JP2012025849A - Photocatalyst coating liquid and product having photocatalytic function - Google Patents
Photocatalyst coating liquid and product having photocatalytic function Download PDFInfo
- Publication number
- JP2012025849A JP2012025849A JP2010165705A JP2010165705A JP2012025849A JP 2012025849 A JP2012025849 A JP 2012025849A JP 2010165705 A JP2010165705 A JP 2010165705A JP 2010165705 A JP2010165705 A JP 2010165705A JP 2012025849 A JP2012025849 A JP 2012025849A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- mass
- parts
- particles
- coating liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 273
- 239000007788 liquid Substances 0.000 title claims abstract description 123
- 239000011248 coating agent Substances 0.000 title claims abstract description 113
- 238000000576 coating method Methods 0.000 title claims abstract description 113
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 225
- 229910000484 niobium oxide Inorganic materials 0.000 claims abstract description 63
- 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 claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000008119 colloidal silica Substances 0.000 claims abstract description 55
- 239000007787 solid Substances 0.000 claims abstract description 39
- -1 silicon alkoxide Chemical class 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 26
- 239000010703 silicon Substances 0.000 claims abstract description 21
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 21
- 239000000758 substrate Substances 0.000 claims abstract description 17
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 51
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 50
- 229910000510 noble metal Inorganic materials 0.000 claims description 24
- 230000001747 exhibiting effect Effects 0.000 abstract description 8
- 230000001678 irradiating effect Effects 0.000 abstract description 4
- 239000010410 layer Substances 0.000 description 83
- 239000006185 dispersion Substances 0.000 description 40
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 238000000034 method Methods 0.000 description 28
- 239000000126 substance Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000000463 material Substances 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 21
- 239000013566 allergen Substances 0.000 description 19
- 239000000047 product Substances 0.000 description 15
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 229920005989 resin Polymers 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 239000002243 precursor Substances 0.000 description 13
- 239000003795 chemical substances by application Substances 0.000 description 12
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- 241000218645 Cedrus Species 0.000 description 10
- 241000588724 Escherichia coli Species 0.000 description 10
- 239000013573 pollen allergen Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 241000191967 Staphylococcus aureus Species 0.000 description 9
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 9
- 244000052616 bacterial pathogen Species 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 8
- 229920000298 Cellophane Polymers 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 238000006748 scratching Methods 0.000 description 6
- 230000002393 scratching effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 239000012790 adhesive layer Substances 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 244000052769 pathogen Species 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 239000002612 dispersion medium Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920000106 Liquid crystal polymer Polymers 0.000 description 2
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011362 coarse particle Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 230000001717 pathogenic effect Effects 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- JZLWSRCQCPAUDP-UHFFFAOYSA-N 1,3,5-triazine-2,4,6-triamine;urea Chemical compound NC(N)=O.NC1=NC(N)=NC(N)=N1 JZLWSRCQCPAUDP-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 241000589248 Legionella Species 0.000 description 1
- 208000007764 Legionnaires' Disease Diseases 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- JYDBGJYYVQRPTE-UHFFFAOYSA-L P(=O)(O)([O-])[O-].[Pt+2] Chemical compound P(=O)(O)([O-])[O-].[Pt+2] JYDBGJYYVQRPTE-UHFFFAOYSA-L 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 241000607768 Shigella Species 0.000 description 1
- 241000295644 Staphylococcaceae Species 0.000 description 1
- 206010043376 Tetanus Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 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
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 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
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- VUCAVCCCXQVHAN-UHFFFAOYSA-L azane dichlorocopper Chemical compound N.Cl[Cu]Cl VUCAVCCCXQVHAN-UHFFFAOYSA-L 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229920000229 biodegradable polyester Polymers 0.000 description 1
- 239000004622 biodegradable polyester Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- SKQUUKNCBWILCD-UHFFFAOYSA-J dicopper;chloride;trihydroxide Chemical compound [OH-].[OH-].[OH-].[Cl-].[Cu+2].[Cu+2] SKQUUKNCBWILCD-UHFFFAOYSA-J 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 206010013023 diphtheria Diseases 0.000 description 1
- PKRPQASGRXWUOJ-UHFFFAOYSA-L dipotassium;dichloride Chemical compound [Cl-].[Cl-].[K+].[K+] PKRPQASGRXWUOJ-UHFFFAOYSA-L 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 description 1
- PMCMJPXEJUKOAO-UHFFFAOYSA-M gold(1+);bromide Chemical compound [Au]Br PMCMJPXEJUKOAO-UHFFFAOYSA-M 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- NXVGPAMSCPIKEY-UHFFFAOYSA-N hydroxy-imino-oxo-$l^{5}-chlorane Chemical compound OCl(=N)=O NXVGPAMSCPIKEY-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- YXEUGTSPQFTXTR-UHFFFAOYSA-K lanthanum(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[La+3] YXEUGTSPQFTXTR-UHFFFAOYSA-K 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 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
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- KABWJWZACJCALW-UHFFFAOYSA-J platinum tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl.[Pt] KABWJWZACJCALW-UHFFFAOYSA-J 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- NFOHLBHARAZXFQ-UHFFFAOYSA-L platinum(2+);dihydroxide Chemical compound O[Pt]O NFOHLBHARAZXFQ-UHFFFAOYSA-L 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical class [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 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
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- 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
- C09D183/04—Polysiloxanes
- C09D183/06—Polysiloxanes containing silicon bound to oxygen-containing groups
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/71—Photocatalytic coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Paints Or Removers (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、光触媒体コーティング液、および光触媒機能製品に関する。 The present invention relates to a photocatalyst coating liquid and a photocatalytic functional product.
半導体にバンドギャップ以上のエネルギーを持つ光を照射すると、価電子帯の電子が伝導帯に励起され、価電子帯に正孔が生成する。このようにして生成した正孔は強い酸化力を有し、励起した電子は強い還元力を有することから、半導体に接触した物質に酸化還元作用を及ぼす。この酸化還元作用によりＯＨラジカルをはじめとする活性酸素種が生成し、有機物等を分解することができる。このような作用を示し得る半導体は光触媒体と呼ばれており、光触媒体として酸化チタンや酸化タングステンが知られている。これらの中でも特に、酸化タングステンは蛍光灯の照明下で高い光触媒作用を示す光触媒体である。 When a semiconductor is irradiated with light having energy greater than or equal to the band gap, electrons in the valence band are excited to the conduction band and holes are generated in the valence band. The holes generated in this manner have a strong oxidizing power, and the excited electrons have a strong reducing power, so that the material in contact with the semiconductor has a redox action. By this oxidation-reduction action, active oxygen species such as OH radicals are generated, and organic substances and the like can be decomposed. A semiconductor capable of exhibiting such an action is called a photocatalyst, and titanium oxide and tungsten oxide are known as the photocatalyst. Among these, tungsten oxide is a photocatalyst that exhibits high photocatalytic action under illumination of a fluorescent lamp.
特許文献１には、基材上に接着層を設け、光触媒体を含む光触媒体コーティング液に金属酸化物ゲルもしくは金属水酸化物ゲルからなるバインダー成分を混合して、光触媒体コーティング液を接着層上に塗布すると、光触媒体粒子が脱落し難い光触媒担持構造体が得られることが開示されている。 In Patent Document 1, an adhesive layer is provided on a substrate, a binder component made of a metal oxide gel or a metal hydroxide gel is mixed with a photocatalyst coating liquid containing a photocatalyst, and the photocatalyst coating liquid is applied to the adhesive layer. It is disclosed that a photocatalyst-supporting structure in which photocatalyst particles are less likely to fall off when applied on top is obtained.
しかしながら、上記のような光触媒担持構造体では、接着層と基材または光触媒体層と接着層との密着強度が必ずしも十分ではなく、基材から光触媒体が剥離しやすく、高い光触媒活性を発現しなかった。 However, in the photocatalyst-supporting structure as described above, the adhesion strength between the adhesive layer and the base material or the photocatalyst body layer and the adhesive layer is not necessarily sufficient, and the photocatalyst body is easily peeled off from the base material, and exhibits high photocatalytic activity. There wasn't.
そこで、本発明の課題は、基材の表面に光触媒体層を形成したときに、基材との密着性に優れる光触媒体層が得られ、しかも光触媒体層が蛍光灯などの実用光源の照射によって、高い光触媒活性を示す光触媒体コーティング液と、光触媒体層を表面に備える光触媒機能製品を提供することである。 Thus, the problem of the present invention is that when a photocatalyst layer is formed on the surface of the substrate, a photocatalyst layer having excellent adhesion to the substrate is obtained, and the photocatalyst layer is irradiated with a practical light source such as a fluorescent lamp. Thus, a photocatalyst coating liquid exhibiting high photocatalytic activity and a photocatalytic functional product having a photocatalyst layer on the surface are provided.
本発明者らは、上記課題を解決すべく鋭意研究を重ねた結果、以下に示す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 completed the present invention shown below.
すなわち、本発明は、以下の構成からなる。
（Ｉ）（１）光触媒体粒子、（２）酸化ニオブゾル粒子、（３）コロイダルシリカ粒子、（４）シリコンアルコキシド、及び（５）溶媒を含む光触媒体コーティング液であって、前記（２）の酸化物換算の含有量が前記（４）の酸化物換算の含有量１００質量部に対して０〜２００質量部であり、前記（３）の酸化物換算の含有量が前記（４）の酸化物換算の含有量１００質量部に対して０〜２８０質量部であり、前記（２）と（３）の酸化物換算の含有量の合計が前記（４）の酸化物換算の含有量１００質量部に対して０〜４８０質量部であり、前記（２）、（３）および（４）の酸化物換算の含有量の合計が前記（１）１００質量部に対して２０〜５００質量部であり、前記光触媒体コーティング液から揮発成分を揮発させて得られる固形分の酸化物換算の含有量が前記光触媒体コーティング液１００質量部に対して０．５質量部〜３０重量部である、ことを特徴とする光触媒活性を有する光触媒体層を形成するための光触媒体コーティング液を提供する。
（ＩＩ）前記光触媒体層が少なくとも可視光線の照射で光触媒活性を示す前記（Ｉ）に記載の光触媒体コーティング液。
（ＩＩＩ）前記光触媒体粒子が酸化タングステン粒子である前記（Ｉ）または（ＩＩ）に記載の光触媒体コーティング液。
（ＩＶ）前記光触媒体粒子が貴金属を担持している前記（Ｉ）〜（ＩＩＩ）のいずれかに記載の光触媒体コーティング液。
That is, this invention consists of the following structures.
(I) (1) photocatalyst particles, (2) niobium oxide sol particles, (3) colloidal silica particles, (4) silicon alkoxide, and (5) a photocatalyst coating liquid comprising (2) The content in terms of oxide is 0 to 200 parts by mass with respect to 100 parts by mass in terms of oxide in (4), and the content in terms of oxide in (3) is the oxidation in (4). It is 0 to 280 parts by mass with respect to 100 parts by mass in terms of product, and the total of oxides in terms of (2) and (3) is 100 masses in terms of oxide in (4). 0 to 480 parts by mass with respect to parts, and the total of the oxide-converted contents of (2), (3) and (4) is 20 to 500 parts by mass with respect to (1) 100 parts by mass. Yes, solid solution obtained by volatilizing volatile components from the photocatalyst coating liquid The photocatalyst for forming a photocatalyst layer having photocatalytic activity is characterized in that the content in terms of oxide is 0.5 to 30 parts by weight with respect to 100 parts by weight of the photocatalyst coating liquid Provide body coating fluid.
(II) The photocatalyst coating liquid according to (I), wherein the photocatalyst layer exhibits photocatalytic activity when irradiated with at least visible light.
(III) The photocatalyst coating liquid according to (I) or (II), wherein the photocatalyst particles are tungsten oxide particles.
(IV) The photocatalyst coating liquid according to any one of (I) to (III), wherein the photocatalyst particles carry a noble metal.
また、本発明は、基材表面に光触媒体層を備える光触媒機能製品であって、前記光触媒体層が前記（Ｉ）〜（ＩＶ）のいずれかに記載の光触媒体コーティング液を用いて形成されていることを特徴とする光触媒機能製品を提供する。 Further, the present invention is a photocatalytic functional product comprising a photocatalyst layer on a substrate surface, wherein the photocatalyst layer is formed using the photocatalyst coating liquid according to any one of (I) to (IV). Provided is a photocatalytic functional product.
本発明の光触媒体コーティング液によれば、基材上に接着層を設けずに、直接基材に塗布しても密着力に優れ、十分な光触媒活性を示す光触媒体層を形成することができる。さらに、該光触媒体層は、優れた表面硬度と優れた親水性をも示し、本来の優れた光触媒作用を維持する光触媒機能製品を提供することができる。 According to the photocatalyst coating liquid of the present invention, it is possible to form a photocatalyst layer that exhibits excellent photocatalytic activity with excellent adhesion even when directly applied to a substrate without providing an adhesive layer on the substrate. . Furthermore, the photocatalyst layer can also provide a photocatalytic functional product that exhibits excellent surface hardness and excellent hydrophilicity and maintains the original excellent photocatalytic action.
本発明の光触媒体コーティング液は、光触媒体粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、シリコンアルコキシド及び溶媒を所定の割合で含有し、光触媒体コーティング液の固形分を所定の割合としたものである。 The photocatalyst coating liquid of the present invention contains photocatalyst particles, niobium oxide sol particles, colloidal silica particles, silicon alkoxide and a solvent in a predetermined ratio, and the solid content of the photocatalyst coating liquid is a predetermined ratio.
