JP2013240731A - Photocatalyst structure and photocatalyst functional product using the same - Google Patents
Photocatalyst structure and photocatalyst functional product using the same Download PDFInfo
- Publication number
- JP2013240731A JP2013240731A JP2012114141A JP2012114141A JP2013240731A JP 2013240731 A JP2013240731 A JP 2013240731A JP 2012114141 A JP2012114141 A JP 2012114141A JP 2012114141 A JP2012114141 A JP 2012114141A JP 2013240731 A JP2013240731 A JP 2013240731A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- layer
- tungsten oxide
- oxide particles
- noble metal
- 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 155
- 239000002245 particle Substances 0.000 claims abstract description 50
- 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 abstract description 38
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 29
- 239000011347 resin Substances 0.000 claims abstract description 29
- 229910000510 noble metal Inorganic materials 0.000 claims description 30
- 239000002243 precursor Substances 0.000 claims description 19
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052737 gold Inorganic materials 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- 229910052703 rhodium Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 82
- 239000006185 dispersion Substances 0.000 description 37
- 239000007788 liquid Substances 0.000 description 30
- 230000001699 photocatalysis Effects 0.000 description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 21
- 238000000576 coating method Methods 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- 239000013566 allergen Substances 0.000 description 20
- 239000000126 substance Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 19
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 18
- 229920001296 polysiloxane Polymers 0.000 description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 14
- 241000700605 Viruses Species 0.000 description 14
- 239000002612 dispersion medium Substances 0.000 description 14
- 239000010949 copper Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 241000712461 unidentified influenza virus Species 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 241000218645 Cedrus Species 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000013573 pollen allergen Substances 0.000 description 10
- 241000588724 Escherichia coli Species 0.000 description 9
- 241000191967 Staphylococcus aureus Species 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- -1 oxynitrides Chemical class 0.000 description 9
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 244000052616 bacterial pathogen Species 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 229920002799 BoPET Polymers 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 244000052769 pathogen Species 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 239000010970 precious metal Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 101150003085 Pdcl gene Proteins 0.000 description 3
- 241000125945 Protoparvovirus Species 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 208000015181 infectious disease Diseases 0.000 description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 241000282898 Sus scrofa Species 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007607 die coating method Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004049 embossing Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 238000007756 gravure coating Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000007759 kiss coating 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
- 239000012046 mixed solvent Substances 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 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
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 1
- PAITUROHVRNCEN-UHFFFAOYSA-J 2-hydroxyacetate;zirconium(4+) Chemical compound [Zr+4].OCC([O-])=O.OCC([O-])=O.OCC([O-])=O.OCC([O-])=O PAITUROHVRNCEN-UHFFFAOYSA-J 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
- 239000004925 Acrylic resin Substances 0.000 description 1
- 241001036151 Aichi virus 1 Species 0.000 description 1
- 241001533362 Astroviridae Species 0.000 description 1
- 241000711404 Avian avulavirus 1 Species 0.000 description 1
- 241000714230 Avian leukemia virus Species 0.000 description 1
- 241001516406 Avian orthoreovirus Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 208000027312 Bursal disease Diseases 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000725585 Chicken anemia virus Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- 241000711573 Coronaviridae Species 0.000 description 1
- 241000700626 Cowpox virus Species 0.000 description 1
- 241000709687 Coxsackievirus Species 0.000 description 1
- 229920008651 Crystalline Polyethylene terephthalate Polymers 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000469171 Duck astrovirus Species 0.000 description 1
- 241001466953 Echovirus Species 0.000 description 1
- 241000710188 Encephalomyocarditis virus Species 0.000 description 1
- 241000709661 Enterovirus Species 0.000 description 1
- 241001239777 Erbovirus A Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 241000710198 Foot-and-mouth disease virus Species 0.000 description 1
- 241000700662 Fowlpox virus Species 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 241000701047 Gallid alphaherpesvirus 2 Species 0.000 description 1
- 241001517118 Goose parvovirus Species 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 241001479210 Human astrovirus Species 0.000 description 1
- 241000702617 Human parvovirus B19 Species 0.000 description 1
- 241000430519 Human rhinovirus sp. Species 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
- 241000589248 Legionella Species 0.000 description 1
- 208000007764 Legionnaires' Disease Diseases 0.000 description 1
- 241000712079 Measles morbillivirus Species 0.000 description 1
- 241001502481 Meleagrid alphaherpesvirus 1 Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 241001263478 Norovirus Species 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 241000709664 Picornaviridae Species 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000712909 Reticuloendotheliosis virus Species 0.000 description 1
- 241000607768 Shigella Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000725681 Swine influenza virus Species 0.000 description 1
- 206010043376 Tetanus Diseases 0.000 description 1
- 206010044302 Tracheitis Diseases 0.000 description 1
- 241001223089 Tremovirus A Species 0.000 description 1
- 241000132980 Turkey adenovirus 3 Species 0.000 description 1
- 241001223090 Turkey astrovirus Species 0.000 description 1
- 241000700647 Variola virus Species 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 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
- 238000005299 abrasion Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 241000701792 avian adenovirus Species 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
- 229910052797 bismuth Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 206010006451 bronchitis Diseases 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000008119 colloidal silica 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
- 230000003247 decreasing effect Effects 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
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 206010013023 diphtheria Diseases 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000009408 flooring Methods 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
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 description 1
- 229910001922 gold oxide Inorganic materials 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
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 206010022000 influenza Diseases 0.000 description 1
- 229910052742 iron 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
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 201000009837 laryngotracheitis Diseases 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 229910052748 manganese Inorganic materials 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
- 229910001960 metal nitrate Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- WPCMRGJTLPITMF-UHFFFAOYSA-I niobium(5+);pentahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[Nb+5] WPCMRGJTLPITMF-UHFFFAOYSA-I 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- JVJQPDTXIALXOG-UHFFFAOYSA-N nitryl fluoride Chemical class [O-][N+](F)=O JVJQPDTXIALXOG-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 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
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-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
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000002256 photodeposition Methods 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 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
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001155 polypropylene 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
- 239000002244 precipitate Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 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
- 241000701161 unidentified adenovirus Species 0.000 description 1
- 241001529453 unidentified herpesvirus Species 0.000 description 1
- 241001430294 unidentified retrovirus Species 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- OEERILNPOAIBKF-UHFFFAOYSA-J zirconium(4+);tetraformate Chemical compound [Zr+4].[O-]C=O.[O-]C=O.[O-]C=O.[O-]C=O OEERILNPOAIBKF-UHFFFAOYSA-J 0.000 description 1
Abstract
Description
本発明は、光触媒構造体、およびこれを用いた光触媒機能製品に関する。 The present invention relates to a photocatalyst structure and a photocatalytic functional product using the same.
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。この酸化還元作用は光触媒作用と呼ばれており、かかる光触媒作用を示し得る半導体は光触媒体と呼ばれている。このような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。 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. This redox action is called a photocatalytic action, and a semiconductor that can exhibit such a photocatalytic action is called a photocatalyst. As such a photocatalyst, titanium oxide or tungsten oxide is known.
特許文献１には、平板上に、接着層、酸化チタンからなる光触媒層がこの順に積層されてなる光触媒構造体が開示されている。 Patent Document 1 discloses a photocatalyst structure in which an adhesive layer and a photocatalyst layer made of titanium oxide are laminated in this order on a flat plate.
しかしながら、特許文献１に開示の光触媒構造体は、光触媒層面が擦れると、該面に擦り傷が多量に発生することがわかった。 However, it was found that the photocatalyst structure disclosed in Patent Document 1 generates a large amount of scratches on the photocatalyst layer surface when the photocatalyst layer surface is rubbed.
そこで、本発明は、擦り傷の発生が抑制された光触媒構造体を提供することを目的とする。 Accordingly, an object of the present invention is to provide a photocatalyst structure in which the generation of scratches is suppressed.
本発明者らは上記課題を解決するべく鋭意検討を行った結果、本発明を完成するに至った。すなわち、本発明は以下の構成からなる。
（１）樹脂基材と、下地層と、光触媒層とを有し、樹脂基材の少なくとも一方の面に下地層、光触媒層をこの順に備えてなる光触媒構造体であって、光触媒層面が日本工業規格ＪＩＳ Ｂ０６０１：１９９４に規定される算術平均粗さ（Ｒａ）が０．６μｍ以上の凹凸形状を有し、光触媒層が酸化タングステン粒子を含むことを特徴とする光触媒構造体。
（２）前記酸化タングステン粒子が、ＢＥＴ比表面積が５〜１００ｍ２／ｇである前記（１）に記載の光触媒構造体。
（３）前記酸化タングステン粒子が、表面に貴金属もしくは貴金属前駆体が担持されている前記（１）または（２）に記載の光触媒構造体。
（４）前記貴金属がＣｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｒｕ、Ｉｒ及びＲｈから選ばれる少なくとも１種類の貴金属である前記（３）に記載の光触媒構造体。
（５）前記（１）〜（４）のいずれかに記載の光触媒構造体を用いた光触媒機能製品。
As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention has the following configuration.
