JP5001003B2 - Photocatalytically active thin film - Google Patents
Photocatalytically active thin film Download PDFInfo
- Publication number
- JP5001003B2 JP5001003B2 JP2006513741A JP2006513741A JP5001003B2 JP 5001003 B2 JP5001003 B2 JP 5001003B2 JP 2006513741 A JP2006513741 A JP 2006513741A JP 2006513741 A JP2006513741 A JP 2006513741A JP 5001003 B2 JP5001003 B2 JP 5001003B2
- Authority
- JP
- Japan
- Prior art keywords
- thin film
- photocatalytically active
- metal
- active thin
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000010409 thin film Substances 0.000 title claims description 128
- 239000000758 substrate Substances 0.000 claims description 95
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000002184 metal Substances 0.000 claims description 59
- -1 organic acid salt Chemical class 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 46
- 150000002736 metal compounds Chemical class 0.000 claims description 45
- 239000010408 film Substances 0.000 claims description 39
- 230000007062 hydrolysis Effects 0.000 claims description 39
- 238000006460 hydrolysis reaction Methods 0.000 claims description 39
- 150000001875 compounds Chemical class 0.000 claims description 38
- 229920003023 plastic Polymers 0.000 claims description 33
- 239000004033 plastic Substances 0.000 claims description 33
- 230000001699 photocatalysis Effects 0.000 claims description 31
- 239000013522 chelant Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 14
- 229910052715 tantalum Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000000576 coating method Methods 0.000 claims description 10
- 229910052732 germanium Inorganic materials 0.000 claims description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 8
- 229910052738 indium Inorganic materials 0.000 claims description 8
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052718 tin Inorganic materials 0.000 claims description 8
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052721 tungsten Inorganic materials 0.000 claims description 8
- 239000010937 tungsten Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 150000004703 alkoxides Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000011521 glass Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000005871 repellent Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 21
- 239000011941 photocatalyst Substances 0.000 description 19
- 239000000203 mixture Substances 0.000 description 18
- 239000003960 organic solvent Substances 0.000 description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 239000003822 epoxy resin Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229920000647 polyepoxide Polymers 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 6
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004721 Polyphenylene oxide Substances 0.000 description 5
- 230000001747 exhibiting effect Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920000570 polyether Polymers 0.000 description 5
- 229920001721 polyimide Polymers 0.000 description 5
- 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 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- HSXKFDGTKKAEHL-UHFFFAOYSA-N tantalum(v) ethoxide Chemical compound [Ta+5].CC[O-].CC[O-].CC[O-].CC[O-].CC[O-] HSXKFDGTKKAEHL-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 235000005985 organic acids Nutrition 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 239000009719 polyimide resin Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- KFBXUKHERGLHLG-UHFFFAOYSA-N 2,4-Nonanedione Chemical compound CCCCCC(=O)CC(C)=O KFBXUKHERGLHLG-UHFFFAOYSA-N 0.000 description 2
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- REIYHFWZISXFKU-UHFFFAOYSA-N Butyl acetoacetate Chemical compound CCCCOC(=O)CC(C)=O REIYHFWZISXFKU-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 210000001015 abdomen Anatomy 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- QSTNBMLCULGCQE-UHFFFAOYSA-N butan-2-yl 3-oxobutanoate Chemical compound CCC(C)OC(=O)CC(C)=O QSTNBMLCULGCQE-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 2
- NDOGLIPWGGRQCO-UHFFFAOYSA-N hexane-2,4-dione Chemical compound CCC(=O)CC(C)=O NDOGLIPWGGRQCO-UHFFFAOYSA-N 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000011133 lead Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000005300 metallic glass Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 2
- GVIIRWAJDFKJMJ-UHFFFAOYSA-N propan-2-yl 3-oxobutanoate Chemical compound CC(C)OC(=O)CC(C)=O GVIIRWAJDFKJMJ-UHFFFAOYSA-N 0.000 description 2
- DHGFMVMDBNLMKT-UHFFFAOYSA-N propyl 3-oxobutanoate Chemical compound CCCOC(=O)CC(C)=O DHGFMVMDBNLMKT-UHFFFAOYSA-N 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 239000005361 soda-lime glass Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000011975 tartaric acid Substances 0.000 description 2
- 235000002906 tartaric acid Nutrition 0.000 description 2
- JKUYRAMKJLMYLO-UHFFFAOYSA-N tert-butyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC(C)(C)C JKUYRAMKJLMYLO-UHFFFAOYSA-N 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- IDXCKOANSQIPGX-UHFFFAOYSA-N (acetyloxy-ethenyl-methylsilyl) acetate Chemical compound CC(=O)O[Si](C)(C=C)OC(C)=O IDXCKOANSQIPGX-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- FQYVVSNFPLKMNU-UHFFFAOYSA-N 1,2-dipentylbenzene Chemical compound CCCCCC1=CC=CC=C1CCCCC FQYVVSNFPLKMNU-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- PQSMEVPHTJECDZ-UHFFFAOYSA-N 2,3-dimethylheptan-2-ol Chemical compound CCCCC(C)C(C)(C)O PQSMEVPHTJECDZ-UHFFFAOYSA-N 0.000 description 1
- HQLKZWRSOHTERR-UHFFFAOYSA-N 2-Ethylbutyl acetate Chemical compound CCC(CC)COC(C)=O HQLKZWRSOHTERR-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- BODRLKRKPXBDBN-UHFFFAOYSA-N 3,5,5-Trimethyl-1-hexanol Chemical compound OCCC(C)CC(C)(C)C BODRLKRKPXBDBN-UHFFFAOYSA-N 0.000 description 1
- UUNGBOQAZQUJMZ-UHFFFAOYSA-N 3-bromopropyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CCCBr UUNGBOQAZQUJMZ-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- LEPRPXBFZRAOGU-UHFFFAOYSA-N 3-trichlorosilylpropyl prop-2-enoate Chemical compound Cl[Si](Cl)(Cl)CCCOC(=O)C=C LEPRPXBFZRAOGU-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- MQWCXKGKQLNYQG-UHFFFAOYSA-N 4-methylcyclohexan-1-ol Chemical compound CC1CCC(O)CC1 MQWCXKGKQLNYQG-UHFFFAOYSA-N 0.000 description 1
- SWDDLRSGGCWDPH-UHFFFAOYSA-N 4-triethoxysilylbutan-1-amine Chemical compound CCO[Si](OCC)(OCC)CCCCN SWDDLRSGGCWDPH-UHFFFAOYSA-N 0.000 description 1
- PQCLJXVUAWLNSV-UHFFFAOYSA-N 5-Methyl-2,3-hexanedione Chemical compound CC(C)CC(=O)C(C)=O PQCLJXVUAWLNSV-UHFFFAOYSA-N 0.000 description 1
- DMNALYQQZDWQQL-UHFFFAOYSA-N 8-bromooctyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CCCCCCCCBr DMNALYQQZDWQQL-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005047 Allyltrichlorosilane Substances 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 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
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- FYTPGBJPTDQJCG-UHFFFAOYSA-N Trichloro(chloromethyl)silane Chemical compound ClC[Si](Cl)(Cl)Cl FYTPGBJPTDQJCG-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 description 1
- HITZGLBEZMKWBW-UHFFFAOYSA-N ac1n8rtr Chemical group C1CC2OC2CC1CC[Si](O1)(O2)O[Si](O3)(C4CCCC4)O[Si](O4)(C5CCCC5)O[Si]1(C1CCCC1)O[Si](O1)(C5CCCC5)O[Si]2(C2CCCC2)O[Si]3(C2CCCC2)O[Si]41C1CCCC1 HITZGLBEZMKWBW-UHFFFAOYSA-N 0.000 description 1
- SWTCCCJQNPGXLQ-UHFFFAOYSA-N acetaldehyde di-n-butyl acetal Natural products CCCCOC(C)OCCCC SWTCCCJQNPGXLQ-UHFFFAOYSA-N 0.000 description 1
- 150000001241 acetals Chemical class 0.000 description 1
- 229940022663 acetate Drugs 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229940007550 benzyl acetate Drugs 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GONOPSZTUGRENK-UHFFFAOYSA-N benzyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)CC1=CC=CC=C1 GONOPSZTUGRENK-UHFFFAOYSA-N 0.000 description 1
- CPLASELWOOUNGW-UHFFFAOYSA-N benzyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)CC1=CC=CC=C1 CPLASELWOOUNGW-UHFFFAOYSA-N 0.000 description 1
- 239000003130 blood coagulation factor inhibitor Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- FEHMLIGHNBIRGD-UHFFFAOYSA-N butyl acetate;pentane Chemical compound CCCCC.CCCCOC(C)=O FEHMLIGHNBIRGD-UHFFFAOYSA-N 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 229930007927 cymene Natural products 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- LCZXHHWLLUALLU-UHFFFAOYSA-N dichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[SiH](Cl)Cl LCZXHHWLLUALLU-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- YJQDBHGZUWCUJS-UHFFFAOYSA-N dihydroxy-methoxy-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](O)(O)CCC(F)(F)F YJQDBHGZUWCUJS-UHFFFAOYSA-N 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 1
- DGCTVLNZTFDPDJ-UHFFFAOYSA-N heptane-3,5-dione Chemical compound CCC(=O)CC(=O)CC DGCTVLNZTFDPDJ-UHFFFAOYSA-N 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- WQUADIUTIKGJRO-UHFFFAOYSA-N hydroxy-dimethoxy-(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](O)(OC)CCC(F)(F)F WQUADIUTIKGJRO-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002349 hydroxyamino group Chemical group [H]ON([H])[*] 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 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
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- LVNAMAOHFNPWJB-UHFFFAOYSA-N methanol;tantalum Chemical compound [Ta].OC.OC.OC.OC.OC LVNAMAOHFNPWJB-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- GURMJCMOXLWZHZ-UHFFFAOYSA-N n-ethyl-n-[tris(diethylamino)silyl]ethanamine Chemical compound CCN(CC)[Si](N(CC)CC)(N(CC)CC)N(CC)CC GURMJCMOXLWZHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000004115 pentoxy group Chemical group [*]OC([H])([H])C([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical compound CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical class 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- AIFMYMZGQVTROK-UHFFFAOYSA-N silicon tetrabromide Chemical compound Br[Si](Br)(Br)Br AIFMYMZGQVTROK-UHFFFAOYSA-N 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 235000011044 succinic acid Nutrition 0.000 description 1
- BUUPQKDIAURBJP-UHFFFAOYSA-N sulfinic acid Chemical compound OS=O BUUPQKDIAURBJP-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- OCXPCSGIIJESOA-UHFFFAOYSA-N tert-butyl-dichloro-phenylsilane Chemical compound CC(C)(C)[Si](Cl)(Cl)C1=CC=CC=C1 OCXPCSGIIJESOA-UHFFFAOYSA-N 0.000 description 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 1
- GXMNGLIMQIPFEB-UHFFFAOYSA-N tetraethoxygermane Chemical compound CCO[Ge](OCC)(OCC)OCC GXMNGLIMQIPFEB-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- ACOVYJCRYLWRLR-UHFFFAOYSA-N tetramethoxygermane Chemical compound CO[Ge](OC)(OC)OC ACOVYJCRYLWRLR-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- OOXSLJBUMMHDKW-UHFFFAOYSA-N trichloro(3-chloropropyl)silane Chemical compound ClCCC[Si](Cl)(Cl)Cl OOXSLJBUMMHDKW-UHFFFAOYSA-N 0.000 description 1
- HKFSBKQQYCMCKO-UHFFFAOYSA-N trichloro(prop-2-enyl)silane Chemical compound Cl[Si](Cl)(Cl)CC=C HKFSBKQQYCMCKO-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- UMFJXASDGBJDEB-UHFFFAOYSA-N triethoxy(prop-2-enyl)silane Chemical compound CCO[Si](CC=C)(OCC)OCC UMFJXASDGBJDEB-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- QPQANCNBWQXGTQ-UHFFFAOYSA-N trihydroxy(trimethylsilylperoxy)silane Chemical compound C[Si](C)(C)OO[Si](O)(O)O QPQANCNBWQXGTQ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
-
- 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
- B01D53/88—Handling or mounting catalysts
- B01D53/885—Devices in general for catalytic purification of waste gases
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
Description
本発明は、基体上に形成された光触媒活性薄膜であって、150〜350nmの波長の光照射により光触媒活性を発揮することを特徴とする光触媒活性薄膜に関する。
本願は、2004年5月21日に出願された特願2004−151639号に基づいて優先権を主張し、その内容をここに援用する。The present invention relates to a photocatalytically active thin film formed on a substrate, which exhibits photocatalytic activity when irradiated with light having a wavelength of 150 to 350 nm.
This application claims priority based on Japanese Patent Application No. 2004-151639 for which it applied on May 21, 2004, and uses the content here.