〔光触媒体粒子〕
本発明における光触媒体粒子は、光触媒作用を有する酸化物であって、例えば、酸化チタン粒子や酸化タングステン粒子が挙げられ、特に酸化タングステン粒子では可視光線（波長約４００ｎｍ〜約８００ｎｍ）を照射したとき、高い光触媒活性を示すことから、本発明に好適である。
[Photocatalyst particles]
The photocatalyst particles in the present invention are oxides having a photocatalytic action, and examples thereof include titanium oxide particles and tungsten oxide particles. In particular, tungsten oxide particles are irradiated with visible light (wavelength of about 400 nm to about 800 nm). Since it exhibits high photocatalytic activity, it is suitable for the present invention.
〔酸化チタン粒子〕
酸化チタン粒子は、紫外光線を照射したときに、特に高い光触媒作用を示す粒子状の酸化チタンである。
酸化チタン粒子としては、例えば、メタチタン酸粒子、結晶型がアナターゼ型、ブルッカイト型、ルチル型などである二酸化チタン〔ＴｉＯ2〕粒子などが挙げられる。
[Titanium oxide particles]
Titanium oxide particles are particulate titanium oxides that exhibit particularly high photocatalytic activity when irradiated with ultraviolet light.
Examples of the titanium oxide particles include metatitanic acid particles, titanium dioxide [TiO 2 ] particles whose crystal types are anatase type, brookite type, rutile type, and the like.
メタチタン酸粒子は、例えば、下記方法（Ａ）により得ることができる。
方法（Ａ）：硫酸チタニルの水溶液を加熱することにより、加水分解する方法
Metatitanic acid particles can be obtained, for example, by the following method (A).
Method (A): Method of hydrolysis by heating an aqueous solution of titanyl sulfate
二酸化チタン粒子は、例えば、下記方法（Ｂ−１）〜方法（Ｂ−３）のいずれかの方法により得ることができる。
方法（Ｂ−１）：硫酸チタニルまたは塩化チタンの水溶液を加熱することなく、これに塩基を加えることにより沈殿物を得、得られた沈殿物を焼成する方法
方法（Ｂ−２）：チタンアルコキシドに水、酸の水溶液または塩基の水溶液を加えて沈殿物を得、得られた沈殿物を焼成する方法
方法（Ｂ−３）：メタチタン酸を焼成する方法
Titanium dioxide particles can be obtained, for example, by any of the following methods (B-1) to (B-3).
Method (B-1): Method of obtaining a precipitate by adding a base to this solution without heating an aqueous solution of titanyl sulfate or titanium chloride, and firing the obtained precipitate Method (B-2): Titanium alkoxide A method for obtaining a precipitate by adding water, an aqueous solution of an acid or an aqueous solution of a base, and firing the resulting precipitate Method (B-3): A method of firing metatitanic acid
前記方法（Ｂ−１）〜方法（Ｂ−３）により得られる二酸化チタン粒子は、焼成する際の焼成温度、焼成時間により、アナターゼ型、ブルッカイト型またはルチル型の結晶型として得ることができる。 The titanium dioxide particles obtained by the method (B-1) to the method (B-3) can be obtained as an anatase type, brookite type, or rutile type crystal type depending on the baking temperature and baking time when baking.
また、酸化チタンを得るには、前記方法の他にも、例えば、「酸化チタン」（清野学著、技報堂出版）に記載されている硫酸法や塩素法、特開２００１−７２４１９号公報、特開２００１−１９０９５３号公報、特開２００１−３１６１１６号公報、特開２００１−３２２８１６号公報、特開２００２−２９７４９号公報、特開２００２−９７０１９号公報、国際公開第０１／１０５５２号、特開２００１−２１２４５７公報、特開２００２−２３９３９５号公報、国際公開第０３／０８０２４４号、国際公開第０２／０５３５０１号、特開２００７−６９０９３号公報、Chemistry Letters, Vol.32, No.2, P.196-197(2003)、Chemistry Letters, Vol.32, No.4, P.364-365(2003)、Chemistry Letters, Vol.32, No.8, P.772-773(2003)、Chem. Mater., 17, P.1548-1552(2005)、特開２００１−２７８６２５号公報、特開２００１−２７８６２６号公報、特開２００１−２７８６２７号公報、特開２００１−３０２２４１号公報、特開２００１−３３５３２１号公報、特開２００１−３５４４２２号公報、特開２００２−２９７５０号公報、特開２００２−４７０１２号公報、特開２００２−６０２２１号公報、特開２００２−１９３６１８号公報、特開２００２−２４９３１９号公報などに記載の方法が挙げられる。 In addition to the above-described method, titanium oxide can be obtained by, for example, the sulfuric acid method and the chlorine method described in “Titanium oxide” (Kyoto Kiyono, Gihodo Publishing), JP 2001-72419, JP 2001-190953 A, JP 2001-316116 A, JP 2001-322816 A, JP 2002-29749 A, JP 2002-97019 A, WO 01/10552, JP 2001. No. -21457, JP 2002-239395 A, WO 03/080244, WO 02/053501, JP 2007-69093 A, Chemistry Letters, Vol. 32, No. 2, P.196. -197 (2003), Chemistry Letters, Vol.32, No.4, P.364-365 (2003), Chemistry Letters, Vol.32, No.8, P.772-773 (2003), Chem. Mater. , 17, P.1548-1552 (2005), JP2001-27862. JP, JP-A-2001-278626, JP-A-2001-278627, JP-A-2001-302241, JP-A-2001-335321, JP-A-2001-354422, JP-A-2002-29750. And JP-A-2002-47012, JP-A-2002-60221, JP-A-2002-193618, JP-A-2002-249319, and the like.
前記方法などで得られた酸化チタンは、それぞれ単独で用いても、２種以上組み合わせて用いてもよい。 Titanium oxide obtained by the above method may be used alone or in combination of two or more.
酸化チタン粒子の粒子径は、平均分散粒子径で、効果的に光触媒作用を発現させる観点から、通常２０ｎｍ〜１５０ｎｍ、好ましくは４０ｎｍ〜１００ｎｍである。 The particle diameter of the titanium oxide particles is an average dispersed particle diameter, and is usually 20 nm to 150 nm, preferably 40 nm to 100 nm, from the viewpoint of effectively exhibiting photocatalytic action.
酸化チタン粒子のＢＥＴ比表面積は、効果的に光触媒作用を発現させる観点から、通常１００ｍ2／ｇ〜５００ｍ2／ｇ、好ましくは３００ｍ2／ｇ〜４００ｍ2／ｇである。 BET specific surface area of the titanium oxide particles, from the viewpoint of effectively exhibiting photocatalytic activity, typically 100m 2 / g~500m 2 / g, preferably from 300m 2 / g~400m 2 / g.
〔酸化タングステン粒子〕
酸化タングステン粒子は、可視光線（波長約４００ｎｍ〜約８００ｎｍ）を照射したときにでも高い光触媒作用を示す、粒子状の酸化タングステンである。
酸化タングステン粒子としては、通常は三酸化タングステン〔ＷＯ3〕粒子が挙げられる。
三酸化タングステン粒子は、例えば、タングステン酸塩の水溶液に酸を加えることにより、沈殿物としてタングステン酸を得、得られたタングステン酸を焼成する方法により得ることができる。また、メタタングステン酸アンモニウム、パラタングステン酸アンモニウムを加熱することにより熱分解する方法により得ることもできる。
[Tungsten oxide particles]
The tungsten oxide particles are particulate tungsten oxides that exhibit high photocatalytic action even when irradiated with visible light (wavelength of about 400 nm to about 800 nm).
The tungsten oxide particles usually include tungsten trioxide [WO 3 ] particles.
The tungsten trioxide particles can be obtained, for example, by adding an acid to an aqueous solution of tungstate to obtain tungstic acid as a precipitate, and firing the obtained tungstic acid. Moreover, it can also obtain by the method of thermally decomposing by heating ammonium metatungstate and ammonium paratungstate.
酸化タングステン粒子の粒子径は、平均分散粒子径で、効果的に光触媒作用を発現させる観点から、通常５０ｎｍ〜２００ｎｍ、好ましくは８０ｎｍ〜１３０ｎｍである。 The particle diameter of the tungsten oxide particles is an average dispersed particle diameter, and is usually 50 nm to 200 nm, preferably 80 nm to 130 nm, from the viewpoint of effectively expressing the photocatalytic action.
酸化タングステン粒子のＢＥＴ比表面積は、効果的に光触媒作用を発現させる観点から、通常５ｍ2／ｇ〜１００ｍ2／ｇ、好ましくは２０ｍ2／ｇ〜５０ｍ2／ｇである。 BET specific surface area of the tungsten oxide particles, from the viewpoint of effectively exhibiting photocatalytic activity, typically 5m 2 / g~100m 2 / g, preferably 20m 2 / g~50m 2 / g.
〔酸化ニオブゾル粒子〕
本発明における酸化ニオブゾル粒子の平均粒子径は、通常５０ｎｍ以下、好ましくは３０ｎｍ以下であり、結晶質系のものでも非晶質系のものでもよい。
また、酸化ニオブゾル粒子の分散安定性を向上させるために、適宜分散剤で酸化ニオブゾル粒子の表面が修飾されたものを用いてもよい。このような酸化ニオブゾル粒子としては、例えば、多木化学（株）製の酸化ニオブゾル「Ｎｂ―Ｘ―１０」などが挙げられる。
[Niobium oxide sol particles]
The average particle diameter of the niobium oxide sol particles in the present invention is usually 50 nm or less, preferably 30 nm or less, and may be crystalline or amorphous.
Further, in order to improve the dispersion stability of the niobium oxide sol particles, a material in which the surface of the niobium oxide sol particles is appropriately modified with a dispersant may be used. Examples of such niobium oxide sol particles include niobium oxide sol “Nb-X-10” manufactured by Taki Chemical Co., Ltd.
酸化ニオブゾル粒子の酸化物換算の含有量は、シリコンアルコキシドの酸化物換算の含有量１００質量部に対して、０〜２００質量部、好ましくは２０〜１４０質量部、より好ましくは３０〜８０質量部である。酸化ニオブゾル粒子の酸化物換算の含有量が２００質量部を超えると、得られる光触媒体層と基材との密着性が低下すると共に、光触媒体層が軟らかくなり過ぎて不具合が生じるおそれがある。なお、酸化ニオブゾル粒子の酸化物換算とは、酸化ニオブゾル中のニオブ成分を全てＮｂ2Ｏ5とした場合であり、シリコンアルコキシドの酸化物換算とは、シリコンアルコキシド中の珪素成分を全てＳｉＯ2とした場合であり、以下同様である。 The oxide equivalent content of the niobium oxide sol particles is 0 to 200 parts by mass, preferably 20 to 140 parts by mass, more preferably 30 to 80 parts by mass with respect to 100 parts by mass of the oxide equivalent of the silicon alkoxide. It is. When the content of the niobium oxide sol particles in terms of oxide exceeds 200 parts by mass, the adhesion between the resulting photocatalyst layer and the substrate is lowered, and the photocatalyst layer is too soft and may cause a problem. The oxide conversion of niobium oxide sol particles is a case where all the niobium components in the niobium oxide sol are Nb 2 O 5, and the oxide conversion of silicon alkoxide is the conversion of all silicon components in the silicon alkoxide to SiO 2 . The same applies hereinafter.
〔コロイダルシリカ粒子〕
本発明におけるコロイダルシリカ粒子の平均粒子径は、通常５０ｎｍ以下、好ましくは３０ｎｍ以下であり、例えば、日産化学工業（株）製のコロイダルシリカ、「ＳＴ−ＯＸＳ」、「ＳＴ−ＯＳ」、「ＳＴ−Ｏ」などを用いることができる。
[Colloidal silica particles]
The average particle diameter of the colloidal silica particles in the present invention is usually 50 nm or less, preferably 30 nm or less. For example, colloidal silica manufactured by Nissan Chemical Industries, Ltd., “ST-OXS”, “ST-OS”, “ST -O "can be used.
コロイダルシリカ粒子の酸化物換算の含有量は、シリコンアルコキシドの酸化物換算の含有量１００質量部に対して、０〜２８０質量部、好ましくは１６０〜２６０質量部、より好ましくは１７０〜２３０質量部である。コロイダルシリカ粒子の酸化物換算の含有量が２８０質量部を超えると、得られる光触媒体層と基材との密着性が低下すると共に、光触媒体層が軟らかくなり過ぎて不具合が生じるおそれがある。
なお、コロイダルシリカ粒子の酸化物換算とは、コロイダルシリカ中の珪素成分を全てＳｉＯ2とした場合あり、以下同様である。
The oxide equivalent content of the colloidal silica particles is 0 to 280 parts by mass, preferably 160 to 260 parts by mass, more preferably 170 to 230 parts by mass with respect to 100 parts by mass of the oxide equivalent of the silicon alkoxide. It is. When the content of the colloidal silica particles in terms of oxide exceeds 280 parts by mass, the adhesion between the resulting photocatalyst layer and the substrate is lowered, and the photocatalyst layer is too soft and may cause problems.
In addition, the oxide conversion of colloidal silica particles refers to the case where all silicon components in colloidal silica are SiO 2, and so on.
