施例1~5及比較例1~4中所獲得之各光觸媒塗布液棒塗成膜，於100℃下乾燥5分鐘。 Each of the photocatalyst coating liquid rods obtained in Examples 1 to 5 and Comparative Examples 1 to 4 was applied to COSMOSHINE (registered trademark) A4300 (polyethylene terephthalate film which was easily processed, manufactured by Toyobo Co., Ltd.). The film was applied and dried at 100 ° C for 5 minutes.
對該等成膜樣本進行UV照射(400mJ/cm2)後，於表1所示之期間內進行BLB(Black Light Blue，藍紫光燈)照射(1mW/cm2)，其後進行鋼絲絨摩擦試驗(200g負重，往返20次)、及指甲刮劃試驗。將結果示於表1。表示結果之符號如下所述。 After UV irradiation (400 mJ/cm 2 ) was performed on the film formation samples, BLB (Black Light Blue) irradiation (1 mW/cm 2 ) was performed in the period shown in Table 1, and then steel wool rubbing was performed. Test (200 g load, 20 round trips), and nail scratch test. The results are shown in Table 1. The symbols indicating the results are as follows.
鋼絲絨摩擦‧‧‧◎：基本無傷痕、○：少許傷痕、△：幾道傷痕、×：多道傷痕 Steel wool friction ‧‧‧◎: basically no scars, ○: a little scar, △: several scars, ×: multiple scars
指甲刮劃‧‧‧○：未受損傷、△：刮擦幾次受損傷、×：易受損傷 Nail scratching ‧ ‧ ○: no damage, △: scratches several times damaged, ×: vulnerable to injury
-：未實施 -: Not implemented
由以上內容得知，若添加金屬偶合劑，則於BLB照射下亦長期維持硬度，另外，矽烷偶合劑多於光觸媒之情況下硬度優異。 From the above, it is known that when a metal coupling agent is added, the hardness is maintained for a long period of time under the BLB irradiation, and the decane coupling agent is more excellent in hardness than the photocatalyst.
(粒子二氧化矽之效果) (effect of particle cerium oxide)
於製造例1中所獲得之固形物成分含量2.5質量%之光觸媒懸浮液21.67g中，添加KBM-403(γ-縮水甘油氧基丙基三乙氧基矽烷，信越矽酮公司製造)2.27g並攪拌5分鐘，進而添加T-50 0.86g並攪拌5分鐘，獲得含有光觸媒之塗布液。 To 21.67 g of a photocatalyst suspension having a solid content of 2.5% by mass obtained in Production Example 1, KBM-403 (γ-glycidoxypropyltriethoxydecane, manufactured by Shin-Etsu Chemical Co., Ltd.) was added. After stirring for 5 minutes, T-50 0.86 g was further added and stirred for 5 minutes to obtain a coating liquid containing a photocatalyst.
於實施例5中所獲得之含有光觸媒之塗布液中，進而添加IPA-ST(粒子二氧化矽，粒徑10~15nm，以30質量%懸浮於異丙醇中，日產化學工業公司製造)0.9g(實施例6)、1.8g(實施例7)或3.6g(實施例8)並混合5分鐘，獲得含有光觸媒之塗布液。 In the coating liquid containing the photocatalyst obtained in Example 5, IPA-ST (particle cerium oxide, particle size 10 to 15 nm, suspended in isopropyl alcohol at 30% by mass, manufactured by Nissan Chemical Industries Co., Ltd.) was further added. g (Example 6), 1.8 g (Example 7) or 3.6 g (Example 8) were mixed for 5 minutes to obtain a coating liquid containing a photocatalyst.
除了混合IPA-ST-UP(鏈狀二氧化矽，粒徑40~100nm，以15質量%懸浮於異丙醇中，日產化學工業公司製造)1.8g(實施例9)、3.6g(實 施例10)、或7.2g(實施例11)代替IPA-ST以外，以與實施例6~8相同之方法獲得含有光觸媒之塗布液。 In addition to mixing IPA-ST-UP (chain-shaped cerium oxide, particle size 40-100 nm, suspended in isopropanol at 15% by mass, manufactured by Nissan Chemical Industries Co., Ltd.) 1.8 g (Example 9), 3.6 g (real Example 10) or 7.2 g (Example 11) A photocatalyst-containing coating liquid was obtained in the same manner as in Examples 6 to 8 except that IPA-ST was used.
