JP3844182B2 - Hydrophilic film and method for producing and using the same - Google Patents
Hydrophilic film and method for producing and using the same Download PDFInfo
- Publication number
- JP3844182B2 JP3844182B2 JP34300999A JP34300999A JP3844182B2 JP 3844182 B2 JP3844182 B2 JP 3844182B2 JP 34300999 A JP34300999 A JP 34300999A JP 34300999 A JP34300999 A JP 34300999A JP 3844182 B2 JP3844182 B2 JP 3844182B2
- Authority
- JP
- Japan
- Prior art keywords
- film
- water
- photocatalyst
- exposed
- amorphous silica
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 91
- 239000002344 surface layer Substances 0.000 claims description 44
- 239000011941 photocatalyst Substances 0.000 claims description 41
- 238000000576 coating method Methods 0.000 claims description 37
- 239000000758 substrate Substances 0.000 claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 239000011248 coating agent Substances 0.000 claims description 25
- 239000010410 layer Substances 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 19
- 238000004140 cleaning Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 230000001443 photoexcitation Effects 0.000 claims description 14
- 239000000356 contaminant Substances 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 230000004044 response Effects 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000962 organic group Chemical group 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000011241 protective layer Substances 0.000 claims description 2
- 230000001464 adherent effect Effects 0.000 claims 2
- 238000001035 drying Methods 0.000 claims 2
- 229920002050 silicone resin Polymers 0.000 claims 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 17
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 17
- 239000011521 glass Substances 0.000 description 13
- 239000005357 flat glass Substances 0.000 description 10
- 239000004033 plastic Substances 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 8
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 8
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 8
- 239000005642 Oleic acid Substances 0.000 description 8
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 8
- 229920003023 plastic Polymers 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 239000000428 dust Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 230000005284 excitation Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 238000009736 wetting Methods 0.000 description 5
- 239000003973 paint Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000002772 conduction electron Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000003851 corona treatment Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 229920000578 graft copolymer Polymers 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000006059 cover glass Substances 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- VLBIHEXPWXMGMA-UHFFFAOYSA-N CC(CC)O[Si](OCCC)(C)C=CC Chemical compound CC(CC)O[Si](OCCC)(C)C=CC VLBIHEXPWXMGMA-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 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
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- YSALUHGLIBYTET-UHFFFAOYSA-N benzyl(dibutoxy)silane Chemical compound CCCCO[SiH](OCCCC)CC1=CC=CC=C1 YSALUHGLIBYTET-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- MGQFVQQCNPBJKC-UHFFFAOYSA-N dibutoxy(diethyl)silane Chemical compound CCCCO[Si](CC)(CC)OCCCC MGQFVQQCNPBJKC-UHFFFAOYSA-N 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- BZCJJERBERAQKQ-UHFFFAOYSA-N diethyl(dipropoxy)silane Chemical compound CCCO[Si](CC)(CC)OCCC BZCJJERBERAQKQ-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 239000010459 dolomite Substances 0.000 description 1
- 229910000514 dolomite Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- KUCGHDUQOVVQED-UHFFFAOYSA-N ethyl(tripropoxy)silane Chemical compound CCCO[Si](CC)(OCCC)OCCC KUCGHDUQOVVQED-UHFFFAOYSA-N 0.000 description 1
- 235000013611 frozen food Nutrition 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 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
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 230000007246 mechanism 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
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-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
- 238000011282 treatment Methods 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-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
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F8/00—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying
- F24F8/20—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation
- F24F8/22—Treatment, e.g. purification, of air supplied to human living or working spaces otherwise than by heating, cooling, humidifying or drying by sterilisation using UV light
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/02—Coatings; Surface treatments hydrophilic
Description
【0001】
【発明の属する技術分野】
本発明は、基材の表面を高度の親水性になし、かつ維持するためのフィルムに関する。より詳しくは、本発明は、鏡、レンズ、ガラス、プリズムその他の透明基材の表面を高度に親水化することにより、基材の曇りや水滴形成を防止する防曇性フィルムに関する。本発明は、また、建物や窓ガラスや機械装置や物品の表面を高度に親水化することにより、表面が汚れるのを防止し、又は表面を自己浄化(セルフクリーニング)し若しくは容易に清掃することの可能なフィルムに関する。
【0002】
【従来の技術】
寒冷時に自動車その他の乗物の風防ガラスや窓ガラス、建物の窓ガラス、眼鏡やゴーグルのレンズ、及び各種計器盤のカバーガラスが凝縮湿分で曇るのはしばしば経験されることである。また、浴室や洗面所の鏡や眼鏡のレンズが湯気で曇ることも良く遭遇される。更に、車両の風防ガラスや窓ガラス、建物の窓ガラス、眼鏡やゴーグルのレンズ、マスクやヘルメットのシールドが降雨や水しぶきを受け、離散した多数の水滴が表面に付着すると、それらの表面は翳り、ぼやけ、斑模様になり、或いは曇り、やはり可視性が失われる。ここで用いる“防曇”の用語は、このような曇りや凝縮水滴の成長や水滴の付着による光学的障害を防止する技術を広く意味する。言うまでもなく、上記“曇り”は安全性や種々の作業の能率に深い影響を与える。例えば、車両の風防ガラスや窓ガラス、バックミラーが寒冷時や雨天に翳り、ぼやけ、斑模様になり、或いは曇ると、視界の確保が困難となり、交通の安全性が損なわれる。内視鏡レンズやデンタルミラーが曇ると、的確な診断、手術、処置の障害となる。計器盤のカバーガラスが曇ると、データの読みが困難となる。
