JPH11320750A - Photocatalytic hydrophilic composite material - Google Patents
Photocatalytic hydrophilic composite materialInfo
- Publication number
- JPH11320750A JPH11320750A JP10327322A JP32732298A JPH11320750A JP H11320750 A JPH11320750 A JP H11320750A JP 10327322 A JP10327322 A JP 10327322A JP 32732298 A JP32732298 A JP 32732298A JP H11320750 A JPH11320750 A JP H11320750A
- Authority
- JP
- Japan
- Prior art keywords
- adhesive layer
- composite material
- photocatalytic
- silicone
- layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 32
- 239000002131 composite material Substances 0.000 title claims description 17
- 239000012790 adhesive layer Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002344 surface layer Substances 0.000 claims abstract description 20
- -1 alkyl silicates Chemical class 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 150000003376 silicon Chemical class 0.000 claims description 16
- 239000010703 silicon Substances 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 230000007423 decrease Effects 0.000 claims description 5
- 238000013459 approach Methods 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 27
- 239000011941 photocatalyst Substances 0.000 abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 5
- 239000005751 Copper oxide Substances 0.000 abstract description 5
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 abstract description 5
- 125000000962 organic group Chemical group 0.000 abstract description 5
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract description 4
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 abstract description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 abstract description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001923 silver oxide Inorganic materials 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- 150000004756 silanes Chemical class 0.000 abstract description 2
- 239000007859 condensation product Substances 0.000 abstract 1
- 239000012528 membrane Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 40
- 238000000034 method Methods 0.000 description 39
- 238000000576 coating method Methods 0.000 description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 25
- 239000003973 paint Substances 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 17
- 238000005259 measurement Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 230000001443 photoexcitation Effects 0.000 description 6
- 238000004528 spin coating Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- 229920002799 BoPET Polymers 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 4
- 238000003618 dip coating Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000012643 polycondensation polymerization Methods 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 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 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000007611 bar coating method Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000002772 conduction electron Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 2
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 2
- KUCGHDUQOVVQED-UHFFFAOYSA-N ethyl(tripropoxy)silane Chemical compound CCCO[Si](CC)(OCCC)OCCC KUCGHDUQOVVQED-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000005357 flat glass Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 2
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 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
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 2
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 2
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 2
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc 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
- DAJFVZRDKCROQC-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tripropoxysilane Chemical compound CCCO[Si](OCCC)(OCCC)CCCOCC1CO1 DAJFVZRDKCROQC-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-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
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- JZYAVTAENNQGJB-UHFFFAOYSA-N 3-tripropoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C(C)=C JZYAVTAENNQGJB-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- QMHXOYJCPWNKOY-UHFFFAOYSA-N C(C)O[SiH3].C(CC)[Si](OC)(OC)OC Chemical compound C(C)O[SiH3].C(CC)[Si](OC)(OC)OC QMHXOYJCPWNKOY-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 241000588731 Hafnia Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- XSVRIICVXZBSCH-UHFFFAOYSA-N benzyl(dipropoxy)silane Chemical compound CCCO[SiH](OCCC)CC1=CC=CC=C1 XSVRIICVXZBSCH-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- WXONGBQFFCVVCX-UHFFFAOYSA-N butoxy(propan-2-yl)silane Chemical compound CCCCO[SiH2]C(C)C WXONGBQFFCVVCX-UHFFFAOYSA-N 0.000 description 1
- OQCQMXUAGXYAGL-UHFFFAOYSA-N butoxy(propyl)silane Chemical compound CCCCO[SiH2]CCC OQCQMXUAGXYAGL-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 235000012255 calcium oxide Nutrition 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 230000006866 deterioration Effects 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
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-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
- 238000007865 diluting Methods 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 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
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- SZEGZMUSBCXNLO-UHFFFAOYSA-N propan-2-yl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C(C)C SZEGZMUSBCXNLO-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-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
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-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
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Catalysts (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、部材表面を高度の
親水性になし、かつ維持する技術に関する。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
透明部材の表面を高度に親水化することにより、部材の
曇りや水滴形成を防止する防曇技術に関する。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−ニング）し若しくは
容易に清掃する技術に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a technique for making a member surface highly hydrophilic and maintaining it. More specifically, the present invention relates to an anti-fog technology for preventing the fogging and water droplets from forming on a mirror, lens, glass, prism or other transparent member by making the surface of the member highly hydrophilic. The present invention also prevents the surface from being stained by highly hydrophilizing the surface of a building, a window glass, a mechanical device or an article,
Alternatively, the present invention relates to a technique of self-cleaning (self-cleaning) or easily cleaning a surface.
【０００２】[0002]
【従来の技術】光触媒機能を有する材料を製造する上で
光触媒を直接基材に塗布したのでは十分な密着性が得ら
れない。そのため、特開平９−６１３で示されるような
基材に樹脂層とシリカ層の２層を介して光触媒層を塗布
させる手法がある。しかし、これは樹脂層とシリカ層の
２層を形成しなければならず加工性が低かった。2. Description of the Related Art In order to produce a material having a photocatalytic function, sufficient adhesion cannot be obtained by directly applying a photocatalyst to a substrate. Therefore, there is a method as shown in JP-A-9-613 in which a photocatalyst layer is applied to a base material via two layers, a resin layer and a silica layer. However, this requires formation of two layers, a resin layer and a silica layer, resulting in low workability.
【０００３】また、特開平８−１０３４８８で示される
ような基材と光触媒層のの密着性を向上させるために基
材上に非晶質層を設け、非晶質層が軟化する温度で焼成
することにより光触媒層を埋設させ、密着性の向上を図
る手法がある。しかし、これは、基材がタイル、セラミ
ックなど耐熱性があり、その上の非晶質層がガラス質等
には適応が可能であるが、樹脂等の耐熱温度の低い基材
の場合、適応することができなかった。Further, an amorphous layer is provided on a substrate in order to improve the adhesion between the substrate and the photocatalyst layer as disclosed in JP-A-8-103488, and firing is performed at a temperature at which the amorphous layer softens. Then, there is a method of embedding the photocatalyst layer to improve the adhesion. However, this means that the base material has heat resistance such as tiles and ceramics, and the amorphous layer thereon can be applied to glassy materials, etc. I couldn't.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、上記の欠点
を改善することを目的とし、加工性が高く、基材の耐熱
性が低い場合でも、光触媒層との密着性の高い接着層を
備えた光触媒性親水性複合材料を提供することである。SUMMARY OF THE INVENTION An object of the present invention is to improve the above-mentioned drawbacks, and to provide an adhesive layer having high adhesion to a photocatalyst layer even when the workability is high and the heat resistance of the substrate is low. The present invention is to provide a photocatalytic hydrophilic composite material comprising the same.