除了混合CELNAX(註冊商標)CX-Z210(含有氧化銻之複合氧化物，粒徑15nm，以21質量%懸浮於異丙醇中，日產化學工業公司製造)1.29g(實施例12)、2.57g(實施例13)、或5.14g(實施例14)代替IPA-ST以外，以與實施例6~8相同之方法獲得含有光觸媒之塗布液。 In addition to CELNAX (registered trademark) CX-Z210 (composite oxide containing cerium oxide, particle size 15 nm, suspended in isopropanol at 21% by mass, manufactured by Nissan Chemical Industries, Ltd.) 1.29 g (Example 12), 2.57 g (Example 13) or 5.14 g (Example 14) A photocatalyst-containing coating liquid was obtained in the same manner as in Examples 6 to 8 except for IPA-ST.
於COSMOSHINE A4300上，將實施例5~14中所獲得之各含有光觸媒之塗布液棒塗成膜，於100℃下乾燥15分鐘。 Each of the photocatalyst-containing coating liquid rods obtained in Examples 5 to 14 was applied to a film on COSMOSHINE A4300, and dried at 100 ° C for 15 minutes.
對該等成膜樣本於表2所示之期間內進行BLB照射(1mW/cm2)，其後以與試驗例1相同之方法進行試驗。將結果示於表2。表示結果之符號與表1相同。 These film-forming samples were subjected to BLB irradiation (1 mW/cm 2 ) in the period shown in Table 2, and then tested in the same manner as in Test Example 1. The results are shown in Table 2. The symbols indicating the results are the same as in Table 1.
由以上內容得知，於使用環氧系矽烷偶合劑之情形時，若添加粒子二氧化矽，則於BLB照射下亦長期維持硬度。 From the above, it is known that when an epoxy decane coupling agent is used, if particulate cerium oxide is added, the hardness is maintained for a long period of time under BLB irradiation.
(粒子二氧化矽之效果) (effect of particle cerium oxide)
於實施例4中所獲得之含有光觸媒之塗布液中，進而添加IPA-ST 0.9g(實施例15)、1.8g(實施例16)、或3.6g(實施例17)並混合5分鐘，獲得含有光觸媒之塗布液。 In the coating liquid containing the photocatalyst obtained in Example 4, IPA-ST 0.9 g (Example 15), 1.8 g (Example 16), or 3.6 g (Example 17) were further added and mixed for 5 minutes to obtain A coating liquid containing a photocatalyst.
於COSMOSHINE A4300上，將實施例4及15~17中所獲得之各含有光觸媒之塗布液棒塗成膜，於100℃下乾燥5分鐘。 Each of the photocatalyst-containing coating liquid rods obtained in Examples 4 and 15 to 17 was coated on a COSMOSHINE A4300, and dried at 100 ° C for 5 minutes.
對該等成膜樣本進行Uv照射(400mJ/cm2)後，於表3所示期間內進行BLB照射(1mW/cm2)，其後以與試驗例1相同之方法進行試驗。將結果示於表3。表示結果之符號與表1相同。 After the Uv irradiation (400 mJ/cm 2 ) of the film-forming samples was carried out, BLB irradiation (1 mW/cm 2 ) was carried out in the period shown in Table 3, and thereafter, the test was carried out in the same manner as in Test Example 1. The results are shown in Table 3. The symbols indicating the results are the same as in Table 1.
由以上內容得知，於使用丙烯酸系矽烷偶合劑之情形時，亦若添加粒子二氧化矽，則於UV照射下亦長期維持硬度。 From the above, it is known that when an acrylic decane coupling agent is used, if particulate cerium oxide is added, the hardness is maintained for a long period of time under UV irradiation.
(粒子二氧化矽之效果：比較) (The effect of particle cerium oxide: comparison)
於製造例1中所獲得之固形物成分含量2.5質量%之光觸媒懸浮液21.67g中，添加KRM-8528C 2.25g(比較例6)、或EBECRYL8311(註冊商標)2.14g(比較例7)並攪拌5分鐘，進而添加Irgacure907 0.11g並攪拌5分鐘，獲得含有光觸媒之塗布液。KRM-8528C及EBECRYL8311均為含有高耐候性奈米二氧化矽之丙烯酸胺基甲酸酯樹脂(DAICEL- ALLNEX公司製造)。 To 21.67 g of a photocatalyst suspension having a solid content of 2.5% by mass obtained in Production Example 1, 2.25 g (Comparative Example 6) or EBECRYL 8131 (registered trademark) 2.14 g (Comparative Example 7) was added and stirred. After 5 minutes, 0.11 g of Irgacure 907 was further added and stirred for 5 minutes to obtain a coating liquid containing a photocatalyst. KRM-8528C and EBECRYL8311 are all urethane urethane resins with high weatherability nano cerium oxide (DAICEL- Made by ALLNEX).
