KR101990338B1 - Visible-light responsive photocatalytic coating composition and preparation methods thereof - Google Patents
Visible-light responsive photocatalytic coating composition and preparation methods thereof Download PDFInfo
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- KR101990338B1 KR101990338B1 KR1020170043498A KR20170043498A KR101990338B1 KR 101990338 B1 KR101990338 B1 KR 101990338B1 KR 1020170043498 A KR1020170043498 A KR 1020170043498A KR 20170043498 A KR20170043498 A KR 20170043498A KR 101990338 B1 KR101990338 B1 KR 101990338B1
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- KR
- South Korea
- Prior art keywords
- weight
- coating composition
- visible light
- photocatalytic coating
- resin
- Prior art date
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 239000008199 coating composition Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title 1
- 239000011941 photocatalyst Substances 0.000 claims abstract description 46
- 239000000126 substance Substances 0.000 claims abstract description 13
- -1 tiles Substances 0.000 claims abstract description 10
- 230000000694 effects Effects 0.000 claims abstract description 8
- 241000700605 Viruses Species 0.000 claims abstract description 5
- 241000233866 Fungi Species 0.000 claims abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 24
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 22
- 229920005989 resin Polymers 0.000 claims description 22
- 239000005871 repellent Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000011230 binding agent Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 7
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- 150000002736 metal compounds Chemical class 0.000 claims description 4
- 230000002940 repellent Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 claims description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 claims description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 229920005749 polyurethane resin Polymers 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- ALVYUZIFSCKIFP-UHFFFAOYSA-N triethoxy(2-methylpropyl)silane Chemical compound CCO[Si](CC(C)C)(OCC)OCC ALVYUZIFSCKIFP-UHFFFAOYSA-N 0.000 claims description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 claims description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 2
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 claims description 2
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 2
- LFRDHGNFBLIJIY-UHFFFAOYSA-N trimethoxy(prop-2-enyl)silane Chemical compound CO[Si](OC)(OC)CC=C LFRDHGNFBLIJIY-UHFFFAOYSA-N 0.000 claims description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 claims description 2
- MEWFSXFFGFDHGV-UHFFFAOYSA-N cyclohexyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C1CCCCC1 MEWFSXFFGFDHGV-UHFFFAOYSA-N 0.000 claims 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000012855 volatile organic compound Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 3
- 244000005700 microbiome Species 0.000 abstract description 3
- 208000008842 sick building syndrome Diseases 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000011521 glass Substances 0.000 abstract description 2
- 230000002265 prevention Effects 0.000 abstract description 2
- 230000000840 anti-viral effect Effects 0.000 abstract 1
- 238000012790 confirmation Methods 0.000 abstract 1
- 208000015181 infectious disease Diseases 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 239000011787 zinc oxide Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 206010041925 Staphylococcal infections Diseases 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 208000015688 methicillin-resistant staphylococcus aureus infectious disease Diseases 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000008262 pumice Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 235000003976 Ruta Nutrition 0.000 description 1
- 240000005746 Ruta graveolens Species 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 239000002519 antifouling agent Substances 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical group [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- CIQDYIQMZXESRD-UHFFFAOYSA-N dimethoxy(phenyl)silane Chemical compound CO[SiH](OC)C1=CC=CC=C1 CIQDYIQMZXESRD-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000003905 indoor air pollution Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 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
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000005806 ruta Nutrition 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 235000015096 spirit Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B01J35/004—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
본 발명은 가시광 응답형 광촉매 코팅 조성물 및 이의 제조방법에 관한 것으로서, 본 발명의 여러 구현예에 따르면, 본 발명의 가시광 응답형 광촉매 코팅 조성물은 종래 태양광이 미치지 못하는 실내에서 광촉매 활성화가 어려운 문제점을 해결할 수 있을 뿐만 아니라, 화학적으로 안정하고, 가시광선 및 형광등에서도 활성화 가능하므로, 실외뿐만 아니라 실내에서도 휘발성 유기화합물이나 새집증후군을 발생시키는 유해 유기물, 그리고 곰팡이 및 바이러스 등과 같은 유해 미생물 등을 분해 또는 제거할 수 있는 효과가 확인됨에 따라, 벽재, 타일, 글라스, 가구, 거울, 환경여과장치, 물순환 방식의 인공폭포나 분수의 부석으로서 사용하는 석재, 변기, 세면대 등의 위생도기, MRSA 등의 세균에 대해 병원 내에서 감염 방지용 기재, 주택설비기기, 항곰팡이 기재, 항바이러스 기재 등에 유용하게 사용될 수 있다.The present invention relates to a visible light-responsive photocatalytic coating composition and a method of manufacturing the same, wherein the visible-light-responsive photocatalytic coating composition of the present invention has a problem that it is difficult to activate the photocatalyst in a room where the conventional sunlight can not pass It can be chemically stable and can be activated in visible light and fluorescent lamps. Therefore, it is possible to decompose or remove harmful organic substances such as volatile organic compounds, sick house syndromes, and harmful microorganisms such as fungi and viruses, As a result of the confirmation of the effect that can be made, it is possible to use sanitary ceramics such as wall materials, tiles, glasses, furniture, mirrors, environmental filtration devices, In hospital, infection prevention equipment, housing equipment, anti-mold It may be useful, such as described, antiviral substrate.
Description
본 발명은 가시광 응답형 광촉매 코팅 조성물 및 이의 제조방법에 관한 것이다.
The present invention relates to a visible light-responsive photocatalytic coating composition and a method of manufacturing the same.
최근 광촉매가 발휘하는 높은 산화력과 환원력을 적극적으로 이용하여, 오염대기와 오염수의 청정화 등 글로벌 환경정화로부터, 소취, 오염방지, 항균 등의 생활환경 정화에 이르기까지, 다양한 분야에서 광촉매의 실용화를 향한 연구개발이 진행되고 있다. Recently, photocatalysts have been widely used in various fields, from global environmental purification such as pollution air and purification of polluted water to deodorization, pollution prevention, and purification of living environment such as antibacterial, by positively utilizing the high oxidizing power and reducing power exhibited by photocatalysts Research and development is under way.
이렇게 광촉매 작용을 갖는 화합물은 반응을 촉진하는 조촉매 또는 담체를 병행하여 사용하는 Pt, Rh 등의 귀금속, NiO 등의 천이금속 산화물에 대한 연구가 진행 되었고, 광촉매 작용을 갖는 가장 대표적인 산화물로는 예를 들면, 아나타제형 산화티탄이 알려져 있고, 탈취·항균·오염방지재로서 이미 실용화되어 있다.As the compounds having such a photocatalytic action, studies have been conducted on transition metal oxides such as noble metals, such as Pt and Rh, NiO, etc., which use a cocatalyst or a carrier in parallel to accelerate the reaction, and examples of the most typical oxides having a photocatalytic action include For example, an anatase type titanium oxide is known and has already been put to practical use as a deodorizing, antibacterial and antifouling agent.
