WO2021132206A1 - Self-cleaning agent - Google Patents
Self-cleaning agent Download PDFInfo
- Publication number
- WO2021132206A1 WO2021132206A1 PCT/JP2020/047823 JP2020047823W WO2021132206A1 WO 2021132206 A1 WO2021132206 A1 WO 2021132206A1 JP 2020047823 W JP2020047823 W JP 2020047823W WO 2021132206 A1 WO2021132206 A1 WO 2021132206A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- titanium oxide
- copper
- self
- cleaning agent
- responsive photocatalyst
- Prior art date
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- 239000012459 cleaning agent Substances 0.000 title claims abstract description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 145
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 132
- 239000005749 Copper compound Substances 0.000 claims abstract description 26
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 26
- 239000011941 photocatalyst Substances 0.000 claims abstract description 25
- 150000002736 metal compounds Chemical class 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims description 37
- 239000010955 niobium Substances 0.000 claims description 22
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229910052719 titanium Inorganic materials 0.000 claims description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 10
- 230000000840 anti-viral effect Effects 0.000 abstract description 13
- 239000010454 slate Substances 0.000 abstract description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 5
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 5
- 239000011147 inorganic material Substances 0.000 abstract description 2
- 239000011368 organic material Substances 0.000 abstract description 2
- 238000000034 method Methods 0.000 description 41
- 238000002360 preparation method Methods 0.000 description 38
- 239000000203 mixture Substances 0.000 description 33
- 230000000052 comparative effect Effects 0.000 description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- 238000002156 mixing Methods 0.000 description 19
- 239000010949 copper Substances 0.000 description 18
- 229910052802 copper Inorganic materials 0.000 description 18
- 230000008859 change Effects 0.000 description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 14
- 239000011164 primary particle Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000007791 liquid phase Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 229920000742 Cotton Polymers 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- -1 copper inorganic compound Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 6
- 239000000839 emulsion Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 230000002779 inactivation Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 239000004925 Acrylic resin Substances 0.000 description 4
- 229920000178 Acrylic resin Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005871 repellent Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000012808 vapor phase Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- YDZQQRWRVYGNER-UHFFFAOYSA-N iron;titanium;trihydrate Chemical compound O.O.O.[Ti].[Fe] YDZQQRWRVYGNER-UHFFFAOYSA-N 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 230000004043 responsiveness Effects 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003373 anti-fouling effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- YEOCHZFPBYUXMC-UHFFFAOYSA-L copper benzoate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 YEOCHZFPBYUXMC-UHFFFAOYSA-L 0.000 description 2
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 2
- QNZRVYCYEMYQMD-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu].CC(=O)CC(C)=O QNZRVYCYEMYQMD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000002458 infectious effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- JXSRRBVHLUJJFC-UHFFFAOYSA-N 7-amino-2-methylsulfanyl-[1,2,4]triazolo[1,5-a]pyrimidine-6-carbonitrile Chemical compound N1=CC(C#N)=C(N)N2N=C(SC)N=C21 JXSRRBVHLUJJFC-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 235000002568 Capsicum frutescens Nutrition 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical compound [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QFVJLAYKIQBTGJ-UHFFFAOYSA-N [Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[Cu+2].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-].[O-]B([O-])[O-] QFVJLAYKIQBTGJ-UHFFFAOYSA-N 0.000 description 1
- IBEMBRLWEWSOPP-UHFFFAOYSA-N [Cu].NCc1ccccc1O Chemical compound [Cu].NCc1ccccc1O IBEMBRLWEWSOPP-UHFFFAOYSA-N 0.000 description 1
- UGAPHEBNTGUMBB-UHFFFAOYSA-N acetic acid;ethyl acetate Chemical compound CC(O)=O.CCOC(C)=O UGAPHEBNTGUMBB-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003443 antiviral agent Substances 0.000 description 1
- AWZACWPILWGEQL-UHFFFAOYSA-M azanium;copper(1+);sulfate Chemical compound [NH4+].[Cu+].[O-]S([O-])(=O)=O AWZACWPILWGEQL-UHFFFAOYSA-M 0.000 description 1
- KCLGATRJYMEERW-UHFFFAOYSA-N benzene-1,3-dicarboxylic acid;copper Chemical compound [Cu].OC(=O)C1=CC=CC(C(O)=O)=C1 KCLGATRJYMEERW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- MGIWDIMSTXWOCO-UHFFFAOYSA-N butanedioic acid;copper Chemical compound [Cu].OC(=O)CCC(O)=O MGIWDIMSTXWOCO-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- KBNZVKRXIOSIEG-UHFFFAOYSA-L copper ethyl acetate diacetate Chemical compound C(C)(=O)[O-].[Cu+2].C(C)(=O)OCC.C(C)(=O)[O-] KBNZVKRXIOSIEG-UHFFFAOYSA-L 0.000 description 1
- 229940108925 copper gluconate Drugs 0.000 description 1
- 229940120693 copper naphthenate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 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
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 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
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- SBTSVTLGWRLWOD-UHFFFAOYSA-L copper(ii) triflate Chemical compound [Cu+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F SBTSVTLGWRLWOD-UHFFFAOYSA-L 0.000 description 1
- FXGNPUJCPZJYKO-TYYBGVCCSA-L copper;(e)-but-2-enedioate Chemical compound [Cu+2].[O-]C(=O)\C=C\C([O-])=O FXGNPUJCPZJYKO-TYYBGVCCSA-L 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 1
- AWSWAKKAIQTOLD-UHFFFAOYSA-L copper;2,3-dihydroxypropanoate Chemical compound [Cu+2].OCC(O)C([O-])=O.OCC(O)C([O-])=O AWSWAKKAIQTOLD-UHFFFAOYSA-L 0.000 description 1
- CMRVDFLZXRTMTH-UHFFFAOYSA-L copper;2-carboxyphenolate Chemical compound [Cu+2].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O CMRVDFLZXRTMTH-UHFFFAOYSA-L 0.000 description 1
- SZXCZUDYSKBGSX-UHFFFAOYSA-N copper;2-ethylhexanoic acid Chemical compound [Cu].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O SZXCZUDYSKBGSX-UHFFFAOYSA-N 0.000 description 1
- ALLXRGUFQLZTBP-UHFFFAOYSA-L copper;2-formylbutanedioate Chemical compound [Cu+2].[O-]C(=O)CC(C=O)C([O-])=O ALLXRGUFQLZTBP-UHFFFAOYSA-L 0.000 description 1
- HXXRDHUDBAILGK-UHFFFAOYSA-L copper;2-hydroxyacetate Chemical compound [Cu+2].OCC([O-])=O.OCC([O-])=O HXXRDHUDBAILGK-UHFFFAOYSA-L 0.000 description 1
- WMYBXRITVYIFCO-UHFFFAOYSA-N copper;2-hydroxybutanedioic acid Chemical compound [Cu].OC(=O)C(O)CC(O)=O WMYBXRITVYIFCO-UHFFFAOYSA-N 0.000 description 1
- DYROSKSLMAPFBZ-UHFFFAOYSA-L copper;2-hydroxypropanoate Chemical compound [Cu+2].CC(O)C([O-])=O.CC(O)C([O-])=O DYROSKSLMAPFBZ-UHFFFAOYSA-L 0.000 description 1
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 description 1
- PUHAKHQMSBQAKT-UHFFFAOYSA-L copper;butanoate Chemical compound [Cu+2].CCCC([O-])=O.CCCC([O-])=O PUHAKHQMSBQAKT-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
- ZZBHLLYRFXFBLC-UHFFFAOYSA-N copper;decanedioic acid Chemical compound [Cu].OC(=O)CCCCCCCCC(O)=O ZZBHLLYRFXFBLC-UHFFFAOYSA-N 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
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 1
- NQDSPXCXIOLFGI-UHFFFAOYSA-L copper;heptanoate Chemical compound [Cu+2].CCCCCCC([O-])=O.CCCCCCC([O-])=O NQDSPXCXIOLFGI-UHFFFAOYSA-L 0.000 description 1
- GYPBUYJSHBFNEJ-UHFFFAOYSA-L copper;hexadecanoate Chemical compound [Cu+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GYPBUYJSHBFNEJ-UHFFFAOYSA-L 0.000 description 1
- ZCXLQZOQWCXFNN-UHFFFAOYSA-N copper;hexanedioic acid Chemical compound [Cu].OC(=O)CCCCC(O)=O ZCXLQZOQWCXFNN-UHFFFAOYSA-N 0.000 description 1
- ZOUQIAGHKFLHIA-UHFFFAOYSA-L copper;n,n-dimethylcarbamodithioate Chemical compound [Cu+2].CN(C)C([S-])=S.CN(C)C([S-])=S ZOUQIAGHKFLHIA-UHFFFAOYSA-L 0.000 description 1
- HZULDDWVCRWYCB-UHFFFAOYSA-L copper;nonanoate Chemical compound [Cu+2].CCCCCCCCC([O-])=O.CCCCCCCCC([O-])=O HZULDDWVCRWYCB-UHFFFAOYSA-L 0.000 description 1
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 1
- LMCVMQNMDSVUFJ-UHFFFAOYSA-N copper;pentanedioic acid Chemical compound [Cu].OC(=O)CCCC(O)=O LMCVMQNMDSVUFJ-UHFFFAOYSA-N 0.000 description 1
- NBPFTDFXKORRKN-UHFFFAOYSA-L copper;pentanoate Chemical compound [Cu+2].CCCCC([O-])=O.CCCCC([O-])=O NBPFTDFXKORRKN-UHFFFAOYSA-L 0.000 description 1
- GSCLWPQCXDSGBU-UHFFFAOYSA-L copper;phthalate Chemical compound [Cu+2].[O-]C(=O)C1=CC=CC=C1C([O-])=O GSCLWPQCXDSGBU-UHFFFAOYSA-L 0.000 description 1
- VNGORJHUDAPOQZ-UHFFFAOYSA-N copper;propan-2-olate Chemical compound [Cu+2].CC(C)[O-].CC(C)[O-] VNGORJHUDAPOQZ-UHFFFAOYSA-N 0.000 description 1
- PJBGIAVUDLSOKX-UHFFFAOYSA-N copper;propanedioic acid Chemical compound [Cu].OC(=O)CC(O)=O PJBGIAVUDLSOKX-UHFFFAOYSA-N 0.000 description 1
- LZJJVTQGPPWQFS-UHFFFAOYSA-L copper;propanoate Chemical compound [Cu+2].CCC([O-])=O.CCC([O-])=O LZJJVTQGPPWQFS-UHFFFAOYSA-L 0.000 description 1
- ZISLUDLMVNEAHK-UHFFFAOYSA-L copper;terephthalate Chemical compound [Cu+2].[O-]C(=O)C1=CC=C(C([O-])=O)C=C1 ZISLUDLMVNEAHK-UHFFFAOYSA-L 0.000 description 1
- 235000019503 curry powder Nutrition 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration 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
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- RBTKNAXYKSUFRK-UHFFFAOYSA-N heliogen blue Chemical compound [Cu].[N-]1C2=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=NC([N-]1)=C(C=CC=C3)C3=C1N=C([N-]1)C3=CC=CC=C3C1=N2 RBTKNAXYKSUFRK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- KEMQGTRYUADPNZ-UHFFFAOYSA-M margarate Chemical compound CCCCCCCCCCCCCCCCC([O-])=O KEMQGTRYUADPNZ-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 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
- 239000005011 phenolic resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000005361 soda-lime glass Substances 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
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910000349 titanium oxysulfate 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
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/02—Inorganic compounds
- C11D7/20—Water-insoluble oxides
Definitions
- the present invention relates to a self-cleaning agent having a stain decomposition function.
- Antifouling processing is a processing that makes it difficult for stains and dirt to adhere, and makes it easier to remove dirty things by washing, wiping, etc.
- the antifouling treatment method is roughly classified into, for example, a water-repellent oil-repellent system and a water-absorbing oil-absorbing system.
- the water-repellent oil-repellent system contains a fluorine compound, and a method for decomposing stains is photocatalytic oxidation.
- a method using titanium is known (see, for example, Patent Document 1).
- the photocatalytic titanium oxide has a problem that it requires a strong energy source called ultraviolet light and that the strong oxidizing action causes deterioration of the processed product and the base material itself.
- the problem to be solved by the present invention is to provide a self-cleaning agent capable of decomposing dirt components under room light.
- the present invention provides a self-cleaning agent containing a visible light responsive photocatalyst.
- the self-cleaning agent of the present invention dirt components can be decomposed under practical room light. Further, by using a specific photocatalyst as the visible light responsive photocatalyst, a self-cleaning agent having further excellent antibacterial and antiviral properties can be obtained. Further, when a specific one is used as the visible light responsive photocatalyst, the handling is good even if the concentration of titanium oxide is increased.
- the self-cleaning agent of the present invention preferably contains a visible light responsive photocatalyst in order to solve the problems of the present invention.
- Examples of the visible light-responsive photocatalyst include a composition containing titanium oxide (a), and a metal compound is supported on titanium oxide (a) from the viewpoint of obtaining even more excellent antiviral properties. Is preferably mentioned.
- titanium oxide (a) for example, rutile-type titanium oxide (a1), anatase-type titanium oxide, brookite-type titanium oxide, or the like can be used. These titanium oxides may be used alone or in combination of two or more. Among these, rutile-type titanium oxide (a1) is preferably contained because it has excellent photocatalytic activity in the visible light region.
- the content rate (rutileization rate) of the rutile-type titanium oxide (a1) is preferably 15 mol% or more, more preferably 50 mol% or more, and further preferably 90 mol% or more.
- any titanium oxide produced by either the vapor phase method or the liquid phase method can be used, but it is preferable to use the titanium oxide produced by the liquid phase method.
- the liquid phase method and the gas phase method are generally known as the method for producing the titanium oxide.
- the liquid phase method is a method for obtaining titanium oxide by hydrolyzing or neutralizing titanyl sulfate obtained from a liquid in which a raw material ore such as ilmenite ore is dissolved.
- the vapor phase method is a method for obtaining titanium oxide by a vapor phase reaction between titanium tetrachloride obtained by chlorinating a raw material ore such as rutile ore and oxygen.
- ilmenite ore may be used as the raw material ore for titanium oxide, or titanium slag obtained by metallizing the ilmenite ore to increase the titanium purity may be used.
- the titanium oxide preferably contains a metal element such as zirconium or niobium. ..