(1) A photocatalyst structure having a resin base material, a base layer, and a photocatalyst layer, and having the base layer and the photocatalyst layer in this order on at least one surface of the resin base material, wherein the photocatalyst layer surface is Japan A photocatalyst structure characterized in that the arithmetic average roughness (Ra) defined in the industrial standard JIS B0601: 1994 has an uneven shape of 0.6 μm or more, and the photocatalyst layer contains tungsten oxide particles.
(2) The photocatalyst structure according to (1), wherein the tungsten oxide particles have a BET specific surface area of 5 to 100 m 2 / g.
(3) The photocatalyst structure according to (1) or (2), wherein the tungsten oxide particles have a noble metal or a noble metal precursor supported on a surface thereof.
(4) The photocatalytic structure according to (3), wherein the noble metal is at least one kind of noble metal selected from Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh.
(5) A photocatalytic functional product using the photocatalyst structure according to any one of (1) to (4).
本発明によれば、擦り傷の発生が抑制された光触媒構造体を得ることができる。その結果、擦り傷の発生が抑制された光触媒機能製品を製造することができる。 According to the present invention, a photocatalyst structure in which generation of scratches is suppressed can be obtained. As a result, a photocatalytic functional product in which the generation of scratches is suppressed can be produced.
以下、本発明の実施の形態について、詳細に説明する。以下に示す実施の形態は、本発明の光触媒構造体および光触媒機能製品を例示するものであって、本発明を以下に限定するものではない。 Hereinafter, embodiments of the present invention will be described in detail. The embodiment described below exemplifies the photocatalyst structure and the photocatalytic functional product of the present invention, and the present invention is not limited to the following.
本発明の光触媒構造体は、樹脂基材と、下地層と、光触媒層とを有し、樹脂基材の少なくとも一方の面に下地層、光触媒層をこの順に備えてなる。 The photocatalyst structure of the present invention has a resin base material, a base layer, and a photocatalyst layer, and is provided with a base layer and a photocatalyst layer in this order on at least one surface of the resin base material.
［光触媒層］
光触媒層は、下地層の一方の面に積層されていることが好ましい。
[Photocatalyst layer]
The photocatalyst layer is preferably laminated on one surface of the underlayer.
光触媒層は、酸化タングステン粒子を含む。光触媒層は、酸化タングステン粒子を主成分として含むことが好ましく、該層における酸化タングステン粒子の含有割合は、該層に含まれる固形分の合計量を１００重量％とするとき、５０重量％以上であることが好ましい。酸化タングステン粒子としては、光触媒体として光触媒作用を有していれば、特に限定されず、例えば、三酸化タングステン（ＷＯ3）粒子などが挙げられる。酸化タングステン粒子は、単独で用いてもよく、２種以上を併用してもよい。 The photocatalytic layer includes tungsten oxide particles. The photocatalyst layer preferably contains tungsten oxide particles as a main component, and the content ratio of the tungsten oxide particles in the layer is 50% by weight or more when the total amount of solids contained in the layer is 100% by weight. Preferably there is. The tungsten oxide particles are not particularly limited as long as they have a photocatalytic action as a photocatalyst, and examples thereof include tungsten trioxide (WO3) particles. Tungsten oxide particles may be used alone or in combination of two or more.
酸化タングステン粒子の粒子径は、特に限定されないが、光触媒という用途の観点から、平均粒子径で、通常５０〜３００ｎｍ、好ましくは８０〜２５０ｎｍである。また、酸化タングステン粒子のＢＥＴ比表面積は、特に限定されないが、光触媒作用の観点から、通常５〜１００ｍ2／ｇ、好ましくは２０〜５０ｍ2／ｇである。 The particle diameter of the tungsten oxide particles is not particularly limited, but from the viewpoint of use as a photocatalyst, the average particle diameter is usually 50 to 300 nm, preferably 80 to 250 nm. Further, BET specific surface area of the tungsten oxide particles is not particularly limited, from the viewpoint of photocatalytic activity, it is usually 5 to 100 m 2 / g, preferably 20 to 50 m 2 / g.
三酸化タングステン粒子は、例えば、（ｉ）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、このタングステン酸を焼成する方法、（ｉｉ）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などによって得ることができる。 The tungsten trioxide particles are obtained by, for example, (i) a method of adding tungstic acid as a precipitate by adding an acid to an aqueous solution of tungstate, and firing this tungstic acid, (ii) ammonium metatungstate, paratungstic acid It can be obtained by a method in which ammonium is thermally decomposed by heating.
光触媒層は、少なくとも酸化タングステン粒子を含んでいればよく、更に酸化タングステン粒子以外の光触媒体を含んでいてもよい。酸化タングステン粒子以外の光触媒体としては、例えば、紫外線や可視光線の照射により光触媒作用を発現する半導体であり、具体的には、Ｘ線分析法などで特定の結晶構造を決定できる、金属元素と酸素、窒素、硫黄、フッ素との化合物等が挙げられる。
金属元素としては、例えば、Ｔｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅなどが挙げられる。その化合物としては、これら金属の１種類または２種類以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物などが挙げられる。なかでも、Ｔｉの酸化物が好ましい。光触媒体は粒子状であることが好ましい。
The photocatalyst layer may contain at least tungsten oxide particles, and may further contain a photocatalyst other than the tungsten oxide particles. Examples of photocatalysts other than tungsten oxide particles include semiconductors that exhibit photocatalytic action by irradiation with ultraviolet rays or visible light, and specifically, metal elements that can determine a specific crystal structure by X-ray analysis or the like. Examples thereof include compounds with oxygen, nitrogen, sulfur and fluorine.
Examples of the metal element include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, and Ag. Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce, and the like. Examples of the compound include one or more oxides, nitrides, sulfides, oxynitrides, oxysulfides, nitrofluorides, oxyfluorides, and oxynitrofluorides of these metals. Of these, an oxide of Ti is preferable. The photocatalyst is preferably in the form of particles.
酸化タングステン粒子は分散媒に分散した光触媒体分散液として用いることができる。光触媒体分散液は、酸化タングステン粒子と分散媒を混合した後、例えば媒体撹拌式分散機を用いるなど、従来公知の分散処理を施すことで得ることができる。 The tungsten oxide particles can be used as a photocatalyst dispersion liquid dispersed in a dispersion medium. The photocatalyst dispersion liquid can be obtained by mixing a tungsten oxide particle and a dispersion medium, and then performing a conventionally known dispersion treatment such as using a medium stirring type disperser.
光触媒体分散液を構成する分散媒としては、特に制限はなく、通常は、水を主成分とする水性溶媒が用いられる。具体的には、分散媒は、水単独であってもよいし、水と水溶性有機溶媒との混合溶媒であってもよい。水と水溶性有機溶媒との混合溶媒を用いる場合には、水の含有量が５０質量％以上であることが好ましい。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等が挙げられる。なお、分散媒は、単独で用いてもよいし、２種以上を併用してもよい。 There is no restriction | limiting in particular as a dispersion medium which comprises a photocatalyst body dispersion liquid, Usually, the aqueous solvent which has water as a main component is used. Specifically, the dispersion medium may be water alone or a mixed solvent of water and a water-soluble organic solvent. When a mixed solvent of water and a water-soluble organic solvent is used, the content of water is preferably 50% by mass or more. Examples of the water-soluble organic solvent include water-soluble alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, and methyl ethyl ketone. In addition, a dispersion medium may be used independently and may use 2 or more types together.
光触媒体分散液において、分散媒の含有量は酸化タングステン粒子１００質量部に対して、通常２００〜２００００質量部、好ましくは３００〜１００００質量部である。分散媒がこのような範囲で含有される場合、酸化タングステン粒子が沈降しにくく、また容積効率の点でも好ましい。 In the photocatalyst dispersion liquid, the content of the dispersion medium is usually 200 to 20000 parts by mass, preferably 300 to 10,000 parts by mass with respect to 100 parts by mass of the tungsten oxide particles. When the dispersion medium is contained in such a range, the tungsten oxide particles are less likely to settle, and the volume efficiency is also preferable.