【0003】
周知のように、従来用いられている防曇方法は、ポリエチレングリコールのような親水性化合物或いはシリコーンのような撥水性化合物を含んだ防曇性組成物を表面に塗布することである。しかし、この種の防曇性被膜はあくまで一時的なもので、水洗や接触によって容易に取除かれ、早期に効果を失うという難点がある。
【0004】
他方、建築及び塗料の分野においては、環境汚染に伴い、建築外装材料や屋外建造物やその塗膜の汚れが問題となっている。大気中に浮遊する煤塵や粒子は晴天には建物の屋根や外壁に堆積する。堆積物は降雨に伴い雨水により流され、建物の外壁を流下する。更に、雨天には浮遊煤塵は雨によって持ち運ばれ、建物の外壁や屋外建造物の表面を流下する。その結果、表面には、雨水の道筋に沿って汚染物質が付着する。表面が乾燥すると、表面には縞状の汚れが現れる。建築外装材料や塗膜の汚れは、カーボンブラックのような燃焼生成物や、都市煤塵や、粘土粒子のような無機質物質の汚染物質からなる。このような汚染物質の多様性が防汚対策を複雑にしているものと考えられている(橘高義典著、“外壁仕上材料の汚染の促進試験方法”、日本建築学会構造系論文報告集、第404号、1989年10月、p.15−24)。
【0005】
従来の通念では、上記建築外装などの汚れを防止するためにはポリテトラフルオロエチレン(PTFE)のような撥水性の塗料が好ましいと考えられていたが、最近では、疎水性成分を多く含む都市煤塵に対しては、塗膜の表面をできるだけ親水性にするのが望ましいと考えられている(高分子、44巻、1995年5月号、p.307)。そこで、親水性のグラフトポリマーで建物を塗装することが提案されている(新聞“化学工業日報”1995年1月30日)。報告によれば、この塗膜は水との接触角に換算して30〜40゜の親水性を呈する。しかしながら、粘土鉱物で代表される無機質塵埃の水との接触角は20゜から50゜であり、水との接触角が30〜40゜のグラフトポリマーに対して親和性を有しその表面に付着しやすいので、このグラフトポリマーの塗膜は無機質塵埃による汚れを防止することができないと考えられる。
【0006】
【発明の解決すべき課題】
上記の如く、基材表面を親水性にすることにより、基材の曇りや水滴形成を防止したり、また、建物や窓ガラスや機械装置や物品の表面が汚れるのを防止し、又は表面を自己浄化(セルフクリーニング)し若しくは容易に清掃することができる提案は存在するものの、表面を高度の親水性に長期にわたり維持できないため、その効果は充分でなかった。そこで、本発明では、上記事情に鑑み、基材表面に貼着させるだけで、基材表面を長期にわたり高度の親水性に維持できるフィルム、及びその製造方法、使用方法を提供することを目的とする。
【0007】
【課題を解決するための手段】
本発明は、光触媒を含有する表面層を形成した部材において、光触媒を光励起すると、部材の表面が高度に親水化されるという発見に基づく。この現象は以下に示す機構により進行すると考えられる。すなわち、光触媒の価電子帯上端と伝導帯下端とのエネルギーギャップ以上のエネルギーを有する光が光触媒に照射されると、光触媒の価電子帯中の電子が励起されて伝導電子と正孔が生成し、そのいずれかまたは双方の作用により、おそらく表面に極性が付与され、水や水酸基等の極性成分が集められる。そして伝導電子と正孔のいずれかまたは双方と、上記極性成分との協調的な作用により、表面と前記表面に化学的に吸着した汚染物質との化学結合を切断すると共に、表面に化学吸着水が吸着し、さらに物理吸着水層がその上に形成されるのである。また、一旦部材表面が高度に親水化されたならば、部材を暗所に保持しても、表面の親水性はある程度の期間持続する。
【0008】
本発明では、フィルム基体表面に、光触媒粒子を含有する表面層を備えた親水性フィルムを提供する。光触媒を含有する表面層を備えることにより、光触媒の光励起に応じて、恒久的に表面層の表面は高度の親水性を呈するようになる。透明な表面が高度の親水性を呈するようになると、付着した湿分の凝縮水及び/又は水滴が前記層の表面に一様に広がり、湿分凝縮水及び/又は水滴によって曇り若しくは翳るのが防止されるようになり、可視性が失われるのが防止される。また、表面が高度の親水性を呈するようになると、表面が降雨にさらされた時に、付着堆積物及び/又は汚染物が雨滴により洗い流せるようになり、降雨によるセルフクリーニングが可能となる。さらに、表面が高度の親水性を呈するようになると、表面が水濯ぎや簡単な水拭き程度で洗浄できるようになり、水洗浄が容易になる。
【0009】
本発明の好ましい態様においては、表面層には、さらにシリカが含有されているようにする。シリカが含有されることにより、表面が水濡れ角0゜に近い高度の親水性を呈しやすくなると共に、暗所に保持したときの親水維持性が向上する。その理由はシリカは構造中に水を蓄えることができることと関係していると思われる。
【0010】
本発明の好ましい態様においては、表面層には、さらにシリコーンが含有されているようにする。シリコーンが含有されることにより、光触媒の光励起によって、シリコーン中のシリコン原子に結合する有機基の少なくとも一部が水酸基に置換され、さらにその上に物理吸着水層が形成されることにより、表面が水濡れ角0゜に近い高度の親水性を呈するようになると共に、暗所に保持したときの親水維持性が向上する。
【0011】
【発明の実施の形態】
次に、本発明の具体的な構成について説明する。本発明における親水性フィルム表面には、図1又は図2に示すように、基材の表面に光触媒を含む層が形成されている。このような表面構造をとることで、親水性フィルム表面は、光触媒の光励起に応じて高度に親水化されるのである。それにより、雰囲気の湿分が凝縮して付着しても水滴状には成長せず、一様に水膜化するようになり、湿分凝縮水及び/又は水滴によって曇り若しくは翳るのが防止される。また、表面が降雨にさらされた時に、付着堆積物及び/又は汚染物が雨滴により洗い流せるようになり、降雨によるセルフクリーニングが可能となる。さらに、表面が高度の親水性を呈するようになると、表面が水濯ぎや簡単な水拭き程度で洗浄できるようになり、水洗浄が容易になる。
【0012】
図1においては、表面層が光触媒のみからなる場合には、光触媒は酸化物であることが好ましい。そうすることにより、酸化物は環境中の汚染物質が吸着していない状態では親水性を示すので、光励起作用によりその汚染物質を排斥させ、吸着水層を形成させることで、親水性を呈しやすく、一様な水膜が形成できる。図2において、Mは金属元素を示す。従って、図2の場合、最表面は一般の無機酸化物からなる。この場合も、酸化物は環境中の汚染物質が吸着していない状態では親水性を示すので、上記無機酸化物以外に表面層に混入する光触媒性酸化チタンの光励起作用によりその汚染物質を排斥させ、吸着水層を形成させることで、一様な水膜が形成できる。
【0013】
本発明におけるフィルム基体には、ポリエチレンテレフタレート、塩化ビニル、ポリエチレン等のプラスチック、プラスチック基材の上に透明なハードコートを設けたプラスチック等が好適に利用できる。また、場合によって、これらの基体は飛散防止、意匠付与、耐蝕等の他の機能を兼備えることもできる。
【0014】
また、本発明におけるフィルムは種々の基材に適用できる。本発明におけるフィルムが適用可能な基材としては、上記防曇効果を期待する場合には透明な基材であり、その材質はガラス、透明プラスチック等の基材に好適に利用できる。適用可能な基材を用途でいえば、車両用バックミラー、浴室用鏡、洗面所用鏡、歯科用鏡、道路鏡のような鏡;眼鏡レンズ、光学レンズ、写真機レンズ、照明用レンズ、レーザー光集束レンズ、半導体用レンズ、複写機用レンズのようなレンズ;プリズム;建物や監視塔の窓ガラス;自動車、鉄道車両、航空機、船舶、潜水艇、雪上車、ロープウエイのゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の窓ガラス;自動車、鉄道車両、オートバイ、航空機、船舶、潜水艇、雪上車、ロープウエイのゴンドラ、遊園地のゴンドラ、宇宙船のような乗物の風防ガラス;防護用ゴーグル、スポーツ用ゴーグル、防護用マスクのシールド、スポーツ用マスクのシールド、ヘルメットのシールド、冷凍食品陳列ケースのガラス;計測機器のカバーガラスなどに好適に利用できる。本発明におけるフィルムが適用可能な基材としては、上記表面清浄化効果を期待する場合には、その材質は、例えば、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、それらの組合せ、それらの積層体が好適に利用できる。適用可能な基材を用途でいえば、建材、建物外装、建物内装、窓枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装置や物品の外装、防塵カバー及び塗装、交通標識、各種表示装置、広告塔、道路用防音壁、鉄道用防音壁、橋梁、ガードレールの外装及び塗装、トンネル内装及び塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー、ビニールハウス、車両用照明灯のカバー、住宅設備、便器、浴槽、洗面台、照明器具、照明カバー、台所用品、食器、食器洗浄器、食器乾燥器、流し、調理レンジ、キッチンフード、換気扇などに好適に利用できる。本発明におけるフィルムは、長期にわたり高度の親水性を維持することができるので、帯電防止機能も期待できる。帯電防止効果を期待する場合には、その材質は、例えば、金属、セラミックス、ガラス、プラスチック、木、石、セメント、コンクリート、繊維、布帛、それらの組合せ、それらの積層体が好適に利用できる。適用可能な基材を用途でいえば、ブラウン管、磁気記録メディア、光記録メディア、光磁気記録メディア、オーディオテープ、ビデオテープ、アナログレコード、家庭用電気製品のハウジングや部品や外装及び塗装、OA機器製品のハウジングや部品や外装及び塗装、建材、建物外装、建物内装、窓枠、窓ガラス、構造部材、乗物の外装及び塗装、機械装置や物品の外装、防塵カバー及び塗装などに好適に利用できる。
【0015】
光触媒とは、その結晶の伝導帯と価電子帯との間のエネルギーギャップよりも大きなエネルギー(すなわち短い波長)の光(励起光)を照射したときに、価電子帯中の電子の励起(光励起)が生じて、伝導電子と正孔を生成しうる物質をいい、例えば、アナターゼ型酸化チタン、ルチル型酸化チタン、酸化錫、酸化亜鉛、三酸化二ビスマス、三酸化タングステン、酸化第二鉄、チタン酸ストロンチウム等が好適に利用できる。ここで光触媒の光励起に用いる光源としては、太陽光、一般室内照明等の環境にある光源を利用してもよいし、付属設備や携帯設備として励起光を照射しうる光源を使用してもよい。さらに、本発明のプラスチックレンズ又はプラスチックレンズを備えた眼鏡或いはプラスチックレンズを備えたゴーグル専用の保管容器を設け、そこに励起光を照射しうる光源を設置してもよい。その場合使用する光源には、例えば、白熱電灯、メタルハライドランプ、水銀ランプ、キセノンランプ、殺菌灯、蛍光灯等が好適に利用できる。光触媒の光励起により、基材表面が高度に親水化されるためには、励起光の照度は、0.001mW/cm2以上あればよいが、0.01mW/cm2以上だと好ましく、0.1mW/cm2以上だとより好ましい。
【0016】
光触媒を含有する表面層の膜厚は、0.4μm以下にするのが好ましい。そうすれば、光の乱反射による白濁を防止することができ、表面層は実質的に透明となる。さらに、光触媒を含有する表面層の膜厚を0.2μm以下にすると一層好ましい。そうすれば、光の干渉による表面層の発色を防止することができる。また、表面層が薄ければ薄いほどその透明度は向上する。更に、膜厚を薄くすれば、表面層の耐摩耗性が向上する。上記表面層の表面に、更に、親水化可能な耐摩耗性又は耐食性の保護層や他の機能膜を設けても良い。
【0017】