- the content ratio (Zr / Ti ratio) of zirconium to titanium 100 in titanium oxide is preferably 0.03 or more, more preferably 0.04 or more, still more preferably 0.05 or more, and preferably 0.8 or more. Below, it is more preferably 0.5 or less, still more preferably 0.3 or less. These upper and lower limits may be any combination.
- the content ratio (Zr / Ti ratio) of zirconium to titanium 100 in titanium oxide is preferably 0.03 to 0.8, more preferably 0.04 to 0.5, and further preferably 0.05 to 0.3. is there.
- the content ratio (Nb / Ti ratio) of niobium to titanium 100 in titanium oxide is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 0.8 or more. Below, it is more preferably 0.5 or less, still more preferably 0.3 or less. These upper and lower limits may be any combination.
- the content ratio (Nb / Ti ratio) of niobium to titanium 100 in titanium oxide is preferably 0.05 to 0.8, more preferably 0.08 to 0.5, and further preferably 0.10 to 0.3. is there. If the titanium oxide is within the above range, the dispersibility in the solvent is high, and the mixture can be handled well even if the concentration of titanium oxide is increased.
- the content ratio of the metal element (zirconium and / or niobium) to titanium 100 in the visible light responsive photocatalyst is the same as the above range.
- titanium oxide substantially contains a metal element means that the content ratio of the metal element in titanium oxide is 0.02 or more with respect to titanium 100.
- Titanium oxide substantially containing a metal element (zirconium and / or niobium) in the present invention has a small cohesive force with respect to the specific surface area (BET value) caused by the primary particles and can suppress the viscosity of the mixed solution. It is possible, and it is presumed that it contributes to the improvement of the concentration of titanium oxide.
- the BET specific surface area of the titanium oxide (a) is preferably in the range of 1 to 200 m 2 / g from the viewpoint of obtaining even more excellent antiviral properties and visible light responsiveness, and is preferably 3 to 100 m 2 / g.
- the range of 4 to 70 m 2 / g is more preferable, the range of 8 to 50 m 2 / g is more preferable, and the productivity of the self-cleaning agent can be further increased.
- the range is preferably 9.5 m 2 / g.
- the method for measuring the BET specific surface area of the rutile-type titanium oxide (a1) will be described in Examples described later.
- the primary particle size of the titanium oxide (a) is preferably in the range of 0.01 to 0.5 ⁇ m, preferably 0.03 to 0.5 ⁇ m, from the viewpoint of obtaining even more excellent antiviral properties and visible light responsiveness.
- the range of 0.35 ⁇ m is more preferable, and the range of 0.06 to 0.35 ⁇ m is even more preferable.
- the primary particle size of the titanium oxide (a) is measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). .. Specifically, the minor axis diameter and the major axis diameter of each titanium oxide primary particle are measured, the average is taken as the particle size of the primary particle, and then for 100 or more titanium oxide particles, each particle is used. The volume (weight) of was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was defined as the average primary particle size.
- the visible light responsive photocatalyst further improves the photocatalytic activity in the visible light region and easily exhibits an appropriate activity capable of decomposing dirt components under practical indoor light, and thus titanium oxide (a).
- titanium oxide (a) With a metal compound supported (titanium oxide composition) is preferably used.
- a transition metal such as copper, iron, tungsten, zirconium, or molybdenum
- other metals such as zinc, aluminum, antimony, and tin can be used depending on the desired physical properties.
- the titanium oxide an inorganic compound may be supported depending on desired physical properties, and for example, silicon may be used.
- a copper compound is preferable, and a divalent copper compound is more preferable, from the viewpoint of obtaining even more excellent antibacterial property, antiviral property, and stain component degrading activity.
- a method for supporting the metal compound on the titanium oxide (a) a known method can be used.
- Examples of the method for supporting the divalent copper compound on the titanium oxide (a) include titanium oxide (a) containing rutile-type titanium oxide (a1), a divalent copper compound raw material (b), water (c), and water (c). , A method having a mixing step (i) of the alkaline substance (d) can be mentioned.
- the concentration of the titanium oxide (a) in the mixing step (i) is preferably in the range of 3 to 40% by mass.
- a mixing step with good handling can be performed even if the concentration of titanium oxide (a) is increased.
- the mixing step can be satisfactorily performed even when the concentration of the titanium oxide (a) exceeds 25% by mass and is 40% by mass or less.
- divalent copper compound raw material (b) for example, a divalent copper inorganic compound, a divalent copper organic compound, or the like can be used.
- divalent copper inorganic compound examples include copper sulfate, copper nitrate, copper iodide, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amide sulfate, copper ammonium chloride, and copper pyrophosphate.
- Inorganic acid salts of divalent copper such as copper carbonate; halides of divalent copper such as copper chloride, copper fluoride, copper bromide; copper oxide, copper sulfide, azulite, malakite, copper azide and the like can be used. .. These compounds may be used alone or in combination of two or more.
- divalent copper organic compound examples include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper capricate, and mistinic acid.
- the divalent copper compound raw material (b) it is preferable to use the one represented by the following general formula (1) among the above-mentioned ones.
- CuX 2 (1) In formula (1), X represents a halogen atom, CH 3 COO, NO 3 or (SO 4 ) 1/2 .
- the X in the formula (1) is more preferably a halogen atom, and even more preferably a chlorine atom.
- the amount of the divalent copper compound raw material (b) used in the mixing step (i) is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a).
- the range of 0.1 to 15 parts by mass is more preferable, and the range of 0.3 to 10 parts by mass is further preferable.
- the water (c) is the solvent in the mixing step (i), and water alone is preferable, but other solvents may be contained if necessary.
- the other solvent for example, an alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol; a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide, tetrahydrofuran and the like can be used. These solvents may be used alone or in combination of two or more.
- alkaline substance (d) for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, a basic surfactant and the like can be used, and water can be used. It is preferable to use sodium oxide.
- the alkaline substance (d) is preferably added as a solution from the viewpoint of easy control of the reaction, and the concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L.
- the range of 3 to 4 mol / L is more preferable, and the range of 0.5 to 3 mol / L is even more preferable.
- the titanium oxide (a), the divalent copper compound raw material (b), the water (c), and the alkaline substance (d) may be mixed.
- examples thereof include a method in which titanium oxide (a) is mixed and stirred as necessary, then a divalent copper compound raw material (b) is mixed and stirred, and then an alkaline substance (d) is added and stirred. ..
- the divalent copper compound derived from the divalent copper compound raw material (b) is supported on the titanium oxide (a).
- the total stirring time in the mixing step (i) is, for example, 5 to 120 minutes, preferably 10 to 60 minutes.
- Examples of the temperature in the mixing step (i) include a range of room temperature to 70 ° C.
- the titanium oxide (a), the divalent copper compound raw material (b), and water (c) are mixed and stirred from the viewpoint of good support of the divalent copper compound on the titanium oxide (a), and then alkaline.
- the pH of the mixture after mixing and stirring the substance (d) is preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5.
- the mixed liquid can be separated as a solid content.
- the method for performing the separation include filtration, sedimentation separation, centrifugation, evaporation drying and the like, but filtration is preferable.
- the separated solid content may then be washed with water, crushed, classified, or the like, if necessary.
- the divalent copper compound derived from the divalent copper compound raw material (b) supported on the titanium oxide (a) can be more firmly bonded to the solid content.
- the heat treatment temperature is preferably in the range of 150 to 600 ° C, more preferably in the range of 250 to 450 ° C.
- the heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.
- a titanium oxide composition containing titanium oxide in which a divalent copper compound is supported on titanium oxide (a) can be obtained.
- the amount of the divalent copper compound supported on the titanium oxide (a) is in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a). It is preferable from the viewpoint of photocatalytic activity including.
- the amount of the divalent copper compound carried can be adjusted by adjusting the amount of the divalent copper compound raw material (b) used in the mixing step (i). The method for measuring the amount of the divalent copper compound supported will be described in Examples described later.
- Examples of the above-mentioned embodiment include kneading into fibers and the like, a spray agent, and a coating agent.
- Examples of the method of kneading into the fibers and the like include a method of kneading fibers such as polyester and the self-cleaning agent using an extruder or the like and spinning them.
- spray agent examples include the self-cleaning agent and a mixture of solvents such as water and alcohol.
- the coating agent examples include the self-cleaning agent, a solvent such as water and alcohol, and a mixture of a binder resin and the like.
- a binder resin for example, an acrylic resin, a urethane resin, a phenol resin, a polyester resin, an epoxy resin or the like can be used. These binder resins may be used alone or in combination of two or more.
- the dirt component can be decomposed under practical indoor light in the aspect of the organic material such as fiber and the inorganic material such as slate plate. Further, by using a specific photocatalyst as the visible light responsive photocatalyst, a self-cleaning agent having further excellent antibacterial and antiviral properties can be obtained.
- the self-cleaning agent according to the present invention is excellent in antiviral property, antibacterial property, safety to human body, heat resistance, weather resistance, and water resistance.
- Preparation Example 2 A titanium oxide composition was obtained in the same manner as in Preparation Example 1 except that the amount of copper (ii) chloride dihydrate used was changed from 8 parts by mass to 3.3 parts by mass in Preparation Example 1. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- a titanium oxide composition was obtained in the same manner as in Preparation Example 1 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 1. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- a titanium oxide composition was obtained in the same manner as in Preparation Example 1 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 1. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- the titanium oxide composition was prepared in the same manner as in Preparation Example 1 except that the type of titanium oxide was changed to the titanium oxide and the amount of water used was changed from 900 parts by mass to 4,000 parts by mass. Obtained. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- Preparation Example 6 A titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the amount of copper (ii) chloride dihydrate used was changed from 8 parts by mass to 3.3 parts by mass in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- a titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- a titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- a titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
- titanium oxide As shown in Preparation Examples 1 to 4, if titanium oxide is obtained by the liquid phase method, it can be stably mixed even if the concentration of titanium oxide (a) in the mixture in the mixing step (i) is increased, and it has antiviral properties. It was found that an excellent antiviral agent can be efficiently produced.
- Example 1 25 parts by mass of the titanium oxide composition obtained in Adjustment Example 1, 73.5 parts by mass of water, and 1.5 parts by mass of a dispersant (“DISPERBIK 190” manufactured by Big Chemie) were dispersed with a sand grinder to obtain an aqueous slurry. It was.
- the stain component (A) (0.5 parts by mass of oil red, 49.75 parts by mass of ethanol, and 49.75 parts by mass of oleic acid) was added dropwise to the obtained sample using a micropipette, and 500 lux was added.
- the a * value was measured with a colorimeter (“CR-200 D65 light source” manufactured by Konica Minolta Co., Ltd.) 1 hour (0 days later), 1 day and 2 days after the dropping.
- Example 2 In Example 1, the a * value was measured in the same manner as in Example 1 except that the stain component (A) was changed to the stain component (B) (chili oil manufactured by S & B Co., Ltd.). In addition, ⁇ a * was obtained by the difference from Comparative Example 4.
- Example 3 In Example 1, the stain component (A) was changed to the stain component (C) (1 part by mass of S & B curry powder granules and 99 parts by mass of ethanol) in the same manner as in Example 1. The a * value was measured. In addition, ⁇ a * was obtained by the difference from Comparative Example 6.
- Example 4 In Example 1, the a * value was measured in the same manner as in Example 1 except that the cotton broad cloth was changed to a slate plate (manufactured by Nozawa Corporation). In addition, ⁇ a * was obtained by the difference from Comparative Example 8.
- Example 1 The a * value was measured in the same manner as in Example 1 except that the stain component (A) was directly dropped onto the cotton broad cloth used in Example 1. Further, this a * value was used as a reference for the amount of color change ( ⁇ a *) of Example 1, Comparative Example 2, and Comparative Example 3.
- Comparative Example 4 In Comparative Example 1, the a * value was measured in the same manner as in Comparative Example 1 except that the stain component (A) was changed to the stain component (B). Further, this a * value was used as a reference for the amount of color change ( ⁇ a *) in Example 2 and Comparative Example 5.
- Comparative Example 5 In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that the stain component (A) was changed to the stain component (B).
- Comparative Example 6 In Comparative Example 1, the a * value was measured in the same manner as in Comparative Example 1 except that the stain component (A) was changed to the stain component (C). Further, this a * value was used as a reference for the amount of color change ( ⁇ a *) in Example 3 and Comparative Example 7.
- Comparative Example 7 In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that the stain component (A) was changed to the stain component (C).
- Comparative Example 9 In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that a slate plate (manufactured by Nozawa Corporation) was used instead of the cotton broad cloth.
- the stain decomposition effect was determined by the difference ⁇ a * based on the a * value of the comparative example in which only the stain component was dropped on the base material (cotton broad cloth, slate plate).
- the amount of color change is evaluated from ⁇ a * after n days and ⁇ a * at the initial stage (after 0 days), and the more the amount of color change becomes negative, the more the dye, which is a stain component, is decomposed.
- the self-cleaning agent of the present invention has an excellent stain decomposition function under room light.
- Comparative Examples 1 to 9 did not contain a visible light responsive photocatalyst, but were inferior in stain decomposability under room light.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Catalysts (AREA)
- Paints Or Removers (AREA)
Abstract
The present invention addresses the problem of providing a self-cleaning agent by which dirty components can be decomposed under indoor light. The present invention provides a self-cleaning agent characterized by containing a visible-light-responsive photocatalyst. As the visible-light-responsive photocatalyst, a photocatalyst in which a metal compound is supported on titanium oxide (a) is preferable. The titanium oxide (a) preferably contains rutile-type titanium oxide (a1). The metal compound is preferably a divalent copper compound. According to this self-cleaning agent, in the aspects of an organic material such as a fiber and an inorganic material such as a slate plate, dirty components can be decomposed under practical indoor light. Moreover, a self-cleaning agent having excellent antibacterial properties and antiviral properties as well can be obtained by using a specific photocatalyst as the visible-light-responsive photocatalyst.
Description
本発明は、汚れ分解機能を有するセルフクリーニング剤に関する。
The present invention relates to a self-cleaning agent having a stain decomposition function.
防汚加工は、シミや汚れを付着しにくくしたり、汚れたものを洗濯、拭き取り等で除去しやすくするための加工である。前記防汚加工の手法としては、例えば、撥水撥油系と吸水吸油系とに大別され、撥水撥油系はフッ素化合物を含むものや、また汚れを分解する手法としては、光触媒酸化チタンを用いる方法が知られている（例えば、特許文献１を参照。）。
Antifouling processing is a processing that makes it difficult for stains and dirt to adhere, and makes it easier to remove dirty things by washing, wiping, etc. The antifouling treatment method is roughly classified into, for example, a water-repellent oil-repellent system and a water-absorbing oil-absorbing system. The water-repellent oil-repellent system contains a fluorine compound, and a method for decomposing stains is photocatalytic oxidation. A method using titanium is known (see, for example, Patent Document 1).