従来から、抗菌、防黴、防汚、防臭作用を発揮する、酸化チタン(TiO2)に代表される光触媒が知られている。光触媒は、太陽光等を吸収して活性化し、酸化作用によって上記のような優れた作用を示す。Conventionally, a photocatalyst represented by titanium oxide (TiO 2 ) that exhibits antibacterial, antibacterial, antifouling, and deodorizing effects has been known. The photocatalyst is activated by absorbing sunlight and the like, and exhibits an excellent action as described above due to an oxidizing action.
通常、光触媒は基体に担持して用いられる。光触媒を基体に担持する方法としては、実用性が高いことから、光触媒を含有してなる薄膜(光触媒活性薄膜)を基体上に形成する方法が注目されている。光触媒活性薄膜を基体上に形成する方法としては、基体上に光触媒前駆体組成物を塗工し、500℃前後で焼成する方法が一般的である。例えば、金属アルコキシド又は金属キレート化合物を含有する光触媒前駆体組成物の溶液を用いて形成する方法(特許文献1、2)や、金属酸化物からなる光触媒に金属アルコキシド又は金属キレート化合物を無機バインダーとして加えたものを用いて形成する方法(特許文献3)等が知られている。
しかし、特許文献1〜3の方法では、薄膜の形成のため基体に光触媒前駆体組成物の溶液を塗工した後高温で焼成等する必要があり、使用できる基体等に制限がある等の問題があった。また、上記文献に記載されている光触媒は、350nmより長波長側の光により光触媒活性を発揮するものであり、太陽光等の光照射により基体が劣化するおそれがある。また、バインダーを介さずに直接基体表面に光触媒薄膜を形成することは困難であった。 However, in the methods of Patent Documents 1 to 3, it is necessary to apply a solution of the photocatalyst precursor composition to the substrate to form a thin film, and then calcinate at a high temperature. was there. The photocatalyst described in the above document exhibits photocatalytic activity by light having a wavelength longer than 350 nm, and the substrate may be deteriorated by irradiation with light such as sunlight. Moreover, it was difficult to form a photocatalytic thin film directly on the surface of the substrate without using a binder.
一方、特許文献4には、基体と、基体上に形成されたTi、O、Cを主成分とし、C/O比が1以下である光触媒膜とを具備する光触媒体が開示されている。また、この文献には、得られる光触媒膜はアモルファス金属化合物からなり、比較的低温領域(100〜500℃)の加熱又は焼成で得られる旨が記載されている。
しかしながら、特許文献4に記載される方法は、光触媒膜の形成温度は比較的低温ではあるが、基体の劣化を防止できるほどに十分に低温とはいえないものである。また、この文献に記載されている光触媒膜は、Ti、O、Cを主成分とし、光触媒活性を示すアモルファス金属化合物からなるとしているのみで、該金属化合物の構造等は特定されていない。 However, in the method described in Patent Document 4, although the formation temperature of the photocatalyst film is relatively low, it cannot be said that the temperature is sufficiently low to prevent deterioration of the substrate. Moreover, the photocatalyst film described in this document is only composed of an amorphous metal compound having Ti, O, and C as main components and exhibiting photocatalytic activity, and the structure of the metal compound is not specified.
本発明は、かかる従来技術の実情に鑑みてなされたものであり、基体上に形成された光触媒活性薄膜であって、容易に形成でき、150〜350nmの波長の光照射により光触媒活性を発揮し、しかもプラスチック基体上に形成した場合に、350nm以上の長波長の光を照射した場合であっても、基体が劣化し難い光触媒活性薄膜を提供することを課題とする。 The present invention has been made in view of the state of the prior art, and is a photocatalytically active thin film formed on a substrate, which can be easily formed, and exhibits photocatalytic activity when irradiated with light having a wavelength of 150 to 350 nm. Moreover, it is an object of the present invention to provide a photocatalytically active thin film which is difficult to deteriorate even when irradiated with light having a long wavelength of 350 nm or longer when formed on a plastic substrate.
本発明者らは、上記課題を解決すべく鋭意検討した結果、加水分解性基及び/又は水酸基を合計で2以上有する金属化合物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物、金属有機酸塩、及びこれらの加水分解生成物からなる群から選ばれる少なくとも一種を原料として形成されてなる光触媒活性薄膜は、150〜350nmの低波長の光照射により光触媒活性を発揮すること、この光触媒活性薄膜は、基体上に形成する際、100℃未満の温度で処理することにより形成できること、プラスチックからなる基体上にも直接形成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the present inventors have found that a metal compound having 2 or more hydrolyzable groups and / or hydroxyl groups in total, a metal chelate having 2 or more hydrolyzable groups and / or hydroxyl groups in total. A photocatalytically active thin film formed from at least one selected from the group consisting of a compound, a metal organic acid salt, and a hydrolysis product thereof exhibits photocatalytic activity when irradiated with light having a low wavelength of 150 to 350 nm. The present inventors have found that this photocatalytically active thin film can be formed by processing at a temperature of less than 100 ° C. when it is formed on a substrate, and that it can be directly formed on a substrate made of plastic, thereby completing the present invention.
すなわち、本発明は、以下の(1)〜(16)の光触媒活性薄膜を提供するものである。
(1)基体上に形成された光触媒活性薄膜であって、加水分解性基及び/又は水酸基を合計で2以上有する金属化合物の加水分解生成物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物の加水分解生成物及び金属有機酸塩の加水分解生成物からなる群から選ばれる少なくとも1種で、前記加水分解生成物が、前記加水分解性基及び/又は水酸基を合計で2以上有する金属化合物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物、又は金属有機酸塩を、前記加水分解性基及び/又は水酸基を合計で2以上有する金属化合物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物、又は金属有機酸塩1モルに対して、2モル以下の水を用いて加水分解した生成物であり、前記金属がケイ素、ゲルマニウム、スズ、鉛、チタン、ジルコニウム、アルミニウム、インジウム、タンタル、タングステン及び亜鉛からなる群から選ばれる一種であるものから形成されてなるアモルファス状であり、150〜350nmの波長の光照射により光触媒活性を発揮することを特徴とする光触媒活性薄膜。
That is, the present invention provides the following photocatalytically active thin films (1) to (16) .
(1) A photocatalytically active thin film formed on a substrate, comprising a total of 2 hydrolyzable products, hydrolyzable groups and / or hydroxyl groups of metal compounds having 2 or more hydrolyzable groups and / or hydroxyl groups. The hydrolysis product is at least one selected from the group consisting of hydrolysis products of metal chelate compounds and hydrolysis products of metal organic acid salts, and the hydrolysis product is a total of the hydrolyzable groups and / or hydroxyl groups. A metal compound having two or more metal compounds, a metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups, or a metal organic acid salt, a metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total, metal chelate compounds having 2 or more decomposable group and / or hydroxyl groups in total, or the metal organic acid salt 1 mole, a product was hydrolyzed with 2 moles of water, before Metal is silicon, germanium, tin, lead, titanium, zirconium, aluminum, indium, tantalum, amorphous consisting formed from what is one selected from the group consisting of tungsten and zinc, light having a wavelength of 150~350nm A photocatalytically active thin film characterized by exhibiting photocatalytic activity upon irradiation.
(2)基体上に、加水分解性基及び/又は水酸基を合計で2以上有する金属化合物の加水分解生成物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物の加水分解生成物及び金属有機酸塩の加水分解生成物からなる群から選ばれる少なくとも1種で、前記金属がケイ素、ゲルマニウム、スズ、鉛、チタン、ジルコニウム、アルミニウム、インジウム、タンタル、タングステン及び亜鉛からなる群から選ばれる一種であるものを含有する光触媒活性薄膜形成用溶液を塗工し、得られた該溶液の塗膜を100℃未満の温度で加熱して形成されたものであることを特徴とする(1)の光触媒活性薄膜。 (2) Hydrolysis product of a metal compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups on the substrate, hydrolysis product of a metal chelate compound having 2 or more hydrolyzable groups and / or hydroxyl groups in total And at least one selected from the group consisting of hydrolysis products of metal organic acid salts, wherein the metal is selected from the group consisting of silicon, germanium, tin, lead, titanium, zirconium, aluminum, indium, tantalum, tungsten and zinc. coating the photocatalytic activity thin film-forming solution containing what is one selected, the coating film of the resulting solution, characterized in that one formed by heating at a temperature below 100 ° C. ( The photocatalytically active thin film of 1).
(3)前記基体が、金属、セラミックス、ガラス及びプラスチックからなる群から選ばれる少なくとも1つの材質からなることを特徴とする(1)又は(2)の光触媒活性薄膜。 (3) The photocatalytically active thin film according to (1) or (2), wherein the substrate is made of at least one material selected from the group consisting of metal, ceramics, glass and plastic.
(4)前記基体が、ポリイミド系樹脂、ポリエステル系樹脂、エポキシ系樹脂及びポリエーテル系樹脂からなる群から選ばれる少なくとも一種からなるプラスチック基体であることを特徴とする(1)〜(3)いずれかの光触媒活性薄膜。 (4) Any one of (1) to (3), wherein the base is a plastic base made of at least one selected from the group consisting of a polyimide resin, a polyester resin, an epoxy resin, and a polyether resin. A photocatalytically active thin film.
(5)プラスチック基体上に、前記光触媒活性薄膜形成用溶液を塗工し、得られた該溶液の塗膜を前記基体の軟化点未満、かつ100℃未満の温度で加熱して形成されたものであることを特徴とする(4)の光触媒活性薄膜。 (5) A film formed by applying the photocatalytically active thin film forming solution on a plastic substrate and heating the resulting coating film at a temperature below the softening point of the substrate and below 100 ° C. (4) The photocatalytically active thin film according to (4).
(6)前記加水分解性基及び/又は水酸基を合計で2以上有する金属化合物が、金属アルコキシドであることを特徴とする(1)〜(5)いずれかの光触媒活性薄膜。
(7)前記加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物が、前記加水分解性基及び/又は水酸基を合計で2以上有する金属化合物の加水分解生成物のキレート化合物であることを特徴とする(1)〜(6)いずれかの光触媒活性薄膜。
(6) The photocatalytically active thin film according to any one of (1) to (5) , wherein the metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total is a metal alkoxide.
(7) The metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups in total is a chelate compound of a hydrolysis product of a metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total. The photocatalytically active thin film according to any one of (1) to (6) .
(8)前記加水分解性基及び/又は水酸基を合計で2以上有する金属化合物の加水分解生成物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物の加水分解生成物及び金属有機酸塩の加水分解生成物からなる群から選ばれる少なくとも一種で、前記金属がケイ素、ゲルマニウム、スズ、鉛、チタン、ジルコニウム、アルミニウム、インジウム、タンタル、タングステン及び亜鉛からなる群から選ばれる一種であるものからなる光触媒活性薄膜形成用溶液中の分散質の平均粒径が、10nm以下であることを特徴とする(2)〜(7)いずれかの光触媒活性薄膜。
(9)150〜350nmの波長の光が照射されると、該薄膜に接触した有機物質が分解及び/または除去されることを特徴とする(1)〜(8)いずれかの光触媒活性薄膜。
(8) Hydrolysis product of metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total, hydrolysis product of metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups and metal in at least one member selected from the group consisting of hydrolysis product of an organic acid salt, wherein the metal is silicon, germanium, tin, lead, titanium, zirconium, aluminum, indium, tantalum, with one member selected from the group consisting of tungsten and zinc The photocatalytically active thin film according to any one of (2) to (7) , wherein the average particle size of the dispersoid in the photocatalytically active thin film forming solution is 10 nm or less.
(9) The photocatalytically active thin film according to any one of (1) to (8) , wherein when irradiated with light having a wavelength of 150 to 350 nm, an organic substance in contact with the thin film is decomposed and / or removed.
(10)150〜350nmの波長の光が照射されると、光照射された部分が、撥水性から、水の接触角が20°以下の親水性に変化することを特徴とする(1)〜(9)いずれかの光触媒活性薄膜。
(11)250〜310nmの波長の光照射により光触媒活性を発揮することを特徴とする(1)〜(10)いずれかの光触媒活性薄膜。
(12)照射光量が40J/cm2以下の光照射により光触媒活性を発揮することを特徴とする(10)又は(11)の光触媒活性薄膜。
(10) When irradiated with light having a wavelength of 150 to 350 nm, the irradiated portion changes from water repellency to hydrophilicity with a water contact angle of 20 ° or less. (9) Any photocatalytically active thin film.
(11) The photocatalytically active thin film according to any one of (1) to (10), wherein the photocatalytic activity is exhibited by irradiation with light having a wavelength of 250 to 310 nm.
(12) The photocatalytically active thin film according to (10) or (11) , wherein the photocatalytic activity is exhibited by light irradiation with an irradiation light amount of 40 J / cm 2 or less.