上記表面層は、基材と比較して屈折率があまり高くないのが好ましい。好ましくは表面層の屈折率は2以下であるのがよい。そうすれば、基材と表面層との界面、及び表面層と空気との界面における光の反射を抑制できる。表面層の屈折率を2以下にするには、光触媒に2以下の屈折率を有する物質を用いるか、或いは光触媒が屈折率2以上の場合には、屈折率2以下の他の物質を表面層に添加する。2以下の屈折率を有する光触媒としては、酸化錫(屈折率1.9)等が利用できる。2以上の屈折率を有する光触媒には、アナターゼ型酸化チタン(屈折率2.5)やルチル型酸化チタン(屈折率2.7)があるが、この場合には屈折率2以下の他の物質、例えば、炭酸カルシウム(屈折率1.6)、水酸化カルシウム(屈折率1.6)、炭酸マグネシウム(屈折率1.5)、炭酸ストロンチウム(屈折率1.5)、ドロマイト(屈折率1.7)、フッ化カルシウム(屈折率1.4)、フッ化マグネシウム(屈折率1.4)、シリカ(屈折率1.5)、アルミナ(屈折率1.6)、ケイ砂(屈折率1.6)、モンモリロナイト(屈折率1.5)、カオリン(屈折率1.6)、セリサイト(屈折率1.6)、ゼオライト(屈折率1.5)、酸化錫(屈折率1.9)等を表面層に添加すればよい。
【0018】
上記表面層には、Ag、Cu、Znのような金属を添加することができる。前記金属を添加した表面層は、表面に付着した細菌や黴を暗所でも死滅させることができる。
【0019】
上記表面層には、Pt、Pd、Ru、Rh、Ir、Osのような白金族金属を添加することができる。前記金属を添加した表面層は、光触媒の酸化還元活性を増強でき、脱臭浄化作用等が向上する。
【0020】
親水性とは、表面に水を滴下したときになじみやすい性質をいい、一般に水濡れ角が90゜未満の状態をいう。本発明における高度の親水性とは、表面に水を滴下したときに非常になじみやすい性質をいい、より具体的には平滑表面における水濡れ角が10゜以下程度になる状態をいう。特に、防曇性にはPCT/JP96/00734に開示したように、水濡れ角が10゜以下であると好ましく、5゜以下ではより好ましい。
【0021】
次に、フィルム上への光触媒含有表面層の形成方法について、表面層が光触媒とシリカからなる場合、表面層が光触媒とシリコーンからなる場合を例にとり説明する。まず、表面層が光触媒とシリカからなる場合について、光触媒がアナターゼ型酸化チタンの場合を例にとり説明する。この場合は、基本的には、無定型シリカの前駆体を塗膜形成要素とし、塗膜形成要素をアナターゼ型酸化チタン粒子とともにフィルム基材上にスプレーコーティング法、ディップコーティング法、フローコーティング法、スピンコーティング法、ロールコーティング法等の方法で塗布後、塗膜形成要素の硬化反応により、無定型シリカを生成するとともに、アナターゼ型酸化チタン粒子を無定型シリカを結着剤として固着させる。ここで、塗膜形成要素をアナターゼ型酸化チタン粒子とともに塗布する前に、フィルム基材上にプライマー層やハードコート層、或いはその双方といった中間層を形成するようにしてもよい。このようにすることで、フィルム基材と表面層との密着性を向上させることができる。また、ここで無定型シリカの前駆体には、テトラアルコキシシラン(テトラエトキシシラン、テトラプロポキシシラン、テトラブトキシシラン、テトラメトキシシラン等)、その部分加水分解、脱水縮重合物である平均組成式(OR)xSiOy(0<x≦4、0≦y<2)(Rはアルキル基)からなる4官能性シロキサン樹脂、シラノール、その脱水縮重合物であるシラノール樹脂等の塗膜形成要素が好適に利用できる。このうち、保管安定性が良く、常温で硬化反応を生じさせることが容易であることから、平均組成式(OR)xSiOy(0<x≦4、0≦y<2)(Rはアルキル基)からなる4官能性シロキサン樹脂を使用するのが最も好ましい。上記と同様の理由で、中間層を形成する場合にも、中間層の成分に平均組成式(OR)xSiOy(0<x≦4、0≦y<2)(Rはアルキル基)からなる4官能性シロキサン樹脂を使用すると、保管安定性が良く、常温で硬化反応を生じさせることが容易であることから好ましい。特に常温で硬化反応を生じさせることができると、例えば基材が塩化ビニルフィルムのように耐熱性のない場合に都合がよい。塗膜形成要素の硬化反応は、例えば、無定型シリカの前駆体を水又は空気中の湿分と接触させることにより加水分解反応させた後、加熱、紫外線照射、室温放置等の方法により脱水縮重合反応させることにより行う。
【0022】
次に、表面層が光触媒とシリコーンからなる場合について、光触媒がアナターゼ型酸化チタンの場合を例にとり説明する。この場合の方法は、未硬化の若しくは部分的に硬化したシリコーン又はシリコーンの前駆体からなる塗料とアナターゼ型酸化チタンゾルとを混合し、シリコーンの前駆体を必要に応じて加水分解させた後、混合物を基材の表面にスプレーコーティング法、ディップコーティング法、フローコーティング法、スピンコーティング法、ロールコーティング法等の方法で塗布し、加熱等の方法でシリコーンの前駆体の加水分解物を脱水縮重合に付して、アナターゼ型酸化チタン粒子とシリコーンからなる表面層を形成する。形成された表面層は、紫外線を含む光の照射によりアナターゼ型酸化チタンが光励起されることにより、シリコーン分子中のケイ素原子に結合した有機基の少なくとも一部を水酸基に置換され、さらにその上に物理吸着水層が形成されて、高度の親水性を呈する。ここでシリコーンの前駆体には、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリブトキシシラン、メチルトリプロポキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリブトキシシラン、エチルトリプロポキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、フェニルトリブトキシシラン、フェニルトリプロポキシシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジメチルジブトキシシラン、ジメチルジプロポキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジエチルジブトキシシラン、ジエチルジプロポキシシラン、フェニルメチルジメトキシシラン、フェニルメチルジエトキシシラン、フェニルメチルジブトキシシラン、フェニルメチルジプロポキシシラン、γ−グリシドキシプロピルトリメトキシシラン、及びそれらの加水分解物、それらの混合物が好適に利用できる。
【0023】
【実施例】
実施例1.
10cm角のポリエチレンテレフタレートフィルム上にプライマー塗料(信越シリコーン、PC−7A)をフローコーティング法にて塗布後、120℃で20分乾燥させて、基板をプライマー樹脂層で被覆した。次に、シリコーン系ハードコーティング剤(信越シリコーン、KP−85)をフローコーティング法にて塗布後、120℃で60分乾燥させて、ハードコート層を形成した。次に、ハードコート層をコロナ放電処理した後、酸化チタン含有塗料組成物(アナターゼ型酸化チタンゾル(日産化学、TA−15、固形分15重量%)16重量部とシリカゾル(日本合成ゴム、グラスカA液、固形分13重量%)9重量部を混合し、エタノール希釈後、更にトリメトキシシラン3重量部(日本合成ゴム、グラスカB液)を添加したもの)をフローコーティング法にて塗布後、120℃で30分熱処理して硬化させ、試料を得た。この試料を数日間暗所に放置した後、紫外線光源(三共電気、ブラックライトブルー(BLB)蛍光灯)を用いて試料の表面に0.5mW/cm2の紫外線照度で約2日紫外線を照射し、#1試料を得た。比較のため、10cm角のポリエチレンテレフタレートフィルムを数日間暗所に放置した#2試料も準備した。まず、#1試料と#2試料に水滴を滴下し、滴下後の様子の観察及び水との接触角の測定を行った。ここで水との接触角は接触角測定器(協和界面科学、CA−X150)を用い、滴下後30秒後の水との接触角で評価した。その結果#1試料はマイクロシリンジから試料表面に水滴を滴下されると、水滴が一様に水膜状に試料表面を拡がる様子が観察された。また、30秒後の水との接触角は約0゜まで高度に親水化された。それに対し、#2試料ではマイクロシリンジから試料表面に水滴を滴下されると、水滴は表面にほとんどなじまず、一様に水膜状になるまでには至らなかった。30秒後の水との接触角は約70゜であった。次に、#1試料と#2試料に息を吹きかけ曇り発生の有無を調べた。その結果#2試料では曇りが生じたのに対し、#1試料では曇りは生じなかった。さらに、#1試料を、その後1週間暗所に放置し、#3試料を得た。そして#3試料について、同様に水滴を滴下し、滴下後の様子の観察及び水との接触角の測定を行った。その結果、#3試料にマイクロシリンジから試料表面に水滴を滴下されると、#1試料と同様に、水滴が一様に水膜状に試料表面を拡がる様子が観察された。30秒後の水との接触角は約2゜に維持された。次に#3試料について息を吹きかけた後の曇り発生の有無を観察した。その結果、曇りは観察されなかった。
【0024】
次に、#3試料の裏側にセッケン水を塗布し、10cm角のガラス基材に貼着した。次いで、BLB蛍光灯を用いて試料の表面に0.5mW/cm2の紫外線照度で約1時間紫外線を照射し、#4試料を得た。比較のため、#2試料の裏側にセッケン水を塗布し、10cm角のガラス基材に貼着した。次いで、BLB蛍光灯を用いて試料の表面に0.5mW/cm2の紫外線照度で約1時間紫外線を照射し、#5試料を得た。#4試料、#5試料の夫々の表面にオレイン酸を塗布し、試料表面を水平姿勢に保持しながら夫々の試料を水槽に満たした水の中に浸漬した。その結果、#5試料では、オレイン酸は表面に付着したままであり、軽くこすってもオレイン酸は試料表面を伸びるだけであった。それに対し、#4試料では、オレイン酸は丸くなり、軽くこすると表面から離脱した。従って、#4試料では、#5試料に比較して水洗浄が容易であると考えられる。疎水性カーボンブラック1重量部、親水性カーボンブラック1重量部からなる粉体混合物を1.05g/リッターの濃度で水に懸濁させたスラリーを調製した。45度に傾斜させた#4試料、#5試料に上記スラリー150mlを流下させて15分間乾燥させ、次いで蒸留水150mlを流下させて15分間乾燥させ、このサイクルを25回反復した。試験前後の色差変化を、色差計(東京電色)を用いて計測した。色差は日本工業規格(JIS)H0201に従い、ΔE*表示を用いて評価した。その結果、#5試料では色差変化が20と大きかったのに対し、#4試料では色差変化は0.4と非常に小さかった。
【0025】
実施例2.(常温硬化法)
10cm角のポリエチレンテレフタレートフィルムをコロナ放電処理した後、エチルシリケート5量体相当品(コルコート、エチルシリケート40)30重量部とメチルアルコール23.5重量部を、30℃の恒温槽に入れたビーカー中で混合した。これにイオン交換水45重量部と60%硝酸1.5重量部の混合液を添加し、30℃に保持したまま5時間加水分解させて、中間コーティング液を調製した。この中間コーティング液をコロナ放電処理したプライマー樹脂上にフローコーティング法にて塗布し、常温で10分乾燥させて、中間層を形成した。次に、中間層をコロナ放電処理した後、光触媒コーティング液(石原産業のST−K01とST−K03を1:1で混合後、アルコールで希釈することにより作製した、アナターゼ型酸化チタン粒子とテトラアルコキシシランの部分加水分解物であるアルキルシリケートを13:7で含むコーティング液)をフローコーティング法にて塗布し、常温で10分乾燥させて、光触媒含有表面層を形成した。形成面の水との接触角は5゜であった。また、形成面についてテープ剥離試験(セロファンテープを塗膜表面の片端から他端にわたって貼着した後、素早く剥したときに、塗膜が剥れるか否かを評価する試験)を調べた。その結果、外観に変化はなかった。また試験後の水との接触角も5゜であった。この試料を数日間暗所に放置した後、BLB蛍光灯を用いて試料の表面に0.5mW/cm2の紫外線照度で約2日紫外線を照射し、#6試料を得た。比較のため、10cm角のポリエチレンテレフタレートフィルムを数日間暗所に放置した実施例1と同様の#2試料も準備した。まず、#6試料と#2試料に水滴を滴下し、滴下後の様子の観察及び水との接触角の測定を行った。その結果#6試料はマイクロシリンジから試料表面に水滴を滴下されると、水滴が一様に水膜状に試料表面を拡がる様子が観察された。また、30秒後の水との接触角は約0゜まで高度に親水化された。それに対し、#2試料ではマイクロシリンジから試料表面に水滴を滴下されると、水滴は表面にほとんどなじまず、一様に水膜状になるまでには至らなかった。30秒後の水との接触角は約70゜であった。次に、#6試料と#2試料に息を吹きかけ曇り発生の有無を調べた。その結果#2試料では曇りが生じたのに対し、#6試料では曇りは生じなかった。
【0026】