光触媒体分散液は、その水素イオン濃度が、通常ｐＨ２．０〜ｐＨ７．０、好ましくはｐＨ２．５〜ｐＨ６．０である。水素イオン濃度がｐＨ２．０未満であると、酸性が強すぎて取扱いが面倒であり、一方、ｐＨ７．０を超えると、酸化タングステン粒子が溶解するおそれがあるので、いずれも好ましくない。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すればよい。水素イオン濃度の調整に用いることのできる酸としては、例えば、硝酸、塩酸、硫酸、リン酸、ギ酸、酢酸、蓚酸等が挙げられる。 The hydrogen ion concentration of the photocatalyst dispersion liquid is usually pH 2.0 to pH 7.0, preferably pH 2.5 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. On the other hand, when the pH exceeds 7.0, the tungsten oxide particles may be dissolved. The hydrogen ion concentration of the photocatalyst dispersion liquid may be usually adjusted by adding an acid. Examples of the acid that can be used for adjusting the hydrogen ion concentration include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, and the like.
酸化タングステン粒子には、好ましくは貴金属または貴金属前駆体が担持されている。本明細書において、貴金属とは、酸化タングステン粒子の表面に担持されて電子吸引性を発揮し得る化合物を意味し、貴金属単体だけではなく、貴金属の酸化物、水酸化物なども包含される。また、貴金属の前駆体とは、酸化タングステン粒子の表面で貴金属に遷移し得る化合物（例えば、光照射により貴金属に還元される化合物）を意味し、貴金属の硝酸塩、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。貴金属が光触媒粒子の表面に担持されて存在すると、光の照射により伝導帯に励起された電子と価電子帯に生成した正孔との再結合が抑制され、光触媒活性をより高めることができる。 The tungsten oxide particles preferably carry a noble metal or a noble metal precursor. In the present specification, the noble metal means a compound that is supported on the surface of the tungsten oxide particles and can exhibit electron withdrawing properties, and includes not only a noble metal alone but also an oxide or hydroxide of the noble metal. The noble metal precursor means a compound that can transition to a noble metal on the surface of the tungsten oxide particles (for example, a compound that can be reduced to a noble metal by light irradiation), and the noble metal nitrate, sulfate, halide, organic acid. Examples include salts, carbonates and phosphates. When the noble metal is supported on the surface of the photocatalyst particles, recombination between electrons excited in the conduction band by irradiation of light and holes generated in the valence band is suppressed, and the photocatalytic activity can be further enhanced.
前記貴金属またはその前駆体は、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｒｕ、Ｉｒ、およびＲｈからなる群より選ばれる１種以上の金属原子を含有してなるものであることが好ましい。より好ましくは、Ｃｕ、Ｐｔ、ＡｕおよびＰｄのうちの１種以上の金属原子を含有してなるものである。例えば、前記貴金属としては、前記金属原子からなる金属、もしくは、これらの金属の酸化物や水酸化物等が挙げられ、貴金属の前駆体としては、前記金属原子からなる金属の硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、リン酸塩等が挙げられる。 The noble metal or precursor thereof preferably contains one or more metal atoms selected from the group consisting of Cu, Pt, Au, Pd, Ag, Ru, Ir, and Rh. More preferably, it contains one or more metal atoms of Cu, Pt, Au and Pd. For example, the noble metal includes a metal composed of the metal atom, or an oxide or hydroxide of these metals, and the noble metal precursor includes a metal nitrate composed of the metal atom, a sulfate, Halides, organic acid salts, carbonates, phosphates and the like can be mentioned.
貴金属の好ましい具体例としては、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ等の金属が挙げられる。また、貴金属の前駆体の好ましい具体例としては、Ｃｕを含む前駆体として、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〕等が；Ｐｔを含む前駆体として、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〕、酸化白金〔ＰｔＯ２〕、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)〕、ジニトロアジアミン白金〔Ｐｔ(ＮＯ２)２(ＮＨ３)２〕等が；Ａｕを含む前駆体として、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〕、酸化金〔Ａｕ２Ｏ３〕等が；Ｐｄを含む前駆体として、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〕、酸化パラジウム〔ＰｄＯ〕、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〕、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〕等が；それぞれ挙げられる。なお、貴金属またはその前駆体は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。また、１種以上の貴金属と１種以上の前駆体とを併用してもよいことは勿論である。 Preferable specific examples of the noble metal include metals such as Cu, Pt, Au, and Pd. Moreover, as a preferable specific example of the precursor of a noble metal, as a precursor containing Cu, 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 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 ], etc .; as precursors containing Pt, platinum chloride [PtCl 2 , PtCl 4 ], platinum bromide [PtBr 2 , PtBr 4 ], platinum iodide [PtI] 2 , PtI 4 ], platinum chloride Rium [K 2 (PtCl 4 )], hexachloroplatinic acid [H 2 PtCl 6 ], platinum sulfite [H 3 Pt (SO 3 ) 2 OH], platinum oxide [PtO 2 ], tetraammineplatinum chloride [Pt (NH 3 ) 4 Cl 2 ], tetraammineplatinum bicarbonate [C 2 H 14 N 4 O 6 Pt], tetraammineplatinum hydrogen phosphate [Pt (NH 3 ) 4 HPO 4 ], tetraammineplatinum hydroxide [Pt (NH 3 ) 4 (OH ) 2 ], tetraammineplatinum nitrate [Pt (NO 3 ) 2 (NH 3 ) 4 ], tetraammineplatinum tetrachloroplatinum [(Pt (NH 3 ) 4 ) (PtCl 4 )], dinitroadiamine platinum [Pt (NO 2) ) 2 (NH 3 ) 2 ] and the like; as a precursor containing Au, gold chloride [AuCl], gold bromide [AuBr], gold iodide [AuI], gold hydroxide [Au (OH) 2 ], tetra Chloro Gold acid [HAuCl 4 ], potassium tetrachloroaurate [KAuCl 4 ], potassium tetrabromoaurate [KAuBr 4 ], gold oxide [Au 2 O 3 ] and the like; As a precursor containing Pd, for example, 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 oxide [PdO], palladium sulfate [PdSO 4 ], potassium tetrachloropalladate [K 2 (PdCl 4 )], potassium tetrabromopalladate [K 2 (PdBr 4 )], tetraammine palladium nitrate [Pd ( NH 3) 4 (NO 3) 2 ], tetraammine palladium tetrachloropalladate [(Pd ( H 3) 4) (PdCl 4 ) ], ammonium tetrachloropalladate [(NH 4) 2 PdCl 4], tetraamminepalladium chloride [Pd (NH 3) 4 Cl 2], tetraammine palladium bromide [Pd (NH 3) 4 Br 2 ] and the like; In addition, a noble metal or its precursor may be used independently, respectively and may use 2 or more types together. Of course, one or more kinds of precious metals and one or more kinds of precursors may be used in combination.
前記貴金属またはその前駆体をも含有させる場合、その含有量は、金属原子換算で、光触媒体の合計量１００質量部に対して、通常０．００５〜０．６質量部、好ましくは０．０１〜０．４質量部である。貴金属またはその前駆体が０．００５質量部未満であると、貴金属による光触媒活性の向上効果が充分に得られないおそれがあり、一方、０．６質量部を超えると、却って光触媒活性が低下するおそれがある。 When the precious metal or a precursor thereof is also contained, the content is usually 0.005 to 0.6 parts by mass, preferably 0.01 with respect to 100 parts by mass of the total amount of the photocatalyst in terms of metal atoms. It is -0.4 mass part. If the precious metal or its precursor is less than 0.005 parts by mass, the effect of improving the photocatalytic activity by the precious metal may not be sufficiently obtained. On the other hand, if it exceeds 0.6 parts by mass, the photocatalytic activity is decreased. There is a fear.
貴金属の前駆体を光触媒体分散液に添加する場合、その添加後、光触媒体分散液に光照射を行うのが好ましい。照射する光としては、酸化タングステン粒子のバンドギャップ以上のエネルギーを有する光であれば特に限定されず、可視光線でも紫外線でもよい。光触媒粒子分散液に光照射を行うことにより、光励起によって生成した電子によって前駆体が還元されて貴金属となり、酸化タングステン粒子の表面に担持される。なお、光触媒体分散液に光照射を行なわなくても、得られた分散液により形成された抗菌剤層中の酸化タングステン粒子に光が照射された時点で貴金属へ変換されるため、その光触媒活性が損なわれることはない。光照射は、前駆体を光触媒体分散液に添加後であれば、どの段階で行ってもよい。 When a noble metal precursor is added to the photocatalyst dispersion liquid, it is preferable to irradiate the photocatalyst dispersion liquid with light after the addition. The light to be irradiated is not particularly limited as long as it has energy higher than the band gap of the tungsten oxide particles, and may be visible light or ultraviolet light. By irradiating the photocatalyst particle dispersion with light, the precursor is reduced by electrons generated by photoexcitation to become a noble metal and supported on the surface of the tungsten oxide particles. Even if the photocatalyst dispersion liquid is not irradiated with light, it is converted into a noble metal when the tungsten oxide particles in the antibacterial agent layer formed by the obtained dispersion liquid are irradiated with light, so that the photocatalytic activity Will not be damaged. The light irradiation may be performed at any stage as long as the precursor is added to the photocatalyst dispersion.