【０００５】[0005]
【課題を解決するための手段】上記課題を解決するため
に、請求項１に記載の光触媒性親水性複合材料は、基材
表面に接着層を介して光触媒性材料を含む表面層が形成
されている光触媒性親水性複合材料において、前記接着
層の表面層側が無機分の濃度が高く、基材表面側が有機
分の濃度が高いことを特徴とする。According to a first aspect of the present invention, there is provided a photocatalytic hydrophilic composite material having a surface layer containing a photocatalytic material formed on a surface of a substrate via an adhesive layer. In the photocatalytic hydrophilic composite material described above, the concentration of the inorganic component is high on the surface layer side of the adhesive layer, and the concentration of the organic component is high on the substrate surface side.
【０００６】また、請求項２に記載の光触媒性親水性複
合材料は、請求項１の接着層の無機分の濃度は基材表面
に近づくにつれて連続的または段階的に低くなり、且
つ、有機分の濃度は表面層に近づくにつれて連続的また
は段階的に低くなることを特徴とする。In the photocatalytic hydrophilic composite material according to the present invention, the concentration of the inorganic component in the adhesive layer of the present invention decreases continuously or stepwise as it approaches the surface of the base material, and the concentration of the organic component decreases. Is characterized in that the concentration decreases continuously or stepwise as it approaches the surface layer.
【０００７】また、請求項３に記載の光触媒性親水性複
合材料は、請求項２の接着層がアクリル変性シリコンで
あることを特徴とする。[0007] The photocatalytic hydrophilic composite material according to claim 3 is characterized in that the adhesive layer according to claim 2 is acrylic-modified silicon.
【０００８】請求項４に記載の光触媒性親水性複合材料
は請求項３のアクリル変性シリコンのシリコン成分が１
０〜２０％で、アクリル成分が８０〜９０％であること
を特徴とする。The photocatalytic hydrophilic composite material according to claim 4 is characterized in that the acryl-modified silicon according to claim 3 has a silicon component of 1
0 to 20%, and the acrylic component is 80 to 90%.
【０００９】また、請求項５に記載の光触媒性親水性複
合材料は、請求項１〜３いずれか１項の基材が樹脂であ
ることを特徴とする。The photocatalytic hydrophilic composite material according to claim 5 is characterized in that the substrate according to any one of claims 1 to 3 is a resin.
【００１０】また、請求項６に記載の光触媒性親水性複
合材料は、請求項５の基材がポリエチレンテレフタレー
トであることを特徴とする。The photocatalytic hydrophilic composite material according to claim 6 is characterized in that the base material of claim 5 is polyethylene terephthalate.
【００１１】[0011]
【発明の実施の形態】本発明に示される光触媒性材料と
は伝導電子帯と価電子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中の電子の励起（光励起）
によって、伝導電子と正孔を生成しうるものをいい、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利用可能であ
る。光触媒の光励起に用いる光源としては蛍光灯、白熱
電灯、メタルハライドランプ、水銀ランプのような室内
照明、太陽光それらの光源からの光を低損失のファイバ
ーで誘導した光源等がりようできる。BEST MODE FOR CARRYING OUT THE INVENTION The photocatalytic material shown in the present invention has a valence when irradiated with light (excitation light) having an energy (ie, shorter wavelength) larger than the energy gap between the conduction electron band and the valence electrons. Excitation of electrons in electrons (photoexcitation)
By means of those that can generate conduction electrons and holes, anatase type titanium oxide, rutile type titanium oxide, tin oxide,
Zinc oxide, bismuth trioxide, tungsten trioxide, ferric oxide, strontium titanate and the like can be used. Examples of the light source used for photoexcitation of the photocatalyst include indoor lighting such as a fluorescent lamp, an incandescent lamp, a metal halide lamp, and a mercury lamp, and a light source in which light from the light source is guided by a low-loss fiber.
【００１２】本発明の光触媒性材料を含む表面層にシリ
カ及び／又はケイ素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たシリコ−ンが含有されること
により、暗所における親水維持性能が向上する。 ケイ
素原子に結合する有機基の少なくとも一部が水酸基に置
換されたシリコ−ンとしては、加水分解性シラン、アル
キルシリケ−ト、それらの（部分）加水分解物、加水分
解・縮合物などが使用できる。ここで加水分解性シラン
としては、メチルトリメトキシシラン、エチルトリメト
キシシラン、メチルトリエトキシシラン、エチルトリエ
トキシシラン、メチルトリプロポキシシラン、エチルト
リプロポキシシラン、ｎ−プロピルトリメトキシシラ
ン、ｎ−プロピルトリエトキシシラン、ｎ−プロピルト
リプロポキシシラン、イソプロピルトリメトキシシラ
ン、イソプロピルトリエトキシシラン、イソプロピルト
リプロポキシシラン、メチルトリブトキシシラン、エチ
ルトリブトキシシラン、ｎ−プロピルブトキシシラン、
イソプロピルブトキシシラン、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、フェニルトリプロ
ポキシシラン、フェニルトリブトキシシラン、γ−グリ
シドキシプロピルトリメトキシシラン、γ−グリシドキ
シプロピルトリエトキシシラン、γ−グリシドキシプロ
ピルトリプロポキシシラン、γ−メタクリロキシプロピ
ルトリメトキシシラン、γ−メタクリロキシプロピルト
リエトキシシラン、γ−メタクリロキシプロピルトリプ
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、β−（３、４−エポキ
シシクロヘキシル）エチルトリエトキシシラン、γ−ア
ミノプロピルトリメトキシシラン、γ−アミノプロピル
トリエトキシシラン、γ−メルカプトプロピルトリメト
キシシラン、γ−メルカプトプロピルトリエトキシシラ
ン、トリフルオロプロピルトリメトキシシラン、トリフ
ルオロプロピルトリエトキシシラン、フェニルメチルジ
エトキシシラン、ジメチルジメトキシシラン、ジメチル
ジエトキシシラン、ジエチルジエトキシシラン、フェニ
ルメチルジメトキシシラン、ジフェニルジメトキシシラ
ン、ジフェニルジエトキシシラン等の加水分解性オルガ
ノシラン、テトラエトキシシラン、テトライソプロポキ
シシラン、テトラｎ−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、ジメトキシジエトキ
シシラン等のテトラアルコキシシランなどが使用でき
る。 アルキルシリケ−トとしては、メチルシリケ−
ト、エチルシリケ−ト、プロピルシリケ−ト、ブチルシ
リケ−トなどが使用できる。The surface layer containing the photocatalytic material of the present invention contains silica in which at least a part of the organic group bonded to the silica and / or silicon atom is substituted with a hydroxyl group, thereby maintaining hydrophilicity in a dark place. Performance is improved. As the silicone in which at least a part of the organic group bonded to the silicon atom is substituted with a hydroxyl group, hydrolyzable silanes, alkyl silicates, (partial) hydrolysates thereof, hydrolysis / condensates and the like can be used. . Here, as the hydrolyzable silane, methyltrimethoxysilane, ethyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, methyltripropoxysilane, ethyltripropoxysilane, n-propyltrimethoxysilane, n-propyltrimethoxysilane Ethoxysilane, n-propyltripropoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, isopropyltripropoxysilane, methyltributoxysilane, ethyltributoxysilane, n-propylbutoxysilane,
Isopropylbutoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, phenyltributoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyl Tripropoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltripropoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-mercap Propyltriethoxysilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, phenylmethyldiethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldiethoxysilane, phenylmethyldimethoxysilane, diphenyldimethoxysilane, diphenyldi Hydrolyzable organosilanes such as ethoxysilane and the like, tetraethoxysilane, tetraisopropoxysilane, tetra-n-propoxysilane, tetrabutoxysilane, tetramethoxysilane, tetraalkoxysilane such as dimethoxydiethoxysilane and the like can be used. Alkyl silicates include methyl silicate
And ethyl silicate, propyl silicate, butyl silicate and the like can be used.