次に、#6試料の裏側にセッケン水を塗布し、10cm角のガラス基材に貼着した。次いで、BLB蛍光灯を用いて試料の表面に0.5mW/cm2の紫外線照度で約1時間紫外線を照射し、#7試料を得た。比較のため、実施例1と同様に、#2試料の裏側にセッケン水を塗布し、10cm角のガラス基材に貼着し、次いで、BLB蛍光灯を用いて試料の表面に0.5mW/cm2の紫外線照度で約1時間紫外線を照射し、#5試料を得た。#7試料、#5試料の夫々の表面にオレイン酸を塗布し、試料表面を水平姿勢に保持しながら夫々の試料を水槽に満たした水の中に浸漬した。その結果、#5試料では、オレイン酸は表面に付着したままであり、軽くこすってもオレイン酸は試料表面を伸びるだけであった。それに対し、#7試料では、オレイン酸は丸くなり、軽くこすると表面から離脱した。従って、#7試料では、#5試料に比較して水洗浄が容易であると考えられる。疎水性カーボンブラック1重量部、親水性カーボンブラック1重量部からなる粉体混合物を1.05g/リッターの濃度で水に懸濁させたスラリーを調製した。45度に傾斜させた#7試料、#5試料に上記スラリー150mlを流下させて15分間乾燥させ、次いで蒸留水150mlを流下させて15分間乾燥させ、このサイクルを25回反復した。試験前後の色差変化を、色差計(東京電色)を用いて計測した。色差は日本工業規格(JIS)H0201に従い、ΔE*表示を用いて評価した。その結果、#5試料では色差変化が20と大きかったのに対し、#7試料では色差変化は0.4と非常に小さかった。
【0027】
【発明の効果】
本発明では、フィルム基体表面に、光触媒性酸化チタン粒子を含有する表面層を備えることにより、光触媒の光励起に応じて、表面層の表面は親水性を呈する。それにより、このフィルムを貼着するだけで、透明基材表面の曇り等が防止されて視界確保性が向上する。また、降雨により基材表面がセルフクリーニングされるようになる。さらに、基材表面が水により容易に洗浄されるようになる。
【図面の簡単な説明】
【図1】 本発明に係るフィルムの表面構造を示す図。
【図2】 本発明に係るフィルムの他の表面構造を示す図。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a film for making and maintaining the surface of a substrate highly hydrophilic. More specifically, the present invention relates to an antifogging film that prevents fogging or water droplet formation on a substrate by highly hydrophilizing the surface of a transparent substrate such as a mirror, lens, glass, prism or the like. The present invention also prevents the surface from becoming dirty by highly hydrophilizing the surface of buildings, window glass, mechanical devices and articles, or self-cleans or cleans the surface easily. Relating to possible films.
[0002]
[Prior art]
It is often experienced that windshields and window glass of automobiles and other vehicles, window glass of buildings, lenses of glasses and goggles, and cover glass of various instrument panels are fogged with condensed moisture during cold weather. In addition, it is often encountered that the mirrors in bathrooms and bathrooms and the lenses of spectacles become cloudy with steam. In addition, when windshields and window glass of vehicles, window glass of buildings, lenses of glasses and goggles, shields of masks and helmets are subjected to rain and splashing, and a large number of discrete water droplets adhere to the surface, those surfaces will swell, Blurred, mottled, or cloudy and again loses visibility. As used herein, the term “anti-fogging” broadly means a technique for preventing such haze, growth of condensed water droplets, and optical failure due to adhesion of water droplets. Needless to say, the above “cloudiness” has a profound effect on safety and efficiency of various operations. For example, when the windshield glass, window glass, and rearview mirror of a vehicle are cold, rainy, blurred, mottled, or cloudy, it becomes difficult to ensure visibility and traffic safety is impaired. If the endoscope lens or dental mirror becomes cloudy, it will hinder accurate diagnosis, surgery, and treatment. If the cover glass of the instrument panel is fogged, it will be difficult to read the data.
[0003]
As is well known, a conventionally used antifogging method is to apply an antifogging composition containing a hydrophilic compound such as polyethylene glycol or a water repellent compound such as silicone to the surface. However, this type of anti-fogging film is only temporary, and is easily removed by washing and contact, and has a drawback that it loses its effect at an early stage.
[0004]
On the other hand, in the field of architecture and paint, contamination of building exterior materials, outdoor buildings and coating films has become a problem with environmental pollution. Dust and particles floating in the atmosphere accumulate on the roof and outer walls of buildings in fine weather. Sediment is washed away by rainwater along with the rain and flows down the outer wall of the building. Furthermore, in the rainy weather, suspended dust is carried by the rain and flows down the outer wall of the building and the surface of the outdoor building. As a result, contaminants adhere to the surface along the rainwater path. As the surface dries, striped stains appear on the surface. The dirt on building exterior materials and coatings consists of combustion products such as carbon black, urban dust, and inorganic contaminants such as clay particles. Such diversity of pollutants is considered to complicate anti-fouling measures (Yoshinori Tachibana, “Promotion test method for contamination of exterior wall finishing materials”, Architectural Institute of Japan, Proceedings of Structural Papers, No. 1 404, October 1989, p. 15-24).
[0005]
Conventional wisdom has been that water-repellent paints such as polytetrafluoroethylene (PTFE) have been considered preferable to prevent dirt on the exterior of the building, but recently, cities that contain a large amount of hydrophobic components. For dust, it is considered desirable to make the surface of the coating as hydrophilic as possible (Polymer, Vol. 44, May 1995, p. 307). Therefore, it has been proposed to paint buildings with hydrophilic graft polymers (Newspaper “Chemical Industry Daily”, January 30, 1995). According to reports, this coating film exhibits a hydrophilicity of 30 to 40 ° in terms of a contact angle with water. However, the contact angle with water of inorganic dust typified by clay minerals is 20 ° to 50 °, and it has an affinity for graft polymers with a contact angle with water of 30 to 40 ° and adheres to the surface. Therefore, it is considered that this graft polymer coating film cannot prevent contamination by inorganic dust.