また、貴金属の前駆体を光触媒体分散液に添加する場合、より効率よく貴金属に転化させる目的で、光照射の前に、本発明の効果を損なわない範囲で、メタノール、エタノール、シュウ酸などを光触媒体分散液に加えてもよい。 In addition, when a noble metal precursor is added to the photocatalyst dispersion, methanol, ethanol, oxalic acid, etc. are added to the noble metal within a range that does not impair the effects of the present invention, for the purpose of more efficiently converting to a noble metal. It may be added to the photocatalyst dispersion.
本発明における光触媒体分散液を用いて下地層の一方の面に光触媒層を形成する際に、酸化タングステン粒子をより強固に下地層の表面に保持させるために、光触媒体分散液に光触媒層用バインダを添加してなる光触媒体コーティング液を用いてもよい。 When forming the photocatalyst layer on one surface of the underlayer using the photocatalyst dispersion liquid in the present invention, the photocatalyst dispersion liquid is used for the photocatalyst layer in order to hold the tungsten oxide particles more firmly on the surface of the underlayer. You may use the photocatalyst body coating liquid which adds a binder.
前記光触媒層用バインダとしては、蟻酸ジルコニウム、グリコール酸ジルコニウム、シュウ酸ジルコニウム、水酸化ジルコニウム、酸化ジルコニウム等のジルコニウム化合物、水酸錫、酸化錫等の錫化合物、水酸化二オブ、酸化二オブ等の二オブ化合物、テトラエトキシシラン（ケイ酸エチル）、ケイ酸メチル（テトラメトキシシラン）、メチルトリエトキシシラン、メチルトリエトキシシラン等のシリコンアルコキシドや、コロイダルシリカ、酸化ケイ素等のシリコン化合物などが挙げられ、これらをそれぞれ単独で、又は２種類以上を組み合わせて用いることができる。さらに、例えば、特開平８−６７８３５号公報、特開平９−２５４３７号公報、特開平１０―１８３０６１号公報、特開平１０―１８３０６２号公報、特開平１０―１６８３４９号公報、特開平１０―２２５６５８号公報、特開平１１―１６２０号公報、特開平１１―１６６１号公報、特開２００４―０５９６８６号公報、特開２００４―１０７３８１号公報、特開２００４―２５６５９０号公報、特開２００４―３５９９０２号公報、特開２００５―１１３０２８号公報、特開２００５―２３０６６１号公報、特開２００７―１６１８２４号公報などに記載されている公知の光触媒層用バインダを用いてもよい。 Examples of the binder for the photocatalyst layer include zirconium compounds such as zirconium formate, zirconium glycolate, zirconium oxalate, zirconium hydroxide and zirconium oxide, tin compounds such as tin hydroxide and tin oxide, niobium hydroxide, and niobium oxide. And silicon alkoxides such as tetraethoxysilane (ethyl silicate), methyl silicate (tetramethoxysilane), methyltriethoxysilane, and methyltriethoxysilane, and silicon compounds such as colloidal silica and silicon oxide. These can be used alone or in combination of two or more. Further, for example, JP-A-8-67835, JP-A-9-25437, JP-A-10-183061, JP-A-10-183062, JP-A-10-168349, JP-A-10-225658. JP-A-11-1620, JP-A-11-1661, JP-A-2004-059686, JP-A-2004-107381, JP-A-2004-256590, JP-A-2004-359902, Known photocatalyst layer binders described in JP-A-2005-113028, JP-A-2005-230661, JP-A-2007-161824 may be used.
光触媒層の形成方法としては、例えば、下地層表面に、グラビアコーティング、リバースコーティング、刷毛ロールコーティング、スプレーコーティング、キスコーティング、ダイコーティング、ディッピング、バーコーティングなどの公知の方法で、光触媒体分散液または光触媒体コーティング液を塗布する方法などが挙げられる。 As a method for forming the photocatalyst layer, for example, on the surface of the underlayer, a photocatalyst dispersion liquid or a coating can be formed by a known method such as gravure coating, reverse coating, brush roll coating, spray coating, kiss coating, die coating, dipping, or bar coating. The method of apply | coating a photocatalyst body coating liquid is mentioned.
光触媒体分散液または光触媒体コーティング液を乾燥する方法としては、特に限定されるものではなく、公知の方法を適宜選択すればよい。光触媒体分散液の分散媒を除去する時の圧力や温度は、分散媒の種類に応じて適宜調整すればよく、例えば、分散媒が水である場合は、常圧下、２５℃〜１４０℃に調整すればよい。 The method for drying the photocatalyst dispersion liquid or the photocatalyst coating liquid is not particularly limited, and a known method may be appropriately selected. What is necessary is just to adjust suitably the pressure and temperature at the time of removing the dispersion medium of a photocatalyst body dispersion liquid according to the kind of dispersion medium, for example, when a dispersion medium is water, it is 25 to 140 degreeC under a normal pressure. Adjust it.
光触媒層の層厚は、２００〜１２００ｎｍが好ましく、３００〜１０００ｎｍであるのがより好ましい。光触媒層の層厚が２００ｎｍ未満である場合、光触媒構造体が十分な光触媒性能を発現せず、一方、光触媒層の層厚が１２００ｎｍを越える場合、層厚に見合うだけの十分な光触媒活性が得られず、製造コストの観点から好ましくない。 The layer thickness of the photocatalyst layer is preferably 200 to 1200 nm, and more preferably 300 to 1000 nm. When the layer thickness of the photocatalyst layer is less than 200 nm, the photocatalyst structure does not exhibit sufficient photocatalytic performance. On the other hand, when the layer thickness of the photocatalyst layer exceeds 1200 nm, sufficient photocatalytic activity sufficient for the layer thickness is obtained. This is not preferable from the viewpoint of manufacturing cost.
[下地層]
本発明の光触媒構造体は、樹脂基材の少なくとも一方の面に下地層を備える。下地層により、樹脂基材と光触媒層との密着性が向上する。
[Underlayer]
The photocatalyst structure of the present invention includes an underlayer on at least one surface of the resin base material. The adhesion between the resin base material and the photocatalyst layer is improved by the base layer.
下地層は、変性シリコーンや変成シリコーンポリマーを含む下地層形成用コート液を樹脂基材表面に塗布することによって形成される。変性シリコーンや変成シリコーンポリマーとは、シリコーンの骨格構造であるポリシロキサンの側鎖、末端に有機基を導入したものである。導入する有機基によって、アクリル変性シリコーン、アラルキル変成シリコーン、フェニル変成シリコーン、フェノール変成シリコーン、ポリエーテル変成シリコーン、カルビノール変性シリコーン、カルボキシル変性シリコーン、高級脂肪酸エステル変性シリコーン、長鎖アルキル変性シリコーン、モノアミン変性シリコーン、ジアミン変性シリコーン、ハイドロジェン変成シリコーンなどが挙げられ、本発明においては、いずれも下地層形成用コート液として用いることができる。 このような下地層形成用コート液として、例えば、ビストレイターＮＲＣ−３５０Ａ（日本曹達（株）製）、ビストレイターＮＲＣ−３１７Ａ（日本曹達（株）製）、ビストレイターＮＲＣ−３１８Ａ（日本曹達（株）製）、ビストレイターＮＲＣ−３００（日本曹達製）、ビストレイターＮＲＣ−３００Ａ（日本曹達（株）製）、ビストレイターＮＤＣ−１５０ＡおよびビストレイターＮＤＣ−１５５Ａ（日本曹達（株）製）、などが挙げられる。 The underlayer is formed by applying an underlayer-forming coating solution containing a modified silicone or a modified silicone polymer to the resin substrate surface. The modified silicone and the modified silicone polymer are those in which an organic group is introduced into the side chain and terminal of polysiloxane which is a silicone skeleton structure. Depending on the organic group to be introduced, acrylic modified silicone, aralkyl modified silicone, phenyl modified silicone, phenol modified silicone, polyether modified silicone, carbinol modified silicone, carboxyl modified silicone, higher fatty acid ester modified silicone, long chain alkyl modified silicone, monoamine modified Examples thereof include silicone, diamine-modified silicone, and hydrogen-modified silicone. In the present invention, any of them can be used as a coating solution for forming an underlayer. As such a base layer forming coating solution, for example, Vistraiter NRC-350A (manufactured by Nippon Soda Co., Ltd.), Vistraitor NRC-317A (manufactured by Nippon Soda Co., Ltd.), Vistraiter NRC-318A (Nihon Soda ( Co., Ltd.), Vistraiter NRC-300 (Nihon Soda Co., Ltd.), Vistraiter NRC-300A (Nihon Soda Co., Ltd.), Vistraitor NDC-150A and Vistraiter NDC-155A (Nihon Soda Co., Ltd.), Etc.