【００１３】本発明の光触媒性材料を含む表面層には、
他の無機酸化物も添加できる。無機酸化物としてはセリ
ア、ジルコニア、アルミナ、無定型酸化チタン、酸化
錫、マグネシア、カルシア、イットリア、酸化マンガ
ン、クロミア、酸化バナジウム、酸化銅、酸化コバル
ト、酸化ニッケル、酸化ルテニウム、ハフニア、酸化ス
トロンチウム、酸化銀の群から選ばれる１種又は２種以
上等が挙げられる。 これら無機酸化物は充填剤として
被膜の強度を向上させる。さらに、このうちジルコニア
を添加すると耐水性が向上する。またアルミナ、セリ
ア、イットリアを添加すると暗所親水維持性が向上す
る。また酸化ルテニウム、酸化銅を添加すると酸化還元
力が向上する。また、酸化銀、酸化銅を添加すると抗菌
性が向上する。The surface layer containing the photocatalytic material of the present invention includes:
Other inorganic oxides can also be added. As inorganic oxides, ceria, zirconia, alumina, amorphous titanium oxide, tin oxide, magnesia, calcia, yttria, manganese oxide, chromia, vanadium oxide, copper oxide, cobalt oxide, nickel oxide, ruthenium oxide, hafnia, strontium oxide, One or two or more selected from the group of silver oxides may be mentioned. These inorganic oxides improve the strength of the coating as a filler. Further, when zirconia is added, the water resistance is improved. When alumina, ceria, and yttria are added, the hydrophilicity in a dark place is improved. The addition of ruthenium oxide or copper oxide improves the redox power. The addition of silver oxide or copper oxide improves antibacterial properties.
【００１４】本発明の光触媒性材料を含む表面層には、
銀、銅、パラジウム、白金、ロジウム、プラチウム、ル
テニウム、金、亜鉛、コバルト、鉄、ニッケル、ナトリ
ウム、リチウム、ストロンチウム、カリウム、カルシウ
ム、マグネシウム又はそれら金属の化合物の群から選ば
れる１種以上が添加してもよい。 銀、銅、亜鉛又はそ
れら金属の化合物の群から選ばれる１種以上を添加する
ことで、抗菌性を付与することができる。 パラジウ
ム、白金、ロジウム、プラチウム、ルテニウム、金、コ
バルト、鉄、ニッケル又はそれら金属の化合物の群から
選ばれる１種以上を添加することで、光半導体の光励起
による酸化還元触媒性能を向上させることができる。
ナトリウム、リチウム、ストロンチウム、カリウム、カ
ルシウム、マグネシウム又はそれら金属の化合物の群か
ら選ばれる１種以上を添加することで、光半導体の光励
起に応じた親水化性能を向上させることができる。The surface layer containing the photocatalytic material of the present invention includes:
One or more selected from the group consisting of silver, copper, palladium, platinum, rhodium, platinum, ruthenium, gold, zinc, cobalt, iron, nickel, sodium, lithium, strontium, potassium, calcium, magnesium or compounds of these metals May be. Antibacterial properties can be imparted by adding at least one selected from the group consisting of silver, copper, zinc and compounds of these metals. By adding one or more selected from the group of palladium, platinum, rhodium, platinum, ruthenium, gold, cobalt, iron, nickel or compounds of these metals, it is possible to improve the oxidation-reduction catalytic performance of the optical semiconductor by photoexcitation. it can.
By adding at least one selected from the group consisting of sodium, lithium, strontium, potassium, calcium, magnesium and a compound of these metals, the hydrophilicity of the optical semiconductor according to photoexcitation can be improved.
【００１５】光触媒の光励起により基材表面が高度に親
水化させるためには、励起光の照度は０．００１mW/cｍ
2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。 表
面層の形成方法について説明する。まず表面層が光触媒
のみからなる場合の製法について、光触媒がアナタ−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、大別して３つの方法がある。１つの方法はゾル塗
布焼成法であり、他の方法は有機チタネ−ト法であり、
他の方法は電子ビ−ム蒸着法である。 （１）ゾル塗布焼成法 アナタ−ゼ型酸化チタンゾルを、基材表面に、スプレ−
コ−ティング法、ディップコ−ティング法、フロ−コ−
ティング法、スピンコ−ティング法、ロ−ルコ−ティン
グ法等の方法で塗布し、焼成する。 （２）有機チタネ−ト法 チタンアルコキシド（テトラエトキシチタン、テトラメ
トキシチタン、テトラプロポキシチタン、テトラブトキ
シチタン等）、チタンアセテ−ト、チタンキレ−ト等の
有機チタネ−トに加水分解抑制剤（塩酸、エチルアミン
等）を添加し、アルコ−ル（エタノ−ル、プロパノ−
ル、ブタノ−ル等）などの非水溶媒で希釈した後、部分
的に加水分解を進行させながら又は完全に加水分解を進
行させた後、混合物をスプレ−コ−ティング法、ディッ
プコ−ティング法、フロ−コ−ティング法、スピンコ−
ティング法、ロ−ルコ−ティング法等の方法で塗布し、
乾燥させる。乾燥により、有機チタネ−トの加水分解が
完遂して水酸化チタンが生成し、水酸化チタンの脱水縮
重合により無定型酸化チタンの層が基材表面に形成され
る。その後、アナタ−ゼの結晶化温度以上の温度で焼成
して、無定型酸化チタンをアナタ−ゼ型酸化チタンに相
転移させる。 （３）電子ビ−ム蒸着法 酸化チタンのタ−ゲットに電子ビ−ムを照射することに
より、基材表面に無定型酸化チタンの層を形成する。そ
の後、アナタ−ゼの結晶化温度以上の温度で焼成して、
無定型酸化チタンをアナタ−ゼ型酸化チタンに相転移さ
せる。In order to make the substrate surface highly hydrophilic by photoexcitation of the photocatalyst, the illuminance of the excitation light is 0.001 mW / cm.