그러나 산화티탄은 400 nm 보다 짧은 태양광선 중에서도 4% 정도에 지나지 않는 자외선의 조사하에서만 활성을 나타낸다. 그 때문에 현재의 응용예로서는 옥외, 혹은 자외선 램프(lamp)에만 한정되는 문제점이 있어, 실외에서의 산화티탄의 고기능화·가시광 응답성을 목표로 하여 다양한 개량이 시도되고 있다.However, titanium oxide is only active under irradiation with ultraviolet light of 4% of solar rays shorter than 400 nm. For this reason, current applications are limited to outdoor or ultraviolet lamps, and a variety of improvements have been attempted with the aim of enhancing the performance of titanium oxide in outdoors and the response of visible light.
이렇게 태양광의 46%를 이루고 있는 가시광 응답성을 갖는 광촉매를 개발할 경우 태양광 하에서 고효율 광촉매를 만들 수 있을 뿐만 아니라 태양광이 미치지 못하는 실내에서의 형광등에도 감응할 수 있게 되어 실외뿐만 아니라 실내에서도 광촉매를 이용할 수 있게 된다.When a photocatalyst having a visible light response characteristic of 46% of the sunlight is developed, not only a highly efficient photocatalyst can be produced under the sunlight but also the fluorescent lamp in the room where the sunlight can not reach can be sensitized, .
즉, 유해물질을 제거하는 방법 중 깨끗하고 무한한 태양광 에너지를 이용한 광촉매가 주목받고 있고, 지금까지 가장 효과적이라고 알려진 TiO2의 경우 태양광중 파장이 짧은 자외선만을 흡수하기 때문에, 태양광 중에서 가시광선을 흡수할 수 있는 가시광 응답형 광촉매 조성물 개발이 절실히 필요하다.That is, among the methods for removing harmful substances, a photocatalyst using clean and infinite solar energy has been attracting attention. Since TiO 2 , which has been known to be the most effective so far, absorbs only ultraviolet rays having short wavelengths in the sunlight, There is an urgent need to develop a photocatalytic composition capable of absorbing visible light.
한편, 이러한 가시광 응답형 광촉매 조성물을 제조하기 위한 방법으로는 산화티탄 상에 색소를 흡착시켜 가시광을 흡수하여 생긴 흡착색소의 여기 상태에서 산화티탄에 전자를 주입하는 방법, Cr, V, Mn, Fe, Ni 등의 금속이온을 화학적으로 주입하는 방법, 플라즈마 조사에 의해 산소결함을 도입하는 방법, 이종 이온을 도입하는 방법 등 다양한 시도가 국내외에서 행해져 오고 있다. Examples of the method for producing such visible light responsive photocatalyst composition include a method of injecting electrons into titanium oxide in an excited state of an adsorbed dye formed by adsorbing a dye on titanium oxide to absorb visible light, , A method of chemically injecting metal ions such as Ni, a method of introducing oxygen defects by plasma irradiation, and a method of introducing a hetero ion have been carried out at home and abroad.
그러나 어느 방법도 균일분산이 어렵고, 전자와 정공의 재결합에 의한 광촉매활성이 저하되고, 조정 코스트가 높은 등의 문제가 있기 때문에, 아직도 공업화에는 이르지 못했다.
However, none of these methods has achieved the industrialization because of the difficulty of uniform dispersion, the photocatalytic activity due to the recombination of electrons and holes, and the high adjustment cost.
본 발명이 해결하고자 하는 과제는 우수한 광촉매 활성을 지니며 순간적인 광촉매 반응으로 인해 발생하는 2차 오염물질의 탈리를 방지할 수 있는 고흡착성 가시광 응답형 광촉매 코팅 조성물 및 이의 제조방법을 제공하는 것이다.The present invention provides a high-adsorption visible light-responsive photocatalytic coating composition having superior photocatalytic activity and capable of preventing desorption of secondary pollutants caused by an instantaneous photocatalytic reaction, and a method for producing the same.
또한, 상기 가시광 응답형 광촉매 코팅 조성물을 수처리 필터 및 공기처리용 필터 등에 스프레이법이나 담금법 등으로 코팅함으로써, 유해물질 제거방법을 제공하는 것이다.
The present invention also provides a method for removing harmful substances by coating the visible-light responsive photocatalytic coating composition with a water treatment filter, an air treatment filter, etc. by a spraying method, a dipping method, or the like.
본 발명의 대표적인 일 측면에 따르면, (a) TiO2와 ZnO를 포함하는 광촉매 0.01-30 중량%; (b) 무기 바인더 0.1-25 중량%; (c) 실리콘 변성수지 0.01-10 중량%; (d) 발수성 수지 0.01-10 중량%; (e) 조촉매 전구체 0.01-10 중량%; (f) 알콕시실란 0.001-10 중량%; 및 (g) 유기용매 수용액 10-95 중량%;를 포함하는 가시광 응답형 광촉매 코팅 조성물을 제공한다.According to a representative aspect of the present invention, there is provided a photocatalyst composition comprising: (a) 0.01-30 wt% of a photocatalyst comprising TiO 2 and ZnO; (b) 0.1-25% by weight of inorganic binder; (c) 0.01-10% by weight of a silicone-modified resin; (d) 0.01 to 10% by weight of water repellent resin; (e) 0.01-10% by weight of a cocatalyst precursor; (f) 0.001-10% by weight alkoxysilane; And (g) 10-95 wt% of an aqueous organic solvent solution.
본 발명의 다른 측면에 따르면, 유기용매 수용액 10-95 중량%에 망간나이트레이트 0.01-10 중량%와 알콕시실란 0.001-10 중량%를 첨가한 후, 50-100 ℃로 승온한 후, 교반하면서, TiO2와 ZnO를 포함하는 광촉매 0.01-30 중량%, 무기 바인더 0.1-25 중량%, 실리콘 변성수지 0.01-10 중량% 및 발수성 수지 0.01-10 중량%를 첨가한 후, 교반하는 단계를 포함하는 가시광 응답형 광촉매 코팅 조성물의 제조방법을 제공한다.According to another aspect of the present invention, 0.01-10% by weight of manganese nitrate and 0.001-10% by weight of alkoxysilane are added to 10-95% by weight of the organic solvent aqueous solution, the temperature is raised to 50-100 ° C, Adding 0.01-30% by weight of a photocatalyst comprising TiO 2 and ZnO, 0.1-25% by weight of an inorganic binder, 0.01-10% by weight of a silicone modified resin and 0.01-10% by weight of a water repellent resin, The present invention also provides a method for producing a photocatalyst coating composition.
본 발명의 또 다른 측면에 따르면, 상기 가시광 응답형 광촉매 코팅 조성물을 수처리 필터 또는 공기처리용 필터에 스프레이하거나, 담금처리 하는 유해물질 제거방법을 제공한다.
According to another aspect of the present invention, there is provided a method of removing harmful substances by spraying or immersing the visible light-responsive photocatalytic coating composition on a water treatment filter or an air treatment filter.