下地層の形成方法としては、例えば、樹脂基材表面に、グラビアコーティング、リバースコーティング、刷毛ロールコーティング、スプレーコーティング、キスコーティング、ダイコーティング、ディッピング、バーコーティングなどの公知の方法で、下地層形成用コート液を塗布する方法などが挙げられる。 As a method for forming the underlayer, for example, a known method such as gravure coating, reverse coating, brush roll coating, spray coating, kiss coating, die coating, dipping, or bar coating is applied to the surface of the resin substrate. The method of apply | coating a coating liquid etc. are mentioned.
下地用形成用コーティング液を乾燥する方法としては、特に限定されるものではなく、公知の方法を適宜選択すればよい。下地用形成用コーティング液の分散媒を除去する時の圧力や温度は、分散媒の種類に応じて適宜調整すればよく、例えば、分散媒が水である場合は、常圧下、２５℃〜１４０℃に調整すればよい。 The method for drying the base forming coating liquid is not particularly limited, and a known method may be appropriately selected. What is necessary is just to adjust suitably the pressure and temperature at the time of removing the dispersion medium of the formation liquid for base formation according to the kind of dispersion medium, for example, when a dispersion medium is water, 25 degreeC-140 under normal pressure. Adjust to ℃.
下地層の層厚は、１００〜１２００ｎｍが好ましく、２００〜１０００ｎｍであるのがより好ましい。下地層の層厚が１００ｎｍ未満である場合、光触媒層と樹脂基材の密着性が不十分となり、下地層の層厚が１２００ｎｍを越える場合、層厚に見合うだけの前記密着性が得られず、製造コストの観点から好ましくない。 100-1200 nm is preferable and, as for the layer thickness of a base layer, it is more preferable that it is 200-1000 nm. When the layer thickness of the underlayer is less than 100 nm, the adhesion between the photocatalyst layer and the resin substrate becomes insufficient, and when the layer thickness of the underlayer exceeds 1200 nm, the above-described adhesion sufficient to meet the layer thickness cannot be obtained. From the viewpoint of manufacturing cost, it is not preferable.
［樹脂基材］
本発明の樹脂基材としては、特に限定されず、例えば、ポリエチレン系樹脂、ポリプロピレン系樹脂、ポリ塩化ビニル系樹脂、ＡＢＳ系樹脂、ＡＥＳ系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリエチレンテレフタレート、非結晶性ポリエチレンテレフタレートコポリマー、完全非晶性ポリエステル系樹脂、ポリカーボネート等を挙げることができる。
[Resin substrate]
The resin base material of the present invention is not particularly limited. For example, polyethylene resin, polypropylene resin, polyvinyl chloride resin, ABS resin, AES resin, polyacrylic resin, polyurethane resin, polyethylene terephthalate, Non-crystalline polyethylene terephthalate copolymer, fully amorphous polyester resin, polycarbonate and the like can be mentioned.
[光触媒構造体]
光触媒構造体は、樹脂基材と、下地層と、光触媒層とを有し、樹脂基材の少なくとも一方の面に下地層、光触媒層をこの順に備える。光触媒構造体は、樹脂基材の一方の面に下地層、光触媒層をこの順に備えてもよいし、樹脂基材の両方の面に、それぞれ、下地層、光触媒層をこの順に備えてもよいが、樹脂基材の一方の面に下地層、光触媒層をこの順に備えるのがより好ましい。
[Photocatalyst structure]
The photocatalyst structure has a resin base material, a base layer, and a photocatalyst layer, and includes a base layer and a photocatalyst layer in this order on at least one surface of the resin base material. The photocatalyst structure may include a base layer and a photocatalyst layer in this order on one surface of the resin base material, or may include a base layer and a photocatalyst layer in this order on both surfaces of the resin base material, respectively. However, it is more preferable to provide the base layer and the photocatalyst layer in this order on one surface of the resin base material.
光触媒構造体の光触媒層面は凹凸形状を有し、この凹凸形状は、日本工業規格ＪＩＳ Ｂ０６１０：１９９４に規定される算術平均粗さ（Ｒａ）で表すと、０．６μｍ以上、好ましくは１．５μｍ以上である。Ｒａが０．６μｍ未満の場合、光触媒層面に擦り傷が発生し易くなる。また、Ｒａが大きすぎると、光触媒反応の際の分解対象物質と光触媒層の距離が遠くなることがあるため、２０μｍ以下であることが好ましい。光触媒層面への擦り傷の発生を抑制する観点から、凹凸形状の凸部には、光触媒層が存在していないことが好ましい。 The photocatalyst layer surface of the photocatalyst structure has a concavo-convex shape, and this concavo-convex shape is 0.6 μm or more, preferably 1.5 μm, when expressed by arithmetic mean roughness (Ra) defined in Japanese Industrial Standard JIS B0610: 1994. That's it. When Ra is less than 0.6 μm, scratches are likely to occur on the photocatalyst layer surface. Further, if Ra is too large, the distance between the decomposition target substance and the photocatalyst layer in the photocatalytic reaction may be long, and therefore, it is preferably 20 μm or less. From the viewpoint of suppressing the occurrence of scratches on the surface of the photocatalyst layer, it is preferable that the photocatalyst layer is not present on the convex and concave portions.
光触媒構造体の製造方法としては、例えば、（ｉ）表面に凹凸形状を有する樹脂基材の該表面に下地層、光触媒層をこの順に備える方法、（ｉｉ）表面に凹凸形状を有さない樹脂基材の該表面に下地層、光触媒層を備え、次いで光触媒層面に凹凸形状を形成する方法などが挙げられる。 As a method for producing a photocatalyst structure, for example, (i) a method of providing an underlayer and a photocatalyst layer in this order on a surface of a resin substrate having an uneven shape on the surface, and (ii) a resin having no uneven shape on the surface Examples thereof include a method of providing a base layer and a photocatalyst layer on the surface of the substrate, and then forming an uneven shape on the photocatalyst layer surface.
凹凸形状の形成方法は、特に制限されないが、例えば、熱によるエンボス加工や賦形シートによって、凹凸形状を転写する方法などが挙げられる。 The method for forming the uneven shape is not particularly limited, and examples thereof include a method for transferring the uneven shape by heat embossing or a shaped sheet.
本発明の光触媒構造体の形状は特に限定されず、要求される機能、使用される用途に応じた形状で用いられる。例えば、フィルムやシートなどの板状、棒状、繊維状、球状、三次元構造体状などである。なお、光触媒層は、下地層の面であれば、どの部分に形成されていてもよいが、例えば、光（可視光線など）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やウイルス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。 The shape of the photocatalyst structure of the present invention is not particularly limited, and the photocatalyst structure is used in a shape corresponding to a required function and a use application. For example, a plate shape such as a film or a sheet, a rod shape, a fiber shape, a spherical shape, or a three-dimensional structure shape. The photocatalyst layer may be formed on any surface as long as it is the surface of the base layer. For example, the photocatalyst layer is a surface irradiated with light (such as visible light) and a place where malodorous substances are generated. It is preferably formed on a surface that is continuously or intermittently connected to a place where pathogenic bacteria and viruses exist.