The number is preferably 2 or more, but is preferably 0.01 mW / cm 2 or more, and more preferably 0.1 mW / cm 2 or more. A method for forming the surface layer will be described. First, a production method in the case where the surface layer is made of only a photocatalyst will be described with reference to an example in which the photocatalyst is an anatase type titanium oxide. In this case, there are roughly three methods. One method is a sol coating and baking method, the other is an organic titanate method,
Another method is an electron beam evaporation method. (1) Sol coating and baking method An anatase type titanium oxide sol is sprayed on the surface of a substrate.
Coating method, dip coating method, flow coating
It is applied by a coating method, a spin coating method, a roll coating method, or the like, and baked. (2) Organic titanate method Titanium alkoxides (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, and other organic titanates are treated with a hydrolysis inhibitor (hydrochloric acid, Ethylamine, etc.), and alcohol (ethanol, propanol)
, Butanol, etc.), and after partially or completely allowing hydrolysis to proceed, the mixture is spray-coated or dip-coated. , Flow coating method, Spin coating
Coating method, roll coating method, etc.
dry. By drying, the hydrolysis of the organic titanate is completed to produce titanium hydroxide, and an amorphous titanium oxide layer is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature not lower than the crystallization temperature of the anatase to cause a phase transition of the amorphous titanium oxide to the anatase titanium oxide. (3) Electron beam evaporation method An amorphous titanium oxide layer is formed on the surface of a substrate by irradiating a target of titanium oxide with an electron beam. After that, firing at a temperature higher than the crystallization temperature of the anatase,
Amorphous titanium oxide undergoes a phase transition to an anatase type titanium oxide.
【００１６】次に、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−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、例えば、以下の
３つの方法がある。１つの方法はゾル塗布焼成法であ
り、他の方法は有機チタネ−ト法であり、他の方法は４
官能性シラン法である。 （１）ゾル塗布焼成法 アナタ−ゼ型酸化チタンゾルとシリカゾルとの混合液
を、基材表面にスプレ−コ−ティング法、ディップコ−
ティング法、フロ−コ−ティング法、スピンコ−ティン
グ法、ロ−ルコ−ティング法等の方法で塗布し、焼成す
る。 （２）有機チタネ−ト法 チタンアルコキシド（テトラエトキシチタン、テトラメ
トキシチタン、テトラプロポキシチタン、テトラブトキ
シチタン等）、チタンアセテ−ト、チタンキレ−ト等の
有機チタネ−トに加水分解抑制剤（塩酸、エチルアミン
等）とシリカゾルを添加し、アルコ−ル（エタノ−ル、
プロパノ−ル、ブタノ−ル等）などの非水溶媒で希釈し
た後、部分的に加水分解を進行させながら又は完全に加
水分解を進行させた後、混合物をスプレ−コ−ティング
法、ディップコ−ティング法、フロ−コ−ティング法、
スピンコ−ティング法、ロ−ルコ−ティング法等の方法
で塗布し、乾燥させる。乾燥により、有機チタネ−トの
加水分解が完遂して水酸化チタンが生成し、水酸化チタ
ンの脱水縮重合により無定型酸化チタンの層が基材表面
に形成される。その後、アナタ−ゼの結晶化温度以上の
温度で焼成して、無定型酸化チタンをアナタ−ゼ型酸化
チタンに相転移させる。 （３）４官能性シラン法 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）とアナタ−ゼ型酸化チタンゾルとの混
合物を基材の表面にスプレ−コ−ティング法、ディップ
コ−ティング法、フロ−コ−ティング法、スピンコ−テ
ィング法、ロ−ルコ−ティング法等の方法で塗布し、必
要に応じて加水分解させてシラノ−ルを形成した後、加
熱等の方法でシラノ−ルを脱水縮重合に付す。Next, the case where the surface layer is composed of a photocatalyst and silica will be described by taking as an example the case where the photocatalyst is an anatase type titanium oxide. In this case, for example, there are the following three methods. One method is a sol coating and baking method, the other method is an organic titanate method, and the other method is a 4 method.
This is a functional silane method. (1) Sol coating and firing method A mixture of an anatase-type titanium oxide sol and silica sol is applied to the surface of a substrate by spray coating, dip coating, or the like.
It is applied by a coating method, a flow coating method, a spin coating method, a roll coating method, or the like, and baked. (2) Organic titanate method Titanium alkoxides (tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, etc.), titanium acetate, titanium chelate, and other organic titanates are treated with a hydrolysis inhibitor (hydrochloric acid, Ethylamine, etc.) and silica sol are added, and alcohol (ethanol,
After diluting with a non-aqueous solvent such as propanol or butanol, etc. and then partially or completely allowing the hydrolysis to proceed, the mixture is spray-coated, dip-coated. Method, floating coating method,
It is applied by a method such as spin coating or roll coating, and dried. By drying, hydrolysis of the organic titanate is completed to produce titanium hydroxide, and a layer of amorphous titanium oxide is formed on the surface of the base material by dehydration-condensation polymerization of the titanium hydroxide. Thereafter, the amorphous titanium oxide is calcined at a temperature higher than the crystallization temperature of the anatase to cause a phase transition from the amorphous titanium oxide to the anatase titanium oxide. (3) Tetrafunctional silane method Spray coating a mixture of tetraalkoxysilane (tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetramethoxysilane, etc.) and an anatase type titanium oxide sol on the surface of a substrate Method, dip coating method, flow coating method, spin coating method, roll coating method, and the like, and if necessary, hydrolyze to form a silanol, and then heat, etc. The silanol is subjected to dehydration polycondensation by the method described above.