본 발명의 여러 구현예에 따르면, 본 발명의 가시광 응답형 광촉매 코팅 조성물은 종래 태양광이 미치지 못하는 실내에서 광촉매 활성화가 어려운 문제점을 해결할 수 있을 뿐만 아니라, 화학적으로 안정하고, 가시광선 및 형광등에서도 활성화 가능하므로, 실외뿐만 아니라 실내에서도 휘발성 유기화합물이나 새집증후군을 발생시키는 유해 유기물, 그리고 곰팡이 및 바이러스 등과 같은 유해 미생물 등을 분해 또는 제거할 수 있는 효과가 있으므로, 벽재, 타일, 글라스, 가구, 거울, 환경여과장치, 물순환 방식의 인공폭포나 분수의 부석으로서 사용하는 석재, 변기, 세면대 등의 위생도기, MRSA 등의 세균에 대해 병원 내에서 감염 방지용 기재, 주택설비기기, 항곰팡이 기재, 항바이러스 기재 등에 유용하게 사용될 수 있다.
According to various embodiments of the present invention, the visible light-responsive photocatalytic coating composition of the present invention can solve the problem that the photocatalyst is not easily activated in a room where the conventional sunlight does not reach, and is chemically stable, It is possible to decompose or remove harmful organic substances such as volatile organic compounds or sick house syndromes that cause indoor and outdoor as well as harmful microorganisms such as molds and viruses, Environmental filtration equipment, sanitary ceramics such as stone, toilet, wash basin and so on used as a pumice of artificial waterfall or fountain of water circulation system, bacteria for MRSA, etc. Household equipment, Substrate and the like.
이하에서, 본 발명의 여러 측면 및 다양한 구현예에 대해 더욱 구체적으로 살펴보도록 한다.Hereinafter, various aspects and various embodiments of the present invention will be described in more detail.
본 발명의 일실시예에 따른 가시광 응답형 광촉매 조성물은 (a) TiO2와 ZnO를 포함하는 광촉매 0.01-30 중량%; (b) 무기 바인더 0.1-25 중량%; (c) 실리콘 변성수지 0.01-10 중량%; (d) 발수성 수지 0.01-10 중량%; (e) 조촉매 전구체 0.01-10 중량%; (f) 알콕시실란 0.001-10 중량%; 및 (g) 유기용매 수용액 10-95 중량%를 포함한다.
The visible light responsive photocatalytic composition according to one embodiment of the present invention comprises (a) 0.01-30% by weight of a photocatalyst comprising TiO 2 and ZnO; (b) 0.1-25% by weight of inorganic binder; (c) 0.01-10% by weight of a silicone-modified resin; (d) 0.01 to 10% by weight of water repellent resin; (e) 0.01-10% by weight of a cocatalyst precursor; (f) 0.001-10% by weight alkoxysilane; And (g) 10-95 wt% of an organic solvent aqueous solution.
우선, 본 발명의 일실시예에서, 상기 TiO2와 ZnO를 포함하는 광촉매는 상기 TiO2와 ZnO가 0.9~0.99 : 0.01~0.1 중량비로 혼합되는 것일 수 있다. 바람직하게는 상기 TiO2는 부루카이트형 결정구조를 가지는 것일 수 있다.
First, in one embodiment of the present invention, the photocatalyst including the TiO 2 and ZnO is that the TiO 2 and ZnO 0.9 ~ 0.99: may be mixed with 0.01 to 0.1 weight ratio. Preferably, the TiO 2 may have a brittle crystal structure.
종래 TiO2 광촉매는 254 nm에서 350 nm 정도의 파장에서 밴드갭 에너지인 3.2 eV 이상의 에너지를 얻게 된다. 따라서 일반적인 가시광선 영역인 470~750 nm 사이의 빛을 받게 되면 에너지가 밴드갭 에너지를 넘을 만큼 충분치 못하여 광촉매로서의 효능을 얻기 어렵다. 최근에 일본에서 TiO2의 가시광선 흡수도를 높이기 위하여 표면처리를 하여 350~400 nm 파장까지 흡수도를 높인 광촉매가 출시되고 있으나 가시광선에서 반응하기에는 여전히 부족한 성능을 보여주고 있다.Conventional TiO 2 photocatalysts have an energy of 3.2 eV or more, which is the band gap energy at a wavelength of about 254 nm to 350 nm. Therefore, when light of 470 to 750 nm, which is a general visible light region, is received, the energy is not enough to exceed the band gap energy, and thus it is difficult to obtain the photocatalytic effect. In recent years, in Japan, a photocatalyst having a surface treated to increase the absorption of visible light by TiO 2 has been introduced to a wavelength of 350 to 400 nm. However, the photocatalyst is still lacking in response to visible light.
또한, 일반적으로 산화아연(ZnO)은 TiO2와 유사한 에너지 밴드 구조를 갖고 있으며, 광촉매로서 높은 활성이 있는 것으로 보고되고 있는 반면에, ZnO는 수용액 중에서 광조사하면 Zn2 + 형태로 녹는 문제점이 있고, ZnO는 용액 pH에 대하여 영향을 크게 받아 강한 산성의 용액에서는 Zn2 +가 용해되어 촉매적 성질이 퇴화되는 단점을 가지고 있다.In general, zinc oxide (ZnO) has an energy band structure similar to that of TiO 2, and is reported to have high activity as a photocatalyst, whereas ZnO has a problem of being dissolved in Zn 2 + form when irradiated in an aqueous solution , ZnO is strongly influenced by the pH of the solution, and Zn 2 + is dissolved in a strongly acidic solution, which degrades catalytic properties.
한편, 광촉매로 사용되는 이산화티타늄은 3가지의 결정구조를 가지고 있는데, 아나타제, 루타일, 부루카이트형으로 분류된다. 이중에서 일반적으로 저온상인 아나타제형과 고온상인 루타일형이 보편적으로 발견된다. 이 두 가지 구조는 같은 정방정계 구조를 가지나 루타일 구조상에서는 티타늄 중심금속과 산소 리간드로 이루어진 팔면체 구조의 연결형태가 꼭지점 위치의 산소를 공유하고 있으며, 아나타제 구조상에서는 모서리를 공유하고 있다. 이러한 구조적 차이로 두 상은 서로 다른 물리화학적 특성을 나타내고 있다.On the other hand, titanium dioxide used as a photocatalyst has three kinds of crystal structure, and is classified into anatase, rutile and brucite type. In general, low temperature anatase type and high temperature rutile type are commonly found. These two structures have the same tetragonal structure, but in the rutile structure, the octahedron structure of the titanium center metal and the oxygen ligand shares the oxygen at the vertex position and shares the corner in the anatase structure. Due to these structural differences, the two phases exhibit different physico-chemical properties.