[0006]
Problems to be Solved by the Invention
As described above, by making the substrate surface hydrophilic, it is possible to prevent the substrate from fogging and forming water droplets, to prevent the surface of buildings, window glass, mechanical devices and articles from becoming dirty, or Although there are proposals that can be self-cleaning (self-cleaning) or easily cleaned, the effect is not sufficient because the surface cannot be maintained at a high degree of hydrophilicity for a long time. Therefore, in the present invention, in view of the above circumstances, an object is to provide a film that can maintain a high degree of hydrophilicity for a long period of time just by adhering to the surface of the base material, a manufacturing method thereof, and a usage method. To do.
[0007]
[Means for Solving the Problems]
The present invention is based on the discovery that in a member in which a surface layer containing a photocatalyst is formed, when the photocatalyst is photoexcited, the surface of the member is highly hydrophilized. This phenomenon is considered to proceed by the mechanism shown below. That is, when the photocatalyst is irradiated with light having energy greater than the energy gap between the upper end of the valence band and the lower end of the conduction band of the photocatalyst, electrons in the valence band of the photocatalyst are excited to generate conduction electrons and holes. By the action of either or both of them, polarity is probably imparted to the surface, and polar components such as water and hydroxyl groups are collected. Then, by a cooperative action of either or both of conduction electrons and holes and the polar component, the chemical bond between the surface and the contaminant chemically adsorbed on the surface is cut, and the chemically adsorbed water on the surface. Is adsorbed, and a physical adsorption water layer is formed thereon. Further, once the surface of the member is highly hydrophilized, the hydrophilicity of the surface lasts for a certain period of time even if the member is held in a dark place.
[0008]
In this invention, the hydrophilic film provided with the surface layer containing a photocatalyst particle on the film base | substrate surface is provided. By providing a surface layer containing a photocatalyst, the surface of the surface layer permanently exhibits a high degree of hydrophilicity in response to photoexcitation of the photocatalyst. When the transparent surface becomes highly hydrophilic, the adhering moisture condensate and / or water droplets will spread evenly over the surface of the layer and will be clouded or smeared by the moisture condensate and / or water droplets. Is prevented, and loss of visibility is prevented. In addition, when the surface becomes highly hydrophilic, when the surface is exposed to rain, the deposited deposits and / or contaminants can be washed away by raindrops, and self-cleaning due to rain becomes possible. Furthermore, when the surface exhibits a high degree of hydrophilicity, the surface can be cleaned with water rinsing or simple water wiping, and water cleaning becomes easy.
[0009]
In a preferred embodiment of the present invention, the surface layer further contains silica. By containing silica, the surface tends to exhibit a high degree of hydrophilicity close to a water wetting angle of 0 °, and the hydrophilicity retention when held in a dark place is improved. The reason seems to be related to the fact that silica can store water in its structure.
[0010]
In a preferred embodiment of the present invention, the surface layer further contains silicone. By containing silicone, at least a part of the organic group bonded to the silicon atom in the silicone is substituted with a hydroxyl group by photoexcitation of the photocatalyst, and a physical adsorption water layer is formed thereon, whereby the surface is It exhibits a high degree of hydrophilicity close to a water wetting angle of 0 °, and improves hydrophilicity retention when kept in a dark place.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
Next, a specific configuration of the present invention will be described. As shown in FIG. 1 or 2, a layer containing a photocatalyst is formed on the surface of the substrate on the hydrophilic film surface in the present invention. By taking such a surface structure, the hydrophilic film surface is highly hydrophilized in response to photoexcitation of the photocatalyst. As a result, even if moisture in the atmosphere condenses and adheres, it does not grow in the form of water droplets, but forms a uniform water film, and is prevented from being clouded or fogged by moisture condensed water and / or water droplets. The Further, when the surface is exposed to rain, the deposited deposits and / or contaminants can be washed away by raindrops, and self-cleaning due to rain becomes possible. Furthermore, when the surface exhibits a high degree of hydrophilicity, the surface can be cleaned with water rinsing or simple water wiping, and water cleaning becomes easy.
[0012]
In FIG. 1, when a surface layer consists only of a photocatalyst, it is preferable that a photocatalyst is an oxide. By doing so, the oxide exhibits hydrophilicity in a state where the environmental pollutants are not adsorbed. Therefore, it is easy to exhibit hydrophilicity by eliminating the pollutants by photoexcitation and forming an adsorbed water layer. A uniform water film can be formed. In FIG. 2, M represents a metal element. Therefore, in the case of FIG. 2, the outermost surface is made of a general inorganic oxide. In this case as well, since the oxide is hydrophilic in the state in which no environmental pollutants are adsorbed, the pollutants are eliminated by the photoexcitation action of photocatalytic titanium oxide mixed in the surface layer in addition to the inorganic oxide. A uniform water film can be formed by forming an adsorbed water layer.
[0013]
For the film substrate in the present invention, plastics such as polyethylene terephthalate, vinyl chloride, and polyethylene, plastics provided with a transparent hard coat on a plastic substrate, and the like can be suitably used. Moreover, depending on the case, these base | substrates can also combine other functions, such as scattering prevention, design provision, and corrosion resistance.
[0014]
Moreover, the film in this invention is applicable to various base materials. The substrate to which the film of the present invention can be applied is a transparent substrate when the antifogging effect is expected, and the material can be suitably used for substrates such as glass and transparent plastic. Applicable base materials include vehicle rearview mirrors, bathroom mirrors, toilet mirrors, dental mirrors, mirrors such as road mirrors; spectacle lenses, optical lenses, camera lenses, illumination lenses, lasers Lenses such as light converging lenses, semiconductor lenses, copier lenses; prisms; window glass of buildings and surveillance towers; automobiles, railway vehicles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola Windshields of vehicles such as automobiles, rail vehicles, motorcycles, aircraft, ships, submersibles, snow vehicles, ropeway gondola, amusement park gondola, and spacecraft vehicles; protective goggles , Sports goggles, protective mask shield, sports mask shield, helmet shield, frozen food display case glass; It can be suitably used for such. As the base material to which the film of the present invention can be applied, when the surface cleaning effect is expected, the material is, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric , Combinations thereof, and laminates thereof can be suitably used. Speaking of applicable base materials, building materials, building exteriors, building interiors, window frames, window glass, structural members, exterior and painting of vehicles, exteriors of machinery and equipment, dust covers and paintings, traffic signs, various Display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors and coatings, tunnel interiors and coatings, insulators, solar cell covers, solar water heater heat collection covers, plastic houses, vehicle lighting It can be suitably used for a cover, a housing facility, a toilet, a bathtub, a wash basin, a lighting fixture, a lighting cover, kitchenware, tableware, a dishwasher, a dish dryer, a sink, a cooking range, a kitchen hood, a ventilation fan, and the like. Since the film in the present invention can maintain a high degree of hydrophilicity over a long period of time, an antistatic function can also be expected. When the antistatic effect is expected, for example, metal, ceramics, glass, plastic, wood, stone, cement, concrete, fiber, fabric, a combination thereof, or a laminate thereof can be suitably used as the material. Speaking of applicable base materials, cathode ray tube, magnetic recording media, optical recording media, magneto-optical recording media, audio tapes, video tapes, analog records, household electrical appliance housings and parts, exterior and coating, OA equipment It can be suitably used for product housings and parts, exteriors and coatings, building materials, building exteriors, building interiors, window frames, window glass, structural members, exteriors and coatings for vehicles, exteriors for machinery and equipment, dustproof covers and coatings, etc. .
[0015]
A photocatalyst is an excitation (photoexcitation) of electrons in the valence band when it is irradiated with light (excitation light) with an energy (ie short wavelength) larger than the energy gap between the conduction band and the valence band of the crystal. ) Is generated and can generate conduction electrons and holes, such as anatase titanium oxide, rutile titanium oxide, tin oxide, zinc oxide, dibismuth trioxide, tungsten trioxide, ferric oxide, Strontium titanate or the like can be suitably used. Here, as a light source used for photoexcitation of the photocatalyst, a light source in an environment such as sunlight or general indoor lighting may be used, or a light source capable of irradiating excitation light may be used as an attached facility or a portable facility. . Further, the plastic lens of the present invention, glasses equipped with a plastic lens, or a storage container dedicated to goggles equipped with a plastic lens may be provided, and a light source capable of irradiating excitation light may be installed there. In this case, for example, an incandescent lamp, a metal halide lamp, a mercury lamp, a xenon lamp, a germicidal lamp, or a fluorescent lamp can be suitably used as the light source used. By photoexcitation of the photocatalyst, because the substrate surface is highly hydrophilized, illuminance of the excitation light, may if 0.001 mW / cm 2 or more, preferably that it 0.01 mW / cm 2 or more, 0. More preferably, it is 1 mW / cm 2 or more.
[0016]
The film thickness of the surface layer containing the photocatalyst is preferably 0.4 μm or less. By doing so, white turbidity due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Furthermore, it is more preferable that the film thickness of the surface layer containing the photocatalyst is 0.2 μm or less. By doing so, coloration of the surface layer due to light interference can be prevented. Further, the thinner the surface layer, the higher the transparency. Furthermore, if the film thickness is reduced, the wear resistance of the surface layer is improved. Further, a wear-resistant or corrosion-resistant protective layer that can be hydrophilized or another functional film may be provided on the surface of the surface layer.