【００１７】次に、表面層が光触媒とシリコ−ンからな
る場合について、光触媒がアナタ−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−ン又はシリコ−ンの前
駆体からなる塗料とアナタ−ゼ型酸化チタンゾルとを混
合し、シリコ−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−コ−ティング法、
ディップコ−ティング法、フロ−コ−ティング法、スピ
ンコ−ティング法、ロ−ルコ−ティング法等の方法で塗
布し、加熱等の方法でシリコ−ンの前駆体の加水分解物
を脱水縮重合に付して、アナタ−ゼ型酸化チタン粒子と
シリコ−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−ゼ型酸化チ
タンが光励起されることにより、シリコ−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−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。Next, the case where the surface layer is made of a photocatalyst and a silicone will be described by taking as an example the case where the photocatalyst is an anatase type titanium oxide. The method in this case is to mix an uncured or partially cured silicone or a silicone precursor paint with an anatase type titanium oxide sol, and to prepare the silicone precursor as necessary. After the hydrolysis, the mixture is sprayed on the surface of the substrate,
It is applied by a dip coating method, a flow coating method, a spin coating method, a roll coating method, or the like, and a hydrolysis product of a silicone precursor is subjected to dehydration condensation polymerization by a method such as heating. Then, a surface layer composed of anatase type titanium oxide particles and silicone is formed. In the formed surface layer, at least a part of the organic group bonded to the silicon atom in the silicone molecule is replaced with a hydroxyl group by photoexcitation of the anatase type titanium oxide by irradiation with light including ultraviolet rays, Furthermore, a physisorption water layer is formed on it,
It exhibits a high degree of hydrophilicity. Here, the precursors of silicone include methyltrimethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyltripropoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltributoxysilane, and ethyltripropoxysilane. , Phenyltrimethoxysilane, phenyltriethoxysilane, phenyltributoxysilane,
Phenyltripropoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, diethyldipropoxysilane, phenylmethyldimethoxysilane, phenylmethyl Diethoxysilane, phenylmethyldibutoxysilane, phenylmethyldipropoxysilane, γ-glycidoxypropyltrimethoxysilane, a hydrolyzate thereof, and a mixture thereof can be suitably used.
【００１８】本発明の有機分とは、炭素、水素、酸素を
主たる元素として構成される有機化合物の含まれる割合
を言い、無機分とは、炭素を含まない化合物、金属およ
びその酸化物で無機化合物の含まれる割合のこと言う。The organic component of the present invention refers to the proportion of an organic compound composed mainly of carbon, hydrogen and oxygen, and the inorganic component refers to a compound containing no carbon, a metal and an oxide thereof. It refers to the percentage of the compound contained.
【００１９】アクリル変性シリコンはアクリル樹脂とシ
リコーン樹脂と複合化し、ブロック共重合させたもの、
グラフト重合させたもの、ポリメタクリレート樹脂とシ
リコーン樹脂を複合化させたもの等である。樹脂中のシ
リコン成分の含有量は、光触媒による酸化劣化に対して
強固であれば良いが、５％から８０％が好ましく、中で
も１０％から６０％が特に好ましい。表面硬度を高めた
り、柔軟性を高める目的でアクリル変性シリコン中にシ
リカを添加したり、アクリル変性シリコンを２種以上混
合したり、シリコーン系樹脂を添加してもよい。ここに
用いるシリコーン系樹脂はシリコーン樹脂、アルキド変
性シリコン、ウレタン変性シリコン、ポリエステル変性
シリコン、エポキシ変性シリコン等が利用できる。 ア
クリル変性シリコンは光安定剤を混合すると耐久性の向
上に効果がある。光安定剤としてはヒンダードアミン
系、トリアゾール等の紫外線吸収剤を単独、あるいは混
合して利用することができる。 アクリル変性シリコン
の膜形成方法としてはバーコート、フローコート、スプ
レーコートなど塗料の一般的な塗布方法と同様な方法が
可能である。熱処理により硬化させることも可能であ
り、常温にて硬化させることも可能である。 尚、接着
層としてはアクリル変性シリコン以外に、アルキド変性
シリコン、ウレタン変性シリコン、ポリエステル変性シ
リコン、エポキシ変性シリコン等が使用できる。 本発
明が適用可能な基材としての材質は、例えば金属、セラ
ミックス、ガラス、プラスチックス、木、石、セメン
ト、コンクリート、繊維、布、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、乗り物の外装、および塗装、機械装置や物品
の外装、防塵カバー、および塗装、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、および塗装、トンネル内装、および
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、食器洗浄機、食器乾燥機、流し、調理レン
ジ、キッチンフード、換気扇、および上記物品表面に貼
付させるためのフィルムを含む。Acrylic-modified silicone is obtained by compounding an acrylic resin and a silicone resin and subjecting them to block copolymerization.
Examples thereof include those obtained by graft polymerization and those obtained by compounding a polymethacrylate resin and a silicone resin. The content of the silicon component in the resin is not particularly limited as long as it is strong against oxidative deterioration caused by the photocatalyst, but is preferably 5% to 80%, and particularly preferably 10% to 60%. For the purpose of increasing the surface hardness or the flexibility, silica may be added to the acryl-modified silicon, two or more acryl-modified silicons may be mixed, or a silicone resin may be added. As the silicone resin used here, silicone resin, alkyd-modified silicone, urethane-modified silicone, polyester-modified silicone, epoxy-modified silicone and the like can be used. Acrylic-modified silicon is effective in improving durability when mixed with a light stabilizer. As the light stabilizer, an ultraviolet absorber such as a hindered amine or triazole can be used alone or as a mixture. As a method of forming a film of acrylic-modified silicon, a method similar to a general method of applying a paint, such as a bar coat, a flow coat, and a spray coat, can be used. Curing by heat treatment is also possible, and curing at room temperature is also possible. In addition, besides acrylic-modified silicon, alkyd-modified silicon, urethane-modified silicon, polyester-modified silicon, epoxy-modified silicon and the like can be used as the adhesive layer. As a material to which the present invention can be applied, for example, metal, ceramics, glass, plastics, wood, stone, cement, concrete, fiber, cloth, a combination thereof, and a laminate thereof can be suitably used. Speaking of applicable base materials, building materials, building exteriors, building interiors, window frames, window glasses,
Structural members, vehicle exteriors and paints, machinery and equipment exteriors, dustproof covers and paints, traffic signs, various display devices, advertising towers, road noise barriers, railway noise barriers, bridges, guardrail exteriors, and Painting, tunnel interiors and painting, insulators, solar cell covers, solar water heater heat collecting covers, greenhouses, vehicle lighting covers, housing equipment, toilets, bathtubs, washbasins, lighting fixtures, lighting covers, kitchenware, Dishware, dishwashers, dish dryers, sinks, cooking ranges, kitchen hoods, ventilation fans, and films for affixing to the article surface.