또한, 광촉매 효과 측면에서는 아나타제상이 루타일 구조보다 더 우수하다고 보고되고 있는데, 이것은 아나타제상의 가전자대와 사이의 밴드갭 에너지 3.23 eV가 루타일 구조의 배드갭 에너지인 3.02 eV 보다 커서 산화력이 더 크며 또한 아나타제 표면의 수산기양이 루타일상 표면보다 많기 때문에 우수한 산화력이 나타나서 가능하다는 보고가 있다.It is also reported that the anatase phase structure is superior to the anatase phase structure in terms of the photocatalytic effect because the band gap energy between the anatase phase valence band and the valence band energy of 3.23 eV is larger than the bad gap energy of the rutile structure of 3.02 eV, There is a report that excellent oxidation ability is possible because the surface of the anatase is more than the surface of ruta.
본 발명의 일실시예에 의하면, TiO2와 ZnO를 0.9~0.99 : 0.01~0.1 중량비로 혼합한 광촉매를 사용하게 되면, 밴드갭 전이에 의해 가시광선 영역으로 흡수 파장이 이동하였을 뿐만 아니라, 흡수가 더 많이 일어났음을 알 수 있고, 상기 범위 내에서 TiO2와 ZnO 혼합 광촉매의 경우, 가시광선 영역으로 적색 이동 현상이 뚜렷해지는 것이 확인되었다.According to one embodiment of the present invention, when a photocatalyst comprising TiO 2 and ZnO mixed at a ratio of 0.9-0.99: 0.01-0.1 weight ratio is used, not only the absorption wavelength shifts to the visible ray region due to the bandgap transition, And in the case of TiO 2 and ZnO mixed photocatalyst within the above range, it was confirmed that the red migration phenomenon becomes visible in the visible ray region.
반면, 상기 범위를 벗어나는 경우, 광활성이 증가하거나 크게 향상되지 않음이 확인되었다.On the other hand, it has been confirmed that the optical activity is not increased or greatly improved when it is out of the above range.
또한, 본 발명의 일실시예에서, 위에서 언급된 바와 같이, 광촉매 효과 측면에서 우수한 아나타제형과 루타일형의 결정구조를 가지는 TiO2를 선택하여 사용할 수 있으나, 바람직하게 부루카이트형 결정구조를 가지는 TiO2를 ZnO와 함께 포함하게 됨으로써, 종래 아나타제형의 TiO2나, ZnO만을 사용하는 경우에서 발생하는, 금속 상에서의 역반응(2H2 + O2 = 2H2O)으로 인해서 효율이 떨어지는 문제점이 해결될 수 있다.
In one embodiment of the present invention, as described above, TiO 2 having anatase type and rutile type crystal structure excellent in photocatalytic effect can be selected and used. Preferably, TiO 2 having a brittle crystal structure 2 is contained together with ZnO, the problem that the efficiency is lowered due to the reverse reaction (2H 2 + O 2 = 2H 2 O) on the metal which occurs when only TiO 2 of the anatase type or ZnO alone is used is solved .
본 발명의 조촉매 전구체는 광촉매의 밴드갭 에너지를 줄여주는 역할을 해 가시광선에서 광촉매 효과를 발현시키는 역할을 수행한다.The cocatalyst precursor of the present invention plays the role of reducing the band gap energy of the photocatalyst and thus manifesting the photocatalytic effect in visible light.
본 발명의 일실시예에서 상기 조촉매 전구체는 0.01 중량% 미만인 경우, 너무 적은 양이라 조촉매로서의 역할을 하기 어려워 포름알데히드와 같은 유해물질 제거가 어려운 문제점이 있을 수 있고, 상기 조촉매 전구체는 10 중량% 초과인 경우, TiO2-ZnO 광촉매의 영향을 감소시키거나, 상기 조촉매 자체가 주요 활성성분이 되어 반응 활성의 저하를 일으킬 수 있는 문제점이 있을 수 있다.In an embodiment of the present invention, when the cocatalyst precursor is less than 0.01% by weight, it may be difficult to remove harmful substances such as formaldehyde because it is too small to act as a cocatalyst, If it is more than 10% by weight, there may be a problem that the influence of the TiO 2 -ZnO photocatalyst is reduced, or the co-catalyst itself becomes a main active component and the reaction activity may be lowered.
한편, 본 발명의 일실시예에서 상기 조촉매 전구체는 망간 나이트레이트, 코발트 나이트레이트 및 니켈 나이트레이트로 이루어지는 군에서 선택되는 1종 이상일 수 있다.
Meanwhile, in one embodiment of the present invention, the cocatalyst precursor may be at least one selected from the group consisting of manganese nitrate, cobalt nitrate and nickel nitrate.
본 발명의 일실시예에서, 상기 무기 바인더는 가수분해 하면서, 광촉매와 함께 유기물질을 제거하는 역할을 수행하는 것으로서, 상기 무기 바인더가 0.1 중량% 미만인 경우, 유해물질 제거가 어려운 문제점이 있을 수 있고, 상기 무기바인더가 25 중량% 초과인 경우, 오히려 벽지 등의 부착성이 낮아지는 문제점이 있을 수 있다.In an embodiment of the present invention, the inorganic binder serves to remove organic substances together with the photocatalyst while hydrolyzing. When the inorganic binder is less than 0.1% by weight, it may be difficult to remove harmful substances If the inorganic binder is more than 25% by weight, the adhesion of wallpaper and the like may be lowered.
본 발명의 일실시예에서, 상기 무기 바인더는 티타늄알콕사이드 화합물 또는 실란(silane) 화합물일 수 있고, 예를 들어, 티타늄 테트라이소프록포사이드일 수 있다.In one embodiment of the present invention, the inorganic binder may be a titanium alkoxide compound or a silane compound, and may be, for example, titanium tetraisopropoxide.
한편, 상기 무기 바인더의 가수분해 속도를 조절하기 위하여 산이나 염기촉매를 소량 첨가할 수도 있다.
On the other hand, a small amount of acid or base catalyst may be added to adjust the hydrolysis rate of the inorganic binder.
본 발명의 일실시예에서, 실리콘 변성수지는, 벽지, 콘크리트 및 스텐레스판 등에 코팅시, 부착력을 높이는 효과를 가지고 있다. 실리콘 변성수지로서는 통상 시판되고 있는 실리콘-아크릴계나, 실리콘-에폭시계, 실리콘-알키드계 또는 실리콘-폴리에스테르계인 것을 사용할 수 있으며, 용제에 용해한 것이나 에멀션으로 되어 수중에 분산되어 있는 것을 모두 사용할 수 있다. 예를 들어, 상기 실리콘-아크릴계 변성수지는 5,000 내지 50,000 g/mol의 수평균 분자량을 갖는 모노-메타크릴 관능성 폴리실록산일 수 있고, 상기 실리콘-에폭시계 변성수지는 1,000 내지 10,000 g/mol의 수평균 분자량을 갖는, 에폭시 당량이 100 내지 5,000인 1,2-에폭시기를 하나 이상 가질 수 있다.In one embodiment of the present invention, the silicone modified water has the effect of increasing the adhesion when coating on wallpaper, concrete, and stainless steel plates. As the silicone-modified resin, silicone-acrylic, silicone-epoxy, silicone-alkyd or silicone-polyester resins which are commercially available can be used, and those which are dissolved in a solvent or emulsion and dispersed in water can be used . For example, the silicone-acrylic modified water dispersion may be a mono-methacrylic functional polysiloxane having a number average molecular weight of 5,000 to 50,000 g / mol, and the silicone-epoxy modified water dispersion may have a number average molecular weight And 1,2-epoxy groups having an epoxy equivalent of 100 to 5,000.