(13)照射光量が5J/cm2以下の光照射により光触媒活性を発揮することを特徴とする(10)〜(12)いずれかの光触媒活性薄膜。
(14)有機物を含有する薄膜であることを特徴とする(1)〜(13)いずれかの光触媒活性薄膜。
(15)炭素元素を2〜40重量%含有する薄膜であることを特徴とする(14)の光触媒活性薄膜。
(16)膜厚が50nm以下の薄膜であることを特徴とする(1)〜(15)いずれかの光触媒活性薄膜。
(13) The photocatalytically active thin film according to any one of (10) to (12), wherein the photocatalytic activity is exhibited by light irradiation with an irradiation light amount of 5 J / cm 2 or less.
(14) The photocatalytically active thin film according to any one of (1) to (13), which is a thin film containing an organic substance.
(15) The photocatalytically active thin film according to (14) , which is a thin film containing 2 to 40% by weight of a carbon element.
(16) The photocatalytically active thin film according to any one of (1) to (15), wherein the thin film has a thickness of 50 nm or less.
本発明の光触媒活性薄膜は、250〜350nmの低波長の光照射で優れた光触媒活性を示すという従来にない特性を有する。従って、本発明の光触媒活性薄膜は、350nmより高波長の光(可視光等)に曝す必要がなく、また、曝された場合であっても、基体(特にプラスチック基体)が劣化したり、基体と光触媒活性薄膜との接着性が低下することがない。
本発明の光触媒活性薄膜は、100℃未満の低温加熱処理により形成することができるので、加熱処理により基体を傷めることがなく、用いる基体を、耐熱性のものに限定する必要がない。従って、基体として、軽量で加工が容易なプラスチック基体を好適に用いることができる。
また、本発明の光触媒活性薄膜は良好な接着性を有するため、プラスチック等の基体上に容易に直接形成することができ、かつ長期間劣化することがない。The photocatalytically active thin film of the present invention has an unprecedented property of exhibiting excellent photocatalytic activity when irradiated with light having a low wavelength of 250 to 350 nm. Therefore, the photocatalytically active thin film of the present invention does not need to be exposed to light having a wavelength higher than 350 nm (visible light, etc.), and even when exposed to light, the substrate (particularly plastic substrate) is deteriorated, And adhesion between the photocatalytically active thin film do not deteriorate.
Since the photocatalytically active thin film of the present invention can be formed by low-temperature heat treatment at less than 100 ° C., the heat treatment does not damage the substrate, and the substrate to be used need not be limited to heat-resistant ones. Therefore, a plastic substrate that is lightweight and easy to process can be suitably used as the substrate.
Further, since the photocatalytically active thin film of the present invention has good adhesion, it can be easily formed directly on a substrate such as plastic and does not deteriorate for a long time.
以下、本発明の光触媒活性薄膜を詳細に説明する。
本発明の光触媒活性薄膜は、基体上に形成された光触媒活性薄膜であって、加水分解性基及び/又は水酸基を合計で2以上有する金属化合物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物、金属有機酸塩、並びにこれらの加水分解生成物からなる群から選ばれる少なくとも一種から形成されてなり、250〜350nmの波長の光照射により光触媒活性を発揮することを特徴とする。Hereinafter, the photocatalytically active thin film of the present invention will be described in detail.
The photocatalytically active thin film of the present invention is a photocatalytically active thin film formed on a substrate, and has a total of two or more hydrolyzable groups and / or hydroxyl groups, hydrolyzable groups and / or hydroxyl groups. It is formed from at least one selected from the group consisting of metal chelate compounds, metal organic acid salts, and hydrolysis products thereof, and exhibits photocatalytic activity when irradiated with light having a wavelength of 250 to 350 nm. To do.
本発明に用いる基体としては、本発明の光触媒活性薄膜を担持できるものであれば、特に制限されず、透明なものであっても、半透明なものであっても、不透明なものであってもよい。基体を構成する材料としては、特に制限されず、例えば、金属、セラミックス、ガラス及びプラスチックからなる群から選ばれる少なくとも1つの材質からなるものが挙げられる。なかでも、ソーダーライムガラス、ホウケイ酸ガラス、鉛ケイ酸ガラス等のガラスからなるガラス基体;プラスチックからなるプラスチック基体が好ましく、プラスチック基体がより好ましい。 The substrate used in the present invention is not particularly limited as long as it can support the photocatalytically active thin film of the present invention, and is transparent, translucent or opaque. Also good. The material constituting the substrate is not particularly limited, and examples thereof include a material made of at least one material selected from the group consisting of metal, ceramics, glass, and plastic. Among them, a glass substrate made of glass such as soda lime glass, borosilicate glass, lead silicate glass, etc .; a plastic substrate made of plastic is preferable, and a plastic substrate is more preferable.
プラスチック基体を構成する樹脂としては、例えば、ポリアミドイミド、ポリエーテルイミド、ポリイミド、ポリアミノビスマレインイミド等のポリイミド系樹脂;ポリエチレンテレフタレート、ポリエチレン2,6−ナフタレート等のポリエステル系樹脂;フェノール系エポキシ樹脂、アルコール系エポキシ樹脂、グリシジルエーテル型エポキシ樹脂、グリシジルアミン型エポキシ樹脂等のエポキシ系樹脂;ポリエーテルエーテルケトン、ポリエーテルケトン、ポリエーテルニトリル、ポリエーテルスルホン等のポリエーテル系樹脂;セルローストリアセテート、セルロースジアセテート、ニトロセルロース等のセルロース系樹脂;ポリスチレン、シンジオタクチックポリスチレン等のポリスチレン系樹脂;エチレン、プロピレン、ブテン等のオレフィンの単独重合体又は共重合体等のポリオレフィン系樹脂;ノルボルネン系樹脂等のシクロオレフィン系樹脂;ナイロン6、ナイロン12、共重合ナイロン等のポリアミド系樹脂;エチレン−ポリビニルアルコール共重合体等のポリビニルアルコール系樹脂;エチレン−四フッ化エチレン共重合体、ポリ三フッ化塩化エチレン、四フッ化エチレン−パーフルオロアルキルビニルエーテル共重合体、ポリフッ化ビニル、パーフルオロエチレン−パーフルオロプロピレン−パーフルオロビニルエーテル共重合体等のフッ素系樹脂;ポリカーボネート、ポリビニルブチラート樹脂、ポリアリレート樹脂等が挙げられる。これらの樹脂は一種単独で、あるいは二種以上を組み合わせて用いることができる。 Examples of the resin constituting the plastic substrate include polyimide resins such as polyamideimide, polyetherimide, polyimide, and polyaminobismaleimide; polyester resins such as polyethylene terephthalate and polyethylene 2,6-naphthalate; phenolic epoxy resins, Epoxy resins such as alcohol epoxy resins, glycidyl ether type epoxy resins, glycidyl amine type epoxy resins; polyether resins such as polyether ether ketone, polyether ketone, polyether nitrile, and polyether sulfone; cellulose triacetate, cellulose diester Cellulosic resins such as acetate and nitrocellulose; polystyrene resins such as polystyrene and syndiotactic polystyrene; ethylene, propylene, butene Polyolefin resins such as homopolymers or copolymers of olefins; cycloolefin resins such as norbornene resins; polyamide resins such as nylon 6, nylon 12 and copolymer nylon; ethylene-polyvinyl alcohol copolymers, etc. Polyvinyl alcohol resin; ethylene-tetrafluoroethylene copolymer, polytrifluoroethylene chloride, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, perfluoroethylene-perfluoropropylene-perfluorovinyl ether Fluorine resins such as copolymers; polycarbonates, polyvinyl butyrate resins, polyarylate resins, and the like. These resins can be used alone or in combination of two or more.
また、上記に挙げた樹脂以外にも、ラジカル反応性不飽和化合物を有するアクリル系化合物よりなる樹脂組成物;上記アクリル系化合物とチオール基を有するメルカプト化合物よりなる樹脂組成物;エポキシアクリレート、ウレタンアクリレート、ポリエステルアクリレート、ポリエーテルアクリレート等のオリゴマーを多官能アクリレートモノマーに溶解せしめた樹脂組成物;及びこれらの混合物;等を基体材料として用いることができる。 In addition to the resins listed above, a resin composition comprising an acrylic compound having a radical-reactive unsaturated compound; a resin composition comprising the acrylic compound and a mercapto compound having a thiol group; epoxy acrylate, urethane acrylate A resin composition in which an oligomer such as polyester acrylate or polyether acrylate is dissolved in a polyfunctional acrylate monomer; and a mixture thereof; and the like can be used as a base material.
さらに、これらの樹脂の1又は2種以上をラミネート、コーティング等の手段によって積層させたものを基体として用いることができる。
これらの中でも、本発明においては、ポリイミド系樹脂、ポリエステル系樹脂、エポキシ系樹脂及びポリエーテル系樹脂からなる群から選ばれる少なくとも一種からなるプラスチック基体が特に好ましい。Furthermore, what laminated | stacked 1 or 2 or more types of these resin by means, such as a lamination and a coating, can be used as a base | substrate.
Among these, in the present invention, a plastic substrate made of at least one selected from the group consisting of polyimide resins, polyester resins, epoxy resins and polyether resins is particularly preferable.
これらの基体には、いわゆる寸度安定性を向上する目的で、ポリ塩化ビニリデン系ポリマーを含む防水層や、ガスバリアーの目的で、有機及び/又は無機化合物の薄膜等を設けることができる。有機化合物の例としては、ポリビニルアルコール、ポリエチレン−ビニルアルコール共重合体等が挙げられる。無機化合物の例としては、シリカ、アルミナ、タルク、バーミキュライト、カオリナイト、雲母、合成雲母等が挙げられる。
また、本発明に用いる基体中には、その他諸機能のため各種有機添加物及び/又は無機添加物が加えられていてもよい。These substrates can be provided with a waterproof layer containing a polyvinylidene chloride-based polymer for the purpose of improving so-called dimensional stability, and a thin film of an organic and / or inorganic compound for the purpose of a gas barrier. Examples of the organic compound include polyvinyl alcohol and polyethylene-vinyl alcohol copolymer. Examples of the inorganic compound include silica, alumina, talc, vermiculite, kaolinite, mica, and synthetic mica.
In addition, various organic additives and / or inorganic additives may be added to the substrate used in the present invention for various other functions.
基体の大きさや形には特に制限されず、平板、立体物、フィルム等いずれも使用することができるが、フィルム状のものが好ましい。また、塗装した物品も基体として用いることができる。 The size and shape of the substrate are not particularly limited, and any of a flat plate, a three-dimensional object, and a film can be used, but a film-like one is preferable. A coated article can also be used as a substrate.
前記基体としてプラスチック基体を用いる場合、プラスチック基体は、フィルム状であるのが好ましい。また、フィルム状の基体としては、未延伸フィルムからなるものであっても、延伸フィルムからなるものであってもよい。 When a plastic substrate is used as the substrate, the plastic substrate is preferably a film. Further, the film-like substrate may be made of an unstretched film or a stretched film.
フィルム状のプラスチック基体は、従来公知の方法により製造することができる。例えば、材料となる樹脂を押し出し機により溶融し、環状ダイやTダイにより押し出して急冷することにより、実質的に無定形で配向していない未延伸の基体を製造することができる。 The film-like plastic substrate can be produced by a conventionally known method. For example, an unstretched substrate that is substantially amorphous and not oriented can be produced by melting a resin as a material with an extruder, extruding with an annular die or a T-die, and quenching.
また、未延伸の基体を一軸延伸、テンター式逐次二軸延伸、テンター式同時二軸延伸、チューブラー式同時二軸延伸等の公知の方法により、基体の流れ(縦軸)方向、又は基体の流れ方向と直角(横軸)方向に延伸することにより延伸基体を製造することができる。この場合の延伸倍率は、基体の原料となる樹脂に合わせて適宜選択することできるが、縦軸方向及び横軸方向にそれぞれ2〜10倍が好ましい。 Further, an unstretched substrate is uniaxially stretched, a tenter-type sequential biaxial stretch, a tenter-type simultaneous biaxial stretch, a tubular-type simultaneous biaxial stretch, or the like, by a known method such as a substrate flow (vertical axis) direction or a substrate A stretched substrate can be produced by stretching in the direction perpendicular to the flow direction (horizontal axis). The draw ratio in this case can be appropriately selected according to the resin as the raw material of the substrate, but is preferably 2 to 10 times in each of the vertical axis direction and the horizontal axis direction.
フィルム状のプラスチック基体の厚みは、特に制限されるものではないが、通常1〜1000μm、好ましくは3〜500μmである。 The thickness of the film-like plastic substrate is not particularly limited, but is usually 1-1000 μm, preferably 3-500 μm.
本発明の光触媒活性薄膜は、前述した基体上に形成されてなるものであって、(i)加水分解性基及び/又は水酸基を合計で2以上有する金属化合物、(ii)加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物、(iii)金属有機酸塩、並びに(iv)前記(i)〜(iii)の加水分解生成物からなる群から選ばれる少なくとも一種から形成されてなる。
本発明においては、これらを一種単独で、あるいは二種以上を組み合わせて用いることができる。The photocatalytically active thin film of the present invention is formed on the aforementioned substrate, and (i) a metal compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups, (ii) hydrolyzable groups and And / or a metal chelate compound having two or more hydroxyl groups in total, (iii) a metal organic acid salt, and (iv) at least one selected from the group consisting of the hydrolysis products of (i) to (iii) above. Become.