しかしながら、前記光触媒酸化チタンは、紫外光という強いエネルギー源が必要である点と、その強い酸化作用により、加工物や基材自体の劣化を招いてしまうという課題を有していた。
However, the photocatalytic titanium oxide has a problem that it requires a strong energy source called ultraviolet light and that the strong oxidizing action causes deterioration of the processed product and the base material itself.
本発明が解決しようとする課題は、室内光の下で汚れ成分を分解できるセルフクリーニング剤を提供することである。
The problem to be solved by the present invention is to provide a self-cleaning agent capable of decomposing dirt components under room light.
本発明は、可視光応答型光触媒を含有することを特徴とするセルフクリーニング剤を提供するものである。
The present invention provides a self-cleaning agent containing a visible light responsive photocatalyst.
本発明のセルフクリーニング剤によれば、実用的な室内光の下で、汚れ成分を分解することができる。また、前記可視光応答型光触媒として、特定のものを用いることで、更に抗菌性、及び、抗ウイルス性にも優れたセルフクリーニング剤を得ることができる。また、前記可視光応答型光触媒は、特定のものを用いると、酸化チタンの濃度を高めても取扱いが良好である。
According to the self-cleaning agent of the present invention, dirt components can be decomposed under practical room light. Further, by using a specific photocatalyst as the visible light responsive photocatalyst, a self-cleaning agent having further excellent antibacterial and antiviral properties can be obtained. Further, when a specific one is used as the visible light responsive photocatalyst, the handling is good even if the concentration of titanium oxide is increased.
本発明のセルフクリーニング剤は、本発明の課題を解決するうえで、可視光応答型光触媒を含有することが好ましい。
The self-cleaning agent of the present invention preferably contains a visible light responsive photocatalyst in order to solve the problems of the present invention.
前記可視光応答型光触媒としては、例えば、酸化チタン（ａ）を含む組成物が挙げられ、より一層優れた抗ウイルス性が得られる点から、酸化チタン（ａ）に金属化合物が担持されたものが好ましく挙げられる。
Examples of the visible light-responsive photocatalyst include a composition containing titanium oxide (a), and a metal compound is supported on titanium oxide (a) from the viewpoint of obtaining even more excellent antiviral properties. Is preferably mentioned.
前記酸化チタン（ａ）としては、例えば、ルチル型酸化チタン（ａ１）、アナターゼ型酸化チタン、ブルッカイト型酸化チタン等を用いることができる。これらの酸化チタンは単独で用いても２種以上を併用してもよい。これらの中でも、優れた可視光領域での光触媒活性を有する点から、ルチル型酸化チタン（ａ１）を含むことが好ましい。
As the titanium oxide (a), for example, rutile-type titanium oxide (a1), anatase-type titanium oxide, brookite-type titanium oxide, or the like can be used. These titanium oxides may be used alone or in combination of two or more. Among these, rutile-type titanium oxide (a1) is preferably contained because it has excellent photocatalytic activity in the visible light region.
前記前記ルチル型酸化チタン（ａ１）の含有率（ルチル化率）としては、より一層優れた明所及び暗所における抗ウイルス性、明所における有機化合物分解性、及び、可視光応答性が得られる点から、１５モル％以上であることが好ましく、５０モル％以上あることがより好ましく、９０モル％以上が更に好ましい。
As the content rate (rutileization rate) of the rutile-type titanium oxide (a1), even more excellent antiviral properties in bright and dark places, organic compound decomposability in bright places, and visible light responsiveness can be obtained. From this point of view, it is preferably 15 mol% or more, more preferably 50 mol% or more, and further preferably 90 mol% or more.
本発明においては、前記酸化チタンとしては、気相法及び液相法いずれの方法で製造されたものでも用いることができるが、液相法により製造されたものを用いることが好ましい。
In the present invention, as the titanium oxide, any titanium oxide produced by either the vapor phase method or the liquid phase method can be used, but it is preferable to use the titanium oxide produced by the liquid phase method.
前記酸化チタンの製造方法としては、一般的に、液相法と気相法とが知られている。前記液相法とは、イルメナイト鉱などの原料鉱石を溶解した液から得られる硫酸チタニルを、加水分解又は中和して酸化チタンを得る方法である。また、気相法とは、ルチル鉱などの原料鉱石を塩素化して得られる四塩化チタンと、酸素との気相反応により酸化チタンを得る方法である。
The liquid phase method and the gas phase method are generally known as the method for producing the titanium oxide. The liquid phase method is a method for obtaining titanium oxide by hydrolyzing or neutralizing titanyl sulfate obtained from a liquid in which a raw material ore such as ilmenite ore is dissolved. The vapor phase method is a method for obtaining titanium oxide by a vapor phase reaction between titanium tetrachloride obtained by chlorinating a raw material ore such as rutile ore and oxygen.
本発明において酸化チタンの原料鉱石としてはイルメナイト鉱石を用いてもよいし、イルメナイト鉱石を冶金処理してチタン純度を高めたチタンスラグを用いてもよい。
前記酸化チタンは、ジルコニウム、ニオブなどの金属元素を含むことが好ましい。。 In the present invention, ilmenite ore may be used as the raw material ore for titanium oxide, or titanium slag obtained by metallizing the ilmenite ore to increase the titanium purity may be used.
The titanium oxide preferably contains a metal element such as zirconium or niobium. ..
前記酸化チタンは、ジルコニウム、ニオブなどの金属元素を含むことが好ましい。。 In the present invention, ilmenite ore may be used as the raw material ore for titanium oxide, or titanium slag obtained by metallizing the ilmenite ore to increase the titanium purity may be used.
The titanium oxide preferably contains a metal element such as zirconium or niobium. ..
酸化チタンにおけるチタン１００に対するジルコニウムの含有比（Ｚｒ／Ｔｉ比）は、好ましくは０．０３以上、より好ましくは０．０４以上、さらに好ましくは０．０５以上であり、また、好ましくは０．８以下、より好ましくは０．５以下、さらに好ましくは０．３以下である。これらの上限及び下限はいずれの組み合わせでもよい。酸化チタンにおけるチタン１００に対するジルコニウムの含有比（Ｚｒ／Ｔｉ比）は、好ましくは０．０３～０．８、より好ましくは０．０４～０．５、さらに好ましくは０．０５～０．３である。酸化チタンにおけるチタン１００に対するニオブの含有比（Ｎｂ／Ｔｉ比）は、好ましくは０．０５以上、より好ましくは０．０８以上、さらに好ましくは０．１以上であり、また、好ましくは０．８以下、より好ましくは０．５以下、さらに好ましくは０．３以下である。これらの上限及び下限はいずれの組み合わせでもよい。酸化チタンにおけるチタン１００に対するニオブの含有比（Ｎｂ／Ｔｉ比）は、好ましくは０．０５～０．８、より好ましくは０．０８～０．５、さらに好ましくは０．１０～０．３である。上記範囲内の酸化チタンであれば、溶媒への分散性が高く酸化チタンの濃度を高めても混合液の取扱いが良好である。上記範囲内の酸化チタンで得られた可視光応答型光触媒は、可視光応答型光触媒におけるチタン１００に対する金属元素（ジルコニウム及び／又はニオブ）の含有比が上記範囲と同じになる。
The content ratio (Zr / Ti ratio) of zirconium to titanium 100 in titanium oxide is preferably 0.03 or more, more preferably 0.04 or more, still more preferably 0.05 or more, and preferably 0.8 or more. Below, it is more preferably 0.5 or less, still more preferably 0.3 or less. These upper and lower limits may be any combination. The content ratio (Zr / Ti ratio) of zirconium to titanium 100 in titanium oxide is preferably 0.03 to 0.8, more preferably 0.04 to 0.5, and further preferably 0.05 to 0.3. is there. The content ratio (Nb / Ti ratio) of niobium to titanium 100 in titanium oxide is preferably 0.05 or more, more preferably 0.08 or more, still more preferably 0.1 or more, and preferably 0.8 or more. Below, it is more preferably 0.5 or less, still more preferably 0.3 or less. These upper and lower limits may be any combination. The content ratio (Nb / Ti ratio) of niobium to titanium 100 in titanium oxide is preferably 0.05 to 0.8, more preferably 0.08 to 0.5, and further preferably 0.10 to 0.3. is there. If the titanium oxide is within the above range, the dispersibility in the solvent is high, and the mixture can be handled well even if the concentration of titanium oxide is increased. In the visible light responsive photocatalyst obtained from titanium oxide within the above range, the content ratio of the metal element (zirconium and / or niobium) to titanium 100 in the visible light responsive photocatalyst is the same as the above range.
酸化チタンが金属元素（ジルコニウム及び／又はニオブ）を実質的に含むとは、酸化チタンにおける金属元素の含有比がチタン１００に対して０．０２以上であることを意味する。
本発明における金属元素（ジルコニウム及び／又はニオブ）を実質的に含む酸化チタンは、１次粒子に起因する比表面積（ＢＥＴ値）に対して、凝集力は少なく混合液の粘度を抑制することが可能であり、酸化チタンの濃度向上に貢献していると推察される。 The fact that titanium oxide substantially contains a metal element (zirconium and / or niobium) means that the content ratio of the metal element in titanium oxide is 0.02 or more with respect to titanium 100.
Titanium oxide substantially containing a metal element (zirconium and / or niobium) in the present invention has a small cohesive force with respect to the specific surface area (BET value) caused by the primary particles and can suppress the viscosity of the mixed solution. It is possible, and it is presumed that it contributes to the improvement of the concentration of titanium oxide.
本発明における金属元素（ジルコニウム及び／又はニオブ）を実質的に含む酸化チタンは、１次粒子に起因する比表面積（ＢＥＴ値）に対して、凝集力は少なく混合液の粘度を抑制することが可能であり、酸化チタンの濃度向上に貢献していると推察される。 The fact that titanium oxide substantially contains a metal element (zirconium and / or niobium) means that the content ratio of the metal element in titanium oxide is 0.02 or more with respect to titanium 100.
Titanium oxide substantially containing a metal element (zirconium and / or niobium) in the present invention has a small cohesive force with respect to the specific surface area (BET value) caused by the primary particles and can suppress the viscosity of the mixed solution. It is possible, and it is presumed that it contributes to the improvement of the concentration of titanium oxide.
前記酸化チタン（ａ）のＢＥＴ比表面積としては、より一層優れた抗ウイルス性、及び、可視光応答性が得られる点から、１～２００ｍ２／ｇの範囲が好ましく、３～１００ｍ２／ｇの範囲がより好ましく、４～７０ｍ２／ｇの範囲がより好ましく、８～５０ｍ２／ｇの範囲が更に好ましく、セルフクリーニング剤の生産性をより一層高めることができる点から、７．５～９．５ｍ２／ｇの範囲であることが好ましい。なお、前記ルチル型酸化チタン（ａ１）のＢＥＴ比表面積の測定方法は、後述する実施例にて記載する。
The BET specific surface area of the titanium oxide (a) is preferably in the range of 1 to 200 m 2 / g from the viewpoint of obtaining even more excellent antiviral properties and visible light responsiveness, and is preferably 3 to 100 m 2 / g. The range of 4 to 70 m 2 / g is more preferable, the range of 8 to 50 m 2 / g is more preferable, and the productivity of the self-cleaning agent can be further increased. The range is preferably 9.5 m 2 / g. The method for measuring the BET specific surface area of the rutile-type titanium oxide (a1) will be described in Examples described later.
前記酸化チタン（ａ）の１次粒子径としては、より一層優れた抗ウイルス性、及び、可視光応答性が得られる点から、０．０１～０．５μｍの範囲が好ましく、０．０３～０．３５μｍの範囲がより好ましく０．０６～０．３５μｍの範囲がさらに好ましい。なお、前記酸化チタン（ａ）の１次粒子径の測定方法は、透過型電子顕微鏡（ＴＥＭ）を使用して、電子顕微鏡写真から一次粒子の大きさを直接計測する方法で測定した値を示す。具体的には、個々の酸化チタンの１次粒子の短軸径と長軸径を計測し、平均をその１次粒子の粒子径とし、次に１００個以上の酸化チタン粒子について、それぞれの粒子の体積（重量）を、求めた粒子径の立方体と近似して求め、体積平均粒径を平均１次粒子径とした。
The primary particle size of the titanium oxide (a) is preferably in the range of 0.01 to 0.5 μm, preferably 0.03 to 0.5 μm, from the viewpoint of obtaining even more excellent antiviral properties and visible light responsiveness. The range of 0.35 μm is more preferable, and the range of 0.06 to 0.35 μm is even more preferable. The primary particle size of the titanium oxide (a) is measured by a method of directly measuring the size of the primary particles from an electron micrograph using a transmission electron microscope (TEM). .. Specifically, the minor axis diameter and the major axis diameter of each titanium oxide primary particle are measured, the average is taken as the particle size of the primary particle, and then for 100 or more titanium oxide particles, each particle is used. The volume (weight) of was obtained by approximating it to a cube having the obtained particle size, and the volume average particle size was defined as the average primary particle size.
また、前記可視光応答型光触媒としては、可視光領域における光触媒活性を一層向上し、実用的な室内光の下で、汚れ成分を分解できる適度な活性を発現しやすい点から、酸化チタン（ａ）に金属化合物が担持されたもの（酸化チタン組成物）を用いることが好ましい。
Further, the visible light responsive photocatalyst further improves the photocatalytic activity in the visible light region and easily exhibits an appropriate activity capable of decomposing dirt components under practical indoor light, and thus titanium oxide (a). ) With a metal compound supported (titanium oxide composition) is preferably used.
金属化合物の金属としては、例えば、銅、鉄、タングステン、ジルコニウム、モリブデン等の遷移金属を用いることができる。金属化合物の金属としては、所望の物性に応じて他にも、亜鉛、アルミニウム、アンチモン、スズ等の金属を用いることができる。酸化チタンは、所望の物性に応じて無機化合物を担持してもよく、例えばケイ素を用いてもよい。これらの中でも、より一層優れた抗菌性、抗ウイルス性、及び汚れ成分解活性が得られる点から、銅化合物が好ましく、２価銅化合物がより好ましい。
前記酸化チタン（ａ）への金属化合物の担持方法としては、公知の手法を用いることができる。 As the metal of the metal compound, for example, a transition metal such as copper, iron, tungsten, zirconium, or molybdenum can be used. As the metal of the metal compound, other metals such as zinc, aluminum, antimony, and tin can be used depending on the desired physical properties. As the titanium oxide, an inorganic compound may be supported depending on desired physical properties, and for example, silicon may be used. Among these, a copper compound is preferable, and a divalent copper compound is more preferable, from the viewpoint of obtaining even more excellent antibacterial property, antiviral property, and stain component degrading activity.