【００２０】[0020]
【実施例】実施例１ 光触媒層用の塗料は以下の要領で準備を行う。 光触媒
性材料としてはＴｉＯ 2（昭和電工製 ＦＴ−１ 固形
分１０％）を使用し、ＳｉＯ2はエチルシリケート（コ
ルコート製 ＥＳ４０）をメタノール、硝酸にて加水分
解したものを用いる。エチルシリケート（コルコート製
ＥＳ４０）の加水分解は以下の要領で行う。エチルシ
リケート（コルコート製 ＥＳ４０）を６．０ｇ、メタ
ノール（ＪＩＳ試薬特級）４４．７ｇ、２％硝酸水溶液
（試薬特級） ９．３ｇの混合物を３０℃で保温し、５
時間攪拌したものを用いる。光触媒用塗料は固形分を
１．０％、ＴｉＯ2とＳｉＯ2の重量比を４：１とするた
めにＴｉＯ2（昭和電工製 ＦＴ−１）を４０ｇ、エチ
ルシリケート（コルコート製 ＥＳ４０）加水分解物２
５ｇ、エチルアルコール４３５ｇにて混合する。混合物
をさらに３０℃で保温し、２時間攪拌し光触媒用塗料と
した。Example 1 A coating material for a photocatalyst layer is prepared in the following manner. photocatalyst
TiO as the conductive material Two(Showa Denko FT-1 solid
Min. 10%) using SiO 2TwoIs ethyl silicate
LeCoat ES40) is hydrolyzed with methanol and nitric acid.
Use the one that you understand. Ethyl silicate (Colcoat made
The hydrolysis of ES40) is performed as follows. Ethyl
6.0 g of RECATE (Colcoat ES40), meta
Knoll (JIS reagent special grade) 44.7 g, 2% nitric acid aqueous solution
(Reagent grade) 9.3 g of the mixture was kept warm at 30 ° C.
Use what was stirred for hours. Paint for photocatalyst
1.0%, TiOTwoAnd SiOTwoWeight ratio of 4: 1
TiOTwo40 g of (FT-1 manufactured by Showa Denko)
Lusilicate (Colcoat ES40) hydrolyzate 2
5 g and 435 g of ethyl alcohol are mixed. blend
Is further kept at 30 ° C. and stirred for 2 hours to form a coating for photocatalyst.
did.
【００２１】接着層塗料の調整を以下の要領で準備す
る。シリコン成分量１０〜２０％、アクリル成分量８０
〜９０％のアクリルシリコン塗料（鐘淵化学製 ゼムラ
ック ＹＣ３９１８）を有機スズ系硬化触媒 （鐘淵化
学製、ＢＴ１２０Ｓ）とそれぞれ重量比で１０：１とな
るように計りとり、接着層塗料とする。Preparation of the adhesive layer paint is prepared in the following manner. Silicon component amount 10-20%, acrylic component amount 80
A 90% acrylic silicone paint (Zemurac YC3918 manufactured by Kane-buchi Chemical Co., Ltd.) is weighed with an organotin-based curing catalyst (BT120S manufactured by Kane-buchi Chemical Co., Ltd.) in a weight ratio of 10: 1 to obtain an adhesive layer paint.
【００２２】試験片の作成 １００ミリ角に裁断したＰＥＴフィルム（ダイアホイル
ヘキスト製Ｓ１００）に上記のように調整した接着層を
塗布する。塗布の方法はバーコート、フローコート、ス
プレーコートなど塗料の一般的な塗布方法と同様な方法
が可能である。接着層を塗布したＰＥＴフィルムを１０
０℃の空気中で２０分間乾燥する。室温まで冷却させて
から、上記のように調整した光触媒塗料をバーコート方
により塗布する。光触媒塗料を塗布したＰＥＴフィルム
を１２０℃の空気中で３０分で乾燥させ、試験片を得
た。Preparation of Test Piece An adhesive layer adjusted as described above is applied to a PET film (S100 made by Diafoil Hoechst) cut into a 100 mm square. The application method can be a bar coating, flow coating, spray coating, or the like, which is the same as a general coating method of a paint. 10 PET film coated with adhesive layer
Dry in air at 0 ° C. for 20 minutes. After cooling to room temperature, the photocatalyst paint adjusted as described above is applied by a bar coating method. The PET film coated with the photocatalytic paint was dried in air at 120 ° C. for 30 minutes to obtain a test piece.
【００２３】実施例２ 接着層塗料に使用するアクリルシリコン塗料をシリコン
成分量２０〜３０％、アクリル成分量７０〜８０％のア
クリルシリコン塗料（鐘淵化学製 ゼムラックＹＣ３６
２３）とする以外は実施例１と同様である。Example 2 An acrylic silicone paint used for the adhesive layer paint was a silicone silicone paint having a silicon component content of 20 to 30% and an acrylic component content of 70 to 80% (Zemrak YC36 manufactured by Kaneguchi Chemical Co., Ltd.)
23 is the same as that of the first embodiment except for the case of 23).
【００２４】実施例３ シリコン成分量３０〜４０％、アクリル成分量６０〜７
０％のアクリルシリコン塗料（鐘淵化学製 ゼムラック
ＹＣ５９２０）とする以外は実施例１と同様である。Example 3 Silicon component amount 30-40%, acrylic component amount 60-7
Example 1 is the same as Example 1 except that 0% of acrylic silicon paint (Zemurac YC5920 manufactured by Kaneguchi Chemical Co., Ltd.) is used.