In this invention, these can be used individually by 1 type or in combination of 2 or more types.
(i)加水分解性基及び/又は水酸基を合計で2以上有する金属化合物
本発明に用いる加水分解性基及び/又は水酸基を合計で2以上有する金属化合物は、加水分解性基及び/又は水酸基を合計で2以上有している金属化合物であれば、特に制限されない。ここで、加水分解性基とは、水と接触して加水分解する官能基、又は水存在下で金属原子と酸素原子を介して結合形成し得る官能基のことで、具体的には、ハロゲン原子、アミノ基、アルコキシ基、エステル基、カルボキシ基、ホスホリル基、イソシアナート基、シアノ基、エポキシ基等である。
加水分解性基及び/又は水酸基を合計で2以上有する金属化合物としては、式(II)で表される化合物を好ましく例示することができる。(I) Metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total The metal compound having two or more hydrolyzable groups and / or hydroxyl groups used in the present invention has hydrolyzable groups and / or hydroxyl groups. If it is a metal compound which has 2 or more in total, there will be no restriction | limiting in particular. Here, the hydrolyzable group refers to a functional group that hydrolyzes upon contact with water, or a functional group that can form a bond via a metal atom and an oxygen atom in the presence of water. An atom, an amino group, an alkoxy group, an ester group, a carboxy group, a phosphoryl group, an isocyanate group, a cyano group, an epoxy group, and the like.
Preferred examples of the metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total include compounds represented by the formula (II).
上記式(I)中、Mは金属原子を表し、好ましくは周期律表第13族〜第15族の金属原子である。より具体的には、ケイ素、ゲルマニウム、スズ、鉛、チタン、ジルコニウム、アルミニウム、インジウム、タンタル、タングステン及び亜鉛からなる群から選ばれる少なくとも一種を例示することができる。これらの中でも、チタン、タンタルからなる群から選ばれる少なくとも一種がより好ましい。 In the above formula (I), M represents a metal atom, preferably a metal atom of Groups 13 to 15 of the periodic table. More specifically, at least one selected from the group consisting of silicon, germanium, tin, lead, titanium, zirconium, aluminum, indium, tantalum, tungsten and zinc can be exemplified. Among these, at least one selected from the group consisting of titanium and tantalum is more preferable.
前記Rは、水素原子、又は金属原子と酸素原子を介して結合を形成し得る加水分解性基を有していてもよい有機基を表す。
有機基としては、アルキル基、アルケニル基、芳香族基等が挙げられる。
前記Rの炭素数は特に制限されないが、通常1〜20、好ましくは1〜12である。R represents a hydrogen atom or an organic group which may have a hydrolyzable group capable of forming a bond via a metal atom and an oxygen atom.
Examples of the organic group include an alkyl group, an alkenyl group, and an aromatic group.
The carbon number of R is not particularly limited, but is usually 1-20, preferably 1-12.
前記Rの具体例としては、メチル基、エチル基、プロピル基等のアルキル基;クロロメチル基、クロロエチル基、クロロプロピル基、ブロモプロピル基、ブロモオクチル基、トリフルオロプロピル基等のハロゲン化アルキル基;グリシドキシプロピル基、エポキシシクロヘキシルエチル基等のエポキシアルキル基;アミノプロピル基、アミノブチル基等のアミノアルキル基;ビニル基、アリル基等のアルケニル基;アクリルオキシプロピル基、メタクリルオキシプロピル基等の(メタ)アクリルオキシアルキル基;ベンジル基等のアラルキル基;フェニル基、ナフチル基等の芳香族基;等が挙げられる。 Specific examples of R include alkyl groups such as methyl, ethyl and propyl; halogenated alkyl groups such as chloromethyl, chloroethyl, chloropropyl, bromopropyl, bromooctyl and trifluoropropyl. An epoxyalkyl group such as a glycidoxypropyl group or an epoxycyclohexylethyl group; an aminoalkyl group such as an aminopropyl group or an aminobutyl group; an alkenyl group such as a vinyl group or an allyl group; an acryloxypropyl group or a methacryloxypropyl group; (Meth) acryloxyalkyl groups; aralkyl groups such as benzyl groups; aromatic groups such as phenyl groups and naphthyl groups;
Xは、Mに結合した加水分解性基又は水酸基を表す。具体的には、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、ペンチルオキシ基等の炭素数1〜12のアルコキシ基;ヒドロキシイミノ基、ヒドロキシアミノ基、エノキシ基、アミノ基、カルバモイル基等の窒素原子を含有する基;塩素原子、臭素原子等のハロゲン原子;水酸基;等を例示することができる。 X represents a hydrolyzable group or a hydroxyl group bonded to M. Specifically, alkoxy groups having 1 to 12 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group; nitrogen such as hydroxyimino group, hydroxyamino group, enoxy group, amino group, carbamoyl group Examples thereof include groups containing atoms; halogen atoms such as chlorine atoms and bromine atoms; hydroxyl groups;
a及びbは、それぞれ独立して、0からm(mは金属原子の原子価を表す。)の整数を表す。ただし、a+b=mである。 a and b each independently represent an integer of 0 to m (m represents a valence of a metal atom). However, a + b = m.
前記式(I)で表される化合物は、分子内に加水分解性基及び/又は水酸基を合計で2以上有する化合物である。具体的には、前記式(I)において、bが2以上の化合物;bが1であって、加水分解性基を有するRが1以上である化合物;bが0であって、加水分解性基を有するRが2以上である化合物;を例示することができる。 The compound represented by the formula (I) is a compound having two or more hydrolyzable groups and / or hydroxyl groups in the molecule. Specifically, in the formula (I), b is 2 or more; b is 1 and R having a hydrolyzable group is 1 or more; b is 0 and hydrolysable A compound having R of 2 or more having a group can be exemplified.
前記式(I)で表される化合物の具体例としては、メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、プロピルトリメトキシシラン、プロピルトリエトキシシラン、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、β−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン、(3−グリシドキシプロピル)メチルジエトキシシラン、3−グリシドキシプロピルトリメトキシシラン、ベンジルトリエトキシシラン、アリルトリエトキシシラン、ビニルメチルジアセトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−メタクリロキシプロピルトリメトキシシラン、3−アクリロキシプロピルトリメトキシシラン、2−クロロエチルトリエトキシシラン、4−アミノブチルトリエトキシシラン、3−アミノプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン等のシランアルコキシド; Specific examples of the compound represented by the formula (I) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, tetramethoxysilane, Tetraethoxysilane, tetrapropoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, (3-glycidoxypropyl) methyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, benzyltriethoxysilane , Allyltriethoxysilane, vinylmethyldiacetoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-chloro Triethoxysilane, 4-aminobutyl triethoxysilane, 3-aminopropyl triethoxysilane, silane alkoxides such as 3-aminopropyltrimethoxysilane;
テトラプロポキシチタン、テトラブトキシチタン等のチタンアルコキシド;
テトラプロポキシジルコニウム、テトラブトキシジルコニウム等のジルコニウムアルコキシド;
ペンタメトキシタンタル、ペンタエトキシタンタル、ペンタブトキシタンタル等のタンタルアルコキシド;
テトラメトキシゲルマニウム、テトラエトキシゲルマニウム等のゲルマニウムアルコキシド;
トリエトキシアルミニウム、トリプロポキシアルミニウム、トリブトキシアルミニウム等のアルミニウムアルコキシド;Titanium alkoxides such as tetrapropoxy titanium and tetrabutoxy titanium;
Zirconium alkoxides such as tetrapropoxyzirconium and tetrabutoxyzirconium;
Tantalum alkoxides such as pentamethoxy tantalum, pentaethoxy tantalum and pentaboxy tantalum;
Germanium alkoxides such as tetramethoxygermanium and tetraethoxygermanium;
Aluminum alkoxides such as triethoxyaluminum, tripropoxyaluminum, tributoxyaluminum;
テトラクロロシラン、テトラブロモシラン、ジメチルジクロロシラン、ベンジルトリクロロシラン、t−ブチルフェニルジクロロシラン、3−クロロプロピルトリクロロシラン、8−ブロモオクチルトリクロロシラン、3−ブロモプロピルトリクロロシラン、(3,3,3−トリフルオロプロピル)ジクロロシラン、(3,3,3−トリフルオロプロピル)トリクロロシラン、クロロメチルトリクロロシラン、アリルトリクロロシラン、3−アクリロキシプロピルトリクロロシラン等のハロゲノシラン;
テトラキス(ジエチルアミノ)シラン等のアミノシラン;
ビニルメチルビス(メチルエチルケトキシミン)シラン等の他のシラン化合物;Tetrachlorosilane, tetrabromosilane, dimethyldichlorosilane, benzyltrichlorosilane, t-butylphenyldichlorosilane, 3-chloropropyltrichlorosilane, 8-bromooctyltrichlorosilane, 3-bromopropyltrichlorosilane, (3, 3, 3- Halogenosilanes such as (trifluoropropyl) dichlorosilane, (3,3,3-trifluoropropyl) trichlorosilane, chloromethyltrichlorosilane, allyltrichlorosilane, 3-acryloxypropyltrichlorosilane;
Aminosilanes such as tetrakis (diethylamino) silane;
Other silane compounds such as vinylmethylbis (methylethylketoximine) silane;
3,3,3−トリフルオロプロピルジメトキシヒドロキシシラン、3,3,3−トリフルオロプロピルメトキシジヒドロキシシラン、オクチルエトキシジヒドロキシシラン等のヒドロキシシラン;等が挙げられる。 And hydroxysilanes such as 3,3,3-trifluoropropyldimethoxyhydroxysilane, 3,3,3-trifluoropropylmethoxydihydroxysilane, and octylethoxydihydroxysilane.
これらの中でも、シランアルコキシド、ゲルマニウムアルコキシド、チタンアルコキシド、ジルコニウムアルコキシド及びタンタルアルコキシド等の金属アルコキシドが好ましく、チタンアルコキシド、タンタルアルコキシドがより好ましく、テトラプロポキシチタン、ペンタエトキシタンタルがさらに好ましい。 Among these, metal alkoxides such as silane alkoxide, germanium alkoxide, titanium alkoxide, zirconium alkoxide, and tantalum alkoxide are preferable, titanium alkoxide and tantalum alkoxide are more preferable, and tetrapropoxy titanium and pentaethoxy tantalum are further preferable.
本発明に用いる加水分解性基及び/又は水酸基を合計で2以上有する金属化合物は、前記式(I)で表される化合物に代表される単分子化合物である必要はなく、例えば、式(I)等で表される化合物を同様の方法等を用いて得られた加水分解縮重合物(完全加水分解縮重合物あるいは部分加水分解縮重合物)であっても構わない。この場合、加水分解縮重合物とは、金属酸化物状態になる前の状態の加水分解縮合物をいう。 The metal compound having a total of two or more hydrolyzable groups and / or hydroxyl groups used in the present invention need not be a monomolecular compound typified by the compound represented by the formula (I). ) And the like may be hydrolyzed polycondensate (completely hydrolyzed polycondensate or partially hydrolyzed polycondensate) obtained by using the same method or the like. In this case, the hydrolysis-condensation polymer refers to a hydrolysis-condensation product in a state before becoming a metal oxide state.
(ii)加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物
本発明に用いる加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物は、加水分解性基及び/又は水酸基を合計で2以上有し、かつ、金属キレート化合物が結合してなるものであれば特に制限されない。なかでも、加水分解性基及び/又は水酸基を合計で2以上有する金属化合物の加水分解生成物(完全加水分解生成物あるいは部分加水分解生成物)のキレート化合物が好ましい。(Ii) Metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups in total The metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups used in the present invention comprises a hydrolyzable group and / or There is no particular limitation as long as it has 2 or more hydroxyl groups in total and a metal chelate compound is bonded. Especially, the chelate compound of the hydrolysis product (complete hydrolysis product or partial hydrolysis product) of the metal compound which has a hydrolyzable group and / or a hydroxyl group 2 or more in total is preferable.
用いるキレート化合物としては、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸n−プロピル、アセト酢酸イソプロピル、アセト酢酸n−ブチル、アセト酢酸sec−ブチル、アセト酢酸t−ブチル等のβ−ケトエステル類;アセチルアセトン、ヘキサン−2,4−ジオン、ヘプタン−2,4−ジオン、ヘプタン−3,5−ジオン、オクタン−2,4−ジオン、ノナン−2,4−ジオン、5−メチル−ヘキサン−2,4−ジオン等のβ−ジケトン類;等が挙げられる。 Examples of chelate compounds used include β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate, n-butyl acetoacetate, sec-butyl acetoacetate, t-butyl acetoacetate; acetylacetone, Hexane-2,4-dione, heptane-2,4-dione, heptane-3,5-dione, octane-2,4-dione, nonane-2,4-dione, 5-methyl-hexane-2,4- Β-diketones such as dione; and the like.