As a method for supporting the metal compound on the titanium oxide (a), a known method can be used.
前記酸化チタン（ａ）への金属化合物の担持方法としては、公知の手法を用いることができる。 As the metal of the metal compound, for example, a transition metal such as copper, iron, tungsten, zirconium, or molybdenum can be used. As the metal of the metal compound, other metals such as zinc, aluminum, antimony, and tin can be used depending on the desired physical properties. As the titanium oxide, an inorganic compound may be supported depending on desired physical properties, and for example, silicon may be used. Among these, a copper compound is preferable, and a divalent copper compound is more preferable, from the viewpoint of obtaining even more excellent antibacterial property, antiviral property, and stain component degrading activity.
As a method for supporting the metal compound on the titanium oxide (a), a known method can be used.
次に、最も好ましい態様である、酸化チタン（ａ）に２価銅化合物を担持する方法について説明する。
Next, a method of supporting the divalent copper compound on titanium oxide (a), which is the most preferable embodiment, will be described.
前記酸化チタン（ａ）に２価銅化合物を担持する方法としては、例えば、ルチル型酸化チタン（ａ１）を含む酸化チタン（ａ）、２価銅化合物原料（ｂ）、水（ｃ）、及び、アルカリ性物質（ｄ）の混合工程（ｉ）を有する方法が挙げられる。
Examples of the method for supporting the divalent copper compound on the titanium oxide (a) include titanium oxide (a) containing rutile-type titanium oxide (a1), a divalent copper compound raw material (b), water (c), and water (c). , A method having a mixing step (i) of the alkaline substance (d) can be mentioned.
前記混合工程（ｉ）における前記酸化チタン（ａ）の濃度としては、３～４０質量％の範囲が好ましい。なお、本発明においては、液相法により製造された酸化チタン（ａ）を用いた場合には、酸化チタン（ａ）の濃度を高めても取扱いの良好な混合工程を行うことができ、具体的には、前記酸化チタン（ａ）の濃度が、２５質量％を超えて４０質量％以下の範囲でも良好に混合工程を行うことができる。
The concentration of the titanium oxide (a) in the mixing step (i) is preferably in the range of 3 to 40% by mass. In the present invention, when titanium oxide (a) produced by the liquid phase method is used, a mixing step with good handling can be performed even if the concentration of titanium oxide (a) is increased. Specifically, the mixing step can be satisfactorily performed even when the concentration of the titanium oxide (a) exceeds 25% by mass and is 40% by mass or less.
前記２価銅化合物原料（ｂ）としては、例えば、２価銅無機化合物、２価銅有機化合物等を用いることができる。
As the divalent copper compound raw material (b), for example, a divalent copper inorganic compound, a divalent copper organic compound, or the like can be used.
前記２価銅無機化合物としては、例えば、硫酸銅、硝酸銅、沃素酸銅、過塩素酸銅、シュウ酸銅、四ホウ酸銅、硫酸アンモニウム銅、アミド硫酸銅、塩化アンモニウム銅、ピロリン酸銅、炭酸銅等の２価銅の無機酸塩；塩化銅、フッ化銅、臭化銅等の２価銅のハロゲン化物；酸化銅、硫化銅、アズライト、マラカイト、アジ化銅などを用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。
Examples of the divalent copper inorganic compound include copper sulfate, copper nitrate, copper iodide, copper perchlorate, copper oxalate, copper tetraborate, copper ammonium sulfate, copper amide sulfate, copper ammonium chloride, and copper pyrophosphate. Inorganic acid salts of divalent copper such as copper carbonate; halides of divalent copper such as copper chloride, copper fluoride, copper bromide; copper oxide, copper sulfide, azulite, malakite, copper azide and the like can be used. .. These compounds may be used alone or in combination of two or more.
前記２価銅有機化合物としては、例えば、蟻酸銅、酢酸銅、プロピオン酸銅、酪酸銅、吉草酸銅、カプロン酸銅、エナント酸銅、カプリル酸銅、ペラルゴン酸銅、カプリン酸銅、ミスチン酸銅、パルミチン酸銅、マルガリン酸銅、ステアリン酸銅、オレイン酸銅、乳酸銅、リンゴ酸銅、クエン酸銅、安息香酸銅、フタル酸銅、イソフタル酸銅、テレフタル酸銅、サリチル酸銅、メリト酸銅、シュウ酸銅、マロン酸銅、コハク酸銅、グルタル酸銅、アジピン酸銅、フマル酸銅、グリコール酸銅、グリセリン酸銅、グルコン酸銅、酒石酸銅、アセチルアセトン銅、エチルアセト酢酸銅、イソ吉草酸銅、β－レゾルシル酸銅、ジアセト酢酸銅、ホルミルコハク酸銅、サリチルアミン酸銅、ビス（２-エチルヘキサン酸）銅、セバシン酸銅、ナフテン酸銅、オキシン銅、アセチルアセトン銅、エチルアセト酢酸銅、トリフルオロメタンスルホン酸銅、フタロシアニン銅、銅エトキシド、銅イソプロポキシド、銅メトキシド、ジメチルジチオカルバミン酸銅等を用いることができる。これらの化合物は単独で用いても２種以上を併用してもよい。
Examples of the divalent copper organic compound include copper formate, copper acetate, copper propionate, copper butyrate, copper valerate, copper caproate, copper enanthate, copper caprylate, copper pelargonate, copper capricate, and mistinic acid. Copper, copper palmitate, copper margarate, copper stearate, copper oleate, copper lactate, copper malate, copper citrate, copper benzoate, copper phthalate, copper isophthalate, copper terephthalate, copper salicylate, melitonic acid Copper, copper oxalate, copper malonate, copper succinate, copper glutarate, copper adipate, copper fumarate, copper glycolate, copper glycerate, copper gluconate, copper tartrate, acetylacetone copper, ethylacetate acetate, isokichi Copper herbate, copper β-resolcylate, copper diacetacetate, copper formylsuccinate, copper salicylamine, copper bis (2-ethylhexanoic acid), copper sebacate, copper naphthenate, oxine copper, acetylacetone copper, copper ethylacetate acetate , Copper trifluoromethanesulfonate, copper phthalocyanine, copper ethoxydo, copper isopropoxide, copper methoxydo, copper dimethyldithiocarbamate and the like can be used. These compounds may be used alone or in combination of two or more.
前記２価銅化合物原料（ｂ）としては、前記したものの中でも、下記一般式（１）で示されるものを用いることが好ましい。
ＣｕＸ２ （１）
（式（１）において、Ｘは、ハロゲン原子、ＣＨ３ＣＯＯ、ＮＯ３、又は、（ＳＯ４）１／２を示す。） As the divalent copper compound raw material (b), it is preferable to use the one represented by the following general formula (1) among the above-mentioned ones.
CuX 2 (1)
(In formula (1), X represents a halogen atom, CH 3 COO, NO 3 or (SO 4 ) 1/2 .)
ＣｕＸ２ （１）
（式（１）において、Ｘは、ハロゲン原子、ＣＨ３ＣＯＯ、ＮＯ３、又は、（ＳＯ４）１／２を示す。） As the divalent copper compound raw material (b), it is preferable to use the one represented by the following general formula (1) among the above-mentioned ones.
CuX 2 (1)
(In formula (1), X represents a halogen atom, CH 3 COO, NO 3 or (SO 4 ) 1/2 .)
前記式（１）におけるＸとしては、ハロゲン原子であることがより好ましく、塩素原子が更に好ましい。
The X in the formula (1) is more preferably a halogen atom, and even more preferably a chlorine atom.
前記混合工程（ｉ）における前記２価銅化合物原料（ｂ）の使用量としては、前記酸化チタン（ａ）１００質量部に対して、０．０１～２０質量部の範囲であることが好ましく、０．１～１５質量部の範囲がより好ましく、０．３～１０質量部の範囲が更に好ましい。
The amount of the divalent copper compound raw material (b) used in the mixing step (i) is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a). The range of 0.1 to 15 parts by mass is more preferable, and the range of 0.3 to 10 parts by mass is further preferable.
前記水（ｃ）は、混合工程（ｉ）における溶媒であり、水単独が好ましいが、必要に応じてその他の溶媒を含んでいてもよい。前記その他の溶媒としては、例えば、メタノール、エタノール、１－プロパノール、２－プロパノール、１－ブタノール等のアルコール溶媒；メチルエチルケトン、メチルイソブチルケトン等のケトン溶媒；ジメチルホルムアミド、テトラヒドロフラン等を用いることができる。これらの溶媒は単独で用いても２種以上を併用してもよい。
The water (c) is the solvent in the mixing step (i), and water alone is preferable, but other solvents may be contained if necessary. As the other solvent, for example, an alcohol solvent such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol; a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone; dimethylformamide, tetrahydrofuran and the like can be used. These solvents may be used alone or in combination of two or more.
前記アルカリ性物質（ｄ）としては、例えば、水酸化ナトリウム、水酸化カリウム、テトラメチルアンモニウムハイドロオキサイド、テトラブチルアンモニウムヒドロキシド、トリエチルアミン、トリメチルアミン、アンモニア、塩基性界面活性剤等を用いることができ、水酸化ナトリウムを用いることが好ましい。
As the alkaline substance (d), for example, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, triethylamine, trimethylamine, ammonia, a basic surfactant and the like can be used, and water can be used. It is preferable to use sodium oxide.
前記アルカリ性物質（ｄ）は、反応を制御しやすい点から、溶液として添加するのが好ましく、添加するアルカリ溶液の濃度としては、０．１～５ｍｏｌ／Ｌの範囲であることが好ましく、０．３～４ｍｏｌ／Ｌの範囲がより好ましく、０．５～３ｍｏｌ／Ｌの範囲が更に好ましい。
The alkaline substance (d) is preferably added as a solution from the viewpoint of easy control of the reaction, and the concentration of the alkaline solution to be added is preferably in the range of 0.1 to 5 mol / L. The range of 3 to 4 mol / L is more preferable, and the range of 0.5 to 3 mol / L is even more preferable.
前記混合工程（ｉ）は、前記酸化チタン（ａ）、２価銅化合物原料（ｂ）、水（ｃ）、及び、アルカリ性物質（ｄ）を混合すればよく、例えば、まず水（ｃ）に酸化チタン（ａ）を混合するとともに必要に応じて撹拌し、次いで、２価銅化合物原料（ｂ）を混合し、撹拌し、その後、アルカリ性物質（ｄ）を添加して撹拌する方法が挙げられる。この混合工程（ｉ）により、前記２価銅化合物原料（ｂ）由来の２価銅化合物が前記酸化チタン（ａ）に担持することとなる。
In the mixing step (i), the titanium oxide (a), the divalent copper compound raw material (b), the water (c), and the alkaline substance (d) may be mixed. Examples thereof include a method in which titanium oxide (a) is mixed and stirred as necessary, then a divalent copper compound raw material (b) is mixed and stirred, and then an alkaline substance (d) is added and stirred. .. By this mixing step (i), the divalent copper compound derived from the divalent copper compound raw material (b) is supported on the titanium oxide (a).
前記混合工程（ｉ）における全体の撹拌時間としては、例えば、５～１２０分間が挙げられ、好ましくは１０～６０分間である。混合工程（ｉ）時における温度としては、例えば、室温～７０℃の範囲が挙げられる。
The total stirring time in the mixing step (i) is, for example, 5 to 120 minutes, preferably 10 to 60 minutes. Examples of the temperature in the mixing step (i) include a range of room temperature to 70 ° C.
酸化チタン（ａ）への２価銅化合物の担持が良好である点から、前記酸化チタン（ａ）、２価銅化合物原料（ｂ）、及び、水（ｃ）を混合・撹拌し、その後アルカリ性物質（ｄ）を混合・撹拌した後の混合物のｐＨとしては、好ましくは８～１１の範囲であり、より好ましくは９．０～１０．５の範囲である。
The titanium oxide (a), the divalent copper compound raw material (b), and water (c) are mixed and stirred from the viewpoint of good support of the divalent copper compound on the titanium oxide (a), and then alkaline. The pH of the mixture after mixing and stirring the substance (d) is preferably in the range of 8 to 11, and more preferably in the range of 9.0 to 10.5.
前記混合工程（ｉ）が終了した後には、混合液を固形分として分離することができる。前記分離を行う方法としては、例えば、濾過、沈降分離、遠心分離、蒸発乾燥等が挙げられるが、濾過が好ましい。分離した固形分は、その後必要に応じて、水洗、解砕、分級等を行ってもよい。
After the mixing step (i) is completed, the mixed liquid can be separated as a solid content. Examples of the method for performing the separation include filtration, sedimentation separation, centrifugation, evaporation drying and the like, but filtration is preferable. The separated solid content may then be washed with water, crushed, classified, or the like, if necessary.
前記固形分を得た後には、前記酸化チタン（ａ）上に担持された前記２価銅化合物原料（ｂ）由来の２価銅化合物を、より強固に結合することができる点から、固形分を熱処理することが好ましい。熱処理温度としては、好ましくは１５０～６００℃の範囲であり、より好ましくは２５０～４５０℃の範囲である。また、熱処理時間は、好ましくは１～１０時間であり、より好ましくは、２～５時間である。
After obtaining the solid content, the divalent copper compound derived from the divalent copper compound raw material (b) supported on the titanium oxide (a) can be more firmly bonded to the solid content. Is preferably heat-treated. The heat treatment temperature is preferably in the range of 150 to 600 ° C, more preferably in the range of 250 to 450 ° C. The heat treatment time is preferably 1 to 10 hours, more preferably 2 to 5 hours.