[0017]
The surface layer preferably has a refractive index that is not so high as compared with the base material. Preferably, the refractive index of the surface layer is 2 or less. If it does so, the reflection of the light in the interface of a base material and a surface layer and the interface of a surface layer and air can be suppressed. In order to make the refractive index of the surface layer 2 or less, a substance having a refractive index of 2 or less is used for the photocatalyst, or when the photocatalyst has a refractive index of 2 or more, another substance having a refractive index of 2 or less is used as the surface layer. Add to. As a photocatalyst having a refractive index of 2 or less, tin oxide (refractive index 1.9) or the like can be used. Photocatalysts having a refractive index of 2 or more include anatase-type titanium oxide (refractive index 2.5) and rutile-type titanium oxide (refractive index 2.7). In this case, other substances having a refractive index of 2 or less For example, calcium carbonate (refractive index 1.6), calcium hydroxide (refractive index 1.6), magnesium carbonate (refractive index 1.5), strontium carbonate (refractive index 1.5), dolomite (refractive index 1. 7), calcium fluoride (refractive index 1.4), magnesium fluoride (refractive index 1.4), silica (refractive index 1.5), alumina (refractive index 1.6), silica sand (refractive index 1. 6), montmorillonite (refractive index 1.5), kaolin (refractive index 1.6), sericite (refractive index 1.6), zeolite (refractive index 1.5), tin oxide (refractive index 1.9), etc. May be added to the surface layer.
[0018]
A metal such as Ag, Cu, or Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and sputum attached to the surface even in the dark.
[0019]
A platinum group metal such as Pt, Pd, Ru, Rh, Ir, and Os can be added to the surface layer. The surface layer to which the metal is added can enhance the redox activity of the photocatalyst and improve the deodorizing and purifying action.
[0020]
“Hydrophilic” means a property that is easy to adjust when water is dropped on the surface, and generally refers to a state where the water wetting angle is less than 90 °. The high hydrophilicity in the present invention refers to a property that is very familiar when water is dropped on the surface, and more specifically, refers to a state where the water wetting angle on a smooth surface is about 10 ° or less. In particular, as disclosed in PCT / JP96 / 00734, the antifogging property has a water wetting angle of preferably 10 ° or less, and more preferably 5 ° or less.
[0021]
Next, a method for forming a photocatalyst-containing surface layer on a film will be described by taking as an example the case where the surface layer is composed of a photocatalyst and silica, and the case where the surface layer is composed of a photocatalyst and silicone. First, the case where the surface layer is made of a photocatalyst and silica will be described taking the case where the photocatalyst is anatase-type titanium oxide as an example. In this case, basically, a precursor of amorphous silica is used as a coating film forming element, and the coating film forming element is spray-coated, dip-coating, flow coating method on a film substrate together with anatase-type titanium oxide particles, After application by a method such as a spin coating method or a roll coating method, amorphous silica is generated by a curing reaction of the coating film forming element, and the anatase-type titanium oxide particles are fixed using amorphous silica as a binder. Here, before the coating film forming element is applied together with the anatase-type titanium oxide particles, an intermediate layer such as a primer layer, a hard coat layer, or both may be formed on the film substrate. By doing in this way, the adhesiveness of a film base material and a surface layer can be improved. Here, the amorphous silica precursor includes tetraalkoxysilane (tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane, etc.), an average composition formula (partial hydrolysis, dehydration condensation polymer) OR) xSiOy (0 <x ≦ 4, 0 ≦ y <2) (R is an alkyl group), and a film-forming element such as a tetrafunctional siloxane resin, silanol, or a silanol resin that is a dehydration polycondensation product thereof is suitable. Available. Among these, since the storage stability is good and it is easy to cause a curing reaction at room temperature, the average composition formula (OR) xSiOy (0 <x ≦ 4, 0 ≦ y <2) (R is an alkyl group) Most preferably, a tetrafunctional siloxane resin is used. For the same reason as above, when the intermediate layer is formed, the intermediate layer is composed of an average composition formula (OR) xSiOy (0 <x ≦ 4, 0 ≦ y <2) (R is an alkyl group). The use of a functional siloxane resin is preferred because it has good storage stability and can easily cause a curing reaction at room temperature. In particular, when a curing reaction can be caused at room temperature, it is convenient when the substrate is not heat resistant, such as a vinyl chloride film. The curing reaction of the film-forming element is performed by, for example, subjecting a precursor of amorphous silica to a hydrolysis reaction by bringing it into contact with moisture in water or air, and then dehydrating and shrinking by a method such as heating, ultraviolet irradiation, or standing at room temperature. It is carried out by a polymerization reaction.
[0022]
Next, the case where the surface layer is made of a photocatalyst and silicone will be described taking the case where the photocatalyst is anatase-type titanium oxide as an example. In this case, the coating is made of uncured or partially cured silicone or a silicone precursor and anatase-type titanium oxide sol, and the silicone precursor is hydrolyzed as necessary, and then the mixture is mixed. Is applied to the surface of the substrate by spray coating, dip coating, flow coating, spin coating, roll coating, etc., and the silicone precursor hydrolyzate is subjected to dehydration condensation polymerization by methods such as heating. In addition, a surface layer composed of anatase-type titanium oxide particles and silicone is formed. In the formed surface layer, the anatase-type titanium oxide is photoexcited by irradiation with light containing ultraviolet rays, whereby at least a part of the organic group bonded to the silicon atom in the silicone molecule is replaced with a hydroxyl group, and further thereon A physisorbed water layer is formed and exhibits a high degree of hydrophilicity. Here, the precursors of silicone include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, ethyltripropoxysilane, phenyl Trimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane, phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxy Silane, diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenylmethyldibutoxysilane, Methylpropenylmethyl dipropoxy silane, .gamma.-glycidoxypropyltrimethoxysilane, and hydrolysates thereof, mixtures thereof can be suitably used.
[0023]
【Example】
Example 1.
A primer paint (Shin-Etsu Silicone, PC-7A) was applied on a 10 cm square polyethylene terephthalate film by a flow coating method and then dried at 120 ° C. for 20 minutes to coat the substrate with a primer resin layer. Next, a silicone-based hard coating agent (Shin-Etsu Silicone, KP-85) was applied by a flow coating method and then dried at 120 ° C. for 60 minutes to form a hard coat layer. Next, after corona discharge treatment of the hard coat layer, a titanium oxide-containing coating composition (anatase type titanium oxide sol (Nissan Chemical, TA-15, solid content 15% by weight) 16 parts by weight and silica sol (Nippon Synthetic Rubber, Glassca A) Liquid, solid content 13 wt%) 9 parts by weight were mixed, diluted with ethanol, and further 3 parts by weight of trimethoxysilane (Nippon Synthetic Rubber, Glassca B liquid) was applied by the flow coating method. A sample was obtained by curing by heat treatment at 30 ° C. for 30 minutes. After leaving this sample in a dark place for several days, the surface of the sample was irradiated with ultraviolet light at an ultraviolet illuminance of 0.5 mW / cm 2 for about 2 days using an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp). # 1 sample was obtained. For comparison, a # 2 sample in which a 10 cm square polyethylene terephthalate film was left in the dark for several days was also prepared. First, water droplets were dropped on the # 1 sample and the # 2 sample, the state after the dropping was observed, and the contact angle with water was measured. Here, the contact angle with water was evaluated by using a contact angle measuring device (Kyowa Interface Science, CA-X150) as the contact angle with water 30 seconds after dropping. As a result, when water droplets were dropped from the microsyringe onto the sample surface, it was observed that the water droplets uniformly spread in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the # 2 sample, when a water droplet was dropped from the microsyringe onto the sample surface, the water droplet almost did not conform to the surface and did not reach a uniform water film shape. The contact angle with water after 30 seconds was about 70 °. Next, the # 1 sample and the # 2 sample were blown to check for the occurrence of fogging. As a result, clouding occurred in the # 2 sample, whereas no fogging occurred in the # 1 sample. Further, the # 1 sample was then left in the dark for one week to obtain a # 3 sample. And about # 3 sample, the water drop was dripped similarly and the state after dripping was observed and the contact angle with water was measured. As a result, when water droplets were dropped onto the sample surface from the microsyringe on the # 3 sample, it was observed that the water droplets uniformly spread in the form of a water film as in the case of the # 1 sample. The contact angle with water after 30 seconds was maintained at about 2 °. Next, the # 3 sample was observed for the occurrence of fogging after blowing. As a result, no cloudiness was observed.