상기 실리콘 변성수지의 첨가량은, 고형분으로서 가시광 응답형 광촉매 코팅 조성물 중에 0.01 내지 10 중량% 를 첨가하는 것이 바람직하다. 0.01 중량% 미만에서는 시험후의 부착성이 저하되고, 10 중량% 보다 다량의 첨가에서는 광촉매 활성의 저하가 현저하다. 가시광 응답형 광촉매 코팅 조성물 중에 대한 실리콘 변성수지의 첨가방법으로서는, 광촉매 분말이나 졸의 액중에 첨가하는 방법이나, 광촉매와 함께 첨가하는 금속산화물 겔을 형성하기 위한 금속의 산화물 또는 수산화물의 졸 액중에 첨가하는 방법 등 여러 가지 방법이 가능하다. 또한, 에멀션 타입의 실리콘 변성수지를 상기 졸의 액중에 첨가하는 것은, 광촉매의 활성을 거의 저하시키지 않고 가시광 응답형 광촉매 코팅 조성물 중에서의 광촉매의 부착성을 현저하게 높일 수 있으므로 특히 바람직하다.
The addition amount of the silicone-modified resin is preferably 0.01 to 10% by weight as the solid content in the visible light-responsive photocatalytic coating composition. If the amount is less than 0.01% by weight, the adhesion after the test is deteriorated. When the amount is more than 10% by weight, the photocatalytic activity is remarkably deteriorated. Examples of the method of adding the silicone-modified resin to the visible light-responsive photocatalyst coating composition include a method of adding the resin to the photocatalyst powder or a sol liquid or a method of adding the photocatalyst to a sol of a metal oxide or hydroxide to form a metal oxide gel to be added together with the photocatalyst And the like. Addition of an emulsion type silicone-modified resin into the sol solution is particularly preferable because it can remarkably increase the adhesion of the photocatalyst in the visible light-responsive photocatalyst coating composition without substantially lowering the activity of the photocatalyst.
상기 발수성 수지는 본 발명의 가시광 응답형 광촉매 코팅 조성물의 친수성과 발수성을 개선하기 위해 사용된 것으로서, 본 발명의 일실시예에서, 상기 발수성 수지가 0.01 중량% 미만인 경우, 벽지 등과 같은 곳에 부착성이 불량해지는 문제점이 있을 수 있고, 상기 발수성 수지가 10 중량% 초과인 경우, 오히려 유해물질 제거 성능 지속에 문제점이 있을 수 있다.The water-repellent resin is used for improving the hydrophilicity and water repellency of the visible light-responsive photocatalytic coating composition of the present invention. In one embodiment of the present invention, when the water-repellent resin is less than 0.01% by weight, If the water-repellent resin is more than 10% by weight, there may be a problem in continuing the removal of toxic substances.
한편, 본 발명의 일실시예에서 상기 발수성 수지는 발수성 아크릴 수지, 발수성 폴리우레탄 수지, 발수성 불소 수지로 이루어지는 군에서 선택되는 1종 이상일 수 있으며, 예를 들어, 발수성 아크릴 수지일 수 있다.
In one embodiment of the present invention, the water-repellent resin may be at least one selected from the group consisting of a water-repellent acrylic resin, a water-repellent polyurethane resin, and a water-repellent fluororesin, and may be, for example, a water-repellent acrylic resin.
본 발명의 일실시예에서, 상기 알킬알콕시실란은 본 발명의 가시광 응답형 광촉매 코팅 조성물의 벽지 등과 같은 곳에 부착력을 증진시키는 역할을 수행하는 것으로서, 상기 알킬알콕시실란이 0.001 중량% 미만인 경우, 벽지 등과 같은 곳에 부착성이 불량해지는 문제점이 있을 수 있고, 상기 알킬알콕시실란이 10 중량% 초과인 경우, 내오염성이 발생할 수 있는 문제점이 있을 수 있다.In one embodiment of the present invention, the alkylalkoxysilane improves the adhesion of the visible light-sensitive photocatalytic coating composition of the present invention to a wallpaper or the like. When the alkylalkoxysilane is less than 0.001% by weight, There may be a problem that the adhesion at the same place becomes poor. When the alkylalkoxysilane is more than 10% by weight, stain resistance may occur.
상기 알킬알콕시실란은 메틸트리메톡시실란, 메틸트리에톡시실란, 에틸트리메톡시실란, 에틸트리에톡시실란, 프로필트리메톡시실란, 프로필트리에톡시실란, 이소부틸트리에톡시실란, 시클로헥실트리메톡시실란, 페닐트리메톡시실란, 페닐트리에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 알릴트리메톡시실란 알릴트리에톡시실란, 디메틸디메톡시실란, 디메틸디에톡시실란, 디페닐디메톡시실란 및 디페닐디에톡시실란으로 이루어지는 군에서 선택되는 1종 이상일 수 있고, 바람직하게는 메틸트리메톡시실란을 실리옥산형태로 제조하여 포함할 수 있다.
The alkylalkoxysilane may be selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltri Examples of the silane coupling agent include methoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane allyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, di Phenyldimethoxysilane, diphenyldiethoxysilane, and the like. Preferably, methyltrimethoxysilane may be prepared in the form of siloxane.
본 발명의 일실시예에서, 상기 유기용매 수용액은 C1-C6 직쇄 또는 측쇄 알코올 수용액일 수 있고, 예를 들어, 메탄올 수용액, 에탄올 수용액, 프로판올 수용액, 이소프로판올 수용액, 부탄올 수용액 및 이소부탄올 수용액일 수 있으며, 바람직하게는 이소프로판올 수용액일 수 있다. 더욱 바람직하게, 상기 이소프로판올 수용액은 이소프로판올과 물이 1 : 1 내지 5 부피비로 혼합될 수 있다.
In one embodiment of the present invention, the organic solvent aqueous solution may be a C 1 -C 6 linear or branched alcohol aqueous solution, and examples thereof include an aqueous methanol solution, an aqueous ethanol solution, an aqueous propanol solution, an aqueous isopropanol solution, an aqueous butanol solution and an isobutanol aqueous solution And preferably an isopropanol aqueous solution. More preferably, the isopropanol aqueous solution may be mixed with isopropanol and water in a volume ratio of 1: 1 to 5: 5.
본 발명에 따른 가시광 응답형 광촉매 코팅 조성물의 반응속도 증가 및 항균작용을 향상시키기거나 가시광 응답형 광촉매 코팅 조성물이 코팅된 막에 자외선을 조사할 경우, 색을 부여하거나, 열화를 억제하기 위해, 금속 화합물을 0.01-10 중량%로 더 포함할 수 있고, 바람직하게는 상기 금속 화합물은 0.1~5 중량%로 더 포함될 수 있다.