以上の方法によって、酸化チタン（ａ）に２価銅化合物が担持した酸化チタンを含有する酸化チタン組成物が得られる。前記酸化チタン（ａ）に担持された２価銅化合物の担持量としては、酸化チタン（ａ）１００質量部に対して、０．０１～２０質量部の範囲であることが、抗ウイルス性を含む光触媒活性の点から好ましい。前記２価銅化合物の担持量は、前記混合工程（ｉ）における前記２価銅化合物原料（ｂ）の使用量によって調整することができる。なお、前記２価銅化合物の担持量の測定方法は、後述する実施例にて記載する。
By the above method, a titanium oxide composition containing titanium oxide in which a divalent copper compound is supported on titanium oxide (a) can be obtained. The amount of the divalent copper compound supported on the titanium oxide (a) is in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the titanium oxide (a). It is preferable from the viewpoint of photocatalytic activity including. The amount of the divalent copper compound carried can be adjusted by adjusting the amount of the divalent copper compound raw material (b) used in the mixing step (i). The method for measuring the amount of the divalent copper compound supported will be described in Examples described later.
次に、本発明のセルフクリーニング剤が使用される具体的な態様について説明する。
Next, a specific embodiment in which the self-cleaning agent of the present invention is used will be described.
前記態様としては、繊維等への練りこみ、スプレー剤、コーティング剤が挙げられる。
Examples of the above-mentioned embodiment include kneading into fibers and the like, a spray agent, and a coating agent.
前記繊維等への練りこみを行う方法としては、例えば、ポリエステル等の繊維と、前記セルフクリーニング剤とを、押出機等を使用して練りこみ、紡糸する方法が挙げられる。
Examples of the method of kneading into the fibers and the like include a method of kneading fibers such as polyester and the self-cleaning agent using an extruder or the like and spinning them.
前記スプレー剤としては、例えば、前記セルフクリーニング剤、及び、水、アルコール等の溶剤の混合物などが挙げられる。
Examples of the spray agent include the self-cleaning agent and a mixture of solvents such as water and alcohol.
前記コーティング剤としては、例えば、前記セルフクリーニング剤、水、アルコール等の溶剤、及び、バインダー樹脂の混合物などが挙げられる。前記バインダー樹脂としては、例えば、アクリル樹脂、ウレタン樹脂、フェノール樹脂、ポリエステル樹脂、エポキシ樹脂等を用いることができる。これらのバインダー樹脂は単独で用いても２種以上を併用してもよい。
Examples of the coating agent include the self-cleaning agent, a solvent such as water and alcohol, and a mixture of a binder resin and the like. As the binder resin, for example, an acrylic resin, a urethane resin, a phenol resin, a polyester resin, an epoxy resin or the like can be used. These binder resins may be used alone or in combination of two or more.
以上、本発明のセルフクリーニング剤によれば、繊維等の有機系素材、スレート板等の無機系素材の態様において、実用的な室内光の下で、汚れ成分を分解することができる。また、前記可視光応答型光触媒として、特定のものを用いることで、更に抗菌性、及び、抗ウイルス性にも優れたセルフクリーニング剤を得ることができる。
As described above, according to the self-cleaning agent of the present invention, the dirt component can be decomposed under practical indoor light in the aspect of the organic material such as fiber and the inorganic material such as slate plate. Further, by using a specific photocatalyst as the visible light responsive photocatalyst, a self-cleaning agent having further excellent antibacterial and antiviral properties can be obtained.
また、本発明によるセルフクリーニング剤は、抗ウイルス性、抗菌性、人体への安全性、耐熱性、耐候性、及び、耐水性に優れるものである。
Further, the self-cleaning agent according to the present invention is excellent in antiviral property, antibacterial property, safety to human body, heat resistance, weather resistance, and water resistance.
以下、実施例を用いて、本発明をより詳細に説明する。
Hereinafter, the present invention will be described in more detail with reference to Examples.
［調製例１］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：液相法（硫酸法）
ｃ）物性値
・ＢＥＴ比表面積：９．０ｍ２／ｇ
・ルチル化率：９５．４％
・１次粒子径：０．１８μｍ
・Ｚｒ／Ｔｉ比：０．０５
・Ｎｂ／Ｔｉ比：０．１７ [Preparation Example 1]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method (sulfuric acid method)
c) Physical characteristics / BET specific surface area: 9.0 m 2 / g
-Rutilation rate: 95.4%
-Primary particle size: 0.18 μm
-Zr / Ti ratio: 0.05
-Nb / Ti ratio: 0.17
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：液相法（硫酸法）
ｃ）物性値
・ＢＥＴ比表面積：９．０ｍ２／ｇ
・ルチル化率：９５．４％
・１次粒子径：０．１８μｍ
・Ｚｒ／Ｔｉ比：０．０５
・Ｎｂ／Ｔｉ比：０．１７ [Preparation Example 1]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method (sulfuric acid method)
c) Physical characteristics / BET specific surface area: 9.0 m 2 / g
-Rutilation rate: 95.4%
-Primary particle size: 0.18 μm
-Zr / Ti ratio: 0.05
-Nb / Ti ratio: 0.17
（２）製造工程
ａ）混合工程（反応工程）
前記酸化チタン６００質量部、塩化銅（ｉｉ）二水和物８質量部、水９００質量部をステンレス容器中に混合した。次いで、混合物を撹拌機（特殊機化工業株式会社製「ロボミクス」）で撹拌し、１ｍｏｌ／Ｌの水酸化ナトリウム水溶液を混合液のｐＨが１０になるまで滴下した。
ｂ）脱水工程
定性濾紙（５Ｃ）により減圧濾過をおこない、混合液から固形分を分離し、更にイオン交換水で洗浄を実施した。次いで、洗浄後の固形物を１２０℃で１２時間乾燥し、水分を除去した。乾燥後、ミル（イワタニ産業株式会社製「ミルサー」）で粉状の酸化チタン組成物を得た。
ｃ）熱処理工程
精密恒温器（ヤマト科学株式会社製「ＤＨ６５０」）を用いて酸素存在下で４５０℃、３時間熱処理し、２価銅化合物が担持された酸化チタンを含有する酸化チタン組成物を得た。 (2) Manufacturing process a) Mixing process (reaction process)
600 parts by mass of titanium oxide, 8 parts by mass of copper (ii) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. Then, the mixture was stirred with a stirrer (“Robomics” manufactured by Tokushu Kagaku Kogyo Co., Ltd.), and a 1 mol / L aqueous sodium hydroxide solution was added dropwise until the pH of the mixture reached 10.
b) Dehydration step The qualitative filter paper (5C) was used for vacuum filtration to separate the solid content from the mixed solution, and the mixture was further washed with ion-exchanged water. Then, the washed solid was dried at 120 ° C. for 12 hours to remove water. After drying, a powdery titanium oxide composition was obtained with a mill (“Miller” manufactured by Iwatani Corporation).
c) Heat treatment step A titanium oxide composition containing titanium oxide carrying a divalent copper compound is heat-treated at 450 ° C. for 3 hours in the presence of oxygen using a precision thermostat (“DH650” manufactured by Yamato Scientific Co., Ltd.). Obtained.
ａ）混合工程（反応工程）
前記酸化チタン６００質量部、塩化銅（ｉｉ）二水和物８質量部、水９００質量部をステンレス容器中に混合した。次いで、混合物を撹拌機（特殊機化工業株式会社製「ロボミクス」）で撹拌し、１ｍｏｌ／Ｌの水酸化ナトリウム水溶液を混合液のｐＨが１０になるまで滴下した。
ｂ）脱水工程
定性濾紙（５Ｃ）により減圧濾過をおこない、混合液から固形分を分離し、更にイオン交換水で洗浄を実施した。次いで、洗浄後の固形物を１２０℃で１２時間乾燥し、水分を除去した。乾燥後、ミル（イワタニ産業株式会社製「ミルサー」）で粉状の酸化チタン組成物を得た。
ｃ）熱処理工程
精密恒温器（ヤマト科学株式会社製「ＤＨ６５０」）を用いて酸素存在下で４５０℃、３時間熱処理し、２価銅化合物が担持された酸化チタンを含有する酸化チタン組成物を得た。 (2) Manufacturing process a) Mixing process (reaction process)
600 parts by mass of titanium oxide, 8 parts by mass of copper (ii) chloride dihydrate, and 900 parts by mass of water were mixed in a stainless steel container. Then, the mixture was stirred with a stirrer (“Robomics” manufactured by Tokushu Kagaku Kogyo Co., Ltd.), and a 1 mol / L aqueous sodium hydroxide solution was added dropwise until the pH of the mixture reached 10.
b) Dehydration step The qualitative filter paper (5C) was used for vacuum filtration to separate the solid content from the mixed solution, and the mixture was further washed with ion-exchanged water. Then, the washed solid was dried at 120 ° C. for 12 hours to remove water. After drying, a powdery titanium oxide composition was obtained with a mill (“Miller” manufactured by Iwatani Corporation).
c) Heat treatment step A titanium oxide composition containing titanium oxide carrying a divalent copper compound is heat-treated at 450 ° C. for 3 hours in the presence of oxygen using a precision thermostat (“DH650” manufactured by Yamato Scientific Co., Ltd.). Obtained.
（３）混合工程における混合物の酸化チタン濃度の変更
前記（２）製造工程ａ）混合工程（反応工程）において、酸化チタンの濃度を変更し、各配合率で撹拌可能な状態を判定した。具体的には、容器内で混合液が均一に撹拌される状態であれば「Ｔ」、混合液がゲル状となり、撹拌軸周辺のみの不十分な撹拌状態であれば「Ｆ」とした。 (3) Change in Titanium Oxide Concentration of Mixture in Mixing Step In the above (2) Manufacturing Step a) Mixing Step (Reaction Step), the concentration of titanium oxide was changed and a state in which stirring was possible was determined at each blending ratio. Specifically, it was set as "T" when the mixed solution was uniformly agitated in the container, and "F" when the mixed solution was in a gel state and only around the stirring shaft was inadequately agitated.
前記（２）製造工程ａ）混合工程（反応工程）において、酸化チタンの濃度を変更し、各配合率で撹拌可能な状態を判定した。具体的には、容器内で混合液が均一に撹拌される状態であれば「Ｔ」、混合液がゲル状となり、撹拌軸周辺のみの不十分な撹拌状態であれば「Ｆ」とした。 (3) Change in Titanium Oxide Concentration of Mixture in Mixing Step In the above (2) Manufacturing Step a) Mixing Step (Reaction Step), the concentration of titanium oxide was changed and a state in which stirring was possible was determined at each blending ratio. Specifically, it was set as "T" when the mixed solution was uniformly agitated in the container, and "F" when the mixed solution was in a gel state and only around the stirring shaft was inadequately agitated.
［調製例２］
調製例１において、塩化銅（ｉｉ）二水和物の使用量を、８質量部から３．３質量部に変更した以外は、調整例１と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。 [Preparation Example 2]
A titanium oxide composition was obtained in the same manner as in Preparation Example 1 except that the amount of copper (ii) chloride dihydrate used was changed from 8 parts by mass to 3.3 parts by mass in Preparation Example 1. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
調製例１において、塩化銅（ｉｉ）二水和物の使用量を、８質量部から３．３質量部に変更した以外は、調整例１と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。 [Preparation Example 2]
A titanium oxide composition was obtained in the same manner as in Preparation Example 1 except that the amount of copper (ii) chloride dihydrate used was changed from 8 parts by mass to 3.3 parts by mass in Preparation Example 1. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［調製例３］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：液相法
ｃ）物性値
・ＢＥＴ比表面積：３７．２ｍ２／ｇ
・ルチル化率：９９．６％
・１次粒子径：０．０４μｍ
・Ｚｒ／Ｔｉ比：０．０５
・Ｎｂ／Ｔｉ比：０．２６ [Preparation Example 3]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method c) Physical properties / BET specific surface area: 37.2 m 2 / g
-Rutilation rate: 99.6%
-Primary particle size: 0.04 μm
-Zr / Ti ratio: 0.05
-Nb / Ti ratio: 0.26
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：液相法
ｃ）物性値
・ＢＥＴ比表面積：３７．２ｍ２／ｇ
・ルチル化率：９９．６％
・１次粒子径：０．０４μｍ
・Ｚｒ／Ｔｉ比：０．０５
・Ｎｂ／Ｔｉ比：０．２６ [Preparation Example 3]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method c) Physical properties / BET specific surface area: 37.2 m 2 / g
-Rutilation rate: 99.6%
-Primary particle size: 0.04 μm
-Zr / Ti ratio: 0.05
-Nb / Ti ratio: 0.26
調製例１において、酸化チタンの種類を前記酸化チタンに変更した以外は、調製例１と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。
A titanium oxide composition was obtained in the same manner as in Preparation Example 1 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 1. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［調製例４］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：液相法
ｃ）物性値
・ＢＥＴ比表面積：６ｍ２／ｇ
・ルチル化率：８７．２％
・Ｚｒ／Ｔｉ比：０．１７
・Ｎｂ／Ｔｉ比：０．２０ [Preparation Example 4]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method c) Physical properties / BET specific surface area: 6 m 2 / g
-Rutilation rate: 87.2%
-Zr / Ti ratio: 0.17
-Nb / Ti ratio: 0.20
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：液相法
ｃ）物性値
・ＢＥＴ比表面積：６ｍ２／ｇ
・ルチル化率：８７．２％
・Ｚｒ／Ｔｉ比：０．１７
・Ｎｂ／Ｔｉ比：０．２０ [Preparation Example 4]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Liquid phase method c) Physical properties / BET specific surface area: 6 m 2 / g
-Rutilation rate: 87.2%
-Zr / Ti ratio: 0.17
-Nb / Ti ratio: 0.20
調製例１において、酸化チタンの種類を前記酸化チタンに変更した以外は、調製例１と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。
A titanium oxide composition was obtained in the same manner as in Preparation Example 1 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 1. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［調製例５］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：１３ｍ２／ｇ
・ルチル化率：９５．６％
・１次粒子径：０．１５μｍ
・Ｚｒ／Ｔｉ比：０．００
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 5]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical characteristics / BET specific surface area: 13 m 2 / g
-Rutilation rate: 95.6%
-Primary particle size: 0.15 μm
-Zr / Ti ratio: 0.00
-Nb / Ti ratio: 0.01
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：１３ｍ２／ｇ
・ルチル化率：９５．６％
・１次粒子径：０．１５μｍ
・Ｚｒ／Ｔｉ比：０．００
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 5]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical characteristics / BET specific surface area: 13 m 2 / g
-Rutilation rate: 95.6%
-Primary particle size: 0.15 μm
-Zr / Ti ratio: 0.00
-Nb / Ti ratio: 0.01
調製例１において、酸化チタンの種類を前記酸化チタンに変更し、水の使用量を９００質量部から４，０００質量部に変更した以外は、調製例１と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。
In Preparation Example 1, the titanium oxide composition was prepared in the same manner as in Preparation Example 1 except that the type of titanium oxide was changed to the titanium oxide and the amount of water used was changed from 900 parts by mass to 4,000 parts by mass. Obtained. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［調製例６］
調製例５において、塩化銅（ｉｉ）二水和物の使用量を８質量部から３．３質量部に変更した以外は、調製例５と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。 [Preparation Example 6]
A titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the amount of copper (ii) chloride dihydrate used was changed from 8 parts by mass to 3.3 parts by mass in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
調製例５において、塩化銅（ｉｉ）二水和物の使用量を８質量部から３．３質量部に変更した以外は、調製例５と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。 [Preparation Example 6]
A titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the amount of copper (ii) chloride dihydrate used was changed from 8 parts by mass to 3.3 parts by mass in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［調製例７］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：６．８ｍ２／ｇ
・ルチル化率：９９．６％
・１次粒子径：０．２５μｍ
・Ｚｒ／Ｔｉ比：０．０１
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 7]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical property value / BET specific surface area: 6.8 m 2 / g
-Rutilation rate: 99.6%
-Primary particle size: 0.25 μm
-Zr / Ti ratio: 0.01
-Nb / Ti ratio: 0.01
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：６．８ｍ２／ｇ
・ルチル化率：９９．６％
・１次粒子径：０．２５μｍ
・Ｚｒ／Ｔｉ比：０．０１
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 7]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical property value / BET specific surface area: 6.8 m 2 / g
-Rutilation rate: 99.6%
-Primary particle size: 0.25 μm
-Zr / Ti ratio: 0.01
-Nb / Ti ratio: 0.01
調製例５において、酸化チタンの種類を前記酸化チタンに変更した以外は、調製例５と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。
A titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［調製例８］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：１３．５ｍ２／ｇ
・ルチル化率：７６．５％
・１次粒子径：０．１３μｍ
・Ｚｒ／Ｔｉ比：０．００
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 8]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical characteristics / BET specific surface area: 13.5 m 2 / g
-Rutilation rate: 76.5%
-Primary particle size: 0.13 μm
-Zr / Ti ratio: 0.00
-Nb / Ti ratio: 0.01
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：１３．５ｍ２／ｇ
・ルチル化率：７６．５％
・１次粒子径：０．１３μｍ
・Ｚｒ／Ｔｉ比：０．００
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 8]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical characteristics / BET specific surface area: 13.5 m 2 / g
-Rutilation rate: 76.5%
-Primary particle size: 0.13 μm
-Zr / Ti ratio: 0.00
-Nb / Ti ratio: 0.01
調製例５において、酸化チタンの種類を前記酸化チタンに変更した以外は、調製例５と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。
A titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［調製例９］
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：２０ｍ２／ｇ
・ルチル化率：５３％
・１次粒子径：０．０７μｍ
・Ｚｒ／Ｔｉ比：０．００
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 9]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical properties / BET specific surface area: 20 m 2 / g
・ Rutileization rate: 53%
-Primary particle size: 0.07 μm
-Zr / Ti ratio: 0.00
-Nb / Ti ratio: 0.01
（１）酸化チタン
ａ）結晶性ルチル型酸化チタン
ｂ）製法：気相法
ｃ）物性値
・ＢＥＴ比表面積：２０ｍ２／ｇ
・ルチル化率：５３％
・１次粒子径：０．０７μｍ
・Ｚｒ／Ｔｉ比：０．００
・Ｎｂ／Ｔｉ比：０．０１ [Preparation Example 9]
(1) Titanium oxide a) Crystalline rutile type titanium oxide b) Production method: Gas phase method c) Physical properties / BET specific surface area: 20 m 2 / g
・ Rutileization rate: 53%
-Primary particle size: 0.07 μm
-Zr / Ti ratio: 0.00
-Nb / Ti ratio: 0.01
調製例５において、酸化チタンの種類を前記酸化チタンに変更した以外は、調製例５と同様にして、酸化チタン組成物を得た。また、調製例１と同様にして、酸化チタン濃度の変更試験を行った。
A titanium oxide composition was obtained in the same manner as in Preparation Example 5 except that the type of titanium oxide was changed to the titanium oxide in Preparation Example 5. Moreover, the change test of the titanium oxide concentration was carried out in the same manner as in Preparation Example 1.