[光触媒機能製品]
本発明の光触媒機能製品は、光触媒構造体を、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、タッチパネル、電車のつり革、エレベーターのボタン、デスクマット、テーブルクロス、階段や廊下の手摺等、不特定多数の人が接触する基材表面などに利用したものである。光触媒構造体は、屋外においては勿論のこと、蛍光灯やナトリウムランプ、および発光ダイオード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ことから、本発明における光触媒機能製品は、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、七面鳥ヘルペスウイルス、マレック病ウイルス、伝染性ファブリキウス嚢病ウイルス、ニューカッスル病ウイルス、伝染性気管支炎ウイルス、伝染性喉頭気管炎、鳥脳脊髄炎ウイルス、鶏貧血ウイルス、鶏痘ウイルス、鳥類レオウイルス、鳥類白血病ウイルス、細網内皮症ウイルス、鳥類アデノウイルス及び出血性腸炎ウイルス、ヘルペスウイルス、天然痘ウイルス、牛痘ウイルス、水庖唐ウイルス、麻疹ウイルス、アデノウイルス、コクサッキーウイルス、カリシウイルス、レトロウイルス、コロナウイルス、鳥インフルエンザウイルス、ヒトインフルエンザウイルス、豚インフルエンザウイルス、ノロウイルス、口蹄疫ウイルス、パルボウイルスＢ１９、猫パルボウイルス、犬パルボウイルス、ガチョウパルボウイルス、豚パルボウイルス、ピコルナウイルス科のポリウイルス、エンテロウイルス、ヒトバーエコーウイルス、ヒトライノウイルスA〜B、A型肝炎ウイルス、脳心筋炎ウイルス、馬鼻炎Bウイルス、豚テッショウウイルス、アイチウイルス、アストロウイルス科のヒトアストロウイルス、ウシアストロウイルス、七面鳥アストロウイルス、アヒルアストロウイルス、などを不活化することができ、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。
[Photocatalytic functional products]
The photocatalytic functional product of the present invention comprises a photocatalyst structure, for example, a ceiling material, tile, glass, wallpaper, wall material, flooring and other building materials, automobile interior materials (automobile instrument panels, automobile seats, automobile ceiling materials, etc. ), Home appliances such as refrigerators and air conditioners, textiles such as clothes and curtains, touch panels, train straps, elevator buttons, desk mats, table cloths, handrails on stairs and corridors, etc. It is used for the substrate surface. The photocatalyst structure exhibits a high photocatalytic action by light irradiation not only outdoors but also in an indoor environment receiving only light from a visible light source such as a fluorescent lamp, a sodium lamp, and a light emitting diode. The photocatalytic functional products in the company can reduce the concentration of volatile organic substances such as formaldehyde and acetaldehyde, aldehydes, mercaptans, ammonia and other malodorous substances, and nitrogen oxides by irradiating with indoor lighting. Can kill, decompose, and eliminate pathogenic bacteria such as fungi, tuberculosis, cholera, diphtheria, tetanus, plague, shigella, botulinum, and legionella, turkey herpesvirus, Marek's disease virus, infection Bursal bursal disease virus, Newcastle disease virus, infection Bronchitis virus, infectious laryngotracheitis, avian encephalomyelitis virus, chicken anemia virus, fowlpox virus, avian reovirus, avian leukemia virus, reticuloendotheliosis virus, avian adenovirus and hemorrhagic enteritis virus, herpes virus, Smallpox virus, cowpox virus, varicella virus, measles virus, adenovirus, coxsackie virus, calicivirus, retrovirus, coronavirus, avian influenza virus, human influenza virus, swine influenza virus, norovirus, foot-and-mouth disease virus, parvovirus B19, Cat parvovirus, dog parvovirus, goose parvovirus, swine parvovirus, picornaviridae polyvirus, enterovirus, human bar echovirus, human rhinovirus AB, liver type A It can inactivate viruses, encephalomyocarditis virus, equine rhinitis B virus, swine teshovirus, aichivirus, human astrovirus of Astroviridae, Uciatrovirus, turkey astrovirus, duck astrovirus, etc., tick Allergens such as allergens and cedar pollen allergens can be rendered harmless. 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、本発明を実施例によって詳細に説明するが、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。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples.
なお、実施例および比較例における各物性の測定および光触媒活性の評価については、以下の方法で行った。 In addition, about the measurement of each physical property and evaluation of photocatalytic activity in an Example and a comparative example, it performed with the following method.
（結晶型）
Ｘ線回折装置（（株）リガク製の「ＲＩＮＴ２０００／ＰＣ」）を用いてＸ線回折スペクトルを測定し、そのスペクトルから結晶型を決定した。
(Crystal type)
An X-ray diffraction spectrum was measured using an X-ray diffractometer (“RINT2000 / PC” manufactured by Rigaku Corporation), and a crystal type was determined from the spectrum.
（ＢＥＴ比表面積）
比表面積測定装置（湯浅アイオニクス（株）製の「モノソーブ」）を用いて窒素吸着法により測定した。
(BET specific surface area)
It measured by the nitrogen adsorption method using the specific surface area measuring apparatus ("Monosorb" by Yuasa Ionics Co., Ltd.).
（平均分散粒子径）
サブミクロン粒度分布測定装置（コールター（株）製の「Ｎ４Ｐｌｕｓ」）を用いて粒度分布を測定し、この装置に付属のソフトにより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（ｎｍ）とした。
(Average dispersed particle size)
The particle size distribution is measured using a sub-micron particle size distribution measuring device (“N4Plus” manufactured by Coulter Co., Ltd.), and the result obtained by automatically performing the monodisperse mode analysis with the software attached to this device is the average dispersion. The particle diameter (nm) was used.
（光触媒構造体の表面観察）
レーザー顕微鏡（キーエンス（株）製の「ＶＫ９５１０」）、走査電子顕微鏡（日本電子（株）製の「ＪＳＭ−６３９０ＬＡ」）およびエネルギー分散形Ｘ線分析装置（日本電子（株）製の「ＥＸ−２３０＊＊ＢＵ」）を用いて、光触媒構造体の表面観察を行った。
(Surface observation of photocatalyst structure)
Laser microscope ("VK9510" manufactured by Keyence Corporation), scanning electron microscope ("JSM-6390LA" manufactured by JEOL Ltd.) and energy dispersive X-ray analyzer ("EX-" manufactured by JEOL Ltd.) 230 ** BU ") was used to observe the surface of the photocatalyst structure.
（擦り傷発生評価）
往復磨耗試験機（（株）新東科学製の「トライボギア ＴＹＰＥ３０））に、単一繊維布３−１号（財団法人日本規格協会製）を２０ｍｍ×２０ｍｍの大きさに取り付け、１ｋｇの荷重をかけて光触媒構造体の光触媒層の表面を１００往復させたときに、光触媒層に発生する擦り傷の本数を評価した。
(Abrasion evaluation)
A reciprocating wear tester ("Tribogear TYPE 30" manufactured by Shinto Kagaku Co., Ltd.) is attached with a single fiber cloth 3-1 (manufactured by Japan Standards Association) in a size of 20 mm x 20 mm, and a load of 1 kg is applied. Then, the number of scratches generated in the photocatalyst layer when the surface of the photocatalyst layer of the photocatalyst structure was reciprocated 100 times was evaluated.
（光触媒活性の評価−アセトアルデヒド分解性能）
測定対象の光触媒構造体を５ｃｍ×１０ｃｍに切り出し、紫外線強度が２ｍＷ／ｃｍ２（（株）トプコン製の紫外線強度計「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。
次に、この光触媒活性測定用試料をガスバッグ（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４６９ｍＬを封入し、さらにその中に１容量％でアセトアルデヒドを含む窒素ガスを、ガスバック内のアセトアルデヒドの濃度が２０ｐｐｍとなるように封入して、暗所で室温下で１時間保持した。その後、市販の白色蛍光灯を光源とし、測定サンプル近傍での照度が６０００ルクス〔照度計「Ｔ−１０」（コニカミノルタセンシング（株）製）で測定〕になるようにガスバッグを設置し、アセトアルデヒドの分解反応を行った。測定サンプル近傍の紫外光の強度は４０μＷ／ｃｍ２〔（株）トプコン製の紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を取り付けて測定〕であった。蛍光灯照射後よりガスバッグ内のガスを１．５時間毎にサンプリングして、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、光照射後３．０時間までの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の分解能とした。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は大きい。
(Evaluation of photocatalytic activity-acetaldehyde decomposition performance)
The photocatalyst structure to be measured is cut out to 5 cm × 10 cm, and the ultraviolet intensity is 2 mW / cm 2 (measured by attaching the UV receiver “UD-36” manufactured by the company to the UV intensity meter “UVR-2” manufactured by Topcon Corporation) The sample was irradiated with UV light from a black light for 16 hours, and this was used as a sample for photocatalytic activity measurement.
Next, this photocatalytic activity measurement sample is put in a gas bag (internal volume 1 L) and sealed, and then the inside of the gas bag is evacuated, and then the volume ratio of oxygen and nitrogen is 1: 4. A mixed gas of 469 mL was sealed, and further nitrogen gas containing 1% by volume of acetaldehyde was sealed therein so that the concentration of acetaldehyde in the gas bag was 20 ppm, and the mixture was kept at room temperature in the dark for 1 hour. Then, using a commercially available white fluorescent light as a light source, a gas bag was installed so that the illuminance near the measurement sample was 6000 lux (measured with illuminance meter “T-10” (manufactured by Konica Minolta Sensing Co., Ltd.)) Acetaldehyde was decomposed. The intensity of ultraviolet light in the vicinity of the measurement sample was 40 μW / cm 2 [measured by attaching a UV receiver “UD-36” manufactured by the company to a UV intensity meter “UVR-2” manufactured by Topcon Corporation]. The gas in the gas bag was sampled every 1.5 hours after the fluorescent lamp was irradiated, and the concentration of acetaldehyde was measured with a gas chromatograph (“GC-14A” manufactured by Shimadzu Corporation). The first-order reaction rate constant was calculated from the concentration of acetaldehyde with respect to the irradiation time up to 0 hour, and this was defined as the resolution of acetaldehyde. The higher the first order rate constant, the greater the resolution of acetaldehyde.
（製造例１）
（光触媒体分散液）
酸化タングステン粒子と分散媒としての水とを混合して混合物を得た。湿式媒体撹拌ミルを用いてこの混合物に分散処理を施し、濃度４２質量％の酸化タングステン粒子分散液を得た。
(Production Example 1)
(Photocatalyst dispersion)
Tungsten oxide particles and water as a dispersion medium were mixed to obtain a mixture. This mixture was subjected to a dispersion treatment using a wet medium stirring mill to obtain a tungsten oxide particle dispersion having a concentration of 42% by mass.
得られた酸化タングステン粒子分散液における酸化タングステン粒子の平均粒子径は１８０ｎｍであった。また、この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比表面積は３０ｍ２／ｇであった。なお、分散処理前の混合物についても同様に真空乾燥して固形分を得、分散処理前の混合物の固形分と分散処理後の固形分について、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、同じピーク形状であり、分散処理による結晶型の変化は見られなかった。得られた分散液を２０℃で２４時間保管しても、保管中に固液分離は見られなかった。 The average particle diameter of the tungsten oxide particles in the obtained tungsten oxide particle dispersion was 180 nm. Moreover, when a part of this dispersion was vacuum-dried to obtain a solid content, the BET specific surface area of the obtained solid content was 30 m 2 / g. In addition, when the mixture before the dispersion treatment was similarly vacuum-dried to obtain a solid content, and the solid content of the mixture before the dispersion treatment and the solid content after the dispersion treatment were measured and compared, The peak shape was the same, and no change in crystal form due to dispersion treatment was observed. Even when the obtained dispersion was stored at 20 ° C. for 24 hours, solid-liquid separation was not observed during storage.
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１００質量部に対して０．１２質量部となるように加え、さらに分散液全体に対するメタノールの濃度が１．０質量％となるようにメタノールを添加した。その後、撹拌しながら低圧水銀灯を照射することにより、光電着法により酸化タングステン粒子の表面に白金粒子を担持し、白金担持酸化タングステン粒子を光触媒体とする光触媒体分散液を得た。得られた光触媒体分散液を２０℃で２４時間保管しても、保管後に固液分離は見られなかった。また、この分散液中の固形分濃度は２６質量％であった。 An aqueous solution of hexachloroplatinic acid (H2PtCl6) is added to the tungsten oxide particle dispersion so that hexachloroplatinic acid is 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms, and methanol with respect to the entire dispersion is added. Methanol was added so that the concentration of was 1.0% by mass. Thereafter, irradiation with a low-pressure mercury lamp while stirring was performed, whereby platinum particles were supported on the surface of tungsten oxide particles by a photo-deposition method, and a photocatalyst dispersion liquid using platinum-supported tungsten oxide particles as a photocatalyst was obtained. Even when the obtained photocatalyst dispersion was stored at 20 ° C. for 24 hours, no solid-liquid separation was observed after storage. Moreover, the solid content concentration in this dispersion liquid was 26 mass%.
（製造例２）
（光触媒体コーティング液）
高純度ケイ酸エチル３．５ｇ（多摩化学製）と２−プロパノール１４．７ｇを混合し、次に水１．７ｇを添加して混合して攪拌、攪拌した。次に蓚酸二水和物０．１ｇを混合、攪拌してバインダを得た。
次に、このバインダ６．０ｇと２−プロパノール１．６ｇと製造例１で得られた光触媒体分散液１０．４ｇと水２．０ｇを混合して光触媒体コーティング液を得た。
(Production Example 2)
(Photocatalyst coating liquid)
High purity ethyl silicate 3.5 g (manufactured by Tama Chemical Co., Ltd.) and 2-propanol 14.7 g were mixed, then 1.7 g of water was added and mixed, stirred and stirred. Next, 0.1 g of oxalic acid dihydrate was mixed and stirred to obtain a binder.
Next, 6.0 g of this binder, 1.6 g of 2-propanol, 10.4 g of the photocatalyst dispersion liquid obtained in Production Example 1 and 2.0 g of water were mixed to obtain a photocatalyst coating liquid.
（製造例３）
（樹脂基材）
ＰＥＴフィルム（東レ製「Ｕ−３４、厚み１００μｍ」）とサンドペーパー（ＥＡ３６６Ｂ−８０，エスコ（株）製）とを、サンドペーパーの凹凸形状面がＰＥＴフィルムの一方の面に接触するように重ねて、エンボス機（ＥＭＢＯＳＴＡＲ４５０Ｈ−９０，サイトウエンヂニアーズ（株）製）のスチールロールとゴムロールの間を通過させた。これらロールの間を通過させた後のＰＥＴフィルムは、一方の面にサンドペーパーの凹凸形状が転写されていた。この一方の面に凹凸形状が転写されたＰＥＴフィルムを、樹脂基材とした。
(Production Example 3)
(Resin base material)
A PET film (Toray “U-34, thickness 100 μm”) and sandpaper (EA366B-80, manufactured by Esco Corporation) are stacked so that the uneven surface of the sandpaper is in contact with one surface of the PET film. Then, it was passed between a steel roll and a rubber roll of an embossing machine (EMBOSTAR450H-90, manufactured by Saito Engineering Co., Ltd.). The PET film after passing between these rolls had the concavo-convex shape of the sandpaper transferred on one side. A PET film having a concavo-convex shape transferred on one surface thereof was used as a resin base material.
（実施例１）
製造例３で得られた樹脂基材の凹凸形状を有する面に、下地層形成用コーティング液（日本曹達製、商品名：ＮＲＣ−３５０Ａ）をバーコーター（３番）で塗布し、４０℃で１分間乾燥して、下地層を形成した。この下地層の設計層厚は６８０ｎｍであった。次に、下地層面に、製造例２で得られた光触媒体コーティング液を箱型アプリケーター（液厚２１μｍ）で塗布し、４０℃で１分間乾燥して、光触媒層を形成して光触媒構造体を得た。この光触媒層の設計層厚は８００ｎｍであり、光触媒層面のＲａは２．４μｍであった。また光触媒構造体の表面観察を行ったところ、光触媒層面は凹凸形状を有し、凹凸形状の凸部には光触媒層が存在していなかった。
Example 1
On the surface of the resin base material obtained in Production Example 3 having a concavo-convex shape, a base layer forming coating solution (manufactured by Nippon Soda Co., Ltd., trade name: NRC-350A) was applied with a bar coater (No. 3) at 40 ° C. It dried for 1 minute and formed the base layer. The design layer thickness of this underlayer was 680 nm. Next, the photocatalyst coating liquid obtained in Production Example 2 is applied to the base layer surface with a box-type applicator (liquid thickness: 21 μm) and dried at 40 ° C. for 1 minute to form a photocatalyst layer to form a photocatalyst structure. Obtained. The design layer thickness of this photocatalyst layer was 800 nm, and Ra of the photocatalyst layer surface was 2.4 μm. When the surface of the photocatalyst structure was observed, the photocatalyst layer surface had an uneven shape, and the photocatalyst layer did not exist on the uneven portion.
この光触媒構造体の光触媒活性を評価したところ、一次反応速度定数は２．５ｈ-1で、光照射１．５時間後のアセトアルデヒドの残留濃度は０ｐｐｍであった。 When the photocatalytic activity of this photocatalyst structure was evaluated, the first-order rate constant was 2.5 h-1, and the residual concentration of acetaldehyde after 1.5 hours of light irradiation was 0 ppm.
この光触媒構造体の擦り傷発生評価を行ったところ、光触媒層面に発生した擦り傷の本数は数本であった。 When the occurrence of scratches on this photocatalyst structure was evaluated, the number of scratches generated on the photocatalyst layer surface was several.
（比較例１）
樹脂基材として凹凸形状を転写していないＰＥＴフィルム（東レ製「Ｕ−３４、厚み１００μｍ」）を用いた以外は、実施例１と同様にして光触媒構造体を得た。この光触媒構造体の光触媒層面のＲａは０．４μｍであった。また光触媒構造体の表面観察を行ったところ、光触媒層面は凹凸形状を有しておらず、光触媒層面の全面に光触媒層が存在していた。
(Comparative Example 1)
A photocatalyst structure was obtained in the same manner as in Example 1 except that a PET film (“U-34, thickness 100 μm” manufactured by Toray Industries, Inc.) on which the uneven shape was not transferred was used as the resin base material. Ra of the photocatalyst layer surface of this photocatalyst structure was 0.4 micrometer. When the surface of the photocatalyst structure was observed, the photocatalyst layer surface was not uneven, and the photocatalyst layer was present on the entire surface of the photocatalyst layer.
この光触媒構造体の光触媒活性を評価したところ、一次反応速度定数は２．５ｈ-1で、光照射１．５時間後のアセトアルデヒドの残留濃度は０ｐｐｍであった。 When the photocatalytic activity of this photocatalyst structure was evaluated, the first-order rate constant was 2.5 h-1, and the residual concentration of acetaldehyde after 1.5 hours of light irradiation was 0 ppm.
この光触媒構造体の擦り傷発生評価を行ったところ、光触媒層面に発生した擦り傷の本数は数十本であった。 When the occurrence of scratches on this photocatalyst structure was evaluated, the number of scratches generated on the photocatalyst layer surface was several tens.
実施例１の光触媒構造体は、擦り傷発生評価での擦り傷の発生本数が僅かであり、擦り傷の発生が抑制された。一方、比較例１の光触媒構造体は、擦り傷発生評価で多量の擦り傷が発生した。 In the photocatalyst structure of Example 1, the number of scratches in the scratch generation evaluation was very small, and the generation of scratches was suppressed. On the other hand, the photocatalyst structure of Comparative Example 1 generated a large amount of scratches in the scratch generation evaluation.
（参考例１）
実施例１で得た光触媒構造体を、天井を構成する天井材の表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 1)
By using the photocatalyst structure obtained in Example 1 on the surface of the ceiling material constituting the ceiling, volatile organic matter (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) The concentration of substances can be reduced, and pathogens such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus can be killed, and allergens such as mite allergens and cedar pollen allergens are rendered harmless. You can also. Further, the surface of the base material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例２）
実施例１で得た光触媒構造体を、屋内の壁面に施工されたタイルの表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 2)
By using the photocatalyst structure obtained in Example 1 on the surface of a tile constructed on an indoor wall surface, volatile organic substances in an indoor space (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) by light irradiation by indoor lighting It can reduce the concentration of odorous substances and odorous substances, and can kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus, and it is harmless to allergens such as mite allergens and cedar pollen allergens. It can also be converted. Further, the surface of the base material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例３）
実施例１で得た光触媒構造体を、窓ガラスの屋内側の表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 3)
By using the photocatalyst structure obtained in Example 1 on the indoor surface of the window glass, volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in the indoor space due to light irradiation by indoor lighting In addition, pathogens such as Staphylococcus aureus and Escherichia coli, viruses such as influenza virus can be killed, and allergens such as mite allergen and cedar pollen allergen can be rendered harmless. You can also. Further, the surface of the base material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例４）
実施例１で得た光触媒構造体を、壁紙の表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 4)
By using the photocatalyst structure obtained in Example 1 on the surface of wallpaper, the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces is reduced by light irradiation by indoor lighting. Furthermore, pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, viruses such as influenza virus can be killed, and allergens such as mite allergen and cedar pollen allergen 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.
（参考例５）
実施例１で得た光触媒構造体を、屋内の床面の表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 5)
By using the photocatalyst structure obtained in Example 1 on the surface of an indoor floor surface, volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in an indoor space by irradiation with light by indoor lighting. The concentration can be reduced, and pathogens such as Staphylococcus aureus and Escherichia coli, viruses such as influenza virus can be killed, and allergens such as mite allergen and cedar pollen allergen can be rendered harmless. it can. Further, the surface of the base material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例６）
実施例１で得た光触媒構造体を、自動車用インストルメントパネル、自動車用シート、自動車の天井材などの自動車内装材の表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 6)
By using the photocatalyst structure obtained in Example 1 on the surface of an automotive interior material such as an automotive instrument panel, an automotive seat, or an automotive ceiling material, volatile organic matter ( For example, the concentration of formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus can be killed, Allergens such as mite allergens and cedar pollen allergens can also 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.
（参考例７）
実施例１で得た光触媒構造体を、エアコンの表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 7)
By using the photocatalyst structure obtained in Example 1 on the surface of an air conditioner, the concentration of volatile organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances in indoor spaces is reduced by light irradiation by indoor lighting. Furthermore, pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, viruses such as influenza virus can be killed, and allergens such as mite allergen and cedar pollen allergen 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.
（参考例８）
実施例１で得た光触媒構造体を、冷蔵庫の庫内の表面に用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 8)
By using the photocatalyst structure obtained in Example 1 on the surface of the refrigerator, the concentration of volatile organic substances (for example, ethylene, etc.) and malodorous substances in the refrigerator due to light irradiation by a light source in the interior lighting or the refrigerator. In addition, pathogens such as Staphylococcus aureus and Escherichia coli, viruses such as influenza virus can be killed, and allergens such as mite allergen and cedar pollen allergen can be made harmless. . Further, the surface of the base material becomes hydrophilic, so that dirt can be easily wiped off, and charging can be prevented.
（参考例９）
実施例１で得た光触媒構造体を、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用いることにより、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、さらには、黄色ブドウ球菌や大腸菌等の病原菌や、インフルエンザウイルス等のウイルス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 using the photocatalyst structure obtained in Example 1 on the surface of a substrate that is in contact with an unspecified number of people, such as touch panels, train straps, elevator buttons, etc., the volatility in indoor space due to light irradiation by indoor lighting It can reduce the concentration of organic substances (for example, formaldehyde, acetaldehyde, acetone, toluene, etc.) and malodorous substances, and can also kill pathogenic bacteria such as Staphylococcus aureus and Escherichia coli, and viruses such as influenza virus, In addition, 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)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012114141A JP2013240731A (en) | 2012-05-18 | 2012-05-18 | Photocatalyst structure and photocatalyst functional product using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012114141A JP2013240731A (en) | 2012-05-18 | 2012-05-18 | Photocatalyst structure and photocatalyst functional product using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2013240731A true JP2013240731A (en) | 2013-12-05 |
Family
ID=49842173
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2012114141A Pending JP2013240731A (en) | 2012-05-18 | 2012-05-18 | Photocatalyst structure and photocatalyst functional product using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2013240731A (en) |
-
2012
- 2012-05-18 JP JP2012114141A patent/JP2013240731A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4878141B2 (en) | Composite photocatalyst | |
| WO2011068094A1 (en) | Antiviral agent, and antiviral agent functional product using same | |
| WO2006077839A1 (en) | Visible light-responsive photocatalyst composition and process for producing the same | |
| JP6352527B2 (en) | Photocatalytic functional film and method 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 | |
| EP2255878A1 (en) | Antibacterial material and antibacterial film and antibacterial member using the same | |
| US8298979B2 (en) | Zirconium oxalate sol | |
| JP2010180303A (en) | Hydrophilizing agent, method of producing the same, and use of the same | |
| JP2011136325A (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 | |
| JP4842607B2 (en) | Visible light responsive photocatalyst, visible light responsive photocatalyst composition, and method for producing the same | |
| JP2012035151A (en) | Method for manufacturing photocatalyst structure, and photocatalyst functional product | |
| JP2011078930A (en) | Photocatalyst dispersion and photocatalyst functional product using the same | |
| JP2013166122A (en) | Photocatalyst structure, and photocatalyst functional product using the same, and antiviral functional product | |
| JP2013216596A (en) | Antimicrobial agent, antimicrobial agent dispersion, and antimicrobial-treated product using the same | |
| JP2011132626A (en) | Textile product supporting photocatalyst | |
| JP2011178930A (en) | Photocatalytic coating liquid and article having photocatalytic layer coated with the coating liquid | |
| WO2013008807A1 (en) | Anti-viral agent capable of inactivating virus, and method for inactivating virus | |
| JP2013240731A (en) | Photocatalyst structure and photocatalyst functional product using the same | |
| JP5342370B2 (en) | Precoat liquid for underlayer of photocatalyst layer, wallpaper intermediate with photocatalyst layer, and wallpaper with photocatalyst layer | |
| JP5512223B2 (en) | Noble metal-supported photocatalyst particle dispersion and photocatalyst functional product | |
| JP2010214309A (en) | Photocatalytic body-dispersed liquid and application thereof | |
| JP2012017238A (en) | Method for producing oxide particle dispersion liquid, oxide particle dispersion liquid, and photocatalyst functional product | |
| JP2011050802A (en) | Method for producing dispersion liquid of noble metal-deposited photocatalyst particle | |
| JP5113723B2 (en) | Photocatalyst dispersion | |
| WO2012011367A1 (en) | Photocatalyst coating liquid and product having photocatalytic function |