さらに、本発明の光触媒体コーティング液における酸化ニオブゾル粒子およびコロイダルシリカ粒子の酸化物換算の含有量の合計は、シリコンアルコキシドの酸化物換算の含有量１００質量部に対して、０〜４８０質量部、好ましくは２００〜３３０質量部、より好ましくは２１０〜３１０質量部である。酸化ニオブゾル粒子およびコロイダルシリカ粒子の酸化物換算の含有量の合計が４８０質量部を超えると、得られる光触媒体層と基材との密着性が低下すると共に、光触媒体層が軟らかくなり過ぎて不具合が生じるおそれがある。 Further, the total oxide content of niobium oxide sol particles and colloidal silica particles in the photocatalyst coating liquid of the present invention is 0 to 480 parts by mass with respect to 100 parts by mass of oxide equivalent of silicon alkoxide, Preferably it is 200-330 mass parts, More preferably, it is 210-310 mass parts. If the total oxide content of the niobium oxide sol particles and colloidal silica particles exceeds 480 parts by mass, the adhesion between the resulting photocatalyst layer and the substrate will be lowered, and the photocatalyst layer will be too soft. May occur.
さらに、本発明の光触媒体コーティング液における酸化ニオブゾル粒子、コロイダルシリカ粒子、およびシリコンアルコキシドの酸化物換算の含有量の合計は、本発明の光触媒体コーティング液における光触媒体粒子の含有量１００質量部に対して通常２０〜５００質量部であるが、光触媒体コーティング液から得られる光触媒体層が、基材との良好な密着性を得る目的で、１００〜４５０質量部であってもよい。酸化ニオブゾル粒子、コロイダルシリカ粒子、およびシリコンアルコキシドの酸化物換算の含有量の合計が、２０質量部未満であると、光触媒体層と基材との密着性が低下し、一方、５００質量部を超えると、光触媒体粒子が酸化ニオブゾル粒子などのバインダー成分中に埋没してしまい、十分な光触媒活性の光触媒体層が得にくくなる。 Furthermore, the total of the oxide equivalent content of niobium oxide sol particles, colloidal silica particles, and silicon alkoxide in the photocatalyst coating liquid of the present invention is 100 parts by mass of the photocatalyst particle content in the photocatalyst coating liquid of the present invention. On the other hand, although it is 20-500 mass parts normally, 100-450 mass parts may be sufficient in order for the photocatalyst body layer obtained from a photocatalyst body coating liquid to acquire favorable adhesiveness with a base material. When the total content of niobium oxide sol particles, colloidal silica particles, and silicon alkoxide in terms of oxides is less than 20 parts by mass, the adhesion between the photocatalyst layer and the substrate decreases, while 500 parts by mass is reduced. If it exceeds, the photocatalyst particles are buried in a binder component such as niobium oxide sol particles, making it difficult to obtain a photocatalyst layer having sufficient photocatalytic activity.
〔シリコンアルコキシド〕
シリコンアルコキシドとしては、例えば、テトラエトキシシラン（ケイ酸エチル）、テトラメトキシシラン（ケイ酸メチル）、メチルトリエトキシシラン、メチルトリエトキシシランや、シリコンアルコキシドなどの加水分解物や重合物等が挙げられる。
[Silicon alkoxide]
Examples of the silicon alkoxide include tetraethoxysilane (ethyl silicate), tetramethoxysilane (methyl silicate), methyltriethoxysilane, methyltriethoxysilane, and hydrolyzates and polymers such as silicon alkoxide. .
〔溶媒〕
溶媒としては通常、水を主成分とする水性媒体、具体的には水の使用量が５０質量％以上で含むものが用いられ、水を単独で用いてもよいし、水と水溶性有機溶媒との混合溶媒であってもよい。
水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノールなどの水溶性アルコール溶媒、アセトン、メチルエチルケトン、メチルセルソルブ、およびエチルセルソルブなどが挙げられる。
〔solvent〕
As the solvent, an aqueous medium containing water as a main component, specifically, a solvent containing water in an amount of 50% by mass or more is used. Water may be used alone, or water and a water-soluble organic solvent. And a mixed solvent.
Examples of the water-soluble organic solvent include water-soluble alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, methyl ethyl ketone, methyl cellosolve, and ethyl cellosolve.
本発明の光触媒体コーティング液は、光触媒体コーティング液から溶媒などの揮発成分を揮発させて得られる固形分の酸化物換算の含有量が、光触媒体コーティング液１００質量部に対して、通常０．５質量部〜３０質量部（すなわち、光触媒体コーティング液総量に対して０．５質量％〜３０質量％）、好ましくは１質量部〜２０質量部（１質量％〜１０質量％）、より好ましくは２質量部〜１０質量部（２質量％〜１０質量％）程度となるように水やその他の溶媒で希釈されて用いられる。固形分含有量が０．５質量部未満では、十分な厚さの光触媒体層を形成しにくくなり、また固形分含有量が３０質量部を超えると、得られる光触媒体層の透明性が損なわれ易くなる。 In the photocatalyst coating liquid of the present invention, the content in terms of solid oxide obtained by volatilizing a volatile component such as a solvent from the photocatalyst coating liquid is usually 0. 5 to 30 parts by mass (that is, 0.5 to 30% by mass with respect to the total amount of the photocatalyst coating liquid), preferably 1 to 20 parts by mass (1 to 10% by mass), more preferably Is used after being diluted with water or other solvent so as to be about 2 to 10 parts by mass (2 to 10% by mass). When the solid content is less than 0.5 parts by mass, it becomes difficult to form a photocatalyst layer having a sufficient thickness, and when the solid content exceeds 30 parts by mass, the transparency of the resulting photocatalyst layer is impaired. It will be easier.
（光触媒体コーティング液の調整）
本発明の光触媒体コーティング液を調整する際の、光触媒体粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、シリコンアルコキシド及び溶媒の混合順序や混合方法は、特に制限されないが、例えば、（ａ）コロイダルシリカ粒子、シリコンアルコキシド、および溶媒を混合したバインダー液に酸化ニオブゾル粒子を混合し、さらに光触媒体粒子を単独で溶媒に分散させた光触媒体分散液を混合する方法、（ｂ）光触媒体粒子を単独で溶媒に分散させた光触媒体分散液に酸化ニオブゾル粒子、コロイダルシリカ粒子、およびシリコンアルコキシドを順次添加して混合する方法などが挙げられ、必要に応じて撹拌しながら行ってもよいし、加熱しながら行ってもよい。さらに光触媒体分散液を調製する際に、酸化ニオブゾル粒子、コロイダルシリカ粒子、シリコンアルコキシドの他にバインダーを構成する成分を添加することも可能である。
(Adjustment of photocatalyst coating liquid)
The mixing order and mixing method of the photocatalyst particles, niobium oxide sol particles, colloidal silica particles, silicon alkoxide and solvent when preparing the photocatalyst coating liquid of the present invention are not particularly limited. For example, (a) colloidal silica particles , A method of mixing niobium oxide sol particles with a binder liquid in which silicon alkoxide and a solvent are mixed, and further mixing a photocatalyst dispersion liquid in which the photocatalyst particles are dispersed in a solvent alone, (b) the photocatalyst particles are a solvent alone Examples include a method in which niobium oxide sol particles, colloidal silica particles, and silicon alkoxide are sequentially added to the photocatalyst dispersion dispersed in and mixed, and may be performed with stirring or heating as necessary. May be. Furthermore, when preparing the photocatalyst dispersion liquid, it is possible to add a component constituting the binder in addition to the niobium oxide sol particles, colloidal silica particles, and silicon alkoxide.
〔光触媒体分散液〕
光触媒体粒子を単独で溶媒に分散させた光触媒体分散液の水素イオン濃度は、通常ｐＨ２．０〜ｐＨ７．０、好ましくはｐＨ３．０〜ｐＨ６．０である。水素イオン濃度がｐＨ２．０未満では酸性が強すぎて取扱いが面倒であり、ｐＨ７．０を越えると、光触媒体粒子が酸化タングステン粒子の場合、酸化タングステン粒子が溶解するおそれがある。光触媒体分散液の水素イオン濃度は通常、酸を加えることにより調整できる。酸としては、例えば硝酸、塩酸、硫酸、リン酸、ギ酸、酢酸、蓚酸などが使用できる。
[Photocatalyst dispersion]
The hydrogen ion concentration of the photocatalyst dispersion in which the photocatalyst particles are dispersed alone in a solvent is usually pH 2.0 to pH 7.0, preferably pH 3.0 to pH 6.0. When the hydrogen ion concentration is less than pH 2.0, the acidity is too strong and the handling is troublesome. When the pH exceeds 7.0, when the photocatalyst particles are tungsten oxide particles, the tungsten oxide particles may be dissolved. The hydrogen ion concentration of the photocatalyst dispersion liquid can be usually adjusted by adding an acid. Examples of the acid that can be used include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, and succinic acid.
〔光触媒体分散液の製造〕
光触媒体分散液は、必要に応じて適当な分散剤存在下で光触媒体粒子を溶媒に添加し、分散処理を施して得ることができる。分散処理は、例えば、媒体撹拌式分散機を用いる通常の方法により行うことができる。
光触媒体粒子の溶媒への添加は、例えば、光触媒体粒子をそのまま溶媒へ添加し混合する方法で行なってもよいが、通常は、あらかじめ光触媒体粒子を分散媒中に分散させた状態で溶媒に混合する方法で行なわれ、好ましくはあらかじめ光触媒体粒子を分散媒中に分散させた状態でさらに分散処理を施してから、溶媒に混合する方法で行なわれる。
分散媒としては、例えば、前述した溶媒などが挙げられる。
[Production of photocatalyst dispersion]
The photocatalyst dispersion liquid can be obtained by adding a photocatalyst particle to a solvent in the presence of a suitable dispersant as necessary and subjecting it to a dispersion treatment. The dispersion treatment can be performed, for example, by an ordinary method using a medium stirring type disperser.
The addition of the photocatalyst particles to the solvent may be performed, for example, by adding the photocatalyst particles directly to the solvent and mixing them. Usually, however, the photocatalyst particles are dispersed in the dispersion medium in advance in the solvent. It is carried out by a method of mixing, and is preferably carried out by a method of further dispersing the photocatalyst particles previously dispersed in a dispersion medium and then mixing them with a solvent.
Examples of the dispersion medium include the solvents described above.
〔貴金属担持光触媒体分散液の製造〕
本発明における光触媒体粒子は、光触媒活性を向上させるために表面に貴金属を担持しているのが好ましい。
光触媒体粒子の表面に貴金属を担持する方法としては、例えば、前述した光触媒体分散液に犠牲剤を溶解させ、これに光照射を行う方法、光触媒体粒子を貴金属の前駆体と犠牲剤が溶解した水溶液中に分散させ、これに光照射を行う方法などがあげられる。
[Production of precious metal-supported photocatalyst dispersion]
The photocatalyst particles in the present invention preferably have a noble metal supported on the surface in order to improve the photocatalytic activity.
As a method for supporting the noble metal on the surface of the photocatalyst particle, for example, a method of dissolving a sacrificial agent in the above-described photocatalyst dispersion liquid and irradiating it with light, a photocatalyst particle is dissolved in a noble metal precursor and a sacrificial agent And a method of irradiating it with light.
〔貴金属の前駆体〕
貴金属の前駆体としては、溶媒中に溶解し得るものが使用される。かかる前駆体が溶解すると、これを構成する貴金属元素は通常、プラスの電荷を帯びた貴金属イオンとなって、溶媒中に存在する。そして、この貴金属イオンが、光の照射による光触媒体粒子の光触媒作用で０価の貴金属に還元されて、光触媒体粒子の表面に担持される。
貴金属としては、例えば、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｒｕ、Ｉｒ、Ｒｈなどが挙げられる。その前駆体としては、これら貴金属の水酸化物、硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、リン酸塩などが挙げられる。これらの中でも高い光触媒活性を得る目的で、貴金属は、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄが好ましい。
[Precursor of precious metal]
As the noble metal precursor, one that can be dissolved in a solvent is used. When such a precursor is dissolved, the noble metal element constituting the precursor usually becomes a noble metal ion having a positive charge and exists in the solvent. The noble metal ions are reduced to zero-valent noble metal by the photocatalytic action of the photocatalyst particles by light irradiation, and are supported on the surfaces of the photocatalyst particles.
Examples of the noble metal include Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh. Examples of the precursor include hydroxides, nitrates, sulfates, halides, organic acid salts, carbonates, and phosphates of these noble metals. Among these, for the purpose of obtaining high photocatalytic activity, the noble metal is preferably Cu, Pt, Au, or Pd.
Ｃｕの前駆体としては、例えば、硝酸銅（Ｃｕ(ＮＯ3)2）、硫酸銅（ＣｕＳＯ4）、塩化銅（ＣｕＣｌ2、ＣｕＣｌ）、臭化銅（ＣｕＢｒ2，ＣｕＢｒ）、沃化銅（ＣｕＩ）、沃素酸銅（ＣｕＩ2Ｏ6）、塩化アンモニウム銅（Ｃｕ(ＮＨ4)2Ｃｌ4）、オキシ塩化銅（Ｃｕ2Ｃｌ(ＯＨ)3）、酢酸銅（ＣＨ3ＣＯＯＣｕ、(ＣＨ3ＣＯＯ)2Ｃｕ）、蟻酸銅（(ＨＣＯＯ)2Ｃｕ）、炭酸銅（ＣｕＣＯ3）、蓚酸銅（ＣｕＣ2Ｏ4）、クエン酸銅（Ｃｕ2Ｃ6Ｈ4Ｏ7）、リン酸銅（ＣｕＰＯ4）などが挙げられる。 Examples of the precursor of Cu include copper nitrate (Cu (NO 3 ) 2 ), copper sulfate (CuSO 4 ), copper chloride (CuCl 2 , CuCl), copper bromide (CuBr 2 , CuBr), copper iodide ( CuI), copper iodate (CuI 2 O 6 ), ammonium copper chloride (Cu (NH 4 ) 2 Cl 4 ), copper oxychloride (Cu 2 Cl (OH) 3 ), copper acetate (CH 3 COOCu, (CH 3 COO) 2 Cu), copper formate ((HCOO) 2 Cu), copper carbonate (CuCO 3 ), copper oxalate (CuC 2 O 4 ), copper citrate (Cu 2 C 6 H 4 O 7 ), copper phosphate ( CuPO 4 ) and the like.