［酸化チタン（ａ）のＢＥＴ比表面積の測定方法］
株式会社マウンテック製全自動ＢＥＴ比表面積測定装置「ＭａｃＳＯＲＢＨＭ ｍｏｄｅｌ－１２０８」を使用して、比表面積測定（ＢＥＴ１点法）による測定を行った。 [Measurement method of BET specific surface area of titanium oxide (a)]
The measurement was performed by the specific surface area measurement (BET 1-point method) using the fully automatic BET specific surface area measuring device "MacSORBHM model-1208" manufactured by Mountech Co., Ltd.
株式会社マウンテック製全自動ＢＥＴ比表面積測定装置「ＭａｃＳＯＲＢＨＭ ｍｏｄｅｌ－１２０８」を使用して、比表面積測定（ＢＥＴ１点法）による測定を行った。 [Measurement method of BET specific surface area of titanium oxide (a)]
The measurement was performed by the specific surface area measurement (BET 1-point method) using the fully automatic BET specific surface area measuring device "MacSORBHM model-1208" manufactured by Mountech Co., Ltd.
［酸化チタン（ａ）のルチル化率の測定方法］
島津製作所株式会社製Ｘ線回折装置「ＸＲＤ－６１００」を使用して、ルチル型結晶に対応するピーク高さ割合を酸化チタン全体の結晶（ルチル型、ブルッカイト型、アナターゼ型）に対応するピーク高さから算出した。 [Measurement method of rutileization rate of titanium oxide (a)]
Using the X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to the rutile type crystal is set to the peak height corresponding to the crystal of the whole titanium oxide (rutile type, brookite type, anatase type). Calculated from the above.
島津製作所株式会社製Ｘ線回折装置「ＸＲＤ－６１００」を使用して、ルチル型結晶に対応するピーク高さ割合を酸化チタン全体の結晶（ルチル型、ブルッカイト型、アナターゼ型）に対応するピーク高さから算出した。 [Measurement method of rutileization rate of titanium oxide (a)]
Using the X-ray diffractometer "XRD-6100" manufactured by Shimadzu Corporation, the peak height ratio corresponding to the rutile type crystal is set to the peak height corresponding to the crystal of the whole titanium oxide (rutile type, brookite type, anatase type). Calculated from the above.
［酸化チタン（ａ）のＺｒ／Ｔｉ比、Ｎｂ／Ｔｉ比の算出方法］
セイコーインスツル株式会社製蛍光Ｘ線分析装置「ＳＥＡ１２００ＶＸ」を使用して、バルクファンダメンタルパラメータ（バルクＦＰ）法による金属元素組成分析を行った。酸化チタン（ａ）試料を測定して得られた、各金属元素の蛍光強度（ｃｐｓ：ｃｏｕｎｔ ｐｅｒ ｓｅｃｏｎｄ）について、チタンの蛍光強度（ｃｐｓ）を１００としたときのジルコニウムまたはニオブの蛍光強度（ｃｐｓ）の強度比を、それぞれＺｒ／Ｔｉ比、またはＮｂ／Ｔｉ比として算出した。 [Method of calculating Zr / Ti ratio and Nb / Ti ratio of titanium oxide (a)]
A metal element composition analysis was performed by the bulk fundamental parameter (bulk FP) method using a fluorescent X-ray analyzer "SEA1200VX" manufactured by Seiko Instruments Inc. Regarding the fluorescence intensity (cps: count per second) of each metal element obtained by measuring the titanium oxide (a) sample, the fluorescence intensity (cps) of zirconium or niobium when the fluorescence intensity (cps) of titanium is 100. ) Was calculated as a Zr / Ti ratio or an Nb / Ti ratio, respectively.
セイコーインスツル株式会社製蛍光Ｘ線分析装置「ＳＥＡ１２００ＶＸ」を使用して、バルクファンダメンタルパラメータ（バルクＦＰ）法による金属元素組成分析を行った。酸化チタン（ａ）試料を測定して得られた、各金属元素の蛍光強度（ｃｐｓ：ｃｏｕｎｔ ｐｅｒ ｓｅｃｏｎｄ）について、チタンの蛍光強度（ｃｐｓ）を１００としたときのジルコニウムまたはニオブの蛍光強度（ｃｐｓ）の強度比を、それぞれＺｒ／Ｔｉ比、またはＮｂ／Ｔｉ比として算出した。 [Method of calculating Zr / Ti ratio and Nb / Ti ratio of titanium oxide (a)]
A metal element composition analysis was performed by the bulk fundamental parameter (bulk FP) method using a fluorescent X-ray analyzer "SEA1200VX" manufactured by Seiko Instruments Inc. Regarding the fluorescence intensity (cps: count per second) of each metal element obtained by measuring the titanium oxide (a) sample, the fluorescence intensity (cps) of zirconium or niobium when the fluorescence intensity (cps) of titanium is 100. ) Was calculated as a Zr / Ti ratio or an Nb / Ti ratio, respectively.
［酸化チタン（ａ）への２価銅化合物の担持量の測定方法］
調製例１～９で得られた酸化チタン組成物を、フッ酸溶液で全溶解し、抽出液をＩＣＰ発光分光分析装置により分析して、酸化チタン（ａ）１００質量部に対する２価銅化合物の担持量（質量部）を定量した。なお、前記担持量の測定まで行わなかったものは「－」とした。 [Method for measuring the amount of divalent copper compound supported on titanium oxide (a)]
The titanium oxide compositions obtained in Preparation Examples 1 to 9 were completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP emission spectroscopic analyzer to obtain a divalent copper compound based on 100 parts by mass of titanium (a) oxide. The amount carried (parts by mass) was quantified. In addition, those which did not perform the measurement of the supported amount were marked with "-".
調製例１～９で得られた酸化チタン組成物を、フッ酸溶液で全溶解し、抽出液をＩＣＰ発光分光分析装置により分析して、酸化チタン（ａ）１００質量部に対する２価銅化合物の担持量（質量部）を定量した。なお、前記担持量の測定まで行わなかったものは「－」とした。 [Method for measuring the amount of divalent copper compound supported on titanium oxide (a)]
The titanium oxide compositions obtained in Preparation Examples 1 to 9 were completely dissolved in a hydrofluoric acid solution, and the extract was analyzed by an ICP emission spectroscopic analyzer to obtain a divalent copper compound based on 100 parts by mass of titanium (a) oxide. The amount carried (parts by mass) was quantified. In addition, those which did not perform the measurement of the supported amount were marked with "-".
［抗ウイルス性］
ＪＩＳ Ｒ １７５６：２０１３に準拠して、抗ウイルス性試験を行った。抗ウイルス性はソーダライムガラス板上に実施例及び比較例で得られた酸化チタン組成物を１ｇ／ｍ２を均一に塗布し、Ｎ－１１３フィルターで４００ｎｍ以下の波長をカットした光源を用いて、４時間照射後の試料について以下の式により求めた値、不活化度で評価した。
不活化度＝ｌｏｇ（Ｎ／Ｎ０）
Ｎ：反応後のサンプルの感染価 、Ｎ０：接種ファージの感染価。
不活化度－１が９０％、不活化度－２が９９％、不活化度－３ が９９．９％不活化していることを示す。
なお、抗ウイルス性試験まで行わなかったものは「－」とした。 [Antiviral]
Antiviral tests were performed in accordance with JIS R 1756: 2013. For anti-virus property, 1 g / m 2 of the titanium oxide composition obtained in Examples and Comparative Examples was uniformly applied on a soda lime glass plate, and a light source having a wavelength of 400 nm or less cut with an N-113 filter was used. The sample after irradiation for 4 hours was evaluated by the value obtained by the following formula and the degree of inactivation.
Degree of inactivation = log (N / N 0 )
N: Infectious titer of the sample after the reaction, N 0 : Infectious titer of the inoculated phage.
The inactivation degree -1 is 90%, the inactivation degree -2 is 99%, and the inactivation degree -3 is 99.9%.
Those that did not undergo the antiviral test were marked with "-".
ＪＩＳ Ｒ １７５６：２０１３に準拠して、抗ウイルス性試験を行った。抗ウイルス性はソーダライムガラス板上に実施例及び比較例で得られた酸化チタン組成物を１ｇ／ｍ２を均一に塗布し、Ｎ－１１３フィルターで４００ｎｍ以下の波長をカットした光源を用いて、４時間照射後の試料について以下の式により求めた値、不活化度で評価した。
不活化度＝ｌｏｇ（Ｎ／Ｎ０）
Ｎ：反応後のサンプルの感染価 、Ｎ０：接種ファージの感染価。
不活化度－１が９０％、不活化度－２が９９％、不活化度－３ が９９．９％不活化していることを示す。
なお、抗ウイルス性試験まで行わなかったものは「－」とした。 [Antiviral]
Antiviral tests were performed in accordance with JIS R 1756: 2013. For anti-virus property, 1 g / m 2 of the titanium oxide composition obtained in Examples and Comparative Examples was uniformly applied on a soda lime glass plate, and a light source having a wavelength of 400 nm or less cut with an N-113 filter was used. The sample after irradiation for 4 hours was evaluated by the value obtained by the following formula and the degree of inactivation.
Degree of inactivation = log (N / N 0 )
N: Infectious titer of the sample after the reaction, N 0 : Infectious titer of the inoculated phage.
The inactivation degree -1 is 90%, the inactivation degree -2 is 99%, and the inactivation degree -3 is 99.9%.
Those that did not undergo the antiviral test were marked with "-".
調製例１～４に示す通り、酸化チタンを液相法で得れば、混合工程（ｉ）中における混合物中の酸化チタン（ａ）の濃度を高めても安定的に混合でき、抗ウイルス性に優れる抗ウイルス剤が効率よく生産できることが分かった。
As shown in Preparation Examples 1 to 4, if titanium oxide is obtained by the liquid phase method, it can be stably mixed even if the concentration of titanium oxide (a) in the mixture in the mixing step (i) is increased, and it has antiviral properties. It was found that an excellent antiviral agent can be efficiently produced.
一方、調製例５～９はいずれも、酸化チタン（ａ）に代えて、気相法により製造されたルチル型酸化チタンを用いた態様であるが、混合工程（ｉ）における酸化チタン濃度が２０質量％を超えると、混合液の粘度が極めて高くなり、取扱いが困難であり、生産性に劣ることが分かった。
On the other hand, in each of Preparation Examples 5 to 9, instead of titanium oxide (a), rutile-type titanium oxide produced by the vapor phase method was used, but the titanium oxide concentration in the mixing step (i) was 20. It was found that when it exceeds% by mass, the viscosity of the mixed solution becomes extremely high, it is difficult to handle, and the productivity is inferior.