於COSMOSHINE A4300上，將比較例5及6中所獲得之各含有光觸媒之塗布液棒塗成膜，於100℃下乾燥5分鐘。 Each of the photocatalyst-containing coating liquid rods obtained in Comparative Examples 5 and 6 was coated on a COSMOSHINE A4300, and dried at 100 ° C for 5 minutes.
對該等成膜樣本進行UV照射(400mJ/cm2)後，於表4所示之期間內進行BLB照射(1mW/cm2)，其後以與試驗例1相同之方法進行試驗。將結果示於表4。表示結果之符號與表1相同。 After the UV-irradiation (400 mJ/cm 2 ) of the film-forming samples was carried out, BLB irradiation (1 mW/cm 2 ) was carried out in the period shown in Table 4, and then the test was carried out in the same manner as in Test Example 1. The results are shown in Table 4. The symbols indicating the results are the same as in Table 1.
由以上內容得知，即便含有粒子二氧化矽，丙烯酸胺基甲酸酯系樹脂亦因BLB照射而無法維持硬度。 From the above, it has been found that even if the particulate cerium oxide is contained, the urethane urethane resin cannot maintain the hardness due to the BLB irradiation.
除了使用製造例1中所獲得之固形物成分濃度為0.25質量%(實施例18)、0.5質量%(實施例19)、或1.0質量%(實施例20)之光觸媒懸浮液21.67g以外，以與實施例6相同之方法獲得含有光觸媒之塗布液。 Except that 21.67 g of the photocatalyst suspension having a solid content concentration of 0.25 mass% (Example 18), 0.5 mass% (Example 19), or 1.0 mass% (Example 20) obtained in Production Example 1 was used. A coating liquid containing a photocatalyst was obtained in the same manner as in Example 6.
(矽烷偶合劑之水解效果) (hydrolysis effect of decane coupling agent)
於KBM-403 236g中，一面於室溫下攪拌一面一次性添加0.01N鹽酸54g，結果立即可見白濁及液溫之上升，於30秒左右溶液變透明。進而攪拌30分鐘左右，於液溫回到室溫時停止攪拌，獲得水解KBM-403。 In KBM-403 236g, while stirring 54 g of 0.01 N hydrochloric acid at room temperature, the white turbidity and the rise of the liquid temperature were immediately observed, and the solution became transparent in about 30 seconds. Further, the mixture was stirred for about 30 minutes, and when the liquid temperature was returned to room temperature, the stirring was stopped to obtain hydrolyzed KBM-403.
於該水解KBM-403 60g中加入異丙醇140g，繼而加入三(乙醯丙 酮)鋁(ALDRICH公司製造)2.62g並進行攪拌，獲得水解KBM-403混合液。 140 g of isopropanol was added to 60 g of the hydrolyzed KBM-403, followed by the addition of tris(ethyl acetate) 2.62 g of ketone)aluminum (manufactured by ALDRICH Co., Ltd.) was stirred to obtain a hydrolyzed KBM-403 mixture.
於製造例1中所獲得之固形物成分濃度0.25質量%(實施例21)、0.5質量%(實施例22)、1.0質量%(實施例23)、或2.5質量%(實施例24)之各光觸媒懸浮液21.67g中，添加上述水解KBM-403混合液9.41g並攪拌5分鐘，獲得含有光觸媒之塗布液。 The solid content concentration obtained in Production Example 1 was 0.25 mass% (Example 21), 0.5 mass% (Example 22), 1.0 mass% (Example 23), or 2.5% by mass (Example 24). In 21.67 g of the photocatalyst suspension, 9.41 g of the above-mentioned hydrolyzed KBM-403 mixture was added and stirred for 5 minutes to obtain a coating liquid containing a photocatalyst.
於COSMOSHINE A4300上，將實施例6及19~25中所獲得之各含有光觸媒之塗布液棒塗成膜，於100℃下乾燥5分鐘。 Each of the photocatalyst-containing coating liquid rods obtained in Examples 6 and 19 to 25 was coated on a COSMOSHINE A4300, and dried at 100 ° C for 5 minutes.