In order to enhance the reaction rate and antimicrobial activity of the photocatalytic coating composition for visible light response according to the present invention or to irradiate ultraviolet rays to a film coated with a visible light responsive photocatalytic coating composition, The metal compound may further comprise 0.01 to 10% by weight of the compound, and preferably 0.1 to 5% by weight of the metal compound.
한편, 본 발명의 일실시예에서, 상기 금속 화합물은 코발트, 팔라듐, 은, 크롬, 납, 동, 바나듐, 백금, 텅스텐, 수은, 란탄, 창연 및 몰리브덴으로 이루어지는 군에서 선택되는 1종 이상일 수 있으며, 예를 들어, 은과 동을 0.1~0.8 : 0.2~0.9의 비율로 혼합하여 사용할 수 있다.
Meanwhile, in one embodiment of the present invention, the metal compound may be at least one selected from the group consisting of cobalt, palladium, silver, chromium, lead, copper, vanadium, platinum, tungsten, mercury, lanthanum, bismuth and molybdenum , For example, silver and copper may be mixed at a ratio of 0.1 to 0.8: 0.2 to 0.9.
본 발명의 일실시예에서 상기 가시광 응답형 광촉매 조성물은 졸(sol) 또는 겔(gel) 형태일 수 있는데, 상기 졸 또는 겔 상태를 원활하게 유지하기 위해 질산 0.001 내지 5 중량% 및 과산화수소 0.001 내지 5중량%를 더 포함할 수 있다.
In one embodiment of the present invention, the visible light-responsive photocatalytic composition may be in the form of a sol or a gel. In order to keep the sol or gel state smooth, 0.001 to 5% by weight of nitric acid and 0.001 to 5% % ≪ / RTI > by weight.
이상으로 설명한 상기 가시광 응답형 광촉매 코팅 조성물을 제조하는 방법은 아래에서 구체적으로 설명된다.The above-described method for producing the visible light responsive photocatalytic coating composition will be specifically described below.
유기용매 수용액 10-95 중량%에 망간나이트레이트 0.01-10 중량%와 알콕시실란 0.001-10 중량%를 첨가한 후, 50-100 ℃로 승온한 후, 교반하면서, TiO2와 ZnO를 포함하는 광촉매 0.01-30 중량%, 무기 바인더 0.1-25 중량%, 실리콘 변성수지 0.01-10 중량% 및 발수성 아크릴수지 0.01-10 중량%를 첨가한 후, 교반하는 단계를 거쳐 제조된다.0.01-10% by weight of manganese nitrate and 0.001-10% by weight of alkoxysilane are added to 10-95% by weight of an organic solvent aqueous solution, and the temperature is raised to 50-100 ° C. Then, with stirring, a photocatalyst containing TiO 2 and ZnO 0.01 to 30% by weight of an inorganic binder, 0.1 to 25% by weight of an inorganic binder, 0.01 to 10% by weight of a silicone-modified resin and 0.01 to 10% by weight of a water-repellent acrylic resin.
한편, 상기 조성물 제조 시, 온도는 상기 설명한 바와 같은 50-100 ℃에서 교반할 수 있다.
On the other hand, at the time of preparing the composition, the temperature can be stirred at 50-100 ° C as described above.
상기한 바와 같이 설명한 본 발명에 따라 상기 가시광 응답형 광촉매 코팅 조성물은 가시광선에서도 뛰어난 광촉매 활성을 나타내며 항균성을 겸하고 있어, 수처리 필터나 공기처리용 필터에 스프레이하거나, 담금처리 하는 유해물질 제거방법에 적용할 경우 실내의 유기화합물을 쉽게 분해하여 쾌적한 환경을 유지할 수 있을 뿐 아니라 공기 중의 균을 살균하는 작용하기 때문에 실내에서 사용할 수 있다.The visible light-responsive photocatalytic coating composition according to the present invention described above exhibits excellent photocatalytic activity even in the visible light and has antimicrobial activity. Therefore, it can be applied to a method for removing harmful substances by spraying or immersing in a water treatment filter or an air treatment filter It is possible to easily decompose organic compounds in the room to maintain a pleasant environment, and to sterilize airborne bacteria, so that it can be used indoors.
한편, 상기 유해물질은 포름알데히드, 일산화탄소, 이산화탄소, 미세입자, 휘발성 유기화합물(VOC, Volatile Organic Carbon), 바이러스, 곰팡이 등으로 이루어지는 군에서 선택되는 1종 이상일 수 있다.Meanwhile, the harmful substance may be at least one selected from the group consisting of formaldehyde, carbon monoxide, carbon dioxide, fine particles, volatile organic carbon (VOC), virus, fungus and the like.
일반적으로 통용되는 VOCs는 벤젠, 톨루엔, 자일렌, 메틸에틸케톤(MEK), 아세톤, 이소프로필 알코올, 글리콜 에테르, 원유정제화합물, 납사 및 미네랄 스피릿일 수 있고, VOCs 물질의 종류를 발생원별로 보면, 대부분의 유기용제가 해당되며, 파라핀, 올레핀과 아로마틱에는 실제로 많은 종류의 화합물이 포함될 수 있다.
VOCs commonly used may be benzene, toluene, xylene, methyl ethyl ketone (MEK), acetone, isopropyl alcohol, glycol ethers, crude oil refining compounds, naphtha and mineral spirits, Most organic solvents are concerned, and paraffins, olefins and aromatics can actually contain many kinds of compounds.
이하에서 실시예 등을 통해 본 발명을 더욱 상세히 설명하고자 하며, 다만 이하에 실시예 등에 의해 본 발명의 범위와 내용이 축소되거나 제한되어 해석될 수 없다. 또한, 이하의 실시예를 포함한 본 발명의 개시 내용에 기초한다면, 구체적으로 실험 결과가 제시되지 않은 본 발명을 통상의 기술자가 용이하게 실시할 수 있음은 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연하다.
Hereinafter, the present invention will be described in more detail with reference to Examples and the like, but the scope and content of the present invention can not be construed to be limited or limited by the following Examples. It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. It is natural that it belongs to the claims.
실시예Example 1 One
반응기에 이소프로필알콜 5중량%과 물 50중량%을 넣은 후, 질산 5 중량%와 과산화수소 5 중량%를 첨가한 다음, 망간나이트레이트 3 중량% 및 메틸트리메톡시실란 2중량%를 반응기에 넣고 온도를 60 ℃까지 승온시켜 200 rpm으로 교반한 후, TiO2과 ZnO를 0.9 : 0.1 중량비로 혼합한 광촉매 15중량%, 티타늄 테트라이소프록포사이드 5중량%, 실리콘 변성 에폭시 수지 5중량%, 발수성 아크릴 수지 5중량%를 첨가하여 교반시켜 가시광 응답형 광촉매 코팅 조성물을 제조하였다.