特に、調製例５～９では、酸化チタンのＢＥＴ比表面積の幅を振った実験を行ったものの、その値が小さい調製例７においても酸化チタン濃度が上がると混合液の粘度が極めて高くなり、生産性の改善効果は見られなかった。
In particular, in Preparation Examples 5 to 9, an experiment was conducted in which the width of the BET specific surface area of titanium oxide was changed, but even in Preparation Example 7 in which the value was small, the viscosity of the mixed solution became extremely high as the titanium oxide concentration increased. No productivity improvement effect was seen.
［実施例１］
調整例１で得られた酸化チタン組成物２５質量部、水７３．５質量部、分散剤（ビックケミー社製「ＤＩＳＰＥＲＢＩＫ １９０」）１．５質量部をサンドグラインダーにて分散し、水性スラリーを得た。
得られた水性スラリー３５質量部、アクリル樹脂バインダー（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＦＩＸＥＲ ２５４ＰＫ」）５質量部、Ｏ／Ｗ型エマルジョン（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＲＥＤＵＣＥＲ ＣＯＮＣ ７２０ＥＮＦ」５部、水４５部、ミネラルスピリット５０部の乳化物）６０質量部を混合し、綿ブロード生地（１２２．５ｇ／ｍ２）上にオートスクリーン捺染機（辻井染機工業株式会社製）を用いて乾燥前塗布量が１００ｇ／ｍ２となるようにプリントを実施し、熱風循環式乾燥機にて１５０℃で２分間乾燥させ、評価用試料を得た。 [Example 1]
25 parts by mass of the titanium oxide composition obtained in Adjustment Example 1, 73.5 parts by mass of water, and 1.5 parts by mass of a dispersant (“DISPERBIK 190” manufactured by Big Chemie) were dispersed with a sand grinder to obtain an aqueous slurry. It was.
35 parts by mass of the obtained aqueous slurry, 5 parts by mass of an acrylic resin binder (“RYUDYE-W FIXER 254PK” manufactured by DIC Corporation), 5 parts by mass of an O / W type emulsion (“RYUDYE-W REDUCER CONC 720ENF” manufactured by DIC Corporation), Mix 45 parts of water and 50 parts of mineral spirit emulsion) and mix them on cotton broad cloth (122.5 g / m 2 ) before drying using an auto screen printing machine (manufactured by Tsujii Dyeing Machinery Co., Ltd.). Printing was carried out so that the coating amount was 100 g / m 2, and the mixture was dried in a hot air circulation type dryer at 150 ° C. for 2 minutes to obtain a sample for evaluation.
調整例１で得られた酸化チタン組成物２５質量部、水７３．５質量部、分散剤（ビックケミー社製「ＤＩＳＰＥＲＢＩＫ １９０」）１．５質量部をサンドグラインダーにて分散し、水性スラリーを得た。
得られた水性スラリー３５質量部、アクリル樹脂バインダー（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＦＩＸＥＲ ２５４ＰＫ」）５質量部、Ｏ／Ｗ型エマルジョン（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＲＥＤＵＣＥＲ ＣＯＮＣ ７２０ＥＮＦ」５部、水４５部、ミネラルスピリット５０部の乳化物）６０質量部を混合し、綿ブロード生地（１２２．５ｇ／ｍ２）上にオートスクリーン捺染機（辻井染機工業株式会社製）を用いて乾燥前塗布量が１００ｇ／ｍ２となるようにプリントを実施し、熱風循環式乾燥機にて１５０℃で２分間乾燥させ、評価用試料を得た。 [Example 1]
25 parts by mass of the titanium oxide composition obtained in Adjustment Example 1, 73.5 parts by mass of water, and 1.5 parts by mass of a dispersant (“DISPERBIK 190” manufactured by Big Chemie) were dispersed with a sand grinder to obtain an aqueous slurry. It was.
35 parts by mass of the obtained aqueous slurry, 5 parts by mass of an acrylic resin binder (“RYUDYE-W FIXER 254PK” manufactured by DIC Corporation), 5 parts by mass of an O / W type emulsion (“RYUDYE-W REDUCER CONC 720ENF” manufactured by DIC Corporation), Mix 45 parts of water and 50 parts of mineral spirit emulsion) and mix them on cotton broad cloth (122.5 g / m 2 ) before drying using an auto screen printing machine (manufactured by Tsujii Dyeing Machinery Co., Ltd.). Printing was carried out so that the coating amount was 100 g / m 2, and the mixture was dried in a hot air circulation type dryer at 150 ° C. for 2 minutes to obtain a sample for evaluation.
得られた試料に、汚れ成分（Ａ）（オイルレッド０．５質量部、エタノール４９．７５質量部、及び、オレイン酸４９．７５質量部）３０μＬを、マイクロピペットを用いて滴下し、５００ルクスの室内に放置し、滴下後１時間後（０日後）、１日後、２日後に色彩計（コニカミノルタ株式会社製「ＣＲ－２００ Ｄ６５光源」）にてａ＊値を測定した。
30 μL of the stain component (A) (0.5 parts by mass of oil red, 49.75 parts by mass of ethanol, and 49.75 parts by mass of oleic acid) was added dropwise to the obtained sample using a micropipette, and 500 lux was added. The a * value was measured with a colorimeter (“CR-200 D65 light source” manufactured by Konica Minolta Co., Ltd.) 1 hour (0 days later), 1 day and 2 days after the dropping.
［実施例２］
実施例１において、汚れ成分（Ａ）を、汚れ成分（Ｂ）（Ｓ＆Ｂ株式会社製ラー油）に変更した以外は、実施例１と同様にして、ａ＊値を測定した。なお、Δａ＊は、比較例４との差分によって求めた。 [Example 2]
In Example 1, the a * value was measured in the same manner as in Example 1 except that the stain component (A) was changed to the stain component (B) (chili oil manufactured by S & B Co., Ltd.). In addition, Δa * was obtained by the difference from Comparative Example 4.
実施例１において、汚れ成分（Ａ）を、汚れ成分（Ｂ）（Ｓ＆Ｂ株式会社製ラー油）に変更した以外は、実施例１と同様にして、ａ＊値を測定した。なお、Δａ＊は、比較例４との差分によって求めた。 [Example 2]
In Example 1, the a * value was measured in the same manner as in Example 1 except that the stain component (A) was changed to the stain component (B) (chili oil manufactured by S & B Co., Ltd.). In addition, Δa * was obtained by the difference from Comparative Example 4.
［実施例３］
実施例１において、汚れ成分（Ａ）を、汚れ成分（Ｃ）（エスビーカレーパウダー顆粒１質量部、及び、エタノール９９質量部）に変更した以外は、実施例１と同様にして、
ａ＊値を測定した。なお、Δａ＊は、比較例６との差分によって求めた。 [Example 3]
In Example 1, the stain component (A) was changed to the stain component (C) (1 part by mass of S & B curry powder granules and 99 parts by mass of ethanol) in the same manner as in Example 1.
The a * value was measured. In addition, Δa * was obtained by the difference from Comparative Example 6.
実施例１において、汚れ成分（Ａ）を、汚れ成分（Ｃ）（エスビーカレーパウダー顆粒１質量部、及び、エタノール９９質量部）に変更した以外は、実施例１と同様にして、
ａ＊値を測定した。なお、Δａ＊は、比較例６との差分によって求めた。 [Example 3]
In Example 1, the stain component (A) was changed to the stain component (C) (1 part by mass of S & B curry powder granules and 99 parts by mass of ethanol) in the same manner as in Example 1.
The a * value was measured. In addition, Δa * was obtained by the difference from Comparative Example 6.
［実施例４］
実施例１において、綿ブロード生地に代えて、スレート板（ノザワ株式会社製）に変更した以外は、実施例１と同様にして、ａ＊値を測定した。なお、Δａ＊は、比較例８との差分によって求めた。 [Example 4]
In Example 1, the a * value was measured in the same manner as in Example 1 except that the cotton broad cloth was changed to a slate plate (manufactured by Nozawa Corporation). In addition, Δa * was obtained by the difference from Comparative Example 8.
実施例１において、綿ブロード生地に代えて、スレート板（ノザワ株式会社製）に変更した以外は、実施例１と同様にして、ａ＊値を測定した。なお、Δａ＊は、比較例８との差分によって求めた。 [Example 4]
In Example 1, the a * value was measured in the same manner as in Example 1 except that the cotton broad cloth was changed to a slate plate (manufactured by Nozawa Corporation). In addition, Δa * was obtained by the difference from Comparative Example 8.
［比較例１］
実施例１で用いた綿ブロード生地に直接汚れ成分（Ａ）を滴下した以外は、実施例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例１、比較例２、及び比較例３の色変化量（Δａ＊）の基準とした。 [Comparative Example 1]
The a * value was measured in the same manner as in Example 1 except that the stain component (A) was directly dropped onto the cotton broad cloth used in Example 1. Further, this a * value was used as a reference for the amount of color change (Δa *) of Example 1, Comparative Example 2, and Comparative Example 3.
実施例１で用いた綿ブロード生地に直接汚れ成分（Ａ）を滴下した以外は、実施例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例１、比較例２、及び比較例３の色変化量（Δａ＊）の基準とした。 [Comparative Example 1]
The a * value was measured in the same manner as in Example 1 except that the stain component (A) was directly dropped onto the cotton broad cloth used in Example 1. Further, this a * value was used as a reference for the amount of color change (Δa *) of Example 1, Comparative Example 2, and Comparative Example 3.
［比較例２］
アクリル樹脂バインダー（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＦＩＸＥＲ ２５４ＰＫ」）５質量部、、Ｏ／Ｗ型エマルジョン（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＲＥＤＵＣＥＲ ＣＯＮＣ ７２０ＥＮＦ」５部、水４５部、ミネラルスピリット５０部の乳化物）９５質量部を混合し、実施例１で用いた綿ブロード生地に、オートスクリーン捺染機（辻井染機工業株式会社製）を用いて乾燥前塗布量が１００ｇ／ｍ２となるようにプリントを実施し、熱風循環式乾燥機にて１５０℃で２分間乾燥させ、評価用試料を得た。これに汚れ成分（Ａ）を滴下した以外は、実施例１と同様にして、ａ＊値を測定した。 [Comparative Example 2]
Acrylic resin binder ("RYUDYE-W FIXER 254PK" manufactured by DIC Corporation) 5 parts by mass, O / W type emulsion ("RYUDYE-W REDUCER CONC 720ENF" manufactured by DIC Corporation) 5 parts, water 45 parts, mineral spirit 50 parts (Emulsion) 95 parts by mass was mixed, and the cotton broad cloth used in Example 1 was coated with an auto screen printing machine (manufactured by Tsujii Dyeing Machinery Co., Ltd.) so that the coating amount before drying was 100 g / m 2. Was printed and dried in a hot air circulation type dryer at 150 ° C. for 2 minutes to obtain a sample for evaluation. The a * value was measured in the same manner as in Example 1 except that the dirt component (A) was added dropwise thereto.
アクリル樹脂バインダー（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＦＩＸＥＲ ２５４ＰＫ」）５質量部、、Ｏ／Ｗ型エマルジョン（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＲＥＤＵＣＥＲ ＣＯＮＣ ７２０ＥＮＦ」５部、水４５部、ミネラルスピリット５０部の乳化物）９５質量部を混合し、実施例１で用いた綿ブロード生地に、オートスクリーン捺染機（辻井染機工業株式会社製）を用いて乾燥前塗布量が１００ｇ／ｍ２となるようにプリントを実施し、熱風循環式乾燥機にて１５０℃で２分間乾燥させ、評価用試料を得た。これに汚れ成分（Ａ）を滴下した以外は、実施例１と同様にして、ａ＊値を測定した。 [Comparative Example 2]
Acrylic resin binder ("RYUDYE-W FIXER 254PK" manufactured by DIC Corporation) 5 parts by mass, O / W type emulsion ("RYUDYE-W REDUCER CONC 720ENF" manufactured by DIC Corporation) 5 parts, water 45 parts, mineral spirit 50 parts (Emulsion) 95 parts by mass was mixed, and the cotton broad cloth used in Example 1 was coated with an auto screen printing machine (manufactured by Tsujii Dyeing Machinery Co., Ltd.) so that the coating amount before drying was 100 g / m 2. Was printed and dried in a hot air circulation type dryer at 150 ° C. for 2 minutes to obtain a sample for evaluation. The a * value was measured in the same manner as in Example 1 except that the dirt component (A) was added dropwise thereto.
［比較例３］
調整例１の酸化チタン組成物に代えて、紫外光応答型光触媒（石原産業株式会社製「ＳＴ－４１」）２５質量部、水７３．５質量部、分散剤（ビックケミー社製「ＤＩＳＰＥＲＢＩＫ １９０」）１．５質量部をサンドグラインダーにて分散し、水性スラリーを得た。
得られた水性スラリー３５質量部、アクリル樹脂バインダー（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＦＩＸＥＲ ２５４ＰＫ」）５質量部、Ｏ／Ｗ型エマルジョン（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＲＥＤＵＣＥＲ ＣＯＮＣ ７２０ＥＮＦ」５部、水４５部、ミネラルスピリット５０部の乳化物）６０質量部を混合し、綿ブロード生地（１２２．５ｇ／ｍ２）上にオートスクリーン捺染機（辻井染機工業株式会社製）を用いて乾燥前塗布量が１００ｇ／ｍ２となるようにプリントを実施し、熱風循環式乾燥機にて１５０℃で２分間乾燥させ、評価用試料を得た。これに汚れ成分（Ａ）を滴下した以外は、実施例１と同様にして、ａ＊値を測定した。 [Comparative Example 3]
Instead of the titanium oxide composition of Adjustment Example 1, 25 parts by mass of an ultraviolet light-responsive photocatalyst (“ST-41” manufactured by Ishihara Sangyo Co., Ltd.), 73.5 parts by mass of water, and a dispersant (“DISPERBIK 190” manufactured by Big Chemie Co., Ltd.” ) 1.5 parts by mass was dispersed with a sand grinder to obtain an aqueous slurry.