[0024]
Next, soapy water was applied to the back side of the # 3 sample and adhered to a 10 cm square glass substrate. Next, using a BLB fluorescent lamp, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour to obtain a # 4 sample. For comparison, soapy water was applied to the back side of the # 2 sample and adhered to a 10 cm square glass substrate. Next, using a BLB fluorescent lamp, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour to obtain a # 5 sample. Oleic acid was applied to the surface of each of the # 4 sample and the # 5 sample, and each sample was immersed in water filled in a water tank while maintaining the sample surface in a horizontal posture. As a result, in the # 5 sample, the oleic acid remained attached to the surface, and the oleic acid only extended on the sample surface even when rubbed lightly. In contrast, in the # 4 sample, oleic acid was rounded and detached from the surface when gently rubbed. Therefore, it is considered that the # 4 sample is easier to wash with water than the # 5 sample. A slurry was prepared by suspending a powder mixture composed of 1 part by weight of hydrophobic carbon black and 1 part by weight of hydrophilic carbon black in water at a concentration of 1.05 g / liter. The slurry # 4 and # 5 inclined at 45 degrees were allowed to flow 150 ml of the slurry and dried for 15 minutes, and then 150 ml of distilled water was allowed to flow and dried for 15 minutes. This cycle was repeated 25 times. The color difference change before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standard (JIS) H0201, using ΔE * display. As a result, the change in color difference was as large as 20 in the sample # 5, whereas the change in color difference was very small as 0.4 in the sample # 4.
[0025]
Example 2 (Normal temperature curing method)
In a beaker in which a 10 cm square polyethylene terephthalate film was subjected to corona discharge treatment, and 30 parts by weight of ethyl silicate pentamer (corcoat, ethyl silicate 40) and 23.5 parts by weight of methyl alcohol were placed in a thermostat at 30 ° C. Mixed. A mixed solution of 45 parts by weight of ion-exchanged water and 1.5 parts by weight of 60% nitric acid was added thereto, and the mixture was hydrolyzed for 5 hours while maintaining at 30 ° C. to prepare an intermediate coating solution. This intermediate coating solution was applied on a corona discharge-treated primer resin by a flow coating method and dried at room temperature for 10 minutes to form an intermediate layer. Next, after the corona discharge treatment of the intermediate layer, the photocatalyst coating solution (STD-K01 and ST-K03 from Ishihara Sangyo Co., Ltd. were mixed 1: 1, and then diluted with alcohol to produce anatase-type titanium oxide particles and tetra A coating solution containing 13: 7 alkyl silicate, which is a partial hydrolyzate of alkoxysilane, was applied by a flow coating method and dried at room temperature for 10 minutes to form a photocatalyst-containing surface layer. The contact angle of the formed surface with water was 5 °. Moreover, the tape peeling test (The test which evaluates whether a coating film peels when it peels quickly after sticking a cellophane tape from the other end of a coating film surface over the other end) about the formation surface was investigated. As a result, there was no change in appearance. The contact angle with water after the test was 5 °. After leaving this sample in a dark place for several days, the surface of the sample was irradiated with ultraviolet light at an ultraviolet illuminance of 0.5 mW / cm 2 for about 2 days using a BLB fluorescent lamp to obtain a # 6 sample. For comparison, a # 2 sample similar to Example 1 in which a 10 cm square polyethylene terephthalate film was left in a dark place for several days was also prepared. First, water droplets were dropped on the # 6 sample and the # 2 sample, the state after the dropping was observed, and the contact angle with water was measured. As a result, when water droplets were dropped from the microsyringe onto the sample surface, it was observed that the water droplets uniformly spread in the form of a water film. Further, the contact angle with water after 30 seconds was highly hydrophilized to about 0 °. On the other hand, in the # 2 sample, when a water droplet was dropped from the microsyringe onto the sample surface, the water droplet almost did not conform to the surface and did not reach a uniform water film shape. The contact angle with water after 30 seconds was about 70 °. Next, the # 6 sample and the # 2 sample were blown to check for the occurrence of fogging. As a result, fogging occurred in the # 2 sample, whereas no fogging occurred in the # 6 sample.
[0026]
Next, soapy water was applied to the back side of the # 6 sample and adhered to a 10 cm square glass substrate. Next, using a BLB fluorescent lamp, the surface of the sample was irradiated with ultraviolet rays at an ultraviolet illuminance of 0.5 mW / cm 2 for about 1 hour to obtain a # 7 sample. For comparison, as in Example 1, soap water was applied to the back side of the # 2 sample, adhered to a 10 cm square glass substrate, and then 0.5 mW / mm on the sample surface using a BLB fluorescent lamp. A sample of # 5 was obtained by irradiating with UV light at a UV intensity of cm 2 for about 1 hour. Oleic acid was applied to the surface of each of the # 7 sample and # 5 sample, and each sample was immersed in water filled in a water tank while maintaining the sample surface in a horizontal posture. As a result, in the # 5 sample, the oleic acid remained attached to the surface, and the oleic acid only extended on the sample surface even when rubbed lightly. In contrast, in the sample # 7, oleic acid was rounded and detached from the surface when gently rubbed. Therefore, it is considered that the # 7 sample is easier to wash with water than the # 5 sample. A slurry was prepared by suspending a powder mixture composed of 1 part by weight of hydrophobic carbon black and 1 part by weight of hydrophilic carbon black in water at a concentration of 1.05 g / liter. The # 7 sample and the # 5 sample inclined at 45 degrees were allowed to flow down 150 ml of the slurry and dried for 15 minutes, then 150 ml of distilled water was allowed to flow down and dried for 15 minutes, and this cycle was repeated 25 times. The color difference change before and after the test was measured using a color difference meter (Tokyo Denshoku). The color difference was evaluated according to Japanese Industrial Standard (JIS) H0201, using ΔE * display. As a result, the change in color difference was as large as 20 in the sample # 5, whereas the change in color difference was very small as 0.4 in the sample # 7.
[0027]
【The invention's effect】
In the present invention, by providing a surface layer containing photocatalytic titanium oxide particles on the surface of the film substrate, the surface of the surface layer exhibits hydrophilicity in response to photoexcitation of the photocatalyst. Thereby, only by sticking this film, fogging of the transparent base material surface etc. are prevented and visibility ensuring property improves. In addition, the substrate surface is self-cleaned by rain. Furthermore, the surface of the base material is easily cleaned with water.
[Brief description of the drawings]
FIG. 1 is a view showing the surface structure of a film according to the present invention.
FIG. 2 is a view showing another surface structure of a film according to the present invention.
Claims (13)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP7-354649 | 1995-12-22 | ||
JP35464995 | 1995-12-22 |
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JP28453496A Division JP3173391B2 (en) | 1995-12-22 | 1996-09-19 | Hydrophilic film, and method for producing and using the same |
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JP2000141537A JP2000141537A (en) | 2000-05-23 |
JP3844182B2 true JP3844182B2 (en) | 2006-11-08 |
Family
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JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
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JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
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JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
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JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
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JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
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JP8281225A Pending JPH09230107A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging glass lens and its anti-fogging method |
JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
JP8281222A Pending JPH09230106A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging camera filter and its anti-fogging method |
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JP28579796A Expired - Lifetime JP3697795B2 (en) | 1995-12-22 | 1996-09-20 | Display and cleaning method thereof |
JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
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JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
JP8306997A Pending JPH09226060A (en) | 1995-12-22 | 1996-11-01 | Lid for heating container having fog resistance |
JP8323516A Pending JPH09241038A (en) | 1995-12-22 | 1996-11-19 | Photocatalytic hydrophilic member and its production |
JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
JP23956799A Expired - Lifetime JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
JP34300999A Expired - Fee Related JP3844182B2 (en) | 1995-12-22 | 1999-12-02 | Hydrophilic film and method for producing and using the same |
JP2000180301A Expired - Lifetime JP3414365B2 (en) | 1995-12-22 | 2000-06-15 | Building materials for exterior walls |
JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
JP2001140242A Pending JP2002030258A (en) | 1995-12-22 | 2001-05-10 | Coated material and method for coating |