After adding 5 wt% of isopropyl alcohol and 50 wt% of water to the reactor, 5 wt% of nitric acid and 5 wt% of hydrogen peroxide were added, and 3 wt% of manganese nitrate and 2 wt% of methyltrimethoxysilane were put into the reactor After raising the temperature to 60 ° C and stirring at 200 rpm, 15 wt% of a photocatalyst mixed with TiO 2 and ZnO at a weight ratio of 0.9: 0.1, 5 wt% of titanium tetraisopropoxide, 5 wt% of a silicone-modified epoxy resin, And 5 wt% of a resin were added and stirred to prepare a visible light-responsive photocatalytic coating composition.
비교예Comparative Example 1 One
광촉매 20 중량%를 첨가하고, 무기바인더를 첨가하지 않는 것을 제외하고는 상기 실시예 1과 동일한 방법을 수행하여 가시광 응답형 광촉매 코팅 조성물을 제조하였다.
A photocatalyst coating composition was prepared in the same manner as in Example 1 except that 20 wt% of a photocatalyst was added and an inorganic binder was not added.
비교예Comparative Example 2 2
광촉매 20 중량%를 첨가하고, 실리콘 변성 에폭시 수지를 첨가하지 않는 것을 제외하고는 상기 실시예 1과 동일한 방법을 수행하여 가시광 응답형 광촉매 코팅 조성물을 제조하였다.
A photocatalyst coating composition was prepared in the same manner as in Example 1 except that 20 wt% of a photocatalyst was added and no silicon-modified epoxy resin was added.
비교예Comparative Example 3 3
광촉매 20 중량%를 첨가하고, 발수성 아크릴 수지를 첨가하지 않는 것을 제외하고는 상기 실시예 1과 동일한 방법을 수행하여 가시광 응답형 광촉매 코팅 조성물을 제조하였다.
A photocatalytic coating composition for visible light responsive photocatalyst was prepared in the same manner as in Example 1, except that 20 wt% of a photocatalyst was added and no water-repellent acrylic resin was added.
비교예Comparative Example 4 4
광촉매 18 중량%를 첨가하고, 망간나이트레이트를 첨가하지 않는 것을 제외하고는 상기 실시예 1과 동일한 방법을 수행하여 가시광 응답형 광촉매 코팅 조성물을 제조하였다.
A photocatalyst coating composition was prepared in the same manner as in Example 1 except that 18 wt% of a photocatalyst was added and no manganese nitrate was added.
비교예Comparative Example 5 5
광촉매 17 중량%를 첨가하고, 메틸트리메톡시실란을 첨가하지 않는 것을 제외하고는 상기 실시예 1과 동일한 방법을 수행하여 가시광 응답형 광촉매 코팅 조성물을 제조하였다.
A photocatalyst coating composition was prepared in the same manner as in Example 1 except that 17 wt% of a photocatalyst was added and no methyltrimethoxysilane was added.
실험예Experimental Example 1 One
본 발명에 따른 광촉매의 형광등빛에서 포름알데히드, 아세톤, 톨루엔, 아세트알데히드의 제거율과 벽지, 콘크리트 및 스텐레스판에 부착성 결과를 나타낸 것이다. The removal efficiency of formaldehyde, acetone, toluene, and acetaldehyde in fluorescent lamp light of the photocatalyst according to the present invention and adhesion results to wallpaper, concrete and stainless steel plate are shown.
실내 공기질 악화의 주범인 휘발성 유기화합물과 실내 공기질 오염의 주 원인인 포름알데히드, 아세톤, 톨루엔 및 아세트알데히드 제거율을 확인한 결과, 본 발명의 일실시예의 가시광 응답형 광촉매 코팅 조성물은 포름알데히드, 아세톤, 톨루엔 및 아세트알데히드가 약 97% 이상 제거되는 것이 확인되었고, 벽지, 콘크리트 및 스텐레스판에 대한 부착성 확인 결과, 매우 우수한 것으로 확인되었다.The visible light-responsive photocatalytic coating composition of the present invention was found to contain formaldehyde, acetone, toluene and acetaldehyde, which are the major causes of indoor air pollution and volatile organic compounds, And acetaldehyde were found to be removed by about 97% or more. As a result, adhesion to wallpaper, concrete and stainless steel was confirmed to be excellent.
이러한 결과는 종래 태양광이 미치지 못하는 실내에서 광촉매 활성화가 어려운 문제점을 해결할 수 있을 뿐만 아니라, 화학적으로 안정하고, 가시광선 및 형광등에서도 활성화 가능하므로, 실외뿐만 아니라 실내에서도 휘발성 유기화합물이나 새집증후군을 발생시키는 유해 유기물, 그리고 곰팡이 및 바이러스 등과 같은 유해 미생물 등을 분해 또는 제거할 수 있는 효과가 있으므로, 벽재, 타일, 글라스, 가구, 거울, 환경여과장치, 물순환 방식의 인공폭포나 분수의 부석으로서 사용하는 석재, 변기, 세면대 등의 위생도기, MRSA 등의 세균에 대해 병원 내에서 감염 방지용 기재, 주택설비기기, 항곰팡이 기재, 항바이러스 기재 등에 유용하게 사용될 수 있음을 알 수 있다.These results not only solve the problem of difficulty in activating the photocatalyst in the room where the conventional sunlight is insufficient, but also can be chemically stable and can be activated in visible light and fluorescent lamps, so that volatile organic compounds or sick house syndrome Tiles, glass, furniture, mirrors, environmental filtration equipment, water circulation type artificial waterfalls, and pumice poured into fountains because it has the effect of decomposing or removing harmful microorganisms such as fungi and viruses. It can be seen that it is useful for bacteria such as stone, toilet, sink and sanitary pottery such as washstand, MRSA and the like in hospitals, anti-infection substrate, housing equipment, antifungal substrate, antivirus substrate and the like.
Claims (9)
(b) 조촉매 전구체 0.01-10 중량%;
(c) 무기 바인더 0.1-25 중량%;
(d) 실리콘 변성 수지 0.01-10 중량%;
(e) 발수성 수지 0.01-10 중량%;
(f) 알콕시실란 0.001-10 중량%; 및
(g) 유기용매 수용액 10-95 중량%;를 포함하고,
여기에서,
상기 TiO2와 ZnO는 0.9~0.99 : 0.01~0.1 중량비로 혼합되고,
TiO2는 아나타제형 및 루타일형 중 선택되는 1종 이상의 TiO2; 및 부루카이트형 TiO2를 포함하며;
조촉매 전구체는 망간 나이트레이트, 코발트 나이트레이트 및 니켈 나이트레이트로 이루어지는 군에서 선택되는 1종 이상이고,
상기 무기 바인더는 티타늄알콕사이드 화합물 또는 실란(silane) 화합물이며,
상기 실리콘 변성 수지는 실리콘 아크릴계 변성 수지 또는 실리콘 변성 에폭시 수지이고,
상기 발수성 수지는 발수성 아크릴 수지, 발수성 폴리우레탄 수지 및 발수성 불소 수지로 이루어지는 군에서 선택되는 1종 이상이며,
상기 알콕시실란은 메틸트리메톡시실란, 메틸트리에톡시실란, 에틸트리메톡시실란, 에틸트리에톡시실란, 프로필트리메톡시실란, 프로필트리에톡시실란, 이소부틸트리에톡시실란, 시클로헥실트리메톡시실란, 페닐트리메톡시실란, 페닐트리에톡시실란, 비닐트리메톡시실란, 비닐트리에톡시실란, 알릴트리메톡시실란 알릴트리에톡시실란, 디메틸디메톡시실란, 디메틸디에톡시실란, 디페닐디메톡시실란 및 디페닐디에톡시실란으로 이루어지는 군에서 선택되는 1종 이상이고,
상기 유기용매 수용액은 C1 내지 C6 직쇄 또는 측쇄 알코올 수용액이며,
포름알데히드, 아세톤, 톨루엔 및 아세트알데히드를 97% 이상 제거하는 효과를 나타내는,
가시광 응답형 광촉매 코팅 조성물.
(a) 0.01-30% by weight of a photocatalyst comprising TiO 2 and ZnO;
(b) 0.01-10% by weight of a cocatalyst precursor;
(c) 0.1 to 25% by weight of an inorganic binder;
(d) 0.01-10% by weight of a silicone-modified resin;
(e) 0.01 to 10% by weight of a water repellent resin;
(f) 0.001-10% by weight alkoxysilane; And
(g) 10-95 wt% of an organic solvent aqueous solution,
From here,
The TiO 2 and ZnO are mixed in a weight ratio of 0.9 to 0.99: 0.01 to 0.1,
TiO 2 is at least one selected of the anatase type and the rutile TiO 2; And brittle TiO 2 ;
The cocatalyst precursor is at least one selected from the group consisting of manganese nitrate, cobalt nitrate and nickel nitrate,
The inorganic binder is a titanium alkoxide compound or a silane compound,
The silicone-modified resin is a silicone-modified resin or a silicone-modified epoxy resin,
Wherein the water-repellent resin is at least one selected from the group consisting of a water-repellent acrylic resin, a water-repellent polyurethane resin, and a water-repellent fluororesin,
The alkoxysilane may be at least one selected from the group consisting of methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, Vinyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane allyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, phenyltrimethoxysilane, phenyltrimethoxysilane, Dimethoxysilane, and diphenyldiethoxysilane, and at least one member selected from the group consisting of
Wherein the organic solvent aqueous solution is a C 1 to C 6 linear or branched alcohol aqueous solution,
Which shows an effect of removing 97% or more of formaldehyde, acetone, toluene and acetaldehyde,
A visible light responsive photocatalytic coating composition.
상기 가시광 응답형 광촉매 코팅 조성물은 금속 화합물을 0.01-10 중량% 더 포함하는 가시광 응답형 광촉매 코팅 조성물.
The method according to claim 1,
Wherein the visible light responsive photocatalytic coating composition further comprises 0.01 to 10% by weight of a metal compound.
상기 가시광 응답형 광촉매 코팅 조성물은 질산 0.001 내지 5 중량% 및 과산화수소 0.001 내지 5중량% 더 포함하는 가시광 응답형 광촉매 코팅 조성물.
The method according to claim 1,
Wherein the visible light responsive photocatalytic coating composition further comprises 0.001 to 5% by weight of nitric acid and 0.001 to 5% by weight of hydrogen peroxide.
여기에서 유해물질은 포름알데히드, 일산화탄소, 이산화탄소, 미세입자, 휘발성 유기화합물(VOC, Volatile Organic Carbon), 바이러스 및 곰팡이 중에서 선택되는 1종 이상인 가시광 응답형 광촉매 코팅 조성물.
The visible-light responsive photocatalytic coating composition according to claim 1, which exhibits an activity of removing harmful substances,
Wherein the harmful substance is at least one selected from formaldehyde, carbon monoxide, carbon dioxide, fine particles, volatile organic carbon (VOC), virus and fungus.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220082324A (en) * | 2020-12-10 | 2022-06-17 | 주식회사 에어크린 | Photocatalyst composite particle having antibacterial property, and duct for using the same, and method of fabricating of the same |
| KR20230050043A (en) | 2021-10-07 | 2023-04-14 | 한국생산기술연구원 | Visible Light Active Si-Al Organic Composite Sol-Gel Coating Solution And Method For Preparing Same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100524050B1 (en) * | 2005-03-21 | 2005-10-26 | 주식회사 케이닉스공사 | Antifouling coating composition and a method for manufacturing thereof |
| KR100614416B1 (en) * | 2004-10-11 | 2006-08-21 | 김문찬 | Coating solution of visible photo catalyst and prepation method |
| WO2014141812A1 (en) * | 2013-03-15 | 2014-09-18 | 昭和電工株式会社 | Antibacterial, antiviral photocatalytic titanium oxide, and antibacterial, antiviral photocatalytic titanium oxide slurry dispersed in a neutral area, as well as method for manufacturing same |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100280910B1 (en) * | 1995-06-19 | 2001-02-01 | 쓰끼하시 다미까따 | Photocatalyst-carrying structure and photocatalyst coating material |
| KR100403275B1 (en) * | 2001-03-30 | 2003-10-30 | 주식회사 매그린 | Photocatalytic Coating Composition, Preparation Method Thereof and Coated Body Using the Same |
| KR100945035B1 (en) | 2008-01-29 | 2010-03-05 | 재단법인서울대학교산학협력재단 | Tungstates based visible-light induced oxides photocatalysts and synthesis methods thereof |
| KR20140061842A (en) * | 2012-11-14 | 2014-05-22 | 백승호 | Preparation of photocatalytic water system having anti-reflection effect, super-hydrophilicity action and uv-cut character, and the glass substrate coated with the composition |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100614416B1 (en) * | 2004-10-11 | 2006-08-21 | 김문찬 | Coating solution of visible photo catalyst and prepation method |
| KR100524050B1 (en) * | 2005-03-21 | 2005-10-26 | 주식회사 케이닉스공사 | Antifouling coating composition and a method for manufacturing thereof |
| WO2014141812A1 (en) * | 2013-03-15 | 2014-09-18 | 昭和電工株式会社 | Antibacterial, antiviral photocatalytic titanium oxide, and antibacterial, antiviral photocatalytic titanium oxide slurry dispersed in a neutral area, as well as method for manufacturing same |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20220082324A (en) * | 2020-12-10 | 2022-06-17 | 주식회사 에어크린 | Photocatalyst composite particle having antibacterial property, and duct for using the same, and method of fabricating of the same |
| KR102455126B1 (en) | 2020-12-10 | 2022-10-17 | 주식회사 에어크린 | Photocatalyst composite particle having antibacterial property, and duct for using the same, and method of fabricating of the same |
| KR20230050043A (en) | 2021-10-07 | 2023-04-14 | 한국생산기술연구원 | Visible Light Active Si-Al Organic Composite Sol-Gel Coating Solution And Method For Preparing Same |
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