35 parts by mass of the obtained aqueous slurry, 5 parts by mass of an acrylic resin binder (“RYUDYE-W FIXER 254PK” manufactured by DIC Corporation), 5 parts by mass of an O / W type emulsion (“RYUDYE-W REDUCER CONC 720ENF” manufactured by DIC Corporation), Mix 45 parts of water and 50 parts of mineral spirit emulsion) and mix them on cotton broad cloth (122.5 g / m 2 ) before drying using an auto screen printing machine (manufactured by Tsujii Dyeing Machinery Co., Ltd.). Printing was carried out so that the coating amount was 100 g / m 2, and the mixture was dried in a hot air circulation type dryer at 150 ° C. for 2 minutes to obtain a sample for evaluation. The a * value was measured in the same manner as in Example 1 except that the dirt component (A) was added dropwise thereto.
調整例１の酸化チタン組成物に代えて、紫外光応答型光触媒（石原産業株式会社製「ＳＴ－４１」）２５質量部、水７３．５質量部、分散剤（ビックケミー社製「ＤＩＳＰＥＲＢＩＫ １９０」）１．５質量部をサンドグラインダーにて分散し、水性スラリーを得た。
得られた水性スラリー３５質量部、アクリル樹脂バインダー（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＦＩＸＥＲ ２５４ＰＫ」）５質量部、Ｏ／Ｗ型エマルジョン（ＤＩＣ株式会社製「ＲＹＵＤＹＥ－Ｗ ＲＥＤＵＣＥＲ ＣＯＮＣ ７２０ＥＮＦ」５部、水４５部、ミネラルスピリット５０部の乳化物）６０質量部を混合し、綿ブロード生地（１２２．５ｇ／ｍ２）上にオートスクリーン捺染機（辻井染機工業株式会社製）を用いて乾燥前塗布量が１００ｇ／ｍ２となるようにプリントを実施し、熱風循環式乾燥機にて１５０℃で２分間乾燥させ、評価用試料を得た。これに汚れ成分（Ａ）を滴下した以外は、実施例１と同様にして、ａ＊値を測定した。 [Comparative Example 3]
Instead of the titanium oxide composition of Adjustment Example 1, 25 parts by mass of an ultraviolet light-responsive photocatalyst (“ST-41” manufactured by Ishihara Sangyo Co., Ltd.), 73.5 parts by mass of water, and a dispersant (“DISPERBIK 190” manufactured by Big Chemie Co., Ltd.” ) 1.5 parts by mass was dispersed with a sand grinder to obtain an aqueous slurry.
35 parts by mass of the obtained aqueous slurry, 5 parts by mass of an acrylic resin binder (“RYUDYE-W FIXER 254PK” manufactured by DIC Corporation), 5 parts by mass of an O / W type emulsion (“RYUDYE-W REDUCER CONC 720ENF” manufactured by DIC Corporation), Mix 45 parts of water and 50 parts of mineral spirit emulsion) and mix them on cotton broad cloth (122.5 g / m 2 ) before drying using an auto screen printing machine (manufactured by Tsujii Dyeing Machinery Co., Ltd.). Printing was carried out so that the coating amount was 100 g / m 2, and the mixture was dried in a hot air circulation type dryer at 150 ° C. for 2 minutes to obtain a sample for evaluation. The a * value was measured in the same manner as in Example 1 except that the dirt component (A) was added dropwise thereto.
［比較例４］
比較例１において、汚れ成分（Ａ）を、汚れ成分（Ｂ）に変更した以外は、比較例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例２、及び比較例５の色変化量（Δａ＊）の基準とした。 [Comparative Example 4]
In Comparative Example 1, the a * value was measured in the same manner as in Comparative Example 1 except that the stain component (A) was changed to the stain component (B). Further, this a * value was used as a reference for the amount of color change (Δa *) in Example 2 and Comparative Example 5.
比較例１において、汚れ成分（Ａ）を、汚れ成分（Ｂ）に変更した以外は、比較例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例２、及び比較例５の色変化量（Δａ＊）の基準とした。 [Comparative Example 4]
In Comparative Example 1, the a * value was measured in the same manner as in Comparative Example 1 except that the stain component (A) was changed to the stain component (B). Further, this a * value was used as a reference for the amount of color change (Δa *) in Example 2 and Comparative Example 5.
［比較例５］
比較例２において、汚れ成分（Ａ）を、汚れ成分（Ｂ）に変更した以外は、比較例２と同様にして、ａ＊値を測定した。 [Comparative Example 5]
In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that the stain component (A) was changed to the stain component (B).
比較例２において、汚れ成分（Ａ）を、汚れ成分（Ｂ）に変更した以外は、比較例２と同様にして、ａ＊値を測定した。 [Comparative Example 5]
In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that the stain component (A) was changed to the stain component (B).
［比較例６］
比較例１において、汚れ成分（Ａ）を、汚れ成分（Ｃ）に変更した以外は、比較例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例３、及び比較例７の色変化量（Δａ＊）の基準とした。 [Comparative Example 6]
In Comparative Example 1, the a * value was measured in the same manner as in Comparative Example 1 except that the stain component (A) was changed to the stain component (C). Further, this a * value was used as a reference for the amount of color change (Δa *) in Example 3 and Comparative Example 7.
比較例１において、汚れ成分（Ａ）を、汚れ成分（Ｃ）に変更した以外は、比較例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例３、及び比較例７の色変化量（Δａ＊）の基準とした。 [Comparative Example 6]
In Comparative Example 1, the a * value was measured in the same manner as in Comparative Example 1 except that the stain component (A) was changed to the stain component (C). Further, this a * value was used as a reference for the amount of color change (Δa *) in Example 3 and Comparative Example 7.
［比較例７］
比較例２において、汚れ成分（Ａ）を、汚れ成分（Ｃ）に変更した以外は、比較例２と同様にして、ａ＊値を測定した。 [Comparative Example 7]
In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that the stain component (A) was changed to the stain component (C).
比較例２において、汚れ成分（Ａ）を、汚れ成分（Ｃ）に変更した以外は、比較例２と同様にして、ａ＊値を測定した。 [Comparative Example 7]
In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that the stain component (A) was changed to the stain component (C).
［比較例８］
比較例１の綿ブロード生地に代えて、スレート板（ノザワ株式会社製）を用いた以外は、比較例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例４、及び比較例９の色変化量（Δａ＊）の基準とした。 [Comparative Example 8]
The a * value was measured in the same manner as in Comparative Example 1 except that a slate plate (manufactured by Nozawa Corporation) was used instead of the cotton broad cloth of Comparative Example 1. Further, this a * value was used as a reference for the amount of color change (Δa *) in Example 4 and Comparative Example 9.
比較例１の綿ブロード生地に代えて、スレート板（ノザワ株式会社製）を用いた以外は、比較例１と同様にして、ａ＊値を測定した。また、このａ＊値を、実施例４、及び比較例９の色変化量（Δａ＊）の基準とした。 [Comparative Example 8]
The a * value was measured in the same manner as in Comparative Example 1 except that a slate plate (manufactured by Nozawa Corporation) was used instead of the cotton broad cloth of Comparative Example 1. Further, this a * value was used as a reference for the amount of color change (Δa *) in Example 4 and Comparative Example 9.
［比較例９］
比較例２において、綿ブロード生地に代えて、スレート板（ノザワ株式会社製）を用いた以外は、比較例２と同様にして、ａ＊値を測定した。 [Comparative Example 9]
In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that a slate plate (manufactured by Nozawa Corporation) was used instead of the cotton broad cloth.
比較例２において、綿ブロード生地に代えて、スレート板（ノザワ株式会社製）を用いた以外は、比較例２と同様にして、ａ＊値を測定した。 [Comparative Example 9]
In Comparative Example 2, the a * value was measured in the same manner as in Comparative Example 2 except that a slate plate (manufactured by Nozawa Corporation) was used instead of the cotton broad cloth.
［汚れ分解性の評価］
汚れを滴下した評価用試料を日中１１時間（照度５００～５５０ルクス、照度計「ＹＯＫＯＧＡＷＡ３２８１Ａ」）で日中１１時間、夜間（照度１０ルクス以下）１３時間静置し、滴下後１時間後（０日後）、ｎ日後に、色彩色差計（コニカミノルタ株式会社製「ＣＲ－２００」を使用して、汚れ滴下部分の測色を実施した。
汚れの分解効果は、基材（綿ブロード生地、スレート板）に汚れ成分のみを滴下した比較例のａ＊値を基準として差分Δａ＊により求めた。ｎ日後のΔａ＊と初期（０日後）のΔａ＊から色変化量を評価し、色変化量がマイナス側になればなるほど、汚れ成分である色素が分解していることを示す。 [Evaluation of stain degradability]
The evaluation sample to which the dirt was dropped was allowed to stand for 11 hours during the day (illuminance 500 to 550 lux, illuminance meter "YOKOGAWA3281A") for 11 hours during the day and at night (illuminance 10 lux or less) for 13 hours, and 1 hour after the dropping (illuminance 10 lux or less). After 0 days) and n days later, a color difference meter (“CR-200” manufactured by Konica Minolta Co., Ltd.) was used to measure the color of the dirt dropping portion.
The stain decomposition effect was determined by the difference Δa * based on the a * value of the comparative example in which only the stain component was dropped on the base material (cotton broad cloth, slate plate). The amount of color change is evaluated from Δa * after n days and Δa * at the initial stage (after 0 days), and the more the amount of color change becomes negative, the more the dye, which is a stain component, is decomposed.
汚れを滴下した評価用試料を日中１１時間（照度５００～５５０ルクス、照度計「ＹＯＫＯＧＡＷＡ３２８１Ａ」）で日中１１時間、夜間（照度１０ルクス以下）１３時間静置し、滴下後１時間後（０日後）、ｎ日後に、色彩色差計（コニカミノルタ株式会社製「ＣＲ－２００」を使用して、汚れ滴下部分の測色を実施した。
汚れの分解効果は、基材（綿ブロード生地、スレート板）に汚れ成分のみを滴下した比較例のａ＊値を基準として差分Δａ＊により求めた。ｎ日後のΔａ＊と初期（０日後）のΔａ＊から色変化量を評価し、色変化量がマイナス側になればなるほど、汚れ成分である色素が分解していることを示す。 [Evaluation of stain degradability]
The evaluation sample to which the dirt was dropped was allowed to stand for 11 hours during the day (illuminance 500 to 550 lux, illuminance meter "YOKOGAWA3281A") for 11 hours during the day and at night (illuminance 10 lux or less) for 13 hours, and 1 hour after the dropping (illuminance 10 lux or less). After 0 days) and n days later, a color difference meter (“CR-200” manufactured by Konica Minolta Co., Ltd.) was used to measure the color of the dirt dropping portion.
The stain decomposition effect was determined by the difference Δa * based on the a * value of the comparative example in which only the stain component was dropped on the base material (cotton broad cloth, slate plate). The amount of color change is evaluated from Δa * after n days and Δa * at the initial stage (after 0 days), and the more the amount of color change becomes negative, the more the dye, which is a stain component, is decomposed.
本発明のセルフクリーニング剤は、室内光の下で、優れた汚れ分解機能を有することが分かった。
It was found that the self-cleaning agent of the present invention has an excellent stain decomposition function under room light.
一方、比較例１～９はいずれも、可視光応答型光触媒を含有しない態様であるが、室内光の下での汚れ分解性に劣っていた。
On the other hand, all of Comparative Examples 1 to 9 did not contain a visible light responsive photocatalyst, but were inferior in stain decomposability under room light.
Claims (8)
- 可視光応答型光触媒を含有することを特徴とするセルフクリーニング剤。 A self-cleaning agent containing a visible light responsive photocatalyst.
- 前記可視光応答型光触媒が、酸化チタン（ａ）に金属化合物が担持されたものである請求項１記載のセルフクリーニング剤。 The self-cleaning agent according to claim 1, wherein the visible light responsive photocatalyst is a titanium oxide (a) on which a metal compound is supported.
- 前記酸化チタン（ａ）が、ルチル型酸化チタン（ａ１）を含むものである請求項２記載のセルフクリーニング剤。 The self-cleaning agent according to claim 2, wherein the titanium oxide (a) contains rutile-type titanium oxide (a1).
- 前記金属化合物が、２価銅化合物である請求項２又は３記載のセルフクリーニング剤。 The self-cleaning agent according to claim 2 or 3, wherein the metal compound is a divalent copper compound.
- 前記酸化チタン（ａ）のＢＥＴ比表面積が、１～２００ｍ２／ｇである請求項２～４のいずれか１項に記載のセルフクリーニング剤。 The self-cleaning agent according to any one of claims 2 to 4, wherein the titanium oxide (a) has a BET specific surface area of 1 to 200 m 2 / g.
- 前記可視光応答型光触媒が、ジルコニウム及びニオブからなる群から選ばれる少なくとも１種の金属元素を実質的に含む、請求項１～５のいずれか１項に記載のセルフクリーニング剤。 The self-cleaning agent according to any one of claims 1 to 5, wherein the visible light responsive photocatalyst substantially contains at least one metal element selected from the group consisting of zirconium and niobium.
- 前記可視光応答型光触媒がジルコニウムを含み、前記可視光応答型光触媒におけるチタン１００に対するジルコニウムの含有比（Ｚｒ／Ｔｉ比）が、０．０３～０．８である請求項１～６のいずれか１項に記載のセルフクリーニング剤。 Any of claims 1 to 6, wherein the visible light responsive photocatalyst contains zirconium, and the zirconium content ratio (Zr / Ti ratio) to titanium 100 in the visible light responsive photocatalyst is 0.03 to 0.8. The self-cleaning agent according to item 1.
- 前記可視光応答型光触媒がニオブを含み、前記可視光応答型光触媒におけるチタン１００に対するニオブの含有比（Ｎｂ／Ｔｉ比）が、０．０５～０．８である請求項１～７のいずれか１項に記載のセルフクリーニング剤。 Any of claims 1 to 7, wherein the visible light responsive photocatalyst contains niobium, and the content ratio (Nb / Ti ratio) of niobium to titanium 100 in the visible light responsive photocatalyst is 0.05 to 0.8. The self-cleaning agent according to item 1.
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| WO2008146711A1 (en) * | 2007-05-25 | 2008-12-04 | Ishihara Sangyo Kaisha, Ltd. | Complex, method for production of the same, and composition comprising the same |
| JP2011020033A (en) * | 2009-07-14 | 2011-02-03 | Ishihara Sangyo Kaisha Ltd | Visible light-responsive photocatalyst, method for producing the same and photocatalyst coating agent and photocatalyst dispersion obtained by using the same |
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| JP2004082088A (en) * | 2001-10-15 | 2004-03-18 | Jfe Steel Kk | Photocatalyst and photocatalyst material |
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