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Family Applications Before (60)
Application Number | Title | Priority Date | Filing Date |
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JP8083499A Pending JPH09231821A (en) | 1995-12-22 | 1996-04-05 | Luminaire and method for maintaining illuminance |
JP13408196A Expired - Lifetime JP3385850B2 (en) | 1995-12-22 | 1996-04-19 | Composite material with hydrophilicity |
JP10079496A Expired - Lifetime JP3740736B2 (en) | 1995-12-22 | 1996-04-23 | HEAT EXCHANGER AND HEAT EXCHANGER OPERATION METHOD |
JP15017196A Expired - Lifetime JP3760509B2 (en) | 1995-12-22 | 1996-05-22 | Greenhouse ceiling and its condensation prevention method |
JP8150410A Pending JPH09225263A (en) | 1995-12-22 | 1996-05-23 | Air pollutant removing filter, air pollutant removing fan and ventilator using the fan |
JP8156383A Pending JPH09231849A (en) | 1995-12-22 | 1996-05-29 | Insulator and dirt preventing method therefore |
JP8136777A Pending JPH09227178A (en) | 1995-12-22 | 1996-05-30 | Laminated glass and its production |
JP13653596A Expired - Lifetime JP3339304B2 (en) | 1995-12-22 | 1996-05-30 | Painted object and painting method |
JP13782996A Ceased JP3189682B2 (en) | 1995-12-22 | 1996-05-31 | Antifouling material |
JP8168643A Pending JPH09232096A (en) | 1995-12-22 | 1996-06-06 | Electrification preventing method, and electrification preventive composite material |
JP8145265A Pending JPH09225276A (en) | 1995-12-22 | 1996-06-07 | Separating membrane and formation of surface layer to separating membrane |
JP8168662A Pending JPH09225389A (en) | 1995-12-22 | 1996-06-10 | Method for making member hydrophilic and preventing deterioration by ultraviolet ray, hydrophilic ultraviolet resistant member and its manufacture |
JP8158518A Pending JPH09225021A (en) | 1995-12-22 | 1996-06-19 | Medical material |
JP8195184A Expired - Lifetime JP3003581B2 (en) | 1995-12-22 | 1996-06-20 | A member that exhibits hydrophilicity in response to optical excitation of an optical semiconductor |
JP8272815A Pending JPH09224957A (en) | 1995-12-22 | 1996-09-06 | Laser beam focusing lens, dentistry and oral surgery treatment device using the same, and preventing device of laser beam irregular reflection due to stuck waterdrop |
JP8272814A Pending JPH09226041A (en) | 1995-12-22 | 1996-09-06 | Member for preventing attachment of condensation water drop and method for preventing attachment of condensation water drop of the member |
JP8272808A Pending JPH09229724A (en) | 1995-12-22 | 1996-09-07 | Non-fogging cover for instrument panel of motorcycle, motorcycle equipped with the cover, and fogging-preventing method for the cover |
JP27280996A Expired - Fee Related JP3588202B2 (en) | 1995-12-22 | 1996-09-07 | Anti-fog road mirror and its anti-fog method |
JP8238927A Pending JPH09227159A (en) | 1995-12-22 | 1996-09-10 | Front and rear window glass of vehicle |
JP27519096A Expired - Lifetime JP3277983B2 (en) | 1995-12-22 | 1996-09-10 | Outdoor display panel and its cleaning method |
JP8275189A Pending JPH09231807A (en) | 1995-12-22 | 1996-09-10 | Vehicle headlight cover, vehicle with it, and its defogging method |
JP28122196A Expired - Lifetime JP3743075B2 (en) | 1995-12-22 | 1996-09-17 | Antifogging dental mirror and antifogging method |
JP8281220A Expired - Lifetime JP3003593B2 (en) | 1995-12-22 | 1996-09-17 | Photocatalytic hydrophilic member |
JP8281224A Pending JPH09228134A (en) | 1995-12-22 | 1996-09-17 | Antifogging helmet shield and antifogging method |
JP8281225A Pending JPH09230107A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging glass lens and its anti-fogging method |
JP8281223A Expired - Lifetime JP3063968B2 (en) | 1995-12-22 | 1996-09-17 | Anti-fog vehicle mirror, automobile equipped with the same, anti-fog film for vehicle mirror and anti-fog method for vehicle mirror |
JP8281222A Pending JPH09230106A (en) | 1995-12-22 | 1996-09-17 | Anti-fogging camera filter and its anti-fogging method |
JP8282808A Pending JPH09228765A (en) | 1995-12-22 | 1996-09-18 | Blind and manufacture thereof |
JP8282805A Pending JPH09231499A (en) | 1995-12-22 | 1996-09-18 | Light source cover for traffic signal, traffic signal with it, and cleaning method for light source cover for traffic signal |
JP8246180A Pending JPH09230493A (en) | 1995-12-22 | 1996-09-18 | Camera |
JP8282806A Pending JPH09228057A (en) | 1995-12-22 | 1996-09-18 | Wheel and its cleaning method |
JP8282810A Pending JPH09228545A (en) | 1995-12-22 | 1996-09-18 | Glass block and its cleaning method |
JP8282809A Pending JPH09230108A (en) | 1995-12-22 | 1996-09-18 | Anti-fogging plastic lens and its anti-fogging method |
JP8282807A Pending JPH09224874A (en) | 1995-12-22 | 1996-09-18 | Water-closet bowl made of resin |
JP28281296A Expired - Lifetime JP3612896B2 (en) | 1995-12-22 | 1996-09-18 | Exterior wall building materials and methods for cleaning them |
JP08282811A Expired - Fee Related JP3075195B2 (en) | 1995-12-22 | 1996-09-18 | Anti-fog wash mirror, vanity table provided with the same, anti-fog film for wash mirror and anti-fog method for wash mirror |
JP8284533A Pending JPH09227161A (en) | 1995-12-22 | 1996-09-19 | Pane, film for applying thereto and antifogging and cleaning thereof |
JP8284532A Pending JPH09227805A (en) | 1995-12-22 | 1996-09-19 | Photocatalytic hydrophilic coating composition |
JP28453496A Expired - Lifetime JP3173391B2 (en) | 1995-12-22 | 1996-09-19 | Hydrophilic film, and method for producing and using the same |
JP28579796A Expired - Lifetime JP3697795B2 (en) | 1995-12-22 | 1996-09-20 | Display and cleaning method thereof |
JP28895696A Expired - Fee Related JP3588206B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning road decorative panel, and method of cleaning road decorative panel |
JP28895596A Expired - Lifetime JP3774955B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning handrail and handrail cleaning method |
JP28895496A Expired - Fee Related JP3588205B2 (en) | 1995-12-22 | 1996-09-25 | Self-cleaning guard fence and method of cleaning guard fence |
JP8291007A Pending JPH09225054A (en) | 1995-12-22 | 1996-09-26 | Gas mask and storing device for gas mask |
JP8291005A Pending JPH09230031A (en) | 1995-12-22 | 1996-09-26 | Inter-vehicle distance detecting device and automobile having it |
JP8291006A Pending JPH09229767A (en) | 1995-12-22 | 1996-09-26 | Pyroelectric infrared detector |
JP8297248A Pending JPH09227169A (en) | 1995-12-22 | 1996-10-18 | Transfer sheet, and transferring of photocatalytic and hydrophilic thin film |
JP8298234A Pending JPH09226531A (en) | 1995-12-22 | 1996-10-22 | Rainy weather visibility securable vehicular mirror, automobile and two wheeler having it |
JP8298236A Pending JPH09227162A (en) | 1995-12-22 | 1996-10-22 | Vehicle pane for securing rainy weather view, and automobile mounted therewith |
JP8298237A Pending JPH09229546A (en) | 1995-12-22 | 1996-10-22 | Door for refrigerated showcase having see-through ensuring property |
JP8298235A Pending JPH09230119A (en) | 1995-12-22 | 1996-10-22 | Road mirror for assuring visual field in rainy weather |
JP8307000A Pending JPH09224800A (en) | 1995-12-22 | 1996-11-01 | Glassware and water-washing method |
JP8306997A Pending JPH09226060A (en) | 1995-12-22 | 1996-11-01 | Lid for heating container having fog resistance |
JP8323516A Pending JPH09241038A (en) | 1995-12-22 | 1996-11-19 | Photocatalytic hydrophilic member and its production |
JP34047296A Expired - Fee Related JP3348613B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP8340470A Pending JPH09225387A (en) | 1995-12-22 | 1996-12-05 | Hydrophilic member and method to make surface of member hydrophilic |
JP34047196A Expired - Lifetime JP3303696B2 (en) | 1995-12-22 | 1996-12-05 | Photocatalytic hydrophilic coating composition |
JP08344585A Expired - Lifetime JP3141802B2 (en) | 1995-12-22 | 1996-12-09 | Hydrophilic member and method for maintaining hydrophilicity |
JP23956799A Expired - Lifetime JP3613084B2 (en) | 1995-12-22 | 1999-08-26 | A member that exhibits hydrophilicity in response to photoexcitation of an optical semiconductor |
JP23956899A Expired - Lifetime JP3613085B2 (en) | 1995-12-22 | 1999-08-26 | Photocatalytic hydrophilic member |
Family Applications After (10)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2000180301A Expired - Lifetime JP3414365B2 (en) | 1995-12-22 | 2000-06-15 | Building materials for exterior walls |
JP2000181286A Expired - Lifetime JP3414367B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000181284A Pending JP2001048679A (en) | 1995-12-22 | 2000-06-16 | Photocatalytic hydrophilic tile and its production |
JP2000181287A Expired - Fee Related JP3465664B2 (en) | 1995-12-22 | 2000-06-16 | Building materials for exterior walls |
JP2000227056A Pending JP2001129916A (en) | 1995-12-22 | 2000-07-27 | Photocatalytic hydrophilic member |
JP2000227055A Withdrawn JP2001089752A (en) | 1995-12-22 | 2000-07-27 | Member capable of obtaining hydrophilic nature in accordance with photoexcitation of optical semiconductor and manufacturing method thereof |
JP2000247609A Pending JP2001122679A (en) | 1995-12-22 | 2000-08-17 | Antifouling tile |
JP2001140242A Pending JP2002030258A (en) | 1995-12-22 | 2001-05-10 | Coated material and method for coating |
JP2002020533A Expired - Fee Related JP3882625B2 (en) | 1995-12-22 | 2002-01-29 | Sound insulation wall and cleaning method for sound insulation wall |
JP2002244772A Pending JP2003113345A (en) | 1995-12-22 | 2002-08-26 | Antistatic coating composition |
Country Status (1)
Country | Link |
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JP (71) | JPH09231821A (en) |
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Publication number | Priority date | Publication date | Assignee | Title |
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WO2019069250A1 (en) * | 2017-10-06 | 2019-04-11 | 3M Innovative Properties Company | Window film |
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