Ｐｔの前駆体としては、例えば、塩化白金（ＰｔＣｌ2、ＰｔＣｌ4）、臭化白金（ＰｔＢｒ2、ＰｔＢｒ4）、沃化白金（ＰｔＩ2、ＰｔＩ4）、塩化白金カリウム（Ｋ2(ＰｔＣｌ4)）、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）、亜硫酸白金（Ｈ3Ｐｔ(ＳＯ3)2ＯＨ）、塩化テトラアンミン白金（Ｐｔ(ＮＨ3)4Ｃｌ2）、炭酸水素テトラアンミン白金（Ｃ2Ｈ14Ｎ4Ｏ6Ｐｔ）、テトラアンミン白金リン酸水素（Ｐｔ(ＮＨ3)4ＨＰＯ4）、水酸化テトラアンミン白金（Ｐｔ(ＮＨ3)4(ＯＨ)2）、硝酸テトラアンミン白金（Ｐｔ(ＮＯ3)2(ＮＨ3)4）、テトラアンミン白金テトラクロロ白金（(Ｐｔ(ＮＨ3)4)(ＰｔＣｌ4)）、ジニトロジアミン白金（Ｐｔ(ＮＯ2)2（ＮＨ3）2）などが挙げられる。 Examples of the precursor of Pt include platinum chloride (PtCl 2 , PtCl 4 ), platinum bromide (PtBr 2 , PtBr 4 ), platinum iodide (PtI 2 , PtI 4 ), and potassium potassium chloride (K 2 (PtCl 4). )), Hexachloroplatinic acid (H 2 PtCl 6 ), platinum sulfite (H 3 Pt (SO 3 ) 2 OH), tetraammineplatinum chloride (Pt (NH 3 ) 4 Cl 2 ), tetraammineplatinum hydrogen carbonate (C 2 H 14) N 4 O 6 Pt), tetraammine platinum hydrogen phosphate (Pt (NH 3 ) 4 HPO 4 ), tetraammine platinum hydroxide (Pt (NH 3 ) 4 (OH) 2 ), tetraammine platinum nitrate (Pt (NO 3 ) 2 (NH 3 ) 4 ), tetraammine platinum tetrachloroplatinum ((Pt (NH 3 ) 4 ) (PtCl 4 )), dinitrodiamine platinum (Pt (NO 2 ) 2 (NH 3 ) 2 ) and the like.
Ａｕの前駆体としては、例えば、塩化金（ＡｕＣｌ）、臭化金（ＡｕＢｒ）、沃化金（ＡｕＩ）、水酸化金（Ａｕ(ＯＨ)2）、テトラクロロ金酸（ＨＡｕＣｌ4）、テトラクロロ金酸カリウム（ＫＡｕＣｌ4）、テトラブロモ金酸カリウム（ＫＡｕＢｒ4）などが挙げられる。 Examples of the precursor of Au include gold chloride (AuCl), gold bromide (AuBr), gold iodide (AuI), gold hydroxide (Au (OH) 2 ), tetrachloroauric acid (HAuCl 4 ), tetra Examples thereof include potassium chloroaurate (KAuCl 4 ) and potassium tetrabromoaurate (KAuBr 4 ).
Ｐｄの前駆体としては、例えば、酢酸パラジウム（(ＣＨ3ＣＯＯ)2Ｐｄ）、塩化パラジウム（ＰｄＣｌ2）、臭化パラジウム（ＰｄＢｒ2）、沃化パラジウム（ＰｄＩ2）、水酸化パラジウム（Ｐｄ(ＯＨ)2）、硝酸パラジウム（Ｐｄ(ＮＯ3)2）、硫酸パラジウム（ＰｄＳＯ4）、テトラクロロパラジウム酸カリウム（Ｋ2(ＰｄＣｌ4)）、テトラブロモパラジウム酸カリウム（Ｋ2(ＰｄＢｒ4)）、テトラアンミンパラジウム塩化物（Ｐｄ（ＮＨ3）4Ｃｌ2）、テトラアンミンパラジウム臭化物（Ｐｄ（ＮＨ3）4Ｂｒ2）、テトラアンミンパラジウム硝酸塩（Ｐｄ（ＮＨ3）4（ＮＯ3）2）、テトラアンミンパラジウムテトラクロロパラジウム酸（（Ｐｄ（ＮＨ3）4）（ＰｄＣｌ4））、テトラクロロパラジウム酸アンモニウム（（ＮＨ4）2ＰｄＣｌ4）等が挙げられる。 Examples of the precursor of Pd include palladium acetate ((CH 3 COO) 2 Pd), palladium chloride (PdCl 2 ), palladium bromide (PdBr 2 ), palladium iodide (PdI 2 ), palladium hydroxide (Pd ( OH) 2 ), palladium nitrate (Pd (NO 3 ) 2 ), palladium sulfate (PdSO 4 ), potassium tetrachloropalladate (K 2 (PdCl 4 )), potassium tetrabromopalladate (K 2 (PdBr 4 )) , Tetraammine palladium chloride (Pd (NH 3 ) 4 Cl 2 ), tetraammine palladium bromide (Pd (NH 3 ) 4 Br 2 ), tetraammine palladium nitrate (Pd (NH 3 ) 4 (NO 3 ) 2 ), tetraammine palladium tetra Chloropalladium acid ((Pd (NH 3 ) 4 ) (PdCl 4 )), ammonium tetrachloropalladate ( (NH 4 ) 2 PdCl 4 ) and the like.
貴金属の前駆体は、それぞれ単独で、または２種類以上を組み合わせて使用される。その使用量は、貴金属原子に換算して、光触媒体粒子の使用量１００質量部に対して、光触媒作用の向上効果が十分に得られる点で通常０．０１質量部以上、コストに見合った効果が得られる点で通常１質量部以下であり、好ましくは０．０５質量部〜０．６質量部である。 The noble metal precursors may be used alone or in combination of two or more. The amount used is usually 0.01 parts by mass or more, in terms of cost, in terms of sufficiently improving the photocatalytic action with respect to 100 parts by mass of the photocatalyst particles in terms of precious metal atoms. Is usually 1 part by mass or less, preferably 0.05 part by mass to 0.6 part by mass.
〔犠牲剤〕
光触媒体粒子の表面に貴金属を担持させる場合には、犠牲剤を用い、例えば、光触媒体分散液に添加する。
犠牲剤としては、例えば、エタノール、メタノール、プロパノール等のアルコール、アセトン等のケトン、蓚酸等のカルボン酸などが用いられる。
犠牲剤は、光触媒体分散液に一定時間光照射を行った後に添加し、さらに光照射を行う。犠牲剤の量は光触媒体分散液における溶媒に対して、通常０．００１質量倍〜０．３質量倍、好ましくは０．００５質量倍〜０．１質量倍である。犠牲剤の使用量が０．００１質量倍未満では光触媒体粒子への貴金属の担持が不十分となり、０．３質量倍を超えると犠牲剤の量が過剰量となりコストに見合う効果が得られない。
[Sacrificial agent]
When a noble metal is supported on the surface of the photocatalyst particles, a sacrificial agent is used, for example, added to the photocatalyst dispersion.
Examples of the sacrificial agent include alcohols such as ethanol, methanol, and propanol, ketones such as acetone, and carboxylic acids such as oxalic acid.
The sacrificial agent is added after the photocatalyst dispersion liquid is irradiated with light for a certain period of time, and further irradiated with light. The amount of the sacrificial agent is usually 0.001 to 0.3 times, preferably 0.005 to 0.1 times, with respect to the solvent in the photocatalyst dispersion. If the amount of the sacrificial agent used is less than 0.001 times by mass, the noble metal is insufficiently supported on the photocatalyst particles, and if it exceeds 0.3 times by mass, the amount of sacrificial agent is excessive and an effect commensurate with the cost cannot be obtained. .
〔光の照射〕
光触媒体分散液への光の照射は、撹拌しながら行ってもよい。透明なガラスやプラスチック製の管内を通過させながら管の内外から照射してもよく、これを繰り返してもよい。
光源は、光触媒体粒子のバンドギャップ以上のエネルギーを有する光を照射できるものであれば特に制限はなく、具体例としては、殺菌灯、水銀灯、発光ダイオード、蛍光灯、ハロゲンランプ、キセノンランプ、太陽光などを用いることができる。
照射する光の波長は通常、１８０ｎｍ〜５００ｎｍである。
光照射を行う時間は、十分な量の貴金属を光触媒体粒子に担持できることから、犠牲剤の添加前後において、通常２０分以上、好ましくは１時間以上、通常２４時間以下、好ましくは６時間以下である。２４時間を越える場合、それまでに貴金属の前駆体の殆どは貴金属となって光触媒体粒子に担持されてしまい、光照射にかかるコストに見合う効果が得られない。また、犠牲剤の添加前に光照射を行わない場合、光触媒体粒子への貴金属の担持が不均一となり、高い光触媒活性が得られない。
[Light irradiation]
The photocatalyst dispersion liquid may be irradiated with light while stirring. Irradiation may be performed from inside or outside the tube while passing through a transparent glass or plastic tube, or this may be repeated.
The light source is not particularly limited as long as it can irradiate light having energy higher than the band gap of the photocatalyst particles. Specific examples include a germicidal lamp, a mercury lamp, a light emitting diode, a fluorescent lamp, a halogen lamp, a xenon lamp, and a solar light. Light or the like can be used.
The wavelength of the irradiated light is usually 180 nm to 500 nm.
The time for performing the light irradiation is such that a sufficient amount of noble metal can be supported on the photocatalyst particles, so that it is usually 20 minutes or longer, preferably 1 hour or longer, usually 24 hours or shorter, preferably 6 hours or shorter before and after the addition of the sacrificial agent. is there. When the time exceeds 24 hours, most of the precursors of the noble metal have become noble metals and are supported on the photocatalyst particles, and an effect commensurate with the cost of light irradiation cannot be obtained. Moreover, when light irradiation is not performed before the addition of the sacrificial agent, noble metal is not uniformly supported on the photocatalyst particles, and high photocatalytic activity cannot be obtained.
〔ｐＨ調整〕
光触媒体分散液のｐＨを２．５〜５．５、好ましくは３．０〜５．０に維持しながら光照射を行う。通常、光照射により貴金属が光触媒体粒子の表面に担持される際には光触媒体分散液のｐＨが酸性に除々に変化するので、ｐＨを上記範囲内に維持するため、通常塩基を添加すればよい。これにより貴金属が光触媒体粒子の表面に担持された、分散性に優れる貴金属担持光触媒体分散液が得られる。
塩基としては、例えば、アンモニア、水酸化ナトリウム、水酸化カリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウム、水酸化ランタン等の水溶液が挙げられるが、これらの中でもアンモニア水および水酸化ナトリウムを用いるのが好ましい。
[PH adjustment]
Light irradiation is performed while maintaining the pH of the photocatalyst dispersion liquid at 2.5 to 5.5, preferably 3.0 to 5.0. Usually, when noble metal is supported on the surface of the photocatalyst particles by light irradiation, the pH of the photocatalyst dispersion liquid gradually changes to acidic. Therefore, in order to maintain the pH within the above range, a base is usually added. Good. As a result, a noble metal-supported photocatalyst dispersion having excellent dispersibility, in which the noble metal is supported on the surface of the photocatalyst particles, is obtained.
Examples of the base include aqueous solutions of ammonia, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lanthanum hydroxide, etc. Among them, ammonia water and water Sodium oxide is preferably used.
〔貴金属担持光触媒体粒子〕
ｐＨを調整しながら光照射を行い、犠牲剤添加後、さらに光を照射することにより、貴金属前駆体が貴金属となって光触媒体粒子の表面に担持されて、目的の貴金属担持光触媒体粒子を得る。この貴金属担持光触媒体粒子は用いた溶媒中に、沈降することなく分散されている。
[Noble metal-supported photocatalyst particles]
Irradiate light while adjusting the pH, and after adding the sacrificial agent, further irradiate light, whereby the noble metal precursor becomes a noble metal and is supported on the surface of the photocatalyst particle to obtain the desired noble metal-supported photocatalyst particle. . The noble metal-supported photocatalyst particles are dispersed in the solvent used without settling.
〔添加剤〕
上記のようにして調整された光触媒体コーティング液は、光触媒体粒子および／または貴金属担持光触媒体粒子の分散性を損なわない範囲で、添加剤を含んでいてもよい。
〔Additive〕
The photocatalyst coating liquid prepared as described above may contain an additive as long as the dispersibility of the photocatalyst particles and / or noble metal-supported photocatalyst particles is not impaired.