加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物は、例えば、加水分解性基及び/又は水酸基を合計で2以上有する金属化合物に、所定量のキレート化合物を添加し攪拌することにより得ることができる。得られる金属キレート化合物は単離することもできるが、そのまま次の加水分解及び縮重合反応に供することもできる。 The metal chelate compound having 2 or more hydrolyzable groups and / or hydroxyl groups in total is, for example, adding a predetermined amount of chelate compound to a metal compound having 2 or more hydrolyzable groups and / or hydroxyl groups in total and stirring. Can be obtained. Although the obtained metal chelate compound can be isolated, it can be subjected to the subsequent hydrolysis and polycondensation reaction as it is.
(iii)金属有機酸塩
本発明に用いる金属有機酸塩は、金属イオンと有機酸から得られる塩である。
金属としては、チタン、ジルコニウム、アルミニウム、ケイ素、ゲルマニウム、インジウム、スズ、タンタル、亜鉛、タングステン、鉛からなる群から選ばれる一種以上が挙げられる。(Iii) Metal organic acid salt The metal organic acid salt used in the present invention is a salt obtained from a metal ion and an organic acid.
Examples of the metal include one or more selected from the group consisting of titanium, zirconium, aluminum, silicon, germanium, indium, tin, tantalum, zinc, tungsten, and lead.
有機酸としては、酢酸、シュウ酸、酒石酸、安息香酸等のカルボン酸類;スルフォン酸、スルフィン酸、チオフェノール等の含硫黄有機酸;フェノール化合物;エノール化合物;オキシム化合物;イミド化合物;芳香族スルフォンアミド;等の酸性を呈する有機化合物が挙げられる。 Examples of organic acids include carboxylic acids such as acetic acid, oxalic acid, tartaric acid, and benzoic acid; sulfur-containing organic acids such as sulfonic acid, sulfinic acid, and thiophenol; phenol compounds; enol compounds; oxime compounds; imide compounds; Organic compounds exhibiting acidity such as;
(iv)前記(i)〜(iii)の加水分解生成物
本発明に用いる加水分解生成物は、前記(i)〜(iii)からなる群から選ばれる少なくとも一種(以下、これらをまとめて「金属化合物等」という。)の1モルに対して、2モル以下の水を用いて加水分解した生成物である。この場合、加水分解生成物は完全加水分解生成物であっても、部分加水分解生成物であってもよい。(Iv) Hydrolysis product of (i) to (iii) The hydrolysis product used in the present invention is at least one selected from the group consisting of the above (i) to (iii) (hereinafter collectively referred to as “ It is a product hydrolyzed with 2 mol or less of water with respect to 1 mol of “metal compound etc.”). In this case, the hydrolysis product may be a complete hydrolysis product or a partial hydrolysis product.
本発明の光触媒活性薄膜は、前記金属化合物等1モルに対して、2モル以下の水を添加して加水分解及び縮重合することにより、金属酸化物前駆体を含む溶液(以下、「光触媒活性薄膜形成用組成物」ともいう。)を調製し、このものを基体上に塗工し、得られた塗膜を100℃未満の温度で加熱することにより形成することができる。 The photocatalytically active thin film of the present invention is a solution containing a metal oxide precursor (hereinafter referred to as “photocatalytic activity”) by adding 2 mol or less of water to 1 mol of the metal compound and the like, followed by hydrolysis and condensation polymerization. It is also referred to as “a composition for forming a thin film”), this is coated on a substrate, and the resulting coating film is heated at a temperature of less than 100 ° C.
前記光触媒活性薄膜形成用組成物の調製に用いる水としては、一般水道水、蒸溜水、イオン交換水等が挙げられる。これらのうち、蒸溜水又はイオン交換水の使用が好ましく、電気伝導度が2μs/cm以下のイオン交換水の使用が特に好ましい。 Examples of water used for the preparation of the composition for forming a photocatalytically active thin film include general tap water, distilled water, and ion exchange water. Of these, use of distilled water or ion exchange water is preferable, and use of ion exchange water having an electric conductivity of 2 μs / cm or less is particularly preferable.
水の添加量は、前記金属化合物等中の加水分解性基の総モル数に対して、モル比で2未満であり、1/2以上2未満の水を分割して添加するのが好ましい。1/2未満では、加水分解及び縮重合が均一に進行せず、金属化合物等が未反応のまま残り、均質で稠密な膜を形成できない。また、2以上では、加水分解及び縮重合過程において、ゲル化又は粒子が凝集して、均質で稠密な膜を形成することができない。 The amount of water added is less than 2 in terms of molar ratio with respect to the total number of moles of hydrolyzable groups in the metal compound or the like, and it is preferable to add half or more and less than 2 water in portions. If it is less than 1/2, hydrolysis and polycondensation do not proceed uniformly, metal compounds and the like remain unreacted, and a homogeneous and dense film cannot be formed. On the other hand, when the number is 2 or more, gelation or particles aggregate in the hydrolysis and polycondensation process, and a uniform and dense film cannot be formed.
また、水は有機溶媒により希釈したものを添加するのが好ましい。水の希釈に用いる有機溶媒としては、金属化合物との反応性を有しないものであって、かつ、金属化合物が水と反応して加水分解しない温度以下の凝固点を有するもの、すなわち凝固点が0℃以下、特に−10℃以下のものが好ましい。 Moreover, it is preferable to add water diluted with an organic solvent. As an organic solvent used for diluting water, a solvent having no reactivity with a metal compound and having a freezing point below a temperature at which the metal compound does not react with water and hydrolyze, that is, the freezing point is 0 ° C. In particular, those below −10 ° C. are preferred.
用いる有機溶媒としては、メタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール、ヘプタノール、オクタノール、ノナノール、ベンジルアルコール、メチルシクロヘキサノール、エタンジオール、プロパンジオール、ブタンジオール、ペンタンジオール、ヘキシレングリコール、オクチレングリコール、ヘキサントリオール、3,5,5−トリメチル−1−ヘキサノール等のアルコール類;ギ酸ブチル、ギ酸ペンチル、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸ブチル、酢酸ペンチル、酢酸ヘキシル、酢酸ベンジル、3−メトキシブチルアセテート、2−エチルブチルアセテート、2−エチルヘキシルアセテート、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ブチル、プロピオン酸ペンチル等のエステル類;ジメチルケトン、メチルエチルケトン、ペンタノン、ヘキサノン、メチルイソブチルケトン、ヘプタノン、ジイソブチルケトン等のケトン類;アセトニトリル等のニトリル類;ジエチルエーテル、ジプロピルエーテル、ジイソプロピルエーテル、ジブチルエーテル、ジヘキシルエーテル、アニソール、テトラヒドロフラン、テトラヒドロピラン、ジメトキシエタン、ジエトキシエタン、ジブトキシエタン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル等のエーテル類;メチラール等のアセタール類;ペンタン、ヘキサン、ヘプタン、オクタン、ノナン、デカン、ドデカン等の脂肪族炭化水素類;トルエン、キシレン、エチルベンゼン、クメン、ミシチレン、テトラリン、ブチルベンゼン、シメン、ジエチルベンゼン、ペンチルベンゼン、ジペンチルベンゼン等の芳香族炭化水素類;シクロペンタン、シクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、デカリン等の脂環式炭化水素類;ジクロロメタン、クロロホルム、四塩化炭素、ジクロロエタン、トリクロロエタン、クロロベンゼン、ジクロロベンゼン、ブロモベンゼン等のハロゲン化炭化水素類;等が挙げられる。これらの有機溶媒は一種単独で、あるいは二種以上組み合わせて使用することができる。 Organic solvents used include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, benzyl alcohol, methylcyclohexanol, ethanediol, propanediol, butanediol, pentanediol, hexylene glycol, octylene Alcohols such as glycol, hexanetriol, 3,5,5-trimethyl-1-hexanol; butyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, benzyl acetate, 3- Methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, methyl propionate, ethyl propionate, butyl propionate, pentyl propionate, etc. Esters; ketones such as dimethyl ketone, methyl ethyl ketone, pentanone, hexanone, methyl isobutyl ketone, heptanone, diisobutyl ketone; nitriles such as acetonitrile; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, tetrahydrofuran , Tetrahydropyran, dimethoxyethane, diethoxyethane, dibutoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, and other ethers; methylal and other acetals; pentane, hexane, heptane, octane, nonane, decane, dodecane, etc. Aliphatic hydrocarbons: toluene, xylene, ethylbenzene, cumene, Aromatic hydrocarbons such as tylene, tetralin, butylbenzene, cymene, diethylbenzene, pentylbenzene, dipentylbenzene; alicyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, decalin; dichloromethane, chloroform, four And halogenated hydrocarbons such as carbon chloride, dichloroethane, trichloroethane, chlorobenzene, dichlorobenzene, and bromobenzene. These organic solvents can be used singly or in combination of two or more.
これらのうち、アルコール類、エステル類及び炭化水素類が好ましく、特に、ブタノール、ペンタノール、ヘキサノール、トリメチルヘキサノール等のアルコール類;酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル類;ペンタン、ヘキサン、キシレン等の炭化水素類;が好ましい。 Of these, alcohols, esters and hydrocarbons are preferred, and alcohols such as butanol, pentanol, hexanol and trimethylhexanol; esters such as ethyl acetate, propyl acetate and butyl acetate; pentane, hexane and xylene And the like.
水と有機溶媒の混合割合は、有機溶媒100重量部に対し、水の量が、好ましくは1〜50重量部、より好ましくは1〜30重量部、さらに好ましくは1〜15重量部となる量である。水の使用割合が50重量部を超えると、生成する粒子の凝集が激しくなることがある。 The mixing ratio of water and organic solvent is such that the amount of water is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, and even more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the organic solvent. It is. When the proportion of water used exceeds 50 parts by weight, the resulting particles may become intensively aggregated.
なお、水と有機溶媒とが均一に溶解混合する場合には、そのまま使用することができるが、水と有機溶媒とが均一に混合しない場合には、1,2−ビス−(2−エチルヘキシルオキシカルボニル)−1−エタンスルホン酸ナトリウム、ポリオキシエチレン(6)ノニルフェニルエーテル等の界面活性剤を使用したり、撹拌処理、超音波処理等の方法で均一に分散させるのが好ましい。 When water and the organic solvent are uniformly dissolved and mixed, they can be used as they are, but when water and the organic solvent are not uniformly mixed, 1,2-bis- (2-ethylhexyloxy) can be used. It is preferable to use a surfactant such as sodium carbonyl) -1-ethanesulfonate or polyoxyethylene (6) nonylphenyl ether, or to uniformly disperse by a method such as stirring treatment or ultrasonic treatment.
前記金属化合物等の溶液に用いる溶媒としては、水の溶解度が大きく、低温で凝固しないものが好ましい。具体的には、前記添加する水を希釈するのに使用できるものとして列記したものと同様の有機溶媒が使用できる、低級アルコール系溶媒、エーテル系溶媒等の使用が好ましい。また、有機溶媒は一種単独で、あるいは二種以上を混合して用いることができる。 As a solvent used for the solution of the metal compound or the like, a solvent that has high water solubility and does not solidify at a low temperature is preferable. Specifically, it is preferable to use a lower alcohol solvent, an ether solvent, or the like, which can use the same organic solvents as those listed as usable for diluting the water to be added. Moreover, an organic solvent can be used individually by 1 type or in mixture of 2 or more types.
有機溶媒の使用量は、前記金属化合物等100重量部に対し、好ましくは10〜5,000重量部、さらに好ましくは100〜3,000重量部であり、10重量部未満では生成する微粒子が結合した状態で成長し、粒径制御が困難になる場合があり、一方、5,000重量部を超えると溶液が希薄すぎて、微粒子の生成が困難な場合がある。 The amount of the organic solvent used is preferably 10 to 5,000 parts by weight, more preferably 100 to 3,000 parts by weight with respect to 100 parts by weight of the metal compound and the like. However, when the amount exceeds 5,000 parts by weight, the solution may be too dilute and it may be difficult to produce fine particles.
本発明に用いる金属化合物等を含有する溶液中の金属化合物の含有量は、特に制限はないが、緻密な薄膜を製造するためには、0.1〜30重量%の範囲が好ましい。 Although there is no restriction | limiting in particular in content of the metal compound in the solution containing the metal compound etc. which are used for this invention, In order to manufacture a precise | minute thin film, the range of 0.1 to 30 weight% is preferable.