對該等成膜樣本於表5所示期間內進行BLB照射(1mW/cm2)，其後以與驗例1相同之方法進行試驗。將結果示於表5。表示結果之符號與表1相同。 These film-forming samples were subjected to BLB irradiation (1 mW/cm 2 ) in the period shown in Table 5, and then tested in the same manner as in Test Example 1. The results are shown in Table 5. The symbols indicating the results are the same as in Table 1.
由以上內容得知，若將環氧矽烷偶合劑水解縮合而使用則強度優異。 From the above, it is known that the epoxy decane coupling agent is excellent in strength when it is used by hydrolysis and condensation.
(與四官能性矽烷化合物之比較) (Compared with tetrafunctional decane compounds)
於製造例1中所獲得之固形物成分含量2.5質量%之光觸媒懸浮液 21.67g中，添加MKC矽酸鹽MS-51(四甲氧基矽烷之部分水解縮合物，三菱化學公司製造)2.27g並攪拌5分鐘，進而添加T-50 0.86g並攪拌5分鐘，獲得含有光觸媒之塗布液。 Photocatalyst suspension having a solid content of 2.5% by mass obtained in Production Example 1 To 21.67 g, 2.27 g of MKC citrate MS-51 (partial hydrolysis condensate of tetramethoxy decane, manufactured by Mitsubishi Chemical Corporation) was added and stirred for 5 minutes, and further T-50 0.86 g was added and stirred for 5 minutes to obtain a content. Photocatalyst coating solution.
於比較例8之含有光觸媒之塗布液中進而添加IPA-ST 3.6g並混合5分鐘，獲得含有光觸媒之塗布液。 Further, 3.6 g of IPA-ST was further added to the coating liquid containing the photocatalyst of Comparative Example 8 and mixed for 5 minutes to obtain a coating liquid containing a photocatalyst.
於比較例8之含有光觸媒之塗布液中進而添加Irgacure907 0.46g並攪拌5分鐘，獲得含有光觸媒之塗布液。 Further, 0.46 g of Irgacure 907 was further added to the coating liquid containing the photocatalyst of Comparative Example 8 and stirred for 5 minutes to obtain a coating liquid containing a photocatalyst.
於比較例10之含有光觸媒之塗布液中進而添加IPA-ST 3.6g並混合5分鐘，獲得含有光觸媒之塗布液。 Further, 3.6 g of IPA-ST was further added to the coating liquid containing the photocatalyst of Comparative Example 10 and mixed for 5 minutes to obtain a coating liquid containing a photocatalyst.
於COSMOSHINE A4300上，將實施例5、8、4、17、比較例8、9、10、以及11中所獲得之各含有光觸媒之塗布液棒塗成膜，於100℃下乾燥5分鐘。 On each of COSMOSHINE A4300, each of the photocatalyst-containing coating liquid rods obtained in Examples 5, 8, 4, 17, and Comparative Examples 8, 9, 10, and 11 was coated with a film, and dried at 100 ° C for 5 minutes.
對於使用實施例4、17、比較例10、及11之各含有光觸媒之塗布液而獲得之成膜樣本，其後進一步進行UV照射(400mJ/cm2)。 The film-forming samples obtained by using the coating liquid containing the photocatalyst of each of Examples 4 and 17, and Comparative Examples 10 and 11 were further subjected to UV irradiation (400 mJ/cm 2 ).
對該等成膜樣本於表6所示之期間內進行BLB照射(1mW/cm2)，其後以與試驗例1相同之方法進行試驗。將結果示於表6。表示結果之符號與表1相同。 These film-forming samples were subjected to BLB irradiation (1 mW/cm 2 ) in the period shown in Table 6, and then tested in the same manner as in Test Example 1. The results are shown in Table 6. The symbols indicating the results are the same as in Table 1.
由以上內容得知，即便使用四官能性矽烷化合物水解物代替本發明中之環氧矽烷偶合劑或丙烯酸矽烷偶合劑，亦無法獲得充分之強度。 From the above, it has been found that even if a tetrafunctional decane compound hydrolyzate is used in place of the epoxy decane coupling agent or the decyl methacrylate coupling agent of the present invention, sufficient strength cannot be obtained.
(抗病毒性試驗) (antiviral test)
於製造例1中所獲得之固形物成分含量為1.0質量%(實施例25：最終固形物成分中之氧化鈦含量7.0質量%)、0.5質量%(實施例26：最終固形物成分中之氧化鈦含量3.6質量%)、或0.25質量%(實施例27：最終固形物成分中之氧化鈦含量1.7質量%)之光觸媒懸浮液21.67g中，添加KBM-403 2.27g並攪拌5分鐘，進而添加T-50 0.86g並攪拌5分鐘，獲得含有光觸媒之塗布液。 The content of the solid content obtained in Production Example 1 was 1.0% by mass (Example 25: titanium oxide content in the final solid content of 7.0% by mass), 0.5% by mass (Example 26: Oxidation in the final solid component) To 21.67 g of a photocatalyst suspension having a titanium content of 3.6 mass%) or 0.25 mass% (Example 27: titanium oxide content of the final solid content: 1.7% by mass), 2.27 g of KBM-403 was added and stirred for 5 minutes, and further added. T-50 0.86 g was stirred for 5 minutes to obtain a coating liquid containing a photocatalyst.
於COSMOSHINE A4300上，將實施例25~27中所獲得之各含有光觸媒之塗布液棒塗成膜，於100℃下乾燥5分鐘。 Each of the photocatalyst-containing coating liquid rods obtained in Examples 25 to 27 was applied to a film on COSMOSHINE A4300, and dried at 100 ° C for 5 minutes.
關於該等成膜樣本，依據JIS R 1756，進行使用Qβ噬菌體之抗病毒性試驗。光源係使用白色螢光燈，使用UV截止濾波器(N113)，以樣本表面之照度成為1000 Lux之方式照射1小時或4小時之經設定為λ ≧400nm之可見光，評價不活化度。又，於黑暗下(圖中表示為dark)將評價時間設為1小時或4小時而同樣地評價。將結果示於圖1。 Regarding these film-forming samples, an antiviral test using Qβ phage was carried out in accordance with JIS R 1756. The light source is a white fluorescent lamp, and a UV cut filter (N113) is used to illuminate the sample surface with an illumination of 1000 Lux for 1 hour or 4 hours. The visible light was measured at 400 nm, and the degree of inactivation was evaluated. Further, the evaluation time was set to 1 hour or 4 hours in the dark (indicated as dark in the drawing) and evaluated in the same manner. The results are shown in Fig. 1.
於製造例1中所獲得之固形物成分含量為1.0質量%(實施例28：最終固形物成分中之氧化鈦含量6.6質量%)、0.5質量%(實施例29：最終固形物成分中之氧化鈦含量3.4質量%)、或0.25質量%(實施例30：最終固形物成分中之氧化鈦含量1.6質量%)之光觸媒懸浮液21.67g中，添加KBM-5103 2.27g並攪拌5分鐘，添加T-50 0.86g並攪拌5分鐘，添加Irgacure907 0.23g並攪拌5分鐘，獲得含有光觸媒之塗布液。 The content of the solid content obtained in Production Example 1 was 1.0% by mass (Example 28: titanium oxide content in the final solid content: 6.6% by mass), 0.5% by mass (Example 29: Oxidation in the final solid content) To 21.67 g of a photocatalyst suspension having a titanium content of 3.4% by mass or 0.25 mass% (Example 30: titanium oxide content in the final solid content: 1.6% by mass), 2.27 g of KBM-5103 was added and stirred for 5 minutes, and T was added. -50 0.86 g and stirring for 5 minutes, 0.23 g of Irgacure 907 was added and stirred for 5 minutes to obtain a coating liquid containing a photocatalyst.
於COSMOSHINE A4300上，將實施例28~30中所獲得之各含有光觸媒之塗布液棒塗成膜，於100℃下乾燥5分鐘，進而進行UV照射(400mJ/cm2)。 Each of the photocatalyst-containing coating liquid rods obtained in Examples 28 to 30 was coated on a COSMOSHINE A4300, and dried at 100 ° C for 5 minutes, and further subjected to UV irradiation (400 mJ/cm 2 ).
對於該等成膜樣本，以與試驗例6相同之方法進行評價。將結果示於圖2。 The film-forming samples were evaluated in the same manner as in Test Example 6. The results are shown in Figure 2.
所有樣本均於評價時間4小時之情況下顯示出充分之抗病毒性，尤其於使用KBM-5103(丙烯酸矽烷偶合劑)之情形時，1小時之情況下亦顯示出較高之抗病毒性。 All samples showed sufficient antivirality at 4 hours of evaluation time, especially when KBM-5103 (decane coupling agent) was used, and also showed high antivirality at 1 hour.
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