【００２５】実施例４ 光触媒層用の塗料は実施例１と同様の要領で準備を行
う。接着層塗料の調整を以下の要領で準備する。シリコ
ン成分量１０〜２０％、アルキド樹脂成分量８０〜９０
％のアルキド変性シリコン塗料（東レダウコーニングシ
リコーン製 ＳＲ２１１４）を接着層塗料とする。試験
片の作成 １００ミリ角に裁断した塩化ビニルフィルム
（信越ポリマー製ＳＧシート）に上記のように調整した
接着層を塗布する。塗布の方法はバーコート、フローコ
ート、スプレーコートなど塗料の一般的な塗布方法と同
様な方法が可能である。接着層を塗布した塩化ビニルフ
ィルムを８０℃の空気中で３０分間乾燥する。室温まで
冷却させてから、上記のように調整した光触媒塗料をバ
ーコート方により塗布する。光触媒塗料を塗布した塩化
ビニルフィルムを８０℃の空気中で３０分で乾燥させ、
試験片を得た。Example 4 A coating material for the photocatalyst layer is prepared in the same manner as in Example 1. The preparation of the adhesive coating is prepared as follows. Silicon component amount 10-20%, alkyd resin component amount 80-90
% Alkyd-modified silicone paint (SR2114 manufactured by Dow Corning Toray Silicone Co., Ltd.) is used as the adhesive paint. Preparation of Test Piece The adhesive layer adjusted as described above is applied to a vinyl chloride film (SG sheet made by Shin-Etsu Polymer) cut into 100 mm square. The application method can be a bar coating, flow coating, spray coating, or the like, which is the same as a general coating method of a paint. The vinyl chloride film coated with the adhesive layer is dried in air at 80 ° C. for 30 minutes. After cooling to room temperature, the photocatalyst paint adjusted as described above is applied by a bar coating method. The vinyl chloride film coated with the photocatalytic paint is dried in air at 80 ° C. for 30 minutes,
A test piece was obtained.
【００２６】比較例１ 接着層塗料として、シリコン成分量１００％の信越化学
製プラスチック用シリコンハードコート剤（ＫＰ８５
８）を用いる以外は実施例１と同様である。Comparative Example 1 As a coating material for an adhesive layer, a silicone hard coat agent for plastics (KP85, manufactured by Shin-Etsu Chemical Co., Ltd.) having a silicon content of 100%.
This is the same as Example 1 except that 8) is used.
【００２７】親水性能の評価 作成した試験片の親水性
を水との接触角により評価した。なお接触角測定には協
和界面科学製ＣＸ−１５０を使用した。試験片は紫外線
（ＢＬＢランプにより紫外線照度１．０ｍＷ／ｃｍ2）
を２４時間照射した後の水との接触角とした。Evaluation of hydrophilicity The hydrophilicity of the prepared test piece was evaluated by the contact angle with water. In addition, CX-150 made by Kyowa Interface Science was used for the contact angle measurement. The test piece was ultraviolet rays (ultraviolet illuminance 1.0 mW / cm 2 by BLB lamp)
For 24 hours after irradiation.
【００２８】密着性の評価 作成した試験片の基材（ＰＥＴフィルム、塩化ビニルフ
ィルム）との密着性を以下のように評価した。作成した
試験片の塗装膜の上からカッターで1ｍｍ幅の碁盤目の
切り込みを入れる。大きさは１ｃｍ角にし、碁盤目の数
を１００個とする。その後その碁盤目を完全に覆うよう
にセロハンテープを貼付ける。その後すばやく引き剥が
して、付着して残っている碁盤目の数を数える。 密着
性の指標としては引き剥がした後に付着している碁盤目
の数／１００（初期の碁盤目の数）で表すものとする。
各試験片の親水化性能、密着性能を表１に示す。Evaluation of Adhesion The adhesion of the prepared test piece to the substrate (PET film, vinyl chloride film) was evaluated as follows. A 1-mm-wide cross cut is made with a cutter from above the coating film of the prepared test piece. The size is 1 cm square, and the number of grids is 100. After that, a cellophane tape is stuck so as to completely cover the grid. After that, peel off quickly and count the number of grids remaining on the grid. The index of adhesion is represented by the number of grids attached after peeling / 100 (the number of initial grids).
Table 1 shows the hydrophilizing performance and adhesion performance of each test piece.
【００２９】[0029]
【表１】 [Table 1]
【００３０】表１においてアクリル変性シリコンを用い
ることで高い密着性が得られることが確認できた。アル
キド変性シリコンにおいても高い密着性が得られるが、
アクリル変性シリコンよりも若干密着性が落ちる。シリ
コン成分１００％のものでは全く密着性が得られなかっ
た。アクリル変性シリコンのシリコン成分が少ないほど
水との接触角が低いことが確認できた。In Table 1, it was confirmed that high adhesion was obtained by using acrylic-modified silicon. High adhesion is obtained even with alkyd-modified silicon,
Adhesion is slightly lower than acrylic-modified silicon. No adhesion was obtained at all with a silicon component of 100%. It was confirmed that the smaller the silicon component of the acryl-modified silicon, the lower the contact angle with water.
【００３１】実施例５ 実施例１の試験片の断面のＥＤＸ定性スペクトルを測定
し、各元素の強度比により有機分と無機分の存在比を確
認した。有機分と無機分の存在比を各元素の強度比によ
り強度比により存在比とした。測定位置は接着層の光触
媒層側（測定位置 基材面より２．６μｍ）、中間層の
中間部（測定位置基材面より１．３μｍ）、接着層の基
材側（測定位置 基材面より０．０μｍ）とした。 接
着層内でのシリコンとアクリルの存在比をケイ素（Ｓ
ｉ）と炭素（Ｃ）のスペクトル強度比を表２に示す。Example 5 An EDX qualitative spectrum of a cross section of the test piece of Example 1 was measured, and the presence ratio of organic and inorganic components was confirmed based on the intensity ratio of each element. The abundance ratio of the organic component and the inorganic component was defined as the abundance ratio based on the intensity ratio of each element. The measurement position is the photocatalytic layer side of the adhesive layer (2.6 μm from the base surface of the measurement position), the middle part of the intermediate layer (1.3 μm from the base surface of the measurement position), the base side of the adhesive layer (the base position of the measurement position 0.0 μm). The abundance ratio of silicon and acrylic in the adhesive layer
Table 2 shows the spectral intensity ratio between i) and carbon (C).
【００３２】実施例６ 実施例２の試験片の断面のＥＤＸ定性スペクトルを測定
し、各元素の強度比により有機分と無機分の存在比を確
認した。有機分と無機分の存在比を各元素の強度比によ
り強度比により存在比とした。測定位置は接着層の光触
媒層側（測定位置 基材面より２．６μｍ）、中間層の
中間部（測定位置基材面より１．３μｍ）、接着層の基
材側（測定位置 基材面より０．０μｍ）とした。 接
着層内でのシリコンとアクリルの存在比をケイ素（Ｓ
ｉ）と炭素（Ｃ）のスペクトル強度比を表２に示す。Example 6 The EDX qualitative spectrum of the cross section of the test piece of Example 2 was measured, and the ratio of the organic component to the inorganic component was confirmed based on the intensity ratio of each element. The abundance ratio of the organic component and the inorganic component was defined as the abundance ratio based on the intensity ratio of each element. The measurement position is the photocatalytic layer side of the adhesive layer (2.6 μm from the base surface of the measurement position), the middle part of the intermediate layer (1.3 μm from the base surface of the measurement position), the base side of the adhesive layer (the base position of the measurement position 0.0 μm). The abundance ratio of silicon and acrylic in the adhesive layer
Table 2 shows the spectral intensity ratio between i) and carbon (C).