金属化合物等を加水分解及び縮重合する温度は、通常−100℃〜+200℃、好ましくは−80℃〜+150℃である。この場合、金属化合物等を加水分解及び縮重合する温度を段階的に変化させることもできる。例えば、金属化合物等の溶液温度を−80℃〜−20℃に冷却しておき、攪拌下、−10℃〜+20℃の水(又は水と有機溶媒の混合物)をゆっくりと滴下し、水(又は水と有機溶媒の混合物)の滴下終了後、段階的に反応液の温度を溶媒の沸点まで徐々に昇温させて、加水分解・縮合反応を完結させる方法を採用することができる。また、水(又は水と有機溶媒の混合物)の滴下を複数回に分割し、水(又は水と有機溶媒の混合物)の滴下温度を異なる温度に設定することもできる。さらに、金属化合物等を加水分解した後、反応液を適当な塩基で中和してもよい。
金属化合物等を加水分解及び縮重合する時間は、通常、数分間から数十時間である。The temperature for hydrolyzing and polycondensing a metal compound or the like is usually −100 ° C. to + 200 ° C., preferably −80 ° C. to + 150 ° C. In this case, the temperature at which the metal compound and the like are hydrolyzed and polycondensed can be changed stepwise. For example, the solution temperature of a metal compound or the like is cooled to −80 ° C. to −20 ° C., and water (or a mixture of water and an organic solvent) at −10 ° C. to + 20 ° C. is slowly added dropwise with stirring, Alternatively, a method of gradually raising the temperature of the reaction solution to the boiling point of the solvent in a stepwise manner after completion of the dropwise addition of the mixture of water and an organic solvent to complete the hydrolysis / condensation reaction can be employed. Moreover, the dropping of water (or a mixture of water and an organic solvent) can be divided into a plurality of times, and the dropping temperature of water (or a mixture of water and an organic solvent) can be set to different temperatures. Furthermore, after hydrolyzing a metal compound etc., you may neutralize a reaction liquid with a suitable base.
The time for hydrolysis and polycondensation of a metal compound or the like is usually from several minutes to several tens of hours.
以上のようにして得られる光触媒活性薄膜形成用組成物は透明であり、平均粒径1〜10nmの範囲の粒子状物であって、単分散の分散質が有機溶媒中において凝集することなく、溶解若しくは均一に分散したものである。すなわち、金属化合物等は、有機溶媒中、凝集することなく安定に分散してなる、金属−酸素結合を有する分散質となっている。 The composition for forming a photocatalytically active thin film obtained as described above is transparent, and is a particulate matter having an average particle size in the range of 1 to 10 nm, and the monodisperse dispersoid does not aggregate in the organic solvent, Dissolved or uniformly dispersed. That is, the metal compound or the like is a dispersoid having a metal-oxygen bond that is stably dispersed in an organic solvent without aggregation.
なお、有機溶媒中に分散させる際には、酸、塩基及び/又は分散安定化剤を添加することもできる。 In addition, when making it disperse | distribute in an organic solvent, an acid, a base, and / or a dispersion stabilizer can also be added.
添加する酸としては、例えば、塩酸、硝酸、ホウ酸、ホウフッ化水素酸等の鉱酸、酢酸、ギ酸、シュウ酸、炭酸、トリフルオロ酢酸、p−トルエンスルホン酸、メタンスルホン酸等の有機酸等;ジフェニルヨードニウムヘキサフルオロホスフェート、トリフェニルホスホニウムヘキサフルオロホスフェート等の光照射によって酸を発生する光酸発生剤;が挙げられる。
塩基としては、例えば、トリエタノールアミン、トリエチルアミン、1,8−ジアザビシクロ[5.4.0]−7−ウンデセン、アンモニア、ジメチルホルムアミド、ホスフィン等が挙げられる。Examples of the acid to be added include mineral acids such as hydrochloric acid, nitric acid, boric acid, and borofluoric acid, and organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. And the like; and photoacid generators that generate acid by light irradiation, such as diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like.
Examples of the base include triethanolamine, triethylamine, 1,8-diazabicyclo [5.4.0] -7-undecene, ammonia, dimethylformamide, phosphine and the like.
分散安定化剤は、分散質を分散媒中に安定に分散させる効力を有する、解膠剤、保護コロイド、界面活性剤等の凝結防止剤等の剤をいう。例えば、グリコール酸、グルコン酸、乳酸、酒石酸、クエン酸、リンゴ酸、コハク酸等の多価カルボン酸;ヒドロキシカルボン酸;ピロ燐酸、トリポリ燐酸等の燐酸;アセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸n−プロピル、アセト酢酸イソプロピル、アセト酢酸n−ブチル、アセト酢酸sec−ブチル、アセト酢酸t−ブチル、2,4−ヘキサン−ジオン、2,4−ヘプタン−ジオン、3,5−ヘプタン−ジオン、2,4−オクタン−ジオン、2,4−ノナン−ジオン、5−メチル−ヘキサンジオン等の金属原子に対して強いキレート能力を有する多座配位子化合物;スルパース3000、9000、17000、20000、24000(以上、ゼネカ社製)、Disperbyk−161、−162、−163、−164(以上、ビックケミー社製)等の脂肪族アミン系、ハイドロステアリン酸系又はポリエステルアミン;ジメチルポリシロキサン・メチル(ポリシロキシアルキレン)シロキサン共重合体、トリメチルシロキシケイ酸、カルボキシ変性シリコーンオイル、アミン変性シリコーン等(特許文献5、特許文献6等)のシリコーン化合物;等が挙げられる。
本発明においては、上記で得られた溶液をそのまま光触媒活性薄膜形成用組成物として用いることもできるし、適当な溶媒で希釈し、あるいは溶媒を留去した後別の溶媒に再溶解させたものを光触媒活性薄膜形成用組成物として用いることもできる。 In the present invention, the solution obtained above can be used as it is as a composition for forming a photocatalytically active thin film, or is diluted with an appropriate solvent, or the solvent is distilled off and then re-dissolved in another solvent. Can also be used as a composition for forming a photocatalytically active thin film.
光触媒活性薄膜は、得られた光触媒活性薄膜形成用組成物を基体上に塗布又は吹き付け、乾燥することにより形成することができる。 The photocatalytically active thin film can be formed by applying or spraying the obtained composition for forming a photocatalytically active thin film onto a substrate and drying it.
光触媒活性薄膜形成用組成物を基体上に塗布又は吹き付ける方法としては、平滑に塗布できる方法であれば特に制限はされない。例えば、ディッピング法、スピンコート法、メイヤバー法、はけ塗り法等が挙げられ、なかでも、ディッピング法が好ましい。 The method for applying or spraying the composition for forming a photocatalytically active thin film onto the substrate is not particularly limited as long as it can be applied smoothly. For example, a dipping method, a spin coat method, a Mayer bar method, a brush coating method, and the like can be mentioned, and among these, a dipping method is preferable.
得られた光触媒活性薄膜形成用組成物の塗膜を加熱・乾燥する温度は、通常300℃以下、好ましくは100℃未満である。基体としてプラスチック基体を用いる場合には、用いるプラスチック基体の軟化点未満、かつ100℃未満の温度が好ましい。
加熱する時間は、加熱温度、組成物の種類等にもよるが、通常数分から数十時間である。The temperature for heating and drying the coating film of the resulting composition for forming a photocatalytically active thin film is usually 300 ° C. or lower, preferably less than 100 ° C. When a plastic substrate is used as the substrate, a temperature lower than the softening point of the plastic substrate used and lower than 100 ° C. is preferable.
The heating time is usually from several minutes to several tens of hours although it depends on the heating temperature, the type of composition, and the like.
本発明の光触媒活性薄膜は100℃未満の低温で形成することができるものであるため、用いる基体の耐熱温度による制約がなく、基体としてプラスチック基体を好適に用いることができる。また、基体及び光触媒活性薄膜自体の熱劣化を防止することができる。 Since the photocatalytically active thin film of the present invention can be formed at a low temperature of less than 100 ° C., there is no restriction due to the heat resistant temperature of the substrate to be used, and a plastic substrate can be suitably used as the substrate. In addition, thermal deterioration of the substrate and the photocatalytically active thin film itself can be prevented.
従来公知のアナターゼ型酸化チタンからなる光触媒の層は、プラスチック基体との接着性が乏しく、また基体を劣化させることがあるため、プラスチック基体と光触媒の層との間に接着剤層等の下地層を設ける必要があったが、本発明の光触媒活性薄膜は、プラスチックからなる基体と良好な接着性を有し、基体を劣化させることが少ないので、プラスチック基体の表面に直接に光触媒活性薄膜を形成することができる。 Conventionally known photocatalyst layers made of anatase-type titanium oxide have poor adhesion to the plastic substrate and may deteriorate the substrate, so that an underlayer such as an adhesive layer is provided between the plastic substrate and the photocatalyst layer. However, since the photocatalytically active thin film of the present invention has good adhesion to a plastic substrate and hardly deteriorates the substrate, the photocatalytically active thin film is formed directly on the surface of the plastic substrate. can do.
得られる光触媒活性薄膜の厚みは、好ましくは50nm以下、より好ましくは40nm以下、特に好ましくは1〜20nmである。 The thickness of the resulting photocatalytically active thin film is preferably 50 nm or less, more preferably 40 nm or less, and particularly preferably 1 to 20 nm.
形成される光触媒活性薄膜は、有機物を含有するものであるのが好ましい。有機物としては、例えば、前記金属化合物等として金属アルコキシドを使用する場合であれば、アルコキシド基である。 The formed photocatalytically active thin film preferably contains an organic substance. The organic substance is, for example, an alkoxide group when a metal alkoxide is used as the metal compound or the like.
また、形成される光触媒活性薄膜の炭素原子の含有比率は、2〜40重量%であるのが好ましい。このような光触媒活性薄膜は、少ない照射光量で、光触媒活性を発揮することができる。
光触媒活性薄膜に含まれる炭素原子、チタン原子、酸素原子等の含有比率は、例えば、X線光電子分析装置(ESCA)により測定し、求めることができる。Moreover, it is preferable that the content rate of the carbon atom of the photocatalytic active thin film formed is 2 to 40 weight%. Such a photocatalytically active thin film can exhibit photocatalytic activity with a small amount of irradiation light.
The content ratio of carbon atoms, titanium atoms, oxygen atoms and the like contained in the photocatalytically active thin film can be determined by measuring with, for example, an X-ray photoelectron analyzer (ESCA).
以上のようにして得られる本発明の光触媒活性薄膜は、150〜350nmの波長の光、好ましくは250〜310nmの波長の光の照射により、優れた光触媒活性を発揮する。 The photocatalytically active thin film of the present invention obtained as described above exhibits excellent photocatalytic activity when irradiated with light having a wavelength of 150 to 350 nm, preferably 250 to 310 nm.
用いる照射光源としては、150〜350nmの波長の光を照射できるものであれば特に制約はなく、例えば、ハロゲン電球等の白熱電球;蛍光ランプ、殺菌灯、ブラックライト、ケミカルランプ等の低圧放電ランプ;水銀ランプ、メタルハライドランプ、高圧ナトリウムランプ等の高圧放電ランプ;等が挙げられる。 The irradiation light source to be used is not particularly limited as long as it can irradiate light having a wavelength of 150 to 350 nm. For example, an incandescent bulb such as a halogen bulb; a low-pressure discharge lamp such as a fluorescent lamp, a sterilizing lamp, a black light, or a chemical lamp High pressure discharge lamps such as mercury lamps, metal halide lamps, high pressure sodium lamps, and the like.
本発明の光触媒活性薄膜は、150〜350nmの波長の光照射により光触媒活性を発揮し、該薄膜に接触した有機物質を分解及び/又は除去する。 The photocatalytically active thin film of the present invention exhibits photocatalytic activity when irradiated with light having a wavelength of 150 to 350 nm, and decomposes and / or removes an organic substance in contact with the thin film.
また、150〜350nmの波長の光が照射されると、光照射された部分が、撥水性から、水の接触角が20°以下の親水性に変化する。
本発明の光触媒活性薄膜が撥水性から親水性に変化するために必要な照射光量は、40J/cm2以下、好ましくは5J/cm2以下、より好ましくは0.1〜5J/cm2である。
本発明の光触媒活性薄膜は、低波長の光で、かつ少ない照射光量で良好な光触媒活性を発揮する。Further, when light having a wavelength of 150 to 350 nm is irradiated, the irradiated portion changes from water repellency to hydrophilicity with a water contact angle of 20 ° or less.
Light quantity required for photocatalytic activity thin film of the present invention is changed from water-repellent to hydrophilic, 40 J / cm 2 or less, preferably 5 J / cm 2 or less, more preferably at 0.1~5J / cm 2 .
The photocatalytically active thin film of the present invention exhibits good photocatalytic activity with low wavelength light and with a small amount of irradiation light.