添加剤としては、例えば、光触媒作用を向上させる目的で添加されるものが挙げられ、具体的には、水ガラスなどの珪素化合物、非晶質アルミナ、アルミナゾル、水酸化アルミニウムなどのアルミニウム化合物、ゼオライト、カオリナイトなどのアルミノ珪酸塩、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどのアルカリ土類金属酸化物またはアルカリ度類金属水酸化物、リン酸カルシウム、モレキュラーシーブ、活性炭、有機ポリシロキサン化合物の重縮合物、リン酸塩、フッ素系ポリマー、シリコン系ポリマー、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、ウレタン樹脂、アルキド樹脂などが挙げられる。これらの添加剤はそれぞれ単独で、または２種以上を組合せて用いられる。 Examples of the additive include those added for the purpose of improving the photocatalytic action, specifically, silicon compounds such as water glass, aluminum compounds such as amorphous alumina, alumina sol, and aluminum hydroxide, zeolites , Alkaline earth metal oxides such as kaolinite, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, etc. Examples thereof include oxides, calcium phosphates, molecular sieves, activated carbon, polycondensates of organic polysiloxane compounds, phosphates, fluorine-based polymers, silicon-based polymers, acrylic resins, polyester resins, melamine resins, urethane resins, and alkyd resins. These additives are used alone or in combination of two or more.
〔光触媒機能製品〕
本発明の光触媒機能製品は、上記のようにして得られた光触媒体コーティング液を用いて形成された光触媒体層を表面に備える。
光触媒体層は、例えば、光触媒体コーティング液を、スピンコート、ディップコート、ドクターブレード、スプレーまたはハケ塗りなどにより基材（製品）の表面に塗布した後に、室温〜１５０℃、好ましくは室温〜９０℃の温度範囲で溶媒を乾燥蒸発させ、揮発成分を揮発させるなど、従来公知の成膜方法によって形成することができる。
光触媒体層の膜厚は、特に制限されるものではなく、通常、その用途等に応じて、数百ｎｍ〜数ｍｍまで適宜設定すればよい。光触媒体層は、基材（製品）の内表面または外表面であれば、どの部分に形成されていてもよいが、例えば、光（可視光線）が照射される面であって、かつ悪臭物質が発生する箇所や、病原菌が存在する箇所と連続または断続して空間的につながる面に形成されていることが好ましい。
なお、基材（製品）の材質は、形成される光触媒体層を実用に耐えうる強度で保持できる限り、特に制限されるものではなく、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙などのあらゆる材料からなる製品を対象にすることができる。尚、光触媒作用による光触媒体層と基材の密着性の劣化を抑制するために、光触媒体層と基材の間に、例えばシリカ成分等からなる公知のバリア層を形成することができる。
[Photocatalytic functional products]
The photocatalyst functional product of the present invention has a photocatalyst layer formed on the surface using the photocatalyst coating liquid obtained as described above.
The photocatalyst layer is formed, for example, by applying a photocatalyst coating liquid to the surface of the substrate (product) by spin coating, dip coating, doctor blade, spraying or brushing, and then room temperature to 150 ° C., preferably room temperature to 90 ° It can be formed by a conventionally known film forming method such as drying and evaporating the solvent in the temperature range of ° C. and volatilizing the volatile component.
The film thickness of the photocatalyst body layer is not particularly limited, and usually may be appropriately set from several hundred nm to several mm according to the application. The photocatalyst layer may be formed on any part as long as it is an inner surface or an outer surface of the base material (product). For example, the photocatalyst layer is a surface irradiated with light (visible light), and a malodorous substance. It is preferably formed on a surface that is continuously or intermittently connected to a place where the occurrence of a pathogen or a pathogen is present.
The material of the base material (product) is not particularly limited as long as the formed photocatalyst layer can be held at a strength that can be practically used. For example, plastic, metal, ceramics, wood, concrete, paper, etc. Products made of any material can be targeted. In addition, in order to suppress the deterioration of the adhesion between the photocatalyst layer and the substrate due to the photocatalytic action, a known barrier layer made of, for example, a silica component can be formed between the photocatalyst layer and the substrate.
プラスチックとしては、熱硬化性樹脂の場合には、例えば、アラミド樹脂、ポリイミド樹脂、エポキシ樹脂、不飽和ポリエステル樹脂、フェノール樹脂、ユリア樹脂、ポリウレタン樹脂、メラミン樹脂、ベンゾグアナミン樹脂、シリコーン樹脂、メラミンユリア樹脂などがあげられ、熱可塑性樹脂の場合には、例えば、縮重合系樹脂やビニルモノマーを重合して得られる樹脂などがあげられる。 As the plastic, in the case of a thermosetting resin, for example, aramid resin, polyimide resin, epoxy resin, unsaturated polyester resin, phenol resin, urea resin, polyurethane resin, melamine resin, benzoguanamine resin, silicone resin, melamine urea resin In the case of a thermoplastic resin, examples thereof include a condensation polymerization resin and a resin obtained by polymerizing a vinyl monomer.
縮重合系樹脂としては、例えば、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリ乳酸、生分解性ポリエステル、ポリエステル系液晶ポリマーなどのポリエステル系樹脂；エチレンジアミン−アジピン酸重縮合体（ナイロン−６６）、ナイロン−６、ナイロン−１２、ポリアミド系液晶ポリマーなどのポリアミド樹脂；ポリカーボネート樹脂、ポリフェニレンオキシド、ポリメチレンオキシド、アセタール樹脂などのポリエーテル系樹脂；セルロースおよびその誘導体などの多糖類系樹脂；などがあげられる。 Examples of the condensation polymerization resin include polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polylactic acid, biodegradable polyester, and polyester liquid crystal polymer; ethylenediamine-adipic acid polycondensate (nylon-66), nylon-6 And polyamide resins such as nylon-12 and polyamide liquid crystal polymers; polyether resins such as polycarbonate resin, polyphenylene oxide, polymethylene oxide, and acetal resin; polysaccharide resins such as cellulose and derivatives thereof;
ビニルモノマーを重合して得られる樹脂としては、例えば、ポリオレフィン系樹脂；ポリスチレン、ポリ−α−メチルスチレン、スチレン−エチレン−プロピレン共重合体（ポリスチレン−ポリ（エチレン/プロピレン）ブロック共重合体）、スチレン−エチレン−ブテン共重合体（ポリスチレン−ポリ（エチレン/ブテン）ブロック共重合体）、スチレン−エチレン−プロピレン−スチレン共重合体（ポリスチレン−ポリ（エチレン/プロピレン）−ポリスチレンブロック共重合体）、エチレン−スチレン共重合体などの不飽和芳香族含有樹脂；ポリビニルアルコール、ポリビニルブチラールなどのポリビニルアルコール系樹脂；ポリメチルメタクリレート、モノマーとしてメタクリル酸エステル、アクリル酸エステル、メタクリル酸アミド、アクリル酸アミドを含むアクリル系樹脂；ポリ塩化ビニル、ポリ塩化ビニリデンなどの塩素系樹脂；ポリテトラフルオロエチレン、エチレン−テトラフルオロエチレン共重合体、テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、エチレン−テトラフルオロエチレン−ヘキサフルオロプロピレン共重合体、ポリフッ化ビニリデンなどのフッ素系樹脂；などがあげられる。 Examples of resins obtained by polymerizing vinyl monomers include polyolefin resins; polystyrene, poly-α-methylstyrene, styrene-ethylene-propylene copolymers (polystyrene-poly (ethylene / propylene) block copolymers), Styrene-ethylene-butene copolymer (polystyrene-poly (ethylene / butene) block copolymer), styrene-ethylene-propylene-styrene copolymer (polystyrene-poly (ethylene / propylene) -polystyrene block copolymer), Unsaturated aromatic-containing resins such as ethylene-styrene copolymers; polyvinyl alcohol resins such as polyvinyl alcohol and polyvinyl butyral; polymethyl methacrylate, methacrylic acid ester, acrylic acid ester, methacrylic acid amide as monomers Acrylic resin containing chloric acid amide; Chlorine resin such as polyvinyl chloride and polyvinylidene chloride; Polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetra And fluororesin such as fluoroethylene-hexafluoropropylene copolymer and polyvinylidene fluoride.
本発明の光触媒機能製品は、屋外においては勿論のこと、蛍光灯、白熱球、発光ダイオード、およびナトリウムランプのような可視光源からの光しか受けない屋内環境においても、光照射によって高い光触媒作用を示す。したがって、本発明の光触媒体コーティング液を、例えば、天井材、タイル、ガラス、壁紙、壁材、床等の建築資材、自動車内装材（自動車インストルメントパネル、自動車用シート、自動車用天井材）、冷蔵庫やエアコン等の家電製品、衣類やカーテン等の繊維製品、電車のつり革、エレベーターのボタン等、不特定多数の人が接触する基材表面などに塗布して乾燥させると、屋内照明による光照射によって、ホルムアルデヒドやアセトアルデヒドなどの揮発性有機物、アルデヒド類、メルカプタン類、アンモニアなどの悪臭物質、窒素酸化物の濃度を低減させ、黄色ブドウ球菌、大腸菌、炭疽菌、結核菌、コレラ菌、ジフテリア菌、破傷風菌、ペスト菌、赤痢菌、ボツリヌス菌、およびレジオネラ菌等の病原菌等を死滅、分解、除去することができ、さらに、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することができる。また、本発明の光触媒機能製品は、可視光線を照射すれば、充分な親水性を発揮し、防曇性を発現するだけでなく、汚れに水をかけるだけで容易に拭き取ることができるようになり、さらに帯電をも防止できる。 The photocatalytic functional product of the present invention has a high photocatalytic effect by light irradiation not only outdoors but also in an indoor environment that receives only light from a visible light source such as a fluorescent lamp, an incandescent bulb, a light emitting diode, and a sodium lamp. Show. Therefore, the photocatalyst coating liquid of the present invention is, for example, a building material such as a ceiling material, tile, glass, wallpaper, wall material, floor, automobile interior material (automobile instrument panel, automobile seat, automobile ceiling material), Light applied by indoor lighting when applied to the surface of base materials that are in contact with an unspecified number of people, such as household appliances such as refrigerators and air conditioners, textile products such as clothes and curtains, train straps, elevator buttons, etc. Irradiation reduces the concentration of volatile organic substances such as formaldehyde and acetaldehyde, aldehydes, mercaptans, ammonia and other malodorous substances, nitrogen oxides, and Staphylococcus aureus, Escherichia coli, anthrax, tuberculosis, cholera, diphtheria , Kill, decompose, and remove pathogens such as tetanus, plague, shigella, botulinum, and legionella Bets can be can be further harmless allergens such as mite allergen and cedar pollen allergen. In addition, the photocatalytic functional product of the present invention is not only capable of exhibiting sufficient hydrophilicity and exhibiting antifogging properties when irradiated with visible light, but also can be easily wiped off by simply applying water to the dirt. In addition, charging can be prevented.
以下、実施例を挙げて本発明をより詳細に説明するが、本発明はこれらの実施例によって限定されるものではない。
各実施例における測定法は、以下である。
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited by these Examples.
The measurement method in each example is as follows.
１．ＢＥＴ比表面積
白金担持酸化タングステン粒子のＢＥＴ比表面積は、比表面積測定装置〔湯浅アイオニクス社製の「モノソーブ」〕を用いて窒素吸着法により測定した。
1. BET Specific Surface Area The BET specific surface area of the platinum-supported tungsten oxide particles was measured by a nitrogen adsorption method using a specific surface area measuring device [“Monosorb” manufactured by Yuasa Ionics Co., Ltd.].
２．平均分散粒子径（ｎｍ）
サブミクロン粒度分布測定装置〔コールター社製「Ｎ４Ｐｌｕｓ」〕を用いて試料の粒度分布を測定し、この装置に付属のソフトで、自動的に単分散モード解析して得られた結果を平均分散粒子径とした。
2. Average dispersed particle size (nm)
Measure the particle size distribution of the sample using a sub-micron particle size distribution analyzer (“N4Plus” manufactured by Coulter, Inc.), and automatically disperse the result of monodisperse mode analysis using the software provided with this device. The diameter.
３．硬度試験
光触媒体層の硬度は、鉛筆硬度試験法（ＪＩＳ５６００-５-４）により測定した。
3. Hardness test The hardness of the photocatalyst layer was measured by a pencil hardness test method (JIS 5600-5-4).
４．密着性
基材に対する光触媒体層の密着性は、粘着セロファンテープ（ニチバン（株）製の「ＣＴ４０５ＡＰ−２４」）を光触媒体層の表面に貼着した後、素早く剥したときに、光触媒体層が同時に剥れるか否かにより評価した。
4). Adhesiveness Adhesiveness of the photocatalyst layer to the substrate is determined when the adhesive cellophane tape ("CT405AP-24" manufactured by Nichiban Co., Ltd.) is attached to the surface of the photocatalyst layer and then quickly peeled off. It evaluated by whether it peeled simultaneously.
５．限界接触角測定
〔試験片の作製（光触媒体層形成）〕
得られた光触媒体コーティング液を、縦５０ｍｍ、横５０ｍｍ、厚さ２ｍｍのガラス板上にスピンコーター（商品名「１Ｈ−Ｄ７」、ミカサ（株）製）を用いて、回転数１０００ｒｐｍで塗布し、室温で乾燥させた後、この硝子板を７０℃で６０分乾燥して、硝子板の片面全体に光触媒体層を形成して試験片を作製した。
5. Limit contact angle measurement [test specimen preparation (photocatalyst layer formation)]
The obtained photocatalyst coating liquid was applied on a glass plate having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm using a spin coater (trade name “1H-D7”, manufactured by Mikasa Corporation) at a rotation speed of 1000 rpm. After drying at room temperature, this glass plate was dried at 70 ° C. for 60 minutes to form a photocatalyst layer on one side of the glass plate to prepare a test piece.
〔疎水性有機物付着時の親水性評価試験条件〕
試験片の光触媒体層の上から、市販のブラックライトを光源として、室温、大気中で、２日間紫外線を照射した。このとき、光触媒体層近傍での紫外線強度が約２ｍＷ／ｃｍ2（トプコン社製の紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を取り付けて測定）となるようにした。
次いで、オレイン酸の濃度が０．５容量％のｎ−ヘプタンを、試験片にディップコーター（ＳＤＩ社製の「ＤＴ−０３０３−Ｓ１」）で塗布した後、７０℃で１５分乾燥した。ディップコーターの引き上げ速度は１０ｍｍ／秒で、浸漬時間は１０秒であった。その後、このオレイン酸を塗布した試験片に、市販の白色蛍光灯を光源とし、アクリル樹脂板（日東樹脂工業（株）製の「Ｎ１６９」）を通して、試験片に光触媒体層の上から、蛍光灯に含まれる可視光が照射されるようにして行い、所定時間経過後の水滴の接触角θを接触角計（協和界面科学（株）製の「ＣＡ−Ａ型」）を用いて測定した。水滴の接触角θの測定は、いずれの場合も、水滴（約０．４μＬ）を試験片の光触媒体層上に設置してから５秒後に行なった。なお、可視光の照射は、このとき、光触媒体層近傍での照度が６０００ルクス（ミノルタ社製の照度計「Ｔ−１０」で測定）となるようにした。蛍光灯照射後、光触媒体層の光触媒作用でオレイン酸が分解し、水滴の接触角が低下するが、この接触角の低下が飽和に達した角度を限界接触角とした。限界接触角が小さいほど、光触媒体層の光触媒活性、すなわち光誘起親水性と有機物分解性能が高いといえる。
[Hydrophilicity evaluation test conditions for hydrophobic organic substances]
From the top of the photocatalyst layer of the test piece, ultraviolet rays were irradiated for 2 days at room temperature in the atmosphere using a commercially available black light as a light source. At this time, the UV intensity in the vicinity of the photocatalyst layer is about 2 mW / cm 2 (measured by attaching the UV receiver “UD-36” to the UV intensity meter “UVR-2” manufactured by Topcon Corporation). did.
Next, n-heptane having an oleic acid concentration of 0.5 vol% was applied to the test piece with a dip coater (“DT-0303-S1” manufactured by SDI), and then dried at 70 ° C. for 15 minutes. The lifting speed of the dip coater was 10 mm / second, and the immersion time was 10 seconds. Thereafter, a commercially available white fluorescent lamp is used as a light source on the test piece coated with oleic acid, and an acrylic resin plate (“N169” manufactured by Nitto Resin Co., Ltd.) is passed through the test piece from above the photocatalyst layer. Visible light contained in the lamp was irradiated, and the contact angle θ of the water drop after a predetermined time elapsed was measured using a contact angle meter (“CA-A type” manufactured by Kyowa Interface Science Co., Ltd.). . The measurement of the contact angle θ of the water droplet was performed 5 seconds after the water droplet (about 0.4 μL) was placed on the photocatalyst layer of the test piece in each case. In this case, the irradiation with visible light was such that the illuminance in the vicinity of the photocatalyst layer was 6000 lux (measured with an illuminometer “T-10” manufactured by Minolta). After irradiation with a fluorescent lamp, oleic acid is decomposed by the photocatalytic action of the photocatalyst layer, and the contact angle of the water droplet is reduced. It can be said that the smaller the limit contact angle, the higher the photocatalytic activity of the photocatalyst layer, that is, the photo-induced hydrophilicity and the organic substance decomposition performance.
６．揮発性有機物分解活性
〔アセトアルデヒド分解能の測定〕
光触媒活性は、蛍光灯の光の照射下でのアセトアルデヒドの分解反応における一次反応速度定数を測定することにより評価した。すなわち、ガラス製シャーレ（外径７０ｍｍ、内径６６ｍｍ、高さ１４ｍｍ、容量約４８ｍＬ）に、得られた光触媒体コーティング液を底面の単位面積あたりの固形分換算の滴下量が１ｇ／ｍ2となるように滴下し、シャーレの底面全体に均一に形成した。次いで、このシャーレを１１０℃の乾燥機内で大気中で１時間保持することにより乾燥させて、ガラス製シャーレの底面に光触媒体層を形成した。この光触媒体層に紫外線強度が２ｍＷ／ｃｍ2（トプコン社製の紫外線強度計「ＵＶＲ−２」に同社製受光部「ＵＤ−３６」を取り付けて測定）となるようにブラックライトからの紫外線を１６時間照射して、これを光触媒活性測定用試料とした。
6). Volatile organic matter decomposition activity (measurement of acetaldehyde resolution)
The photocatalytic activity was evaluated by measuring a first-order reaction rate constant in the decomposition reaction of acetaldehyde under irradiation of light from a fluorescent lamp. That is, in a glass petri dish (outer diameter 70 mm, inner diameter 66 mm, height 14 mm, capacity about 48 mL), the amount of the resulting photocatalyst coating liquid dropped in terms of solid content per unit area of the bottom surface is 1 g / m 2. It was dripped so that it was uniformly formed on the entire bottom of the petri dish. Next, the petri dish was dried by holding it in the air at 110 ° C. for 1 hour in the air to form a photocatalyst layer on the bottom of the glass petri dish. The photocatalyst layer is irradiated with UV light from a black light so that the UV intensity is 2 mW / cm 2 (measured by attaching a UV receiver “UD-36” to Topcon UV intensity meter “UVR-2”). This was irradiated for 16 hours and used as a photocatalytic activity measurement sample.
次に、この光触媒活性測定用試料をシャーレごとガスバッグ（内容積１Ｌ）の中に入れて密閉し、次いで、このガスバッグ内を真空にした後、酸素と窒素との体積比が１：４である混合ガス０．６Ｌを封入し、さらにその中に１％アセトアルデヒドを含む窒素ガス３ｍＬを封入して、暗所で室温下１時間保持した。その後、市販の白色蛍光灯を光源とし、アクリル樹脂板（日東樹脂工業（株）製の「Ｎ１６９」）を通して、測定用試料近傍での照度が１０００ルクス（ミノルタ社製の照度計「Ｔ−１０」で測定）となるようにガスバッグの外から可視光を照射し、アセトアルデヒドの分解反応を行った。蛍光灯の光照射を開始してから１．５時間毎にガスバッグ内のガスをサンプリングし、アセトアルデヒドの濃度をガスクロマトグラフ（（株）島津製作所製の「ＧＣ−１４Ａ」）にて測定した。そして照射時間に対するアセトアルデヒドの濃度から一次反応速度定数を算出し、これをアセトアルデヒド分解能として評価した。この一次反応速度定数が大きいほど、アセトアルデヒドの分解能、すなわち光触媒活性が高いと言える。 Next, the sample for photocatalytic activity measurement is placed in a gas bag (internal volume 1 L) together with the petri dish, and then the inside of the gas bag is evacuated, and then the volume ratio of oxygen to nitrogen is 1: 4. Was mixed with 0.6 L of a mixed gas, and 3 mL of nitrogen gas containing 1% acetaldehyde was sealed therein, and the mixture was kept in the dark at room temperature for 1 hour. Then, using a commercially available white fluorescent lamp as a light source, the illuminance in the vicinity of the measurement sample is 1000 lux through the acrylic resin plate (“N169” manufactured by Nitto Resin Co., Ltd.) (illuminance meter “T-10 manufactured by Minolta Co., Ltd.). ) Was irradiated with visible light from the outside of the gas bag to cause acetaldehyde decomposition reaction. The gas in the gas bag was sampled every 1.5 hours after the light irradiation of the fluorescent lamp was started, and the concentration of acetaldehyde was measured with a gas chromatograph (“GC-14A” manufactured by Shimadzu Corporation). Then, a first-order rate constant was calculated from the concentration of acetaldehyde with respect to the irradiation time, and this was evaluated as acetaldehyde resolution. It can be said that the higher the first-order rate constant, the higher the resolution of acetaldehyde, that is, the photocatalytic activity.
（実施例１）
〔貴金属担持光触媒体分散液の調製〕
溶媒としてイオン交換水４ｋｇに、酸化タングステン粒子（日本無機化学工業（株）製）１ｋｇを加えて混合して混合物を得た。この混合物を湿式媒体撹拌ミルを用いて分散処理して酸化タングステン粒子分散液を得た。
Example 1
[Preparation of precious metal-supported photocatalyst dispersion]
As a solvent, 1 kg of tungsten oxide particles (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) was added to 4 kg of ion-exchanged water and mixed to obtain a mixture. This mixture was dispersed using a wet medium stirring mill to obtain a tungsten oxide particle dispersion.
この酸化タングステン粒子分散液にヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液をヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．１２質量部になるように加え、原料分散液としてヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は、１７．６質量部（固形分濃度１７．６質量％）であった。その後、この分散液のｐＨは２．０であった。 To this tungsten oxide particle dispersion, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) was added so that hexachloroplatinic acid was 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms, A hexachloroplatinic acid-containing tungsten oxide particle dispersion was obtained as a raw material dispersion. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 17.6 parts by mass (solid content concentration 17.6% by mass). Thereafter, the pH of this dispersion was 2.0.
次いで、ｐＨ電極と、このｐＨ電極に接続され、０．１質量％のアンモニア水を供給してｐＨを一定に調節する制御機構を有するｐＨコントローラ（ｐＨ＝３．５に設定）と、窒素吹込み菅を備え、水中殺菌灯（三共電気（株）製の「ＧＬＤ１５ＭＱ」）を設置したガラス管（内径３７ｍｍ，高さ３６０ｍｍ）からなる光照射装置で、濃度を水で１２質量部（固形分濃度１２．０質量％）に調整した原料分散液１２００ｇを、毎分１Ｌの速度で流通させながら、この分散液のｐＨを３．５にした。原料分散液を流通させながら光照射（紫外線照射）を２時間行い、更にメタノールをその濃度が全溶媒の１質量％となるように加えて、原料分散液を流通させながら光照射を３時間行って粗粒を含む白金担持酸化タングステン粒子分散液を得た。光照射中、ｐＨは３．５で一定であった。その後遠心分離機にて粗粒を分離し、更に透析処理により白金担持酸化タングステン粒子分散液中に含まれる陽イオンと陰イオンの除去を行ったところ、ｐＨが３．８で平均分散粒子径が１０１ｎｍの白金担持酸化タングステン粒子分散液を得た。 Next, a pH electrode, a pH controller (set to pH = 3.5) connected to the pH electrode and having a control mechanism for adjusting the pH to a constant level by supplying 0.1 mass% ammonia water, A light irradiation device comprising a glass tube (inner diameter: 37 mm, height: 360 mm) equipped with an underwater sterilization lamp (“GLD15MQ” manufactured by Sankyo Electric Co., Ltd.) and having a concentration of 12 parts by mass (solid content) While dispersing 1200 g of the raw material dispersion adjusted to a concentration of 12.0% by mass at a rate of 1 L / min, the pH of this dispersion was adjusted to 3.5. Light irradiation (ultraviolet irradiation) is performed for 2 hours while circulating the raw material dispersion, and methanol is further added so that the concentration thereof is 1% by mass of the total solvent, and light irradiation is performed for 3 hours while circulating the raw material dispersion. Thus, a platinum-supported tungsten oxide particle dispersion containing coarse particles was obtained. During light irradiation, the pH was constant at 3.5. Thereafter, coarse particles were separated by a centrifugal separator, and further, cation and anion contained in the platinum-supported tungsten oxide particle dispersion were removed by dialysis, and the pH was 3.8 and the average dispersed particle size was A 101 nm platinum-supported tungsten oxide particle dispersion was obtained.
得られた白金担持酸化タングステン粒子分散液にエタノール水溶液を加えて白金担持光触媒体分散液を得た。白金担持光触媒体分散液１００質量部に対する白金担持酸化タングステン粒子の含有量は５質量部で、エタノールの含有量は３０質量部であった。 An aqueous ethanol solution was added to the obtained platinum-supported tungsten oxide particle dispersion to obtain a platinum-supported photocatalyst dispersion. The content of the platinum-supported tungsten oxide particles with respect to 100 parts by mass of the platinum-supported photocatalyst dispersion liquid was 5 parts by mass, and the content of ethanol was 30 parts by mass.
この白金担持光触媒体分散液を２０℃で２４時間保管したところ、保管後に固液分離は見られなかった。また、白金担持酸化タングステン粒子分散液の一部を真空乾燥して固形分を得たところ、得られた固形分のＢＥＴ比表面積４５ｍ2／ｇであった。 When this platinum-supported photocatalyst dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage. A part of the platinum-supported tungsten oxide particle dispersion was vacuum-dried to obtain a solid content, and the BET specific surface area of the obtained solid content was 45 m 2 / g.
〔光触媒体コーティング液の調製〕
高純度正ケイ酸エチル（多摩化学工業（株）製）４０ｇにエタノール２１０ｇと水３３５ｇを添加した。その後コロイダルシリカ粒子（日産化学工業（株）製の「ＳＴ―ＯＳ」，酸化物換算での固形分濃度２０質量%）を１１７．５ｇ添加してバインダーを得た。
[Preparation of photocatalyst coating liquid]
210 g of ethanol and 335 g of water were added to 40 g of high purity ethyl silicate (manufactured by Tama Chemical Co., Ltd.). Thereafter, 117.5 g of colloidal silica particles (“ST-OS” manufactured by Nissan Chemical Industries, Ltd., solid content concentration of 20% by mass in terms of oxide) was added to obtain a binder.
酸化ニオブゾル粒子（多木化学工業（株）製の「Ｎｂ―Ｘ―１０」，酸化物換算での固形分濃度１０質量％）をエタノール水溶液で希釈し、エタノール含有酸化ニオブゾルを得た。エタノール含有酸化ニオブゾル１００質量部に対するエタノールと酸化物換算での酸化ニオブゾル粒子と含有量は、それぞれ３０質量部および５質量部であった。 Niobium oxide sol particles ("Nb-X-10" manufactured by Taki Chemical Industry Co., Ltd., solid content concentration of 10% by mass in terms of oxide) were diluted with an aqueous ethanol solution to obtain an ethanol-containing niobium oxide sol. The content of ethanol and niobium oxide sol particles in terms of oxide with respect to 100 parts by mass of the ethanol-containing niobium oxide sol was 30 parts by mass and 5 parts by mass, respectively.
次に、バインダー７００ｇにエタノール含有酸化ニオブゾル１００ｇ添加し、さらに白金担持光触媒体分散液（固形分濃度５質量％）を２００ｇ加えて光触媒体コーティング液を得た。尚、これらは全て室温、大気下で行い、各成分の添加は攪拌しながら行った。 Next, 100 g of ethanol-containing niobium oxide sol was added to 700 g of binder, and 200 g of platinum-supported photocatalyst dispersion (solid content concentration 5 mass%) was further added to obtain a photocatalyst coating liquid. All of these were performed at room temperature and in the atmosphere, and each component was added with stirring.
得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部（５質量％）であった。また、全固形分１００質量部には、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算が、それぞれ２０質量部、１０質量部、４７質量部、および２３質量部含まれていた。 The total solid content in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass (5% by mass) with respect to 100 parts by mass of the photocatalyst coating liquid. Further, the total solid content of 100 parts by mass includes platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate oxide conversions of 20 parts by mass, 10 parts by mass, 47 parts by mass, and 23, respectively. Part by mass was included.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、４３質量部、２０４質量部、および２４８質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 43 parts by mass, 204 parts by mass, and 248 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of oxide silicate in ethyl silicate. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
〔光触媒体層の形成〕
上記で得た光触媒体コーティング液を、縦５０ｍｍ、横５０ｍｍ、厚さ２ｍｍの十分に脱脂した硝子板に塗布した後、スピンコーター（商品名「１Ｈ−Ｄ７」、ミカサ（株）製）を用いて、回転数１０００ｒｐｍで塗布し、室温で乾燥させた後、この硝子板を７０℃で６０分乾燥して、硝子板の片面全体に光触媒体層を形成した。光触媒体層の鉛筆硬度を調べたところ、５−６Ｈであった。また、光触媒体層の密着性を、粘着セロファンテープを用いて調べたところ、光触媒体層の剥離は見られず密着性は良好であった。
[Formation of photocatalyst layer]
The photocatalyst coating liquid obtained above was applied to a sufficiently degreased glass plate having a length of 50 mm, a width of 50 mm, and a thickness of 2 mm, and then a spin coater (trade name “1H-D7”, manufactured by Mikasa Co., Ltd.) was used. The glass plate was applied at a rotational speed of 1000 rpm and dried at room temperature, and then the glass plate was dried at 70 ° C. for 60 minutes to form a photocatalyst layer on one side of the glass plate. It was 5-6H when the pencil hardness of the photocatalyst body layer was investigated. Further, when the adhesion of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesion was good.
上記と同様にして光触媒体層を得て、この光触媒体層を用いて疎水性有機物付着時の親水性評価試験を行うと、限界接触角は５度であった。 When a photocatalyst layer was obtained in the same manner as described above and a hydrophilicity evaluation test was performed using this photocatalyst layer when a hydrophobic organic material was adhered, the limit contact angle was 5 degrees.
（実施例２）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、１０質量部、４５質量部、および２５質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Example 2)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 10 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 45 parts by mass and 25 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、４０質量部、１８０質量部、および２２０質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 Niobium oxide sol particles, colloidal silica particles, and the total content thereof were 40 parts by mass, 180 parts by mass, and 220 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると５−６Ｈであった。また、光触媒体層の密着性を、粘着セロファンテープを用いて調べたところ、光触媒体層の剥離は見られず密着性は良好であった。さらに、実施例１と同様にして限界接触角を測定すると、４度であった。 A photocatalyst layer was prepared in the same manner as in Example 1 using the photocatalyst coating liquid obtained above, and the pencil hardness was measured to be 5-6H. Further, when the adhesion of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesion was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 4 degrees.
（実施例３）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、１０質量部、５０質量部、および２０質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Example 3)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 10 parts by mass, respectively. A photocatalyst coating solution was prepared in the same manner as in Example 1 except that the content was 50 parts by mass and 20 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、５０質量部、２５０質量部、および３００質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 50 parts by mass, 250 parts by mass, and 300 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると３−４Ｈであった。また、光触媒体層の密着性を粘着セロファンテープを用いて調べたところ、光触媒体層の剥離は見られず密着性は良好であった。さらに、実施例１と同様にして限界接触角を測定すると、４度であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1, and the pencil hardness was measured to be 3-4H. Moreover, when the adhesiveness of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesiveness was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 4 degrees.
（実施例４）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、２０質量部、４０質量部、および２０質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
Example 4
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 20 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 40 parts by mass and 20 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、１００質量部、２００質量部、および３００質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 100 parts by mass, 200 parts by mass, and 300 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると５−６Ｈであった。また、光触媒体層の密着性を、粘着セロファンテープを用いて調べたところ、光触媒体層の剥離は見られず密着性は良好であった。さらに、実施例１と同様にして限界接触角を測定すると、６度であった。 A photocatalyst layer was prepared in the same manner as in Example 1 using the photocatalyst coating liquid obtained above, and the pencil hardness was measured to be 5-6H. Further, when the adhesion of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesion was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 6 degrees.
（実施例５）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、３０質量部、３３質量部、および１７質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Example 5)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 30 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 33 parts by mass and 17 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、１７６質量部、１９４質量部、および３７１質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 176 parts by mass, 194 parts by mass, and 371 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると３−４Ｈであった。また、光触媒体層の密着性を粘着セロファンテープを用いて調べたところ、光触媒体層の剥離は見られず密着性は良好であった。さらに、実施例１と同様にして限界接触角を測定すると、１２度であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1, and the pencil hardness was measured to be 3-4H. Moreover, when the adhesiveness of the photocatalyst layer was examined using an adhesive cellophane tape, no peeling of the photocatalyst layer was observed, and the adhesiveness was good. Further, when the limit contact angle was measured in the same manner as in Example 1, it was 12 degrees.
（比較例１）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、４０質量部、２７質量部、および１３質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Comparative Example 1)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 40 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 27 parts by mass and 13 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、３０８質量部、２０８質量部、および５１５質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 308 parts by mass, 208 parts by mass, and 515 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると、消しゴムで擦るだけで傷が生じ、鉛筆硬度としては６Ｂ未満であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1 and the pencil hardness was measured. As a result, scratching occurred just by rubbing with an eraser, and the pencil hardness was less than 6B.
（比較例２）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、５０質量部、２０質量部、および１０質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Comparative Example 2)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 50 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 20 parts by mass and 10 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、５００質量部、２００質量部、および７００質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 500 parts by mass, 200 parts by mass, and 700 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると、消しゴムで擦るだけで傷が生じ、鉛筆硬度としては６Ｂ未満であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1 and the pencil hardness was measured. As a result, scratching occurred just by rubbing with an eraser, and the pencil hardness was less than 6B.
（比較例３）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、１０質量部、５２．５質量部、および１７．５質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Comparative Example 3)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 10 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that 52.5 parts by mass and 17.5 parts by mass were used. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、５７質量部、３００質量部、および３５７質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 57 parts by mass, 300 parts by mass, and 357 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると、消しゴムで擦るだけで傷が生じ、鉛筆硬度としては６Ｂ未満であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1 and the pencil hardness was measured. As a result, scratching occurred just by rubbing with an eraser, and the pencil hardness was less than 6B.
（比較例４）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、２０質量部、４５質量部、および１５質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Comparative Example 4)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 20 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the content was 45 parts by mass and 15 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、１３３質量部、３００質量部、および４３３質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 133 parts by mass, 300 parts by mass, and 433 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると、消しゴムで擦るだけで傷が生じ、鉛筆硬度としては６Ｂ未満であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1 and the pencil hardness was measured. As a result, scratching occurred just by rubbing with an eraser, and the pencil hardness was less than 6B.
（比較例５）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、３０質量部、３７．５質量部、および１２．５質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Comparative Example 5)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 30 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that 37.5 parts by mass and 12.5 parts by mass were used. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、２４０質量部、３００質量部、および５４０質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 240 parts by mass, 300 parts by mass, and 540 parts by mass, respectively, in terms of oxides with respect to 100 parts by mass of ethyl silicate in terms of oxides. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると、消しゴムで擦るだけで傷が生じ、鉛筆硬度としては６Ｂ未満であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1 and the pencil hardness was measured. As a result, scratching occurred just by rubbing with an eraser, and the pencil hardness was less than 6B.
（比較例６）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２０質量部、０質量部、６５質量部、および１５質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Comparative Example 6)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 20 parts by mass and 0 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the amount was 65 parts by mass and 15 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、およびこれらの合計の含有量は、酸化物換算のケイ酸エチル１００質量部に対し、酸化物換算でそれぞれ、０質量部、４３３質量部、および４３３質量部であった。また、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの酸化物換算の合計の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で４００質量部であった。 The niobium oxide sol particles, colloidal silica particles, and the total content thereof were 0 parts by mass, 433 parts by mass, and 433 parts by mass, respectively, in terms of oxide with respect to 100 parts by mass of ethyl silicate in terms of oxide. It was. The total content of niobium oxide sol particles, colloidal silica particles, and ethyl silicate in terms of oxide was 400 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると５−６Ｈであった。また、光触媒体層の密着性を、粘着セロファンテープを用いて調べたところ、光触媒体層の剥離は見られず密着性は良好であったが、実施例１と同様にして限界接触角を測定すると、２０度であった。 A photocatalyst layer was prepared in the same manner as in Example 1 using the photocatalyst coating liquid obtained above, and the pencil hardness was measured to be 5-6H. Further, when the adhesion of the photocatalyst layer was examined using an adhesive cellophane tape, the photocatalyst layer was not peeled and the adhesion was good, but the limit contact angle was measured in the same manner as in Example 1. Then, it was 20 degrees.
（比較例７）
光触媒体コーティング液中の酸化物換算での全固形分１００質量部における、白金担持酸化タングステン粒子、酸化ニオブゾル粒子、コロイダルシリカ粒子、およびケイ酸エチルの含有量を、それぞれ２５質量部、１０質量部、６５質量部、および０質量部とした以外は実施例１と同様の方法で光触媒体コーティング液を調製した。また、得られた光触媒体コーティング液中の酸化物換算での全固形分濃度は、光触媒体コーティング液１００質量部に対し、５質量部であった。
(Comparative Example 7)
The content of platinum-supported tungsten oxide particles, niobium oxide sol particles, colloidal silica particles, and ethyl silicate in 100 parts by mass of the total solid content in terms of oxide in the photocatalyst coating liquid is 25 parts by mass and 10 parts by mass, respectively. A photocatalyst coating liquid was prepared in the same manner as in Example 1 except that the amount was 65 parts by mass and 0 parts by mass. Moreover, the total solid content concentration in terms of oxide in the obtained photocatalyst coating liquid was 5 parts by mass with respect to 100 parts by mass of the photocatalyst coating liquid.
酸化ニオブゾル粒子、コロイダルシリカ粒子、および酸化物換算のケイ酸エチルの合計量の含有量は、白金担持酸化タングステン粒子１００質量部に対し、酸化物換算で３００質量部であった。 The total content of niobium oxide sol particles, colloidal silica particles, and oxide-converted ethyl silicate was 300 parts by mass in terms of oxide with respect to 100 parts by mass of platinum-supported tungsten oxide particles.
上記で得た光触媒体コーティング液を用いて実施例１と同様にして光触媒体層を作成し、鉛筆硬度を測定すると、消しゴムで擦るだけで傷が生じ、鉛筆硬度としては６Ｂ未満であった。 Using the photocatalyst coating liquid obtained above, a photocatalyst layer was prepared in the same manner as in Example 1 and the pencil hardness was measured. As a result, scratching occurred just by rubbing with an eraser, and the pencil hardness was less than 6B.
（実施例８）
実施例１で得られた光触媒体コーティング液を用いて形成した光触媒体層の光触媒活性を評価したところ、一次反応速度定数は０．１１ｈ-1であった。
(Example 8)
When the photocatalytic activity of the photocatalyst layer formed using the photocatalyst body coating liquid obtained in Example 1 was evaluated, the first-order rate constant was 0.11 h −1 .
（参考例１）
実施例１〜５で得た光触媒体コーティング液を、天井を構成する天井材の表面に塗布し乾燥させることにより、天井材の表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができ、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、天井材の表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 1)
By applying the photocatalyst body coating liquid obtained in Examples 1 to 5 to the surface of the ceiling material constituting the ceiling and drying it, a photocatalyst body layer can be formed on the surface of the ceiling material. Can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, and can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli. Allergens such as mite allergens and cedar pollen allergens can also be rendered harmless. Furthermore, the surface of the ceiling material becomes hydrophilic, so that dirt can be easily wiped off, and further, charging can be prevented.