【００３３】実施例７ 実施例３の試験片の断面のＥＤＸ定性スペクトルを測定
し、各元素の強度比により有機分と無機分の存在比を確
認した。有機分と無機分の存在比を各元素の強度比によ
り強度比により存在比とした。 測定位置は接着層の光
触媒層側（測定位置 基材面より３．０μｍ）、中間層
の中間部（測定位置基材面より１．５μｍ）、接着層の
基材側（測定位置 基材面より０．０μｍ）とした。
接着層内でのシリコンとアクリルの存在比をケイ素（Ｓ
ｉ）と炭素（Ｃ）のスペクトル強度比を表２に示す。Example 7 The EDX qualitative spectrum of the cross section of the test piece of Example 3 was measured, and the ratio of the organic component to the inorganic component was confirmed based on the intensity ratio of each element. The abundance ratio of the organic component and the inorganic component was defined as the abundance ratio based on the intensity ratio of each element. The measurement position is the photocatalytic layer side of the adhesive layer (3.0 μm from the base surface of the measurement position), the middle part of the intermediate layer (1.5 μm from the base surface of the measurement position), the base side of the adhesive layer (the base position of the measurement position 0.0 μm).
The abundance ratio of silicon and acrylic in the adhesive layer
Table 2 shows the spectral intensity ratio between i) and carbon (C).
【００３４】[0034]
【表２】 [Table 2]
【００３５】表２よりアクリル変性シリコンのシリコン
成分がいずれの場合も中間層内の無機分の濃度が基材表
面に近づくにつれ低くなり、有機分の濃度は表面層に近
づくにつれて低くなることが確認できた。From Table 2, it was confirmed that the concentration of the inorganic component in the intermediate layer became lower as approaching the surface of the base material and the concentration of the organic component became lower as approaching the surface layer in each case where the silicon component of the acryl-modified silicon was used. did it.
【００３６】[0036]
【発明の効果】本発明では、加工性が高く、基材の耐熱
性が低い場合でも、光触媒性材料を含む表面層との密着
性の高い接着層を備えた光触媒性親水性複合材料を提供
することができる。According to the present invention, there is provided a photocatalytic hydrophilic composite material having an adhesive layer having high adhesion to a surface layer containing a photocatalytic material even when the workability is high and the heat resistance of the substrate is low. can do.
フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ０８Ｊ 7/04 ＣＦＤ Ｃ０８Ｊ 7/04 ＣＦＤＥ // Ｂ０５Ｄ 7/24 ３０１ Ｂ０５Ｄ 7/24 ３０１Ｐ Continued on the front page (51) Int.Cl. 6 Identification code FI C08J 7/04 CFD C08J 7/04 CFDE // B05D 7/24 301 B05D 7/24 301P
Claims (6)
を含む表面層が形成されている光触媒性親水性複合材料
において、前記接着層の表面層側が無機分の濃度が高
く、基材表面側が有機分の濃度が高いことを特徴とする
光触媒性親水性複合材料。1. A photocatalytic hydrophilic composite material having a surface layer containing a photocatalytic material formed on a surface of a substrate via an adhesive layer, wherein the surface layer side of the adhesive layer has a high inorganic content, and A photocatalytic hydrophilic composite material, wherein the surface side has a high concentration of organic components.
近づくにつれて連続的または段階的に低くなり、且つ、
有機分の濃度は表面層に近づくにつれて連続的または段
階的に低くなることを特徴とする請求項１記載の光触媒
性親水性複合材料。2. The concentration of the inorganic component in the adhesive layer decreases continuously or stepwise as it approaches the surface of the base material, and
2. The photocatalytic hydrophilic composite material according to claim 1, wherein the concentration of the organic component decreases continuously or stepwise as it approaches the surface layer.
ることを特徴とする請求項２記載の光触媒性親水性複合
材料。3. The photocatalytic hydrophilic composite material according to claim 2, wherein said adhesive layer is made of acrylic-modified silicon.
リコン成分が１０〜２０％で、アクリル成分が８０〜９
０％であることを特徴とする請求項３記載の光触媒性親
水性複合材料。4. The adhesive-modified silicone of the adhesive layer has a silicon component of 10 to 20% and an acrylic component of 80 to 9%.
The photocatalytic hydrophilic composite material according to claim 3, wherein the content is 0%.
請求項１〜４いずれか１項記載の光触媒性親水性複合材
料。5. The photocatalytic hydrophilic composite material according to claim 1, wherein the substrate is a resin.
であることを特徴とする請求項５記載の光触媒性親水性
複合材料。6. The photocatalytic hydrophilic composite material according to claim 5, wherein said base material is polyethylene terephthalate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10327322A JPH11320750A (en) | 1998-03-18 | 1998-11-17 | Photocatalytic hydrophilic composite material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10-89525 | 1998-03-18 | ||
| JP8952598 | 1998-03-18 | ||
| JP10327322A JPH11320750A (en) | 1998-03-18 | 1998-11-17 | Photocatalytic hydrophilic composite material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11320750A true JPH11320750A (en) | 1999-11-24 |
Family
ID=26430946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10327322A Pending JPH11320750A (en) | 1998-03-18 | 1998-11-17 | Photocatalytic hydrophilic composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11320750A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010513006A (en) * | 2006-12-19 | 2010-04-30 | デグサ ノヴァラ テクノロジー ソチエタ ペル アツィオーニ | Sol-gel method for producing protective coatings for polymer substrates |
| JP2011131447A (en) * | 2009-12-24 | 2011-07-07 | Kimoto & Co Ltd | Photocatalyst sheet |
-
1998
- 1998-11-17 JP JP10327322A patent/JPH11320750A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010513006A (en) * | 2006-12-19 | 2010-04-30 | デグサ ノヴァラ テクノロジー ソチエタ ペル アツィオーニ | Sol-gel method for producing protective coatings for polymer substrates |
| JP2011131447A (en) * | 2009-12-24 | 2011-07-07 | Kimoto & Co Ltd | Photocatalyst sheet |
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