本発明の光触媒活性薄膜は、軽量で加工が容易なプラスチック基体を好適に用いることができ、低波長の光で、かつ少ない照射光量で良好な光触媒活性を発揮できる。
本発明の光触媒活性薄膜上に有機金属化合物等からなる薄膜を形成すると光感応性基体を得ることができる。この光感応性基体の所定部分を光照射し、光照射された部分の有機金属化合物を分解及び/又は除去することにより、簡便に、かつ短時間で、従来のフォトリソグラフィーの技術により形成されたパターンと同様の微細なパターニングが可能である。
また、本発明の光触媒活性薄膜をポリエステル等のプラスチック基体上に形成して、不純物が少ない緻密な単分子の化学吸着膜を得ることできる。The photocatalytically active thin film of the present invention can suitably use a plastic substrate that is lightweight and easy to process, and can exhibit good photocatalytic activity with a low wavelength light and with a small amount of irradiation light.
When a thin film made of an organometallic compound or the like is formed on the photocatalytically active thin film of the present invention, a photosensitive substrate can be obtained. A predetermined portion of the photosensitive substrate is irradiated with light, and the organometallic compound in the irradiated portion is decomposed and / or removed, so that it is formed easily and in a short time by a conventional photolithography technique. Fine patterning similar to the pattern is possible.
Further, the photocatalytically active thin film of the present invention can be formed on a plastic substrate such as polyester to obtain a dense monomolecular chemisorbed film with few impurities.
次に、実施例を用いて本発明をさらに詳細に説明するが、本発明は、下記の実施例に何ら限定されるものではない。 EXAMPLES Next, although this invention is demonstrated further in detail using an Example, this invention is not limited to the following Example at all.
(1)光触媒活性薄膜形成用溶液の調製
A−1:テトライソプロポキシチタン〈日本曹達社製、酸化物拠算固形分量28.2重量%〉をエタノールで希釈し、アセト酢酸エチル(和光純薬社製、試薬特級)を滴下、反応後、エタノールで希釈したイオン交換水を滴下、加水分解し、酸化チタン換算固形分1重量%の溶液(A−1)を調製した。この溶液のテトライソプロポキシチタン:アセト酢酸エチル:イオン交換水のモル比は1:2:1であった。(1) Preparation of Photocatalytically Active Thin Film Forming Solution A-1: Tetraisopropoxytitanium (manufactured by Nippon Soda Co., Ltd., oxide-based solid content 28.2% by weight) is diluted with ethanol, and ethyl acetoacetate (Wako Pure Chemical Industries, Ltd.) After the addition and reaction of ion-exchanged water diluted with ethanol, it was hydrolyzed and hydrolyzed to prepare a solution (A-1) having a solid content of 1% by weight in terms of titanium oxide. The molar ratio of tetraisopropoxy titanium: ethyl acetoacetate: ion exchanged water of this solution was 1: 2: 1.
A−2:テトライソプロポキシチタン(日本曹達社製、酸化物拠算固形分量28.2重量%)をエタノールで希釈し、アセチルアセトン(和光純薬社製、試薬特級)を滴下した。80℃で1時間反応後、室温に冷却し、エタノールで希釈したイオン交換水を滴下、加水分解し、酸化チタン換算固形分1重量%の溶液(A−2)を調製した.この溶液のテトライソプロポキシチタン:アセチルアセトン:イオン交換水のモル比は1:2:4であった。 A-2: Tetraisopropoxy titanium (manufactured by Nippon Soda Co., Ltd., oxide-based solid content 28.2% by weight) was diluted with ethanol, and acetylacetone (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade) was added dropwise. After reacting at 80 ° C. for 1 hour, the solution was cooled to room temperature and ion-exchanged water diluted with ethanol was added dropwise and hydrolyzed to prepare a solution (A-2) having a solid content of 1% by weight in terms of titanium oxide. The molar ratio of tetraisopropoxytitanium: acetylacetone: ion exchanged water of this solution was 1: 2: 4.
A−3:酢酸エチル/エタノール=50/50(重量比)混合溶媒47.7gにペンタエトキシタンタル(高純度化学研究所社製、試薬)1.72gを溶解し、室温でアセチルアセトン(和光純薬社製、試薬特級)0.84gを滴下した。室温で1時間反応後、前記酢酸エチル/エタノール40gで希釈したイオン交換水9.74gを滴下、加水分解し、室温で24時間反応後、TaO2.5換算固形分1重量%の溶液(A−3)を調製した。この溶液のペンタエトキシタンタル:アセチルアセトン:イオン交換水のモル比は1:2.5:128であった。A-3: Dissolve 1.72 g of pentaethoxy tantalum (manufactured by Kojundo Chemical Laboratory Co., Ltd., reagent) in 47.7 g of a mixed solvent of ethyl acetate / ethanol = 50/50 (weight ratio), and acetylacetone (Wako Pure Chemical Industries, Ltd.) at room temperature. 0.84 g of a reagent special grade) manufactured by the company was added dropwise. After 1 hour at room temperature, the dropwise addition of ion-exchanged water 9.74g diluted with ethyl acetate / ethanol 40 g, hydrolyzed, after 24 hours at room temperature, TaO 2.5 in terms of solid content 1% by weight of the solution (A -3) was prepared. The molar ratio of pentaethoxytantalum: acetylacetone: ion exchanged water of this solution was 1: 2.5: 128.
AH−1(比較例):テトライソプロポキシチタン〈日本曹達社製、酸化物換算固形分量28,2重量%〉をエタノールで希釈し、酸化チタン換算固形分1重量%の溶液(H−1)を調製した。 AH-1 (comparative example): Tetraisopropoxytitanium (manufactured by Nippon Soda Co., Ltd., oxide equivalent solid content 28, 2% by weight) diluted with ethanol to give a solution (H-1) having a titanium oxide equivalent solid content of 1% by weight Was prepared.
(2)基板
光触媒活性薄膜を形成する基板としては次のものを用いた。
B−1:ソーダライムガラス板
B−2:ポリエステルシート(東レ社製、商品名:ルミラー)
B−3:ポリイミドシート(デュポン社製,商品名:カプトン)
B−4:アクリル板(2) Substrate As the substrate on which the photocatalytically active thin film is formed, the following was used.
B-1: Soda lime glass plate B-2: Polyester sheet (trade name: Lumirror, manufactured by Toray Industries, Inc.)
B-3: Polyimide sheet (manufactured by DuPont, trade name: Kapton)
B-4: Acrylic board
(実施例1〜9、比較例1,2)
上記各基板の表面をエタノールで洗浄・乾燥した。得られた基板上に、上記で調製した光触媒活性薄膜形成用溶液(A−1)、(A−2)、(A−3)、(AH−1)のそれぞれをメイヤーパーNo.3で塗工し、得られた塗膜を60℃で10分間乾燥して、光触媒活性薄膜をそれぞれ得た(C−1〜C−9、CH−1)。(Examples 1 to 9, Comparative Examples 1 and 2)
The surface of each substrate was washed with ethanol and dried. On the obtained substrate, each of the solutions (A-1), (A-2), (A-3) and (AH-1) for photocatalytically active thin film formation prepared above was added to the Mayer-Per No. The coating film thus obtained was dried at 60 ° C. for 10 minutes to obtain photocatalytically active thin films (C-1 to C-9, CH-1), respectively.
(薄膜物性評価試験)
次いで、上記で得た光触媒活性薄膜形成用溶液及び光触媒活性薄膜の物性を以下のように評価した。
(a)溶液中の金属化合物の粒径
溶液中の粒径は、Ma1vern Instruments Ltd製HPPSで測定した。
(b)膜外観
ヘイズ率測定及び目視により、薄膜の外観を観察した。
透明で、ヘイズ率の変化が0.5%未満であり、膜斑がない場合を○、ヘイズ率の変化が0.5%以上で、膜斑がある場合を×として評価した。(Thin film physical property evaluation test)
Next, the physical properties of the photocatalytically active thin film forming solution and the photocatalytically active thin film obtained above were evaluated as follows.
(A) Particle size of the metal compound in the solution The particle size in the solution was measured by HPPS manufactured by Ma1vern Instruments Ltd.
(B) Film appearance The appearance of the thin film was observed by haze ratio measurement and visual observation.
The case where the film was transparent and the change in the haze ratio was less than 0.5% and there was no film spot was evaluated as ◯, and the case where the change in the haze ratio was 0.5% or more and there was a film spot was evaluated as x.
(c)水滴接触角の測定
各薄膜の表面層にマイクロシリンジから水滴5μ1を滴下した後、30秒後に、接触角測定器(エルマ社製、360S型〉を用いて試料表面の接触角を測定した。
膜の結晶性
(d)密着性〈テープ剥離試験〉
各薄膜表面に粘着テープを貼り付け、複数回指の腹で擦りつけその後、テープを引き一剥がした際、基板上の膜が剥離しているかをXPSで元素分析し、剥離しない場合を○、剥離した場合を×で評価した。(C) Measurement of water droplet contact angle After 5 μl of water droplet was dropped from the microsyringe onto the surface layer of each thin film, 30 seconds later, the contact angle of the sample surface was measured using a contact angle measuring device (manufactured by ELMA, Model 360S). did.
Film crystallinity (d) adhesion <tape peeling test>
Stick the adhesive tape on the surface of each thin film and rub it with the belly of the finger several times. Then, when the tape is pulled and peeled off, the elemental analysis is performed by XPS to see if the film on the substrate is peeled off. The case where it peeled was evaluated by x.
(e)膜中の元素の分布
薄膜中の元素の深さ方向の分布の測定は、XPS装置(Quntum2000、アルパックファイ社製)を用いて行った。
アルゴンスパッタリングにより、1kVで0.25分間隔で膜を削り、膜中の炭素原子、酸素原子及びチタン原子の含有率をX線光電子分析装置(ESCA)により測定した。
炭素原子の含有比率(%)は、式:炭素元素の濃度/(炭素元素の濃度+酸素元素の濃度+チタン元素の濃度)×100で求めた。
酸素原子の含有比率(%)は、式:酸素元素の濃度/(炭素元素の濃度+酸素元素の濃度+チタン元素の濃度)×100で求めた。
チタン原子の含有比率(%)は、式:チタン元素の濃度/(炭素元素の濃度+酸素元素の濃度+チタン元素の濃度)×100で求めた。
で求めた。(E) Element distribution in the film The depth distribution of the elements in the thin film was measured using an XPS apparatus (Quantum 2000, manufactured by Alpacphi).
The film was scraped at an interval of 0.25 minutes at 1 kV by argon sputtering, and the contents of carbon atoms, oxygen atoms, and titanium atoms in the film were measured with an X-ray photoelectron analyzer (ESCA).
The carbon atom content ratio (%) was determined by the formula: concentration of carbon element / (concentration of carbon element + concentration of oxygen element + concentration of titanium element) × 100.
The oxygen atom content ratio (%) was determined by the formula: oxygen element concentration / (carbon element concentration + oxygen element concentration + titanium element concentration) × 100.
The content ratio (%) of titanium atoms was determined by the formula: concentration of titanium element / (concentration of carbon element + concentration of oxygen element + concentration of titanium element) × 100.
I asked for it.
(f)光触媒活性評価試験
紫外線照射用ランプとして次の2種を用いた。
UV1:殺菌灯(東芝社製、GL−15;波長254nmの紫外線)、照射光量4mW/cm2
UV2:ブラックライト(東芝社製、FL15BLB;波長365nmの紫外線)、照射光量2mW/cm2
前記(C−1)〜(C−8)の光触媒活性薄膜に上記ランプを使用して紫外線をそれぞれ照射し、表面濡れ性の変化を水の接触角を測定することにより評価した。水の接触角が10°以下の親水化するまでの紫外線照射エネルギーを算出した。(F) Photocatalytic activity evaluation test The following two types were used as ultraviolet irradiation lamps.
UV1: germicidal lamp (manufactured by Toshiba Corporation, GL-15; ultraviolet light with a wavelength of 254 nm), irradiation light amount 4 mW / cm 2
UV2: Black light (manufactured by Toshiba Corporation, FL15BLB; ultraviolet light with a wavelength of 365 nm), irradiation light amount 2 mW / cm 2
The photocatalytically active thin films of (C-1) to (C-8) were each irradiated with ultraviolet rays using the lamp, and the change in surface wettability was evaluated by measuring the contact angle of water. The ultraviolet irradiation energy until the water contact angle became 10 ° or less until hydrophilicity was calculated.
実施例1〜8、比較例1,2の光触媒活性薄膜のそれぞれについて、用いた光触媒活性薄膜形成用溶液及び基板の種類、粒子径、膜外観、密着性、紫外線照射(UV照射)前の接触角、紫外線照射用ランプ(UV光)、及び親水化に必要な照射光量を第1表にまとめた。 For each of the photocatalytically active thin films of Examples 1 to 8 and Comparative Examples 1 and 2, the type of photocatalytically active thin film used and the type of substrate, particle diameter, film appearance, adhesion, contact before ultraviolet irradiation (UV irradiation) Table 1 summarizes the angle, the ultraviolet irradiation lamp (UV light), and the amount of irradiation light necessary for hydrophilization.