（参考例２）
実施例１〜５で得た光触媒体コーティング液を、屋内の壁面に施工されたタイルに塗布し乾燥させることにより、タイル表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、タイルの表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 2)
By applying and drying the photocatalyst coating liquid obtained in Examples 1 to 5 on the tiles installed on the indoor wall surface, a photocatalyst layer can be formed on the tile surface. Irradiation can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, and can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli. Allergens such as allergens and cedar pollen allergens can also be rendered harmless. Furthermore, the surface of the tile becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例３）
実施例１〜５で得た光触媒体コーティング液を、窓ガラスの屋内側表面に塗布し乾燥させることにより、ガラス表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、窓ガラスの表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 3)
By applying and drying the photocatalyst coating liquid obtained in Examples 1 to 5 on the indoor side surface of the window glass, a photocatalyst layer can be formed on the glass surface. It can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli. Allergens such as cedar pollen allergens can also be rendered harmless. Further, the surface of the window glass becomes hydrophilic, so that dirt can be easily wiped off, and further charging can be prevented.
（参考例４）
実施例１〜５で得た光触媒体コーティング液を、壁紙に塗布し乾燥させることにより、壁紙の表面に光触媒体層を形成することができ、さらにこの壁紙を屋内の壁面に施工することによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、壁紙の表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 4)
By applying the photocatalyst coating liquid obtained in Examples 1 to 5 to the wallpaper and drying it, a photocatalyst layer can be formed on the surface of the wallpaper, and by further applying this wallpaper to the indoor wall surface, Light irradiation by indoor lighting can reduce the concentration of volatile organic substances (eg formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces, and can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli. Also, allergens such as mite allergens and cedar pollen allergens can be rendered harmless. Furthermore, the surface of the wallpaper becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例５）
実施例１〜５で得た光触媒体コーティング液を、屋内の床面に塗布し乾燥させることにより、床面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、床面の表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 5)
By applying the photocatalyst coating liquid obtained in Examples 1 to 5 to the indoor floor surface and drying it, a photocatalyst layer can be formed on the floor surface. Can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances, can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and mite allergens and cedar pollen Allergens such as allergens can also be rendered harmless. Furthermore, the surface of the floor becomes hydrophilic, so that dirt can be easily wiped off and charging can be prevented.
（参考例６）
実施例１〜５で得た光触媒体コーティング液を、自動車用インストルメントパネル、自動車用シート、自動車の天井材、自動車用ガラスの車内側などの自動車内装材の表面に塗布し乾燥させることにより、これら自動車内装材の表面に光触媒体層を形成することができ、これによって、車内照明による光照射により車内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、自動車内装材の表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 6)
By applying and drying the photocatalyst coating liquid obtained in Examples 1 to 5 on the surface of an automotive interior panel such as an automotive instrument panel, an automotive seat, an automotive ceiling material, or an automotive glass interior, A photocatalyst layer can be formed on the surface of these automobile interior materials, which can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in the interior space of the vehicle by irradiating light from the interior of the vehicle. It can be reduced, pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed, and allergens such as mite allergen and cedar pollen allergen can be rendered harmless. Furthermore, the surface of the automobile interior material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例７）
実施例１〜５で得た光触媒体コーティング液を、エアコンの表面に塗布し乾燥させることにより、エアコンの表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、エアコンの表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 7)
By applying the photocatalyst body coating liquid obtained in Examples 1 to 5 to the surface of the air conditioner and drying it, a photocatalyst body layer can be formed on the surface of the air conditioner. Can reduce the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances, can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and mite allergens and cedar pollen Allergens such as allergens can also be rendered harmless. Furthermore, the surface of the air conditioner becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例８）
実施例１〜５で得た光触媒体コーティング液を、冷蔵庫の庫内に塗布し乾燥させることにより、冷蔵庫内に光触媒体層を形成することができ、これによって、屋内照明や冷蔵庫内の光源による光照射により冷蔵庫内における揮発性有機物（例えば、エチレン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、冷蔵庫の庫内の表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 8)
By applying and drying the photocatalyst coating liquid obtained in Examples 1 to 5 in the refrigerator cabinet, a photocatalyst layer can be formed in the refrigerator, thereby depending on indoor lighting or the light source in the refrigerator. Light irradiation can reduce the concentration of volatile organic substances (such as ethylene) and malodorous substances in the refrigerator, kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and mite allergens and cedar pollen allergens Allergens such as these can also be rendered harmless. Furthermore, the surface in the refrigerator compartment becomes hydrophilic, so that dirt can be easily wiped off and charging can be prevented.
（参考例９）
実施例１〜５で得た光触媒体コーティング液を、タッチパネル、電車のつり革、エレベーターのボタン等、不特定多数の人が接触する基材表面に塗布し乾燥させることにより、これら基材表面に光触媒体層を形成することができ、これによって、屋内照明による光照射により屋内空間における揮発性有機物（例えば、ホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等）や悪臭物質の濃度を低減することができ、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることもでき、また、ダニアレルゲンやスギ花粉アレルゲン等のアレルゲンを無害化することもできる。さらに、基材表面が親水化し、汚れを容易に拭き取ることができるようになり、さらに帯電をも防止できる。
(Reference Example 9)
By applying and drying the photocatalyst coating liquid obtained in Examples 1 to 5 on the surface of a base material that is touched by an unspecified number of people, such as a touch panel, a train strap, an elevator button, etc. A photocatalyst layer can be formed, whereby the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces can be reduced by light irradiation by indoor lighting, and yellow Pathogens such as staphylococci and Escherichia coli can be killed, and allergens such as mite allergens and cedar pollen allergens can be rendered harmless. Further, the surface of the base material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
Claims (5)
（２）酸化ニオブゾル粒子、
（３）コロイダルシリカ粒子、
（４）シリコンアルコキシド、及び
（５）溶媒を含む光触媒体コーティング液であって、
前記（２）の酸化物換算の含有量が、前記（４）の酸化物換算の含有量１００質量部に対して０〜２００質量部であり、
前記（３）の酸化物換算の含有量が、前記（４）の酸化物換算の含有量１００質量部に対して０〜２８０質量部質量部であり、
前記（２）と（３）の酸化物換算の含有量の合計が、前記（４）の酸化物換算の含有量１００質量部に対して０〜４８０質量部であり、
前記（２）、（３）および（４）の酸化物換算の含有量の合計が、前記（１）１００質量部に対して２０〜５００質量部であり、
前記光触媒体コーティング液から揮発成分を揮発させて得られる固形分の酸化物換算の含有量が、前記光触媒体コーティング液１００質量部に対して０．５質量部〜３０重量部である、ことを特徴とする光触媒活性を有する光触媒体層を形成するための光触媒体コーティング液。 (1) photocatalyst particles,
(2) niobium oxide sol particles,
(3) colloidal silica particles,
(4) a silicon alkoxide, and (5) a photocatalyst coating liquid containing a solvent,
The oxide equivalent content of (2) is 0 to 200 parts by mass with respect to 100 parts by mass of the oxide equivalent of (4),
The oxide equivalent content of (3) is 0 to 280 parts by mass with respect to 100 parts by mass of the oxide equivalent of (4),
The total of the oxide equivalent contents of (2) and (3) is 0 to 480 parts by mass with respect to 100 parts by mass of the oxide equivalent of (4),
The total of the oxide-converted contents of (2), (3) and (4) is 20 to 500 parts by mass with respect to (1) 100 parts by mass,
The content in terms of solid oxide obtained by volatilizing a volatile component from the photocatalyst coating liquid is 0.5 to 30 parts by weight with respect to 100 parts by mass of the photocatalyst coating liquid. A photocatalyst coating liquid for forming a photocatalyst layer having photocatalytic activity.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010165705A JP2012025849A (en) | 2010-07-23 | 2010-07-23 | Photocatalyst coating liquid and product having photocatalytic function |
| PCT/JP2011/064679 WO2012011367A1 (en) | 2010-07-23 | 2011-06-27 | Photocatalyst coating liquid and product having photocatalytic function |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010165705A JP2012025849A (en) | 2010-07-23 | 2010-07-23 | Photocatalyst coating liquid and product having photocatalytic function |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2012025849A true JP2012025849A (en) | 2012-02-09 |
Family
ID=45496795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2010165705A Pending JP2012025849A (en) | 2010-07-23 | 2010-07-23 | Photocatalyst coating liquid and product having photocatalytic function |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2012025849A (en) |
| WO (1) | WO2012011367A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016140146A1 (en) * | 2015-03-03 | 2016-09-09 | 株式会社スリーボンド | Anti-fogging agent composition |
| JP2020196863A (en) * | 2019-05-28 | 2020-12-10 | シャープ株式会社 | Composition, coating method, and multilayer structure |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE69930399T2 (en) * | 1998-09-30 | 2006-12-07 | Nippon Sheet Glass Co., Ltd. | PHOTOCATORATORY ITEMS FOR PREVENTING CONSTROGENSES AND DEPOSITS, METHOD FOR PRODUCING THE ARTICLE |
| JP4868636B2 (en) * | 2000-08-08 | 2012-02-01 | 日本曹達株式会社 | Structure comprising a photocatalyst |
| US7736735B2 (en) * | 2004-09-03 | 2010-06-15 | Jsr Corporation | Coating composition, undercoating composition, multilayer body having coating film made of such composition, photocatalyst coating film, and molded body |
| JP2007117999A (en) * | 2005-09-29 | 2007-05-17 | Sumitomo Metal Ind Ltd | Titanium oxide-based photocatalyst and its use |
| JP2007168137A (en) * | 2005-12-19 | 2007-07-05 | Kubota Matsushitadenko Exterior Works Ltd | Coated object |
| JP2007185556A (en) * | 2006-01-11 | 2007-07-26 | Mitsubishi Plastics Ind Ltd | Substrate formed with photocatalyst layer and composition for forming photocatalyst layer |
| JP2010280859A (en) * | 2009-06-08 | 2010-12-16 | Toto Ltd | Photocatalytic coating composition for high temperature firing, and method for producing photocatalytic material |
| JP5512223B2 (en) * | 2009-10-19 | 2014-06-04 | 住友化学株式会社 | Noble metal-supported photocatalyst particle dispersion and photocatalyst functional product |
| JP2011110542A (en) * | 2009-11-30 | 2011-06-09 | Panasonic Electric Works Co Ltd | Method for cleaning space and facilities for cleaning space |
-
2010
- 2010-07-23 JP JP2010165705A patent/JP2012025849A/en active Pending
-
2011
- 2011-06-27 WO PCT/JP2011/064679 patent/WO2012011367A1/en active Application Filing
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016140146A1 (en) * | 2015-03-03 | 2016-09-09 | 株式会社スリーボンド | Anti-fogging agent composition |
| JPWO2016140146A1 (en) * | 2015-03-03 | 2017-12-07 | 株式会社スリーボンド | Anti-fogging agent composition |
| JP2020196863A (en) * | 2019-05-28 | 2020-12-10 | シャープ株式会社 | Composition, coating method, and multilayer structure |
| JP7349394B2 (en) | 2019-05-28 | 2023-09-22 | シャープ株式会社 | Composition, coating method and multilayer structure |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012011367A1 (en) | 2012-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| WO2011068095A1 (en) | Method for producing liquid dispersion of noble metal-supporting photocatalyst particles, liquid dispersion of noble metal-supporting photocatalyst particles, hydrophilizing agent, and photocatalytic functional product | |
| US20110045964A1 (en) | Method for producing noble metal-supported photocatalyst particles | |
| US8298979B2 (en) | Zirconium oxalate sol | |
| JP2011005475A (en) | Photocatalyst dispersion liquid and photocatalyst functional product using the same | |
| JP2010180303A (en) | Hydrophilizing agent, method of producing the same, and use of the same | |
| EP2130587A2 (en) | Photocatalyst dispersion liquid and process for producing the same | |
| WO2011099510A1 (en) | Precoat solution for underlayer for photocatalyst layer, organic base material having photocatalyst layer attached thereto, and product having photocatalytic function | |
| JP2011078930A (en) | Photocatalyst dispersion and photocatalyst functional product using the same | |
| JP2011178930A (en) | Photocatalytic coating liquid and article having photocatalytic layer coated with the coating liquid | |
| JP2012025849A (en) | Photocatalyst coating liquid and product having photocatalytic function | |
| JP5313051B2 (en) | Zirconium oxalate sol | |
| JP2013166122A (en) | Photocatalyst structure, and photocatalyst functional product using the same, and antiviral functional product | |
| JP2011020009A (en) | Photocatalyst body for decomposing volatile aromatic compound, and functional product of photocatalyst | |
| JP2011050802A (en) | Method for producing dispersion liquid of noble metal-deposited photocatalyst particle | |
| JP2010214309A (en) | Photocatalytic body-dispersed liquid and application thereof | |
| JP5512223B2 (en) | Noble metal-supported photocatalyst particle dispersion and photocatalyst functional product | |
| JP2010215781A (en) | Precoating liquid for photocatalyst layer, wallpaper intermediate including photocatalyst layer with precoating liquid applied thereto, and wallpaper including photocatalyst layer | |
| JP5113723B2 (en) | Photocatalyst dispersion | |
| JP2012017238A (en) | Method for producing oxide particle dispersion liquid, oxide particle dispersion liquid, and photocatalyst functional product | |
| JP2010120805A (en) | Photocatalytic body dispersion | |
| JP2011036825A (en) | Tungsten oxide photocatalyst | |
| JP2010270543A (en) | Product with photocatalytic body layer | |
| JP2011092797A (en) | Hydrophilizing agent, method for producing the same, and product having hydrophilic function | |
| JP2012071253A (en) | Method for producing dispersion liquid of noble metal-supporting photocatalyst particle, dispersion liquid of noble metal-supporting photocatalyst particle, and product having photocatalytic function | |
| JP2012071252A (en) | Photocatalyst structure, and photocatalytic functional product using the same |