実施例9の光触媒活性薄膜について、実施例1と同様にして、光触媒活性薄膜形成用溶液(A−3)を用いて基板(B−2)に塗付乾燥して得られた光触媒活性薄膜に紫外線照射用ランプ(UV光)UV1を照射した。
得られた光触媒活性薄膜は、膜外観、密着性共に良好で親水化に必要な照射光量は1.27J/cm2であった。UV照射前の接触角62.5°は、照射時間3分で8.8°の接触角を示し、親水化した。About the photocatalytically active thin film of Example 9, in the same manner as in Example 1, the photocatalytically active thin film obtained by applying and drying the substrate (B-2) using the photocatalytically active thin film forming solution (A-3) An ultraviolet irradiation lamp (UV light) UV1 was irradiated.
The obtained photocatalytically active thin film had good film appearance and adhesion, and the amount of irradiation light necessary for hydrophilization was 1.27 J / cm 2 . A contact angle of 62.5 ° before UV irradiation showed a contact angle of 8.8 ° with an irradiation time of 3 minutes and became hydrophilic.
第1表に示すように、溶液A−1及びA−2中の金属化合物は、加水分解縮合により、ポリマー化し、2.3及び3.8nmのナノ粒子になっていた。光触媒活性薄膜形成用溶液は共に透明であり、凝集粒子は含まれていなかった。 As shown in Table 1, the metal compounds in the solutions A-1 and A-2 were polymerized by hydrolysis and condensation to form nanoparticles of 2.3 and 3.8 nm. Both the solutions for forming a photocatalytically active thin film were transparent and contained no agglomerated particles.
得られた薄膜は、全て膜厚20〜30nmのアモルファスの膜であった.膜外観、密着性は共に良好であった。紫外線照射前の膜の水の接触角は、40−60°を示し、この膜に254nmの紫外線を照射すると、速やかに親水化し、10°以下の接触角を示した。しかし、365nmの紫外線照射では、親水化することがなかった(比較例2)。通常のアナターゼ型TiO2光触媒の場合、365nmの光で親水化するのとは異なっていた。All of the obtained thin films were amorphous films having a thickness of 20 to 30 nm. The film appearance and adhesion were both good. The water contact angle of the film before UV irradiation was 40-60 °, and when this film was irradiated with UV light of 254 nm, it immediately became hydrophilic and showed a contact angle of 10 ° or less. However, it was not hydrophilized by irradiation with 365 nm ultraviolet light (Comparative Example 2). In the case of a normal anatase type TiO 2 photocatalyst, it was different from hydrophilizing with 365 nm light.
実施例2の膜に紫外線を照射し、水の接触角10°以下に親水化した後の膜のXPSによる深さ方向の元素分析結果を図1に示す。図1中、横軸は表面からの深さ(nm)、縦軸は原子の含有比率(%)をそれぞれ示す。また、C1sは炭素原子の含有比率を、O1sは酸素原子の含有比率を、Ti2pはチタン原子の含有比率をそれぞれ示す。 FIG. 1 shows the results of elemental analysis in the depth direction by XPS of the film after the film of Example 2 was irradiated with ultraviolet rays and hydrophilized to a water contact angle of 10 ° or less. In FIG. 1, the horizontal axis represents the depth (nm) from the surface, and the vertical axis represents the atomic content ratio (%). C1s represents the carbon atom content ratio, O1s represents the oxygen atom content ratio, and Ti2p represents the titanium atom content ratio.
図1より、腹中には炭素が10−40%程度含有しており、炭素元素は深さ方向に傾斜していた。また、膜中の炭素は、紫外線を照射し、親水化した後でも減少することなく変化しなかった。表面近傍の異常に多い炭素は、測定開始までに付着した有機物汚れによるものと考えられる。
通常のアナターゼ型TiO2光触媒の場合、膜中の有機物は紫外線照射により分解されるが、これとは異なっていた。表面層だけが光触媒活性を示していると思われる。As shown in FIG. 1, the abdomen contained about 10-40% carbon, and the carbon element was inclined in the depth direction. Further, the carbon in the film was not changed without decreasing even after being irradiated with ultraviolet rays to be hydrophilic. The abnormally large amount of carbon in the vicinity of the surface is considered to be due to organic contamination adhered by the start of measurement.
In the case of a normal anatase type TiO 2 photocatalyst, the organic matter in the film was decomposed by irradiation with ultraviolet rays, but this was different. Only the surface layer appears to exhibit photocatalytic activity.
(g)光触媒活性薄膜の結晶性
実施例1の光触媒活性薄膜をX線回折装置で測定した。測定したチャートを図2に示す。図2から、実施例1の光触媒活性薄膜はアモルファスであることがわかる。(G) Crystallinity of photocatalytically active thin film The photocatalytically active thin film of Example 1 was measured with an X-ray diffractometer. The measured chart is shown in FIG. FIG. 2 shows that the photocatalytically active thin film of Example 1 is amorphous.
本発明の光触媒活性薄膜は、250〜350nmの低波長の光照射で優れた光触媒活性を示すという特性を有する。従って、本発明の光触媒活性薄膜は、350nmより高波長の光(可視光等)に曝す必要がなく、また、曝された場合であっても、基体(特にプラスチック基体)が劣化したり、基体と光触媒活性薄膜との接着性が低下することがない。
本発明の光触媒活性薄膜は、100℃未満の低温加熱処理により形成することができるので、加熱処理により基体を傷めることがなく、用いる基体を、耐熱性のものに限定する必要がない。従って、基体として、軽量で加工が容易なプラスチック基体を好適に用いることができる。
また、本発明の光触媒活性薄膜は良好な接着性を有するため、プラスチック等の基体上に容易に直接形成することができ、かつ長期間劣化することがない。The photocatalytically active thin film of the present invention has a characteristic of exhibiting excellent photocatalytic activity when irradiated with light having a low wavelength of 250 to 350 nm. Therefore, the photocatalytically active thin film of the present invention does not need to be exposed to light having a wavelength higher than 350 nm (visible light, etc.), and even when exposed to light, the substrate (particularly plastic substrate) is deteriorated, And adhesion between the photocatalytically active thin film do not deteriorate.
Since the photocatalytically active thin film of the present invention can be formed by low-temperature heat treatment at less than 100 ° C., the heat treatment does not damage the substrate, and the substrate to be used need not be limited to heat-resistant ones. Therefore, a plastic substrate that is lightweight and easy to process can be suitably used as the substrate.
Further, since the photocatalytically active thin film of the present invention has good adhesion, it can be easily formed directly on a substrate such as plastic and does not deteriorate for a long time.
Claims (16)
前記加水分解生成物が、前記加水分解性基及び/又は水酸基を合計で2以上有する金属化合物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物、又は金属有機酸塩を、前記加水分解性基及び/又は水酸基を合計で2以上有する金属化合物、加水分解性基及び/又は水酸基を合計で2以上有する金属キレート化合物、又は金属有機酸塩1モルに対して、2モル以下の水を用いて加水分解した生成物であり、
前記金属がケイ素、ゲルマニウム、スズ、鉛、チタン、ジルコニウム、アルミニウム、インジウム、タンタル、タングステン及び亜鉛からなる群から選ばれる一種であるものから形成されてなるアモルファス状であり、150〜350nmの波長の光照射により光触媒活性を発揮することを特徴とする光触媒活性薄膜。A photocatalytically active thin film formed on a substrate, comprising a hydrolyzed product of a metal compound having a total of 2 or more hydrolyzable groups and / or hydroxyl groups, a metal having a total of 2 or more hydrolyzable groups and / or hydroxyl groups At least one selected from the group consisting of a hydrolysis product of a chelate compound and a hydrolysis product of a metal organic acid salt,
The hydrolysis product is a metal compound having two or more hydrolyzable groups and / or hydroxyl groups in total, a metal chelate compound having two or more hydrolyzable groups and / or hydroxyl groups, or a metal organic acid salt. 2 mol or less per 1 mol of the metal chelate compound having 2 or more hydrolysable groups and / or hydroxyl groups in total, or a metal chelate compound having 2 or more hydrolyzable groups and / or hydroxyl groups in total Product hydrolyzed with water of
Wherein the metal is silicon, germanium, tin, lead, titanium, zirconium, aluminum, indium, tantalum, amorphous consisting formed from what is one selected from the group consisting of tungsten and zinc, the wavelength of 150~350nm A photocatalytically active thin film that exhibits photocatalytic activity when irradiated with light.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006513741A JP5001003B2 (en) | 2004-05-21 | 2005-05-20 | Photocatalytically active thin film |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004151639 | 2004-05-21 | ||
JP2004151639 | 2004-05-21 | ||
PCT/JP2005/009248 WO2005113142A1 (en) | 2004-05-21 | 2005-05-20 | Photocatalytically active thin film |
JP2006513741A JP5001003B2 (en) | 2004-05-21 | 2005-05-20 | Photocatalytically active thin film |
Publications (2)
Publication Number | Publication Date |
---|---|
JPWO2005113142A1 JPWO2005113142A1 (en) | 2008-03-27 |
JP5001003B2 true JP5001003B2 (en) | 2012-08-15 |
Family
ID=35428285
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2006513741A Active JP5001003B2 (en) | 2004-05-21 | 2005-05-20 | Photocatalytically active thin film |
Country Status (2)
Country | Link |
---|---|
JP (1) | JP5001003B2 (en) |
WO (1) | WO2005113142A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100922093B1 (en) | 2005-02-18 | 2009-10-16 | 닛뽕소다 가부시키가이샤 | Organic-inorganic composite body |
JP2007237065A (en) * | 2006-03-08 | 2007-09-20 | Miyoshi Oil & Fat Co Ltd | Antimicrobial agent having photocatalytic activity and antimicrobial treatment method |
DE102006037270A1 (en) | 2006-08-09 | 2008-02-14 | Wacker Chemie Ag | Self-dispersible silicone copolymers and process for their preparation and their use |
US20210108339A1 (en) * | 2018-03-29 | 2021-04-15 | Toray Industries, Inc. | Method for producing metal oxide fibers, and metal oxide fibers |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003253157A (en) * | 2002-02-28 | 2003-09-10 | Furukawa Co Ltd | Coating solution of titania or titania-containing composite oxide excellent in storage stability |
-
2005
- 2005-05-20 JP JP2006513741A patent/JP5001003B2/en active Active
- 2005-05-20 WO PCT/JP2005/009248 patent/WO2005113142A1/en active Application Filing
Also Published As
Publication number | Publication date |
---|---|
WO2005113142A1 (en) | 2005-12-01 |
JPWO2005113142A1 (en) | 2008-03-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4602971B2 (en) | Photosensitive substrate and patterning method | |
JP5950399B2 (en) | Organic-inorganic transparent hybrid film and production method thereof | |
JP4746032B2 (en) | Dispersion of titanium oxide particles, titanium oxide thin film, organic functional film forming solution, organic functional film forming substrate, and method for producing the same | |
JP2008040171A (en) | Optical element with antireflection film having self-cleaning effect and method for manufacturing the same | |
JP2000336281A (en) | Organic/inorganic composite gradient material, and its preparation and use | |
WO2014136275A1 (en) | Organic/inorganic transparent hybrid coating film and process for producing same | |
WO2009051271A1 (en) | Photocatalytic film, method for production of photocatalytic film, article, and hydrophilization method | |
JP5001003B2 (en) | Photocatalytically active thin film | |
JP5377820B2 (en) | Organic-inorganic composite containing functional substances | |
JPWO2003072499A1 (en) | Titania nanosheet oriented thin film, manufacturing method thereof, and article provided with titania nanosheet oriented thin film | |
JP4738367B2 (en) | Water-based organic / inorganic composite composition | |
JP7148535B2 (en) | Nanoimprint lithography process and resulting patterned substrates | |
JP2017001327A (en) | Water-repellent member | |
JP2002346393A (en) | Photocatalyst and method for manufacturing the same | |
JP2000280397A (en) | Multilayer having titanium peroxide-containing titanium oxide film | |
JP6592897B2 (en) | Method for producing silica airgel membrane | |
JP5845676B2 (en) | Method for producing gas barrier film | |
JP4942053B2 (en) | Manufacturing method of high refractive index material | |
JP2013133264A (en) | Water-repellent substrate, method for producing the same, and transportation apparatus | |
JPH021307A (en) | Manufacture of organic and inorganic compound and inorganic hollow member | |
JP4225133B2 (en) | Photocatalyst sheet for resin surface modification, laminate and resin surface modification method | |
JP2002273234A (en) | Method for manufacturing photocatalytic body | |
JP5351378B2 (en) | Organic-inorganic composite and method for producing the same | |
JP2008006784A (en) | Super water-repellent material and its manufacturing method | |
JP4894124B2 (en) | Surface treatment method |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080401 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080530 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20081209 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090204 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20090507 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20090804 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20090817 |
|
A912 | Re-examination (zenchi) completed and case transferred to appeal board |
Free format text: JAPANESE INTERMEDIATE CODE: A912 Effective date: 20090904 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20120517 |
|
R150 | Certificate of patent or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 Ref document number: 5001003 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20150525 Year of fee payment: 3 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |