JP2005194309A - Composition for forming adhesive layer and photocatalyst-carrying structure - Google Patents
Composition for forming adhesive layer and photocatalyst-carrying structure Download PDFInfo
- Publication number
- JP2005194309A JP2005194309A JP2003435373A JP2003435373A JP2005194309A JP 2005194309 A JP2005194309 A JP 2005194309A JP 2003435373 A JP2003435373 A JP 2003435373A JP 2003435373 A JP2003435373 A JP 2003435373A JP 2005194309 A JP2005194309 A JP 2005194309A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- adhesive layer
- layer
- composition
- structure according
- 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.)
- Granted
Links
- 239000012790 adhesive layer Substances 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims abstract description 54
- 239000011941 photocatalyst Substances 0.000 claims abstract description 140
- 239000010410 layer Substances 0.000 claims abstract description 63
- 229920005989 resin Polymers 0.000 claims abstract description 46
- 239000011347 resin Substances 0.000 claims abstract description 46
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 17
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 66
- -1 silicon alkoxide Chemical class 0.000 claims description 63
- 239000002245 particle Substances 0.000 claims description 54
- 239000008119 colloidal silica Substances 0.000 claims description 36
- 229910052782 aluminium Inorganic materials 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 150000003755 zirconium compounds Chemical class 0.000 claims description 24
- 229910052710 silicon Inorganic materials 0.000 claims description 22
- 239000010703 silicon Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 150000004703 alkoxides Chemical class 0.000 claims description 16
- 239000000377 silicon dioxide Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 238000002834 transmittance Methods 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000011156 evaluation Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 150000004679 hydroxides Chemical class 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 238000002296 dynamic light scattering Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 description 20
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 229920002050 silicone resin Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 4
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 150000001299 aldehydes Chemical class 0.000 description 3
- 229920000180 alkyd Polymers 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 239000011254 layer-forming composition Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- LVNLBBGBASVLLI-UHFFFAOYSA-N 3-triethoxysilylpropylurea Chemical compound CCO[Si](OCC)(OCC)CCCNC(N)=O LVNLBBGBASVLLI-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- PPQREHKVAOVYBT-UHFFFAOYSA-H dialuminum;tricarbonate Chemical compound [Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O PPQREHKVAOVYBT-UHFFFAOYSA-H 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 229940090181 propyl acetate Drugs 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- MLZYAQWUAMPXFU-UHFFFAOYSA-M C(C(O)C)(=O)[O-].[O-]CCCC.[O-]CCCC.[Zr+3] Chemical compound C(C(O)C)(=O)[O-].[O-]CCCC.[O-]CCCC.[Zr+3] MLZYAQWUAMPXFU-UHFFFAOYSA-M 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910019899 RuO Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- KGBUQHGXOAESDX-UHFFFAOYSA-N [Zr].OOO Chemical compound [Zr].OOO KGBUQHGXOAESDX-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229940118662 aluminum carbonate Drugs 0.000 description 1
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- ZCLVNIZJEKLGFA-UHFFFAOYSA-H bis(4,5-dioxo-1,3,2-dioxalumolan-2-yl) oxalate Chemical compound [Al+3].[Al+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZCLVNIZJEKLGFA-UHFFFAOYSA-H 0.000 description 1
- 238000012661 block copolymerization Methods 0.000 description 1
- NIOLTQNBOYMEQK-UHFFFAOYSA-N butan-1-olate;zirconium(2+) Chemical compound [Zr+2].CCCC[O-].CCCC[O-] NIOLTQNBOYMEQK-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
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- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 239000012046 mixed solvent Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
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- 239000005011 phenolic resin Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- PFWZXDDTAYMUPE-UHFFFAOYSA-N propan-2-ol;1,2-xylene Chemical compound CC(C)O.CC1=CC=CC=C1C PFWZXDDTAYMUPE-UHFFFAOYSA-N 0.000 description 1
- OGHBATFHNDZKSO-UHFFFAOYSA-N propan-2-olate Chemical compound CC(C)[O-] OGHBATFHNDZKSO-UHFFFAOYSA-N 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 125000006225 propoxyethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 239000008279 sol Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Landscapes
- Laminated Bodies (AREA)
- Catalysts (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
本発明は、担体と、該担体上に形成された接着層と、および該接着層上に形成された光触媒層とを有する光触媒担持構造体の接着層の形成に用いる接着層形成用組成物、およびこの接着層形成用組成物から形成されてなる接着層を有する光触媒担持構造体に関する。 The present invention provides a composition for forming an adhesive layer used for forming an adhesive layer of a photocatalyst-supporting structure having a carrier, an adhesive layer formed on the carrier, and a photocatalyst layer formed on the adhesive layer, And a photocatalyst-supporting structure having an adhesive layer formed from the composition for forming an adhesive layer.
従来から、担体上に、接着層を介して光触媒層が形成された光触媒担持構造体が知られている。かかる光触媒担持構造体は、通常担体表面に、接着層形成用塗布液（接着層形成用組成物）を塗布して接着層を形成し、さらにこの接着層上に光触媒成分を含有する光触媒層形成用塗布液を塗布、硬化させることにより光触媒層を形成することにより製造されている（特許文献１、２等）。このような光触媒担持構造体は、レンズ、窓ガラス、粘着フィルム、化粧シート、壁紙、カーテン、ブラインド等のような各種建築材料やインテリア製品等に利用されている。 Conventionally, a photocatalyst carrying structure in which a photocatalyst layer is formed on a carrier via an adhesive layer is known. Such a photocatalyst-supporting structure usually forms an adhesive layer by applying an adhesive layer-forming coating solution (adhesive layer-forming composition) on the surface of the carrier, and further, a photocatalyst layer containing a photocatalytic component is formed on the adhesive layer. It is manufactured by forming a photocatalyst layer by applying and curing a coating solution (Patent Documents 1, 2, etc.). Such a photocatalyst carrying structure is used for various building materials and interior products such as lenses, window glass, adhesive films, decorative sheets, wallpaper, curtains, blinds and the like.
しかしながら、従来の光触媒担持構造体は、耐候性が要求される場所、特に、長期間に亘って風雨にさらされる場合がある屋外で使用する場合に、光触媒層が部分的あるいは全面的に担体から剥離して充分な光触媒活性を発揮できなくなることがあり、問題となっていた。 However, the conventional photocatalyst-supporting structure has a photocatalyst layer partially or completely removed from the support when used in places where weather resistance is required, particularly outdoors where it may be exposed to wind and rain for a long time. This may cause a problem in that the photocatalytic activity may not be exhibited due to peeling.
本発明は、かかる従来技術の問題に鑑みてなされたものであり、担体と、該担体上に形成された接着層と、および該接着層上に形成された光触媒層とを有する光触媒担持構造体において、耐候性に優れる光触媒担持構造体を得ることができる接着層形成用組成物および光触媒担持構造体を提供することを課題とする。 The present invention has been made in view of the problems of the prior art, and has a photocatalyst-supporting structure having a carrier, an adhesive layer formed on the carrier, and a photocatalyst layer formed on the adhesive layer. In the above, it is an object to provide a composition for forming an adhesive layer and a photocatalyst carrying structure capable of obtaining a photocatalyst carrying structure having excellent weather resistance.
本発明者らは、耐候性を向上させるためには、接着層形成用組成物中にシリカの含有量を増加させる必要があると考えた。しかしながら、接着層形成用組成物中におけるシリカの含有量を高くすると、担体と光触媒層との層間密着性が低下するという新たな問題が生じた。そこで、鋭意研究した結果、接着層形成用組成物にシランカップリング剤の所定量を添加すると、シリカの含有量が高くても、優れた層間密着性と耐候性を有する接着層を形成することができ、光触媒の活性も良好な光触媒担持構造体が得られることを見出し、本発明を完成するに至った。 The present inventors considered that it is necessary to increase the content of silica in the composition for forming an adhesive layer in order to improve the weather resistance. However, when the content of silica in the composition for forming an adhesive layer is increased, there arises a new problem that the interlayer adhesion between the carrier and the photocatalyst layer is lowered. Therefore, as a result of earnest research, when a predetermined amount of a silane coupling agent is added to the composition for forming an adhesive layer, an adhesive layer having excellent interlayer adhesion and weather resistance can be formed even if the content of silica is high. Thus, the present inventors have found that a photocatalyst-supporting structure having good photocatalytic activity can be obtained, and the present invention has been completed.
すなわち、本発明は、
（１）担体と光触媒層とを接着する接着層形成用組成物であって、（ａ）シリコン変性樹脂、及び／又は（ｂ）式（１）
That is, the present invention
(1) An adhesive layer forming composition for bonding a carrier and a photocatalyst layer, wherein (a) a silicon-modified resin and / or (b) formula (1)
〔式中、Ｒ１は、（アミノ基、カルボキシル基または塩素原子で置換されていてもよい）炭素数１〜８のアルキル基を表し、Ｒ２は、アルコキシ基で置換されていてもよい炭素数１〜８のアルキル基を表し、ｎ１は０〜２の整数を表し、ｎ２及びｎ３は０〜３の整数を表し、ｎ４は２〜４の整数を表し、かつｎ１＋ｎ２＋ｎ３＋ｎ４＝４である。〕で表される化合物の重縮合反応生成物を含有する樹脂、並びにシランカップリング剤を含有してなり、Ｓｉの総含有量が、ＳｉＯ２に換算して接着層の全固形分に対して５５〜９５重量％であることを特徴とする接着層形成用組成物、
（２）前記接着層形成用組成物が、シランカップリング剤を、（ａ）シリコン変性樹脂及び／又は（ｂ）前記式（１）で表される化合物の重縮合反応生成物を含有する樹脂に対して、１〜１０重量％含有してなることを特徴とする（１）の接着層形成用組成物、
（３）前記シリコン変性樹脂が、アクリルシリコン樹脂であることを特徴とする（１）または（２）の接着層形成用組成物、
（４）前記式（１）で表される化合物の重縮合反応生成物が、炭素数１〜５のアルコキシ基を少なくとも１個有するシリコンアルコキシドの重縮合反応生成物であることを特徴とする（１）〜（３）のいずれかの接着層形成用組成物、を提供する。
[Wherein R 1 represents an alkyl group having 1 to 8 carbon atoms (which may be substituted with an amino group, a carboxyl group or a chlorine atom), and R 2 represents carbon which may be substituted with an alkoxy group. N 1 represents an integer of 0 to 2, n 2 and n 3 represent an integer of 0 to 3, n 4 represents an integer of 2 to 4, and n 1 + n 2 + n 3 + n 4 = 4. A resin containing a polycondensation reaction product of the compound represented by formula ( II) and a silane coupling agent, and the total content of Si is converted to SiO 2 with respect to the total solid content of the adhesive layer. A composition for forming an adhesive layer, which is 55 to 95% by weight;
(2) The adhesive layer forming composition contains a silane coupling agent, (a) a silicon-modified resin and / or (b) a polycondensation reaction product of a compound represented by the formula (1). 1 to 10% by weight of the composition for forming an adhesive layer according to (1),
(3) The composition for forming an adhesive layer according to (1) or (2), wherein the silicon-modified resin is an acrylic silicon resin,
(4) The polycondensation reaction product of the compound represented by the formula (1) is a polycondensation reaction product of a silicon alkoxide having at least one alkoxy group having 1 to 5 carbon atoms ( An adhesive layer forming composition according to any one of 1) to (3) is provided.
また、本発明は、
（５）担体と、該担体上に形成された接着層と、該接着層上に形成された光触媒層とを有する光触媒担持構造体であって、前記接着層が、本発明の接着層形成用組成物から形成されたものであることを特徴とする光触媒担持構造体、
（６）前記光触媒層が、光触媒及びシリカを含有する光触媒複合体からなることを特徴とする（５）の光触媒担持構造体、
（７）前記光触媒層が、光触媒、シリカ、並びにジルコニウム化合物およびアルミニウム化合物から選ばれる少なくとも１種を含有する光触媒複合体からなることを特徴とする（５）または（６）の光触媒担持構造体、
（８）前記シリカが、球状コロイダルシリカ粒子が細長い鎖状に結合してなる鎖状コロイダルシリカ粒子であることを特徴とする（６）または（７）の光触媒担持構造体、
（９）前記球状コロイダルシリカ粒子が、粒子径が１０〜５０ｎｍである球状コロイダルシリカ粒子であることを特徴とする（８）の光触媒担持構造体、
（１０）前記鎖状コロイダルシリカ粒子が、長さ５０〜４００ｎｍの鎖状コロイダルシリカ粒子であることを特徴とする（８）または（９）の光触媒担持構造体、
The present invention also provides:
(5) A photocatalyst carrying structure having a carrier, an adhesive layer formed on the carrier, and a photocatalyst layer formed on the adhesive layer, wherein the adhesive layer is used for forming the adhesive layer of the present invention. A photocatalyst-supporting structure, wherein the photocatalyst-supporting structure is formed from a composition;
(6) The photocatalyst layer is composed of a photocatalyst composite containing a photocatalyst and silica,
(7) The photocatalyst layer comprises a photocatalyst composite containing at least one selected from photocatalyst, silica, and a zirconium compound and an aluminum compound, (5) or (6),
(8) The photocatalyst-supporting structure according to (6) or (7), wherein the silica is a chain colloidal silica particle formed by combining spherical colloidal silica particles in an elongated chain shape,
(9) The photocatalyst-supporting structure according to (8), wherein the spherical colloidal silica particles are spherical colloidal silica particles having a particle diameter of 10 to 50 nm,
(10) The photocatalyst-supporting structure according to (8) or (9), wherein the chain colloidal silica particles are chain colloidal silica particles having a length of 50 to 400 nm,
（１１）前記鎖状コロイダルシリカ粒子が、動的光散乱法による測定粒子径（Ｄ１）が４０〜３００ｎｍであり、Ｄ１と窒素ガス吸着法による測定粒子径（Ｄ２）の比（Ｄ１／Ｄ２）が５以上であって、電子顕微鏡観察による５〜２０ｎｍの範囲内の一様な太さで一平面内のみの伸長を有する非晶質コロイダルシリカ粒子であることを特徴とする（８）〜（１０）の光触媒担持構造体、
（１２）前記ジルコニウム化合物が、ジルコニウムの、酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物であることを特徴とする（７）の光触媒担持構造体、
（１３）前記アルミニウム化合物が、アルミニウムの、酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド及び該アルコキシドの加水分解物からなる群から選ばれる１種または２種以上の混合物であることを特徴とする（７）または（１２）の光触媒担持構造体、
（１４）前記ジルコニウム化合物および／またはアルミニウム化合物が、１５０℃で乾燥後の比表面積が１００ｍ２／ｇ以上の多孔質ゲルであることを特徴とする（７）、（１２）または（１３）の光触媒担持構造体、
（１５）前記光触媒層が、光触媒複合体全体に対して、シリカを５〜５０重量％、光触媒を５〜６０重量％含有する層であることを特徴とする（６）〜（１４）いずれかの光触媒担持構造体、
（１６）前記光触媒層が、光触媒複合体全体に対して、ジルコニウム化合物を、酸化物に換算して５〜４０重量％含有することを特徴とする（７）〜（１５）いずれかの光触媒担持構造体、
(11) The chain colloidal silica particles have a particle diameter (D1) measured by a dynamic light scattering method of 40 to 300 nm, and a ratio (D1 / D2) of D1 and a particle diameter (D2) measured by a nitrogen gas adsorption method. Is an amorphous colloidal silica particle having a uniform thickness within a range of 5 to 20 nm by electron microscope observation and having elongation only in one plane (8) to ( 10) a photocatalyst carrying structure,
(12) The zirconium compound is selected from the group consisting of an oxide, an oxide hydroxide, a hydroxide, an oxynitrate, an oxycarbonate, an alkoxide having 1 to 4 carbon atoms, and a hydrolyzate of the alkoxide of zirconium. The photocatalyst-supporting structure according to (7), which is a single type or a mixture of two or more types,
(13) The aluminum compound is selected from the group consisting of aluminum oxides, oxide hydroxides, hydroxides, oxynitrates, oxycarbonates, alkoxides having 1 to 4 carbon atoms, and hydrolysates of the alkoxides. (7) or (12) a photocatalyst-supporting structure, which is one or a mixture of two or more,
(14) The zirconium compound and / or the aluminum compound is a porous gel having a specific surface area after drying at 150 ° C. of 100 m 2 / g or more, according to (7), (12) or (13) Photocatalyst carrying structure,
(15) The photocatalyst layer is a layer containing 5 to 50% by weight of silica and 5 to 60% by weight of photocatalyst with respect to the entire photocatalyst complex, and any one of (6) to (14) Photocatalyst carrying structure,
(16) The photocatalyst layer contains a zirconium compound in an amount of 5 to 40% by weight in terms of an oxide with respect to the entire photocatalyst complex, (7) to (15) Structure,
（１７）前記光触媒層が、光触媒複合体全体に対して、前記アルミニウム化合物を、酸化物に換算して２０〜９０重量％含有することを特徴とする（７）〜（１６）いずれかの光触媒担持構造体、
（１８）前記接着層の厚さが、０．１〜２００μｍであることを特徴とする（５）〜（１７）いずれかの光触媒担持構造体、
（１９）前記光触媒層の厚さが、０．１〜２００μｍであることを特徴とする（５）〜（１８）いずれかの光触媒担持構造体、
（２０）前記接着層と光触媒層とを合計した、波長５５０ｎｍの光の全光線透過率が７０％以上であることを特徴とする（５）〜（１９）いずれかの光触媒担持構造体、
（２１）紫外線強度３ｍＷ／ｃｍ２のブラックライトの光を、温度４０℃、相対湿度９０％のもとで５００時間照射した後の、ＪＩＳ Ｋ５４００の碁盤目テープ法による付着性の評価点数が、６点以上であることを特徴とする（５）〜（２０）いずれかの光触媒担持構造体、を提供する。
(17) The photocatalyst layer contains the aluminum compound in an amount of 20 to 90% by weight in terms of an oxide with respect to the entire photocatalyst complex, (7) to (16) Carrying structure,
(18) The photocatalyst-supporting structure according to any one of (5) to (17), wherein the adhesive layer has a thickness of 0.1 to 200 μm,
(19) The photocatalyst layer having a thickness of 0.1 to 200 μm, (5) to (18)
(20) The photocatalyst-supporting structure according to any one of (5) to (19), wherein the total light transmittance of light having a wavelength of 550 nm is 70% or more, wherein the adhesive layer and the photocatalyst layer are combined.
(21) The evaluation score of adhesion by the cross-cut tape method of JIS K5400 after irradiating light of a black light with an ultraviolet intensity of 3 mW / cm 2 at a temperature of 40 ° C. and a relative humidity of 90% for 500 hours, The photocatalyst-supporting structure according to any one of (5) to (20), characterized in that it has 6 or more points.
本発明の接着層形成用組成物によれば、優れた層間密着性と耐候性を有する接着層を形成することができる。
本発明の光触媒担持構造体は、接着層により光触媒が担体に強固に接着されており、光触媒活性が非常に高く、しかも光触媒作用により担体が劣化したり、光触媒が脱離したりすることがない。
本発明の光触媒担持構造体は耐候性に優れているため、高温多湿の環境下や屋外の環境下でも長期間使用することができる。
According to the composition for forming an adhesive layer of the present invention, an adhesive layer having excellent interlayer adhesion and weather resistance can be formed.
In the photocatalyst carrying structure of the present invention, the photocatalyst is firmly adhered to the carrier by the adhesive layer, the photocatalytic activity is very high, and the carrier is not deteriorated or detached by the photocatalytic action.
Since the photocatalyst carrying structure of the present invention is excellent in weather resistance, it can be used for a long time even in a high temperature and high humidity environment or an outdoor environment.
以下、本発明を、１）接着層形成用組成物と２）光触媒担持構造体に項分けして詳細に説明する。
１）接着層形成用組成物
本発明の接着層形成用組成物は、担体と光触媒層とを接着する接着層形成用組成物であって、（ａ）シリコン変性樹脂及び／又は（ｂ）前記式（１）で表される化合物の重縮合反応生成物を含有する樹脂、並びにシランカップリング剤を含有してなり、Ｓｉの総含有量が、ＳｉＯ２に換算して接着層の全固形分に対して５５〜９５重量％であることを特徴とする。
Hereinafter, the present invention will be described in detail by dividing it into 1) a composition for forming an adhesive layer and 2) a photocatalyst carrying structure.
1) Adhesive layer forming composition The adhesive layer forming composition of the present invention is an adhesive layer forming composition for adhering a carrier and a photocatalyst layer, and comprises (a) a silicon-modified resin and / or (b) the above-mentioned A resin containing a polycondensation reaction product of the compound represented by formula (1) and a silane coupling agent, and the total content of Si in terms of SiO 2 is the total solid content of the adhesive layer. It is characterized by being 55 to 95% by weight with respect to.
（ａ）シリコン変性樹脂
シリコン変性樹脂としては、シリコンを含有する樹脂であれば特に制約はない。
樹脂としては、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂、アルキッド樹脂、ウレタン樹脂、フェノール樹脂等が挙げられる。
(A) Silicon-modified resin The silicon-modified resin is not particularly limited as long as it is a resin containing silicon.
Examples of the resin include acrylic resin, epoxy resin, polyester resin, alkyd resin, urethane resin, and phenol resin.
シリコンを樹脂に導入する方法としては特に制約はなく、エステル交換反応、シリコンマクロマーや反応性シリコンモノマーを用いたグラフト反応、ヒドロシリル化反応、ブロック共重合法等が挙げられる。 The method for introducing silicon into the resin is not particularly limited, and examples thereof include a transesterification reaction, a graft reaction using a silicon macromer or a reactive silicon monomer, a hydrosilylation reaction, and a block copolymerization method.
シリコン変性樹脂としては、アクリルシリコン樹脂、エポキシシリコン樹脂、ポリエステルシリコン樹脂、アルキドシリコン樹脂、ウレタンシリコン樹脂等が挙げられる。これらの中でも、アクリルシリコン樹脂、エポキシシリコン樹脂、ポリエステルシリコン樹脂が好ましく、成膜性、強靭性、担体との密着性の点から、アクリルシリコン樹脂がより好ましい。これらの樹脂は、溶液状であってもエマルジョンタイプであってもどちらでも使用できる。また、架橋剤等の添加物が含まれていてもよい。 Examples of the silicon-modified resin include acrylic silicone resin, epoxy silicone resin, polyester silicone resin, alkyd silicone resin, and urethane silicone resin. Among these, an acrylic silicon resin, an epoxy silicon resin, and a polyester silicon resin are preferable, and an acrylic silicon resin is more preferable from the viewpoint of film formability, toughness, and adhesion to a carrier. These resins can be used in either a solution form or an emulsion type. Moreover, additives, such as a crosslinking agent, may be contained.
（ｂ）前記式（１）で表される化合物の重縮合反応生成物を含有する樹脂
前記式（１）中、Ｒ１は、（アミノ基、カルボキシル基又は塩素原子で置換されていてもよい）炭素数１〜８のアルキル基を表す。
具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−へキシル基、ｎ−ヘプチル基、ｎ−オクチル基、アミノメチル基、アミノエチル基、カルボキシメチル基、カルボキシエチル基、クロロメチル基、クロロエチル基、クロロプロピル基等が挙げられる。
(B) Resin containing a polycondensation reaction product of the compound represented by the formula (1) In the formula (1), R 1 may be substituted with an amino group, a carboxyl group or a chlorine atom. ) Represents an alkyl group having 1 to 8 carbon atoms.
Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- Examples include hexyl group, n-heptyl group, n-octyl group, aminomethyl group, aminoethyl group, carboxymethyl group, carboxyethyl group, chloromethyl group, chloroethyl group, chloropropyl group and the like.
Ｒ２は、アルコキシ基で置換されていてもよい炭素数１〜８のアルキル基を表す。
具体的には、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔ−ブチル基、ｎ−ペンチル基、イソペンチル基、ネオペンチル基、ｎ−へキシル基、ｎ−ヘプチル基、ｎ−オクチル基等の炭素数１〜８のアルキル基；メトキシメチル基、エトキシメチル基、プロポキシメチル基、イソプロポキシメチル基、ブトキシメチル基、メトキシエチル基、エトキシメチル基、プロポキシエチル基、メトキシプロピル基、メトキシブチル基等のアルコキシ基で置換された炭素数１〜８のアルキル基等が挙げられる。
R 2 represents an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group.
Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n- C1-C8 alkyl groups such as hexyl group, n-heptyl group, n-octyl group; methoxymethyl group, ethoxymethyl group, propoxymethyl group, isopropoxymethyl group, butoxymethyl group, methoxyethyl group, ethoxy Examples thereof include an alkyl group having 1 to 8 carbon atoms substituted with an alkoxy group such as a methyl group, a propoxyethyl group, a methoxypropyl group, and a methoxybutyl group.
ｎ１は０〜２の整数を表し、ｎ２及びｎ３は０〜３の整数を表し、ｎ４は２〜４の整数を表し、かつｎ１＋ｎ２＋ｎ３＋ｎ４＝４である。 n 1 represents an integer of 0 to 2, n 2 and n 3 represent an integer of 0 to 3, n 4 represents an integer of 2 to 4, and n 1 + n 2 + n 3 + n 4 = 4.
前記式（１）で表される化合物（以下、「化合物（１）」という。）の具体例としては、Ｓｉ（ＯＣＨ３）４、Ｓｉ（ＯＣ２Ｈ５）４、Ｓｉ（ＯＣ３Ｈ７）４、Ｓｉ（ＯＣ４Ｈ９）４、Ｓｉ（ＯＣ５Ｈ１１）４、Ｓｉ（ＯＣ６Ｈ１３）４、ＳｉＣＨ３（ＯＣＨ３）３、ＳｉＣＨ３（ＯＣ２Ｈ５）３、ＳｉＣＨ３（ＯＣ３Ｈ７）３、ＳｉＣＨ３（ＯＣ３Ｈ７）３、ＳｉＣＨ３（ＯＣ４Ｈ９）３、ＳｉＣｌ（ＯＣＨ３）３、ＳｉＣｌ（ＯＣ２Ｈ５）３、ＳｉＣｌ（ＯＣ３Ｈ７）３、ＳｉＣｌ（ＯＣ４Ｈ９）３、ＳｉＣｌ（ＯＣ６Ｈ１３）３、ＳｉＣｌ（ＯＨ）（ＯＣＨ３）２、ＳｉＣｌ（ＯＨ）（ＯＣ２Ｈ５）２、ＳｉＣｌ（ＯＨ）（ＯＣ３Ｈ７）２、ＳｉＣｌ（ＯＨ）（ＯＣ４Ｈ９）２、ＳｉＣｌ２（ＯＣＨ３）２、ＳｉＣｌ２（ＯＣ２Ｈ５）２等が挙げられる。 Specific examples of the compound represented by the formula (1) (hereinafter referred to as “compound (1)”) include Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7). ) 4 , Si (OC 4 H 9 ) 4 , Si (OC 5 H 11 ) 4 , Si (OC 6 H 13 ) 4 , SiCH 3 (OCH 3 ) 3 , SiCH 3 (OC 2 H 5 ) 3 , SiCH 3 (OC 3 H 7 ) 3 , SiCH 3 (OC 3 H 7 ) 3 , SiCH 3 (OC 4 H 9 ) 3 , SiCl (OCH 3 ) 3 , SiCl (OC 2 H 5 ) 3 , SiCl (OC 3 H 7 ) 3 , SiCl (OC 4 H 9 ) 3 , SiCl (OC 6 H 13 ) 3 , SiCl (OH) (OCH 3 ) 2 , SiCl (OH) (OC 2 H 5 ) 2 , SiCl (OH) (OC 3 H 7) 2, SiC (OH) (OC 4 H 9 ) 2, SiCl 2 (OCH 3) 2, SiCl 2 (OC 2 H 5) 2 and the like.
化合物（１）の重縮合反応生成物としては、接着性の観点から、炭素数１〜５のアルコキシ基を少なくとも１個有するシリコンアルコキシドの重縮合反応生成物であるのが好ましく、炭素数１〜５のアルコキシ基を少なくとも１個有するシリコンアルコキシドの加水分解物あるいは該加水分解物から生成されるものであるのが好ましい。 The polycondensation reaction product of the compound (1) is preferably a polycondensation reaction product of a silicon alkoxide having at least one alkoxy group having 1 to 5 carbon atoms from the viewpoint of adhesiveness. It is preferable that it is a hydrolyzate of silicon alkoxide having at least one 5 alkoxy group or a hydrolyzate thereof.
化合物（１）の重縮合反応生成物（加水分解物あるいは該加水分解物から生成されるもの）を含有させる樹脂としては特に制約はなく、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂、ウレタン樹脂、アルキド樹脂等が挙げられる。これらの中でも、耐久性、耐アルカリ性の観点から、アクリル樹脂、エポキシ樹脂、ポリエステル樹脂又はこれらの混合樹脂が好ましい。 The resin containing the polycondensation reaction product of compound (1) (hydrolyzate or one produced from the hydrolyzate) is not particularly limited, and is an acrylic resin, epoxy resin, polyester resin, urethane resin, alkyd resin. Etc. Among these, acrylic resins, epoxy resins, polyester resins, or mixed resins thereof are preferable from the viewpoints of durability and alkali resistance.
化合物（１）の重縮合反応生成物（加水分解物あるいは該加水分解物から生成されるもの）を樹脂に含有させる方法としては特に制約はない。具体的には、（ｉ）化合物（１）をモノマーの状態で樹脂溶液と混合し、接着層形成時に空気中の水分で加水分解させる方法、（ｉｉ）予め化合物（１）の部分加水分解物を樹脂と混合し、更に、接着層形成時に空気中の水分で加水分解する方法等が挙げられる。
また、化合物（１）の加水分解速度を調整するために、酸や塩基触媒を少量添加してもよい。
There are no particular restrictions on the method for incorporating the polycondensation reaction product (hydrolyzate or one produced from the hydrolyzate) of compound (1) into the resin. Specifically, (i) a method in which compound (1) is mixed with a resin solution in a monomer state and hydrolyzed with moisture in the air when forming an adhesive layer, (ii) a partial hydrolyzate of compound (1) in advance And the like, and a method of hydrolyzing with moisture in the air when forming an adhesive layer.
Moreover, in order to adjust the hydrolysis rate of the compound (1), a small amount of an acid or a base catalyst may be added.
化合物（１）の重縮合反応生成物の粒子径は１０ｎｍ以下が望ましい。粒子径が１０ｎｍを越えるものであると、分散性が悪くなり、接着層の透光性が低下するため接着層と光触媒層の合計の波長５５０ｎｍの全光線透過率は７０％未満となる場合がある。 The particle size of the polycondensation reaction product of compound (1) is preferably 10 nm or less. If the particle diameter exceeds 10 nm, the dispersibility deteriorates and the translucency of the adhesive layer decreases, so the total light transmittance at a total wavelength of 550 nm of the adhesive layer and the photocatalyst layer may be less than 70%. is there.
（シランカップリング剤）
本発明において用いるシランカップリン剤は、無機物と反応する加水分解基と有機物と反応する官能基を一分子中に持った有機ケイ素化合物である。
シランカップリング剤としては、式：ＲＳｉ（Ｘ）３で表される化合物又は式：（Ｒ）２Ｓｉ（Ｘ）２で表される化合物が挙げられる。
(Silane coupling agent)
The silane coupling agent used in the present invention is an organosilicon compound having a hydrolyzable group that reacts with an inorganic substance and a functional group that reacts with an organic substance in one molecule.
Examples of the silane coupling agent include a compound represented by the formula: RSi (X) 3 or a compound represented by the formula: (R) 2 Si (X) 2 .
前記式中、Ｒは有機性官能基を表す。有機性官能基としては、例えば、メチル基、エチル基等のアルキル基；ビニル基等のアルケニル基；γ−グリシドキシプロピル基、γ−メタクリロキシプロピル基、γ−（２−アミノエチル）アミノプロピル基、γ−クロロプロピル基、γ−メルカプトプロピル基、γ−アミノプロピル基、γ−アクリロキシプロピル基等のγ−置換プロピル基；等が挙げられる。
Ｘは、塩素原子又はアルコキシ基を表す。アルコキシ基としては、メトキシ基、エトキシ基、β−メトキシエトキシ基等の炭素数１〜５のアルコキシ基が挙げられる。
In the above formula, R represents an organic functional group. Examples of the organic functional group include alkyl groups such as methyl group and ethyl group; alkenyl groups such as vinyl group; γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ- (2-aminoethyl) amino And γ-substituted propyl groups such as propyl group, γ-chloropropyl group, γ-mercaptopropyl group, γ-aminopropyl group, γ-acryloxypropyl group, and the like.
X represents a chlorine atom or an alkoxy group. As an alkoxy group, C1-C5 alkoxy groups, such as a methoxy group, an ethoxy group, (beta) -methoxyethoxy group, are mentioned.
シランカップリング剤の具体例としては、３−グリシドキシプロピルトリメトキシシラン、３−メルカプトプロピルトリメトキシシラン、３−アミノプロピルトリエトキシシラン、３−ウレイドプロピルトリエトキシシラン、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシラン等が挙げられる。 Specific examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltriethoxysilane, N-2- (amino And ethyl) -3-aminopropyltrimethoxysilane.
これらのシランカップリング剤は、３−グリシドキシプロピルトリメトキシシランが商品名：ＮＵＣＡ−１８７として、３−メルカプトプロピルトリメトキシシランが商品名：ＮＵＣＡ１８９として、３−アミノプロピルトリエトキシシランが商品名：ＮＵＣＡ１１００として、３−ウレイドプロピルトリエトキシシランが商品名：ＮＵＣＡ１１６０として、Ｎ−２−（アミノエチル）−３−アミノプロピルトリメトキシシランが商品名：ＮＵＣＡ１１２０として、いずれも日本ユニカー（株）から市販されている。 Among these silane coupling agents, 3-glycidoxypropyltrimethoxysilane is trade name: NUCA-187, 3-mercaptopropyltrimethoxysilane is trade name: NUCA189, and 3-aminopropyltriethoxysilane is trade name. : NUCA1100, 3-ureidopropyltriethoxysilane is trade name: NUCA1160, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane is trade name: NUCA1120, both commercially available from Nippon Unicar Co., Ltd. Has been.
シランカップリング剤の配合量は、（ａ）シリコン変性樹脂及び／又は（ｂ）シリコンアルコキシド（１）の重縮合反応生成物を含有する樹脂（以下、「シリコン変性樹脂等」という。）に対して、１〜１０重量％であるのが好ましい。 The compounding amount of the silane coupling agent is based on (a) a silicon-modified resin and / or (b) a resin containing a polycondensation reaction product of silicon alkoxide (1) (hereinafter referred to as “silicon-modified resin etc.”). 1 to 10% by weight is preferable.
本発明の接着層形成用組成物のＳｉの総含有量は、ＳｉＯ２に換算して接着層の全固形分に対して５５〜９５重量％である。Ｓｉの含有量をこの範囲に設定することで、光触媒層及び担体との接着性が良好な接着層が得られ、この接着層を用いると耐候性の優れた光触媒担持構造体を得ることができる。 The total content of Si in the adhesive layer forming composition of the present invention is 55 to 95 percent by weight relative to the total solids of the adhesive layer in terms of SiO 2. By setting the Si content in this range, an adhesive layer having good adhesion to the photocatalyst layer and the carrier can be obtained, and when this adhesive layer is used, a photocatalyst-supporting structure having excellent weather resistance can be obtained. .
本発明の接着層形成用組成物は、前記シリコン変性樹脂等の溶媒溶液に、所定量のシランカップリング剤を添加・混合して調製することができる。
用いる有機溶媒としては、ベンゼン、トルエン、キシレン等の芳香族炭化水素類；ｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタンなどの脂肪族炭化水素類；シクロペンタン、シクロヘキサン等の脂環式炭化水素類；酢酸エチル、酢酸プロピル，酢酸ブチル、乳酸メチルなどのエステル類；アセトン、メチルエチルケトン、メチルイソブチルケトン、ジエチルケトン、シクロヘキサノン等のケトン類；ジエチルエーテル、１，２−ジメトキシエタン、ジオキサン、テトラヒドロフランなどのエーテル類；メチルアルコール、エチルアルコール、プロピルアルコール、イソプロピルアルコール、ブチルアルコール、エチレングリコール、プロピレングリコールなどのアルコール類；Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルアセタミド、Ｎ−メチルピロリドン等のアミド類；水；及びこれらの溶媒の２種以上からなる混合溶媒；等が挙げられる。
The composition for forming an adhesive layer of the present invention can be prepared by adding and mixing a predetermined amount of a silane coupling agent to a solvent solution of the silicon-modified resin or the like.
Examples of the organic solvent used include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; alicyclic rings such as cyclopentane and cyclohexane Formula hydrocarbons; Esters such as ethyl acetate, propyl acetate, butyl acetate and methyl lactate; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone and cyclohexanone; Diethyl ether, 1,2-dimethoxyethane, dioxane, Ethers such as tetrahydrofuran; alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, ethylene glycol, propylene glycol; N, N-dimethylformamide, N, N-dimethyl Setamido, amides such as N- methylpyrrolidone; water; and mixed solvents of two or more of these solvents; and the like.
なお、接着層形成用組成物を調製するにあたっては、前記シリコン変性樹脂等の溶媒溶液に、所定量のシランカップリング剤を添加・混合して得られる溶液を適当な濃度に濃縮したり、適当な溶媒で希釈することで、固形分濃度を調整することもできる。 In preparing an adhesive layer forming composition, a solution obtained by adding and mixing a predetermined amount of a silane coupling agent to a solvent solution of the silicon-modified resin or the like is concentrated to an appropriate concentration, The solid content concentration can be adjusted by diluting with an appropriate solvent.
また、接着層形成用組成物には光触媒作用による劣化を抑える目的で、光安定化剤及び／又は紫外線吸収剤をさらに添加することができる。
光安定化剤としては、ヒンダードアミン系光安定化剤が挙げられる、紫外線吸収剤としては、トリアゾール系紫外線吸収剤等が挙げられる。
光安定化剤及び／又は紫外線吸収剤の添加量は、用いる樹脂に対して、０．００５重量％〜１０重量％、好ましくは０．０１重量％〜５重量％である。
In addition, a light stabilizer and / or an ultraviolet absorber can be further added to the composition for forming an adhesive layer for the purpose of suppressing deterioration due to photocatalytic action.
Examples of the light stabilizer include a hindered amine light stabilizer. Examples of the ultraviolet absorber include a triazole ultraviolet absorber.
The addition amount of the light stabilizer and / or the ultraviolet absorber is 0.005% to 10% by weight, preferably 0.01% to 5% by weight, based on the resin used.
このようにして得られる接着層形成用組成物を用いることにより、優れた層間密着性と耐候性を有する接着層を形成することができる。 By using the adhesive layer forming composition thus obtained, an adhesive layer having excellent interlayer adhesion and weather resistance can be formed.
２）光触媒担持構造体
本発明の光触媒担持構造体は、担体と、該担体上に形成された接着層と、該接着層上に形成された光触媒層とを有する光触媒担持構造体であって、前記接着層が、本発明の接着層形成用組成物から形成されたものであることを特徴とする。
2) Photocatalyst carrying structure The photocatalyst carrying structure of the present invention is a photocatalyst carrying structure having a carrier, an adhesive layer formed on the carrier, and a photocatalyst layer formed on the adhesive layer, The adhesive layer is formed from the adhesive layer forming composition of the present invention.
（１）担体
本発明に用いる担体としては、接着剤層を介して光触媒を担持可能な材質のものであれば特に限定されない。例えば、セラミックス、無機質材料の他、熱をかけられない有機高分子体、熱や水等により酸化腐食し易い金属等からなるものであってもよい。
担体の形状としては、特に制限されず、フィルム状、シート状、板状、管状、繊維状、網状等どのような複雑な形状のものであってもよい。
担体の厚みは、特に制限されないが、光触媒層を強固に担持することができるためには、１０μｍ以上であるのが好ましい。
また、本発明においては、担体と接着層との密着性を良くするために、表面が放電処理やプライマー処理等の易接着処理が施された担体を使用することもできる。
(1) Carrier The carrier used in the present invention is not particularly limited as long as it is a material capable of supporting a photocatalyst via an adhesive layer. For example, in addition to ceramics and inorganic materials, an organic polymer that cannot be heated, a metal that is easily oxidized and corroded by heat, water, or the like may be used.
The shape of the carrier is not particularly limited, and may be any complicated shape such as a film shape, a sheet shape, a plate shape, a tubular shape, a fiber shape, and a net shape.
The thickness of the carrier is not particularly limited, but is preferably 10 μm or more so that the photocatalyst layer can be firmly supported.
In the present invention, in order to improve the adhesion between the carrier and the adhesive layer, a carrier whose surface has been subjected to an easy adhesion treatment such as a discharge treatment or a primer treatment can also be used.
（２）接着層
接着層は、担体を光触媒作用による劣化から保護し、光触媒層を担体に強固に固定する役目を有する。本発明において用いる接着層は、本発明の接着層形成用組成物から形成される。
(2) Adhesive layer The adhesive layer serves to protect the carrier from deterioration due to photocatalysis and to firmly fix the photocatalytic layer to the carrier. The adhesive layer used in the present invention is formed from the adhesive layer forming composition of the present invention.
接着層を担体上に形成する方法としては、本発明の接着層形成用組成物を印刷法、シート成形法、スプレー吹き付け法、ディップコーティング法、スピンコーティング法等でコート、乾燥、硬化させる方法が挙げられる。 As a method for forming an adhesive layer on a carrier, there is a method in which the composition for forming an adhesive layer of the present invention is coated, dried, and cured by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, or the like. Can be mentioned.
乾燥温度は、溶媒や樹脂の種類によっても異なるが、一般的に５０℃〜３００℃程度が好ましい。 Although drying temperature changes with kinds of solvent and resin, generally about 50 to 300 degreeC is preferable.
接着層の厚みは、特に制限されないが、光触媒層との良好な接着を得るためには０．１〜２００μｍであるのが好ましく、１〜５０μｍであるのがより好ましい。接着層の厚みが０．１μｍ以下であると、光触媒層を強固に接着させる働きが弱くなる。一方、厚みが２００μｍ以上の場合は特に問題はないものの、実際の塗布加工を考慮すると２００μｍ以上にするメリットは少ない。 The thickness of the adhesive layer is not particularly limited, but is preferably 0.1 to 200 μm, and more preferably 1 to 50 μm, in order to obtain good adhesion with the photocatalyst layer. When the thickness of the adhesive layer is 0.1 μm or less, the function of firmly bonding the photocatalytic layer is weakened. On the other hand, there is no particular problem when the thickness is 200 μm or more, but there are few merits when the thickness is 200 μm or more in consideration of actual coating.
（３）光触媒層
本発明の光触媒担持構造体の光触媒層は、少なくとも光触媒を含み、光触媒活性を示すものであれば、その構成成分は特に制約されないが、光触媒及びシリカを含有する光触媒複合体からなるものが好ましく、光触媒、シリカ、並びにジルコニウム化合物およびアルミニウム化合物から選ばれる少なくとも１種を含有する光触媒複合体からなるものがより好ましい。
(3) Photocatalyst layer The photocatalyst layer of the photocatalyst-supporting structure of the present invention is not particularly limited as long as it contains at least a photocatalyst and exhibits photocatalytic activity, but from the photocatalyst complex containing the photocatalyst and silica. What consists of a photocatalyst complex containing a photocatalyst, a silica, and at least 1 sort (s) chosen from a zirconium compound and an aluminum compound is more preferable.
光触媒は、乾燥・硬化したときに接着層と固着して光触媒活性を示すものであれば特に制約はない。
光触媒としては、具体的にはＴｉＯ２、ＺｎＯ、ＳｒＴｉＯ３、ＣｄＳ、ＧａＰ、ＩｎＰ、ＧａＡｓ、ＢａＴｉＯ３、ＫＮｂＯ３、Ｆｅ２Ｏ３、Ｔａ２Ｏ５、ＷＯ３、ＳｎＯ２、Ｂｉ２Ｏ３、ＮｉＯ、Ｃｕ２Ｏ、ＳｉＣ、ＳｉＯ２、ＭｏＳ２、ＩｎＰｂ、ＲｕＯ２、ＣｅＯ２等が挙げられる。
これらの光触媒には、Ｐｔ、Ｒｈ、ＲｕＯ２、Ｎｂ、Ｃｕ、Ｓｎ、Ｎｉ、Ｆｅ等の金属もしくはこれらの金属の金属酸化物を添加してもよい。
これらの中でも、耐久性、コスト、光触媒活性の観点から、酸化チタン（ＴｉＯ２）を主成分とするものが好ましく、アナターゼ型酸化チタンが特に好ましい。
また、太陽光のような紫外線を多く含む光で触媒活性を示す酸化チタンのみならず、貴金属をドープ等して紫外線の少ない室内光においても触媒活性を示す酸化チタンを用いることができる。
The photocatalyst is not particularly limited as long as it is fixed to the adhesive layer when dried and cured and exhibits photocatalytic activity.
Specific examples of the photocatalyst include TiO 2 , ZnO, SrTiO 3 , CdS, GaP, InP, GaAs, BaTiO 3 , KNbO 3 , Fe 2 O 3 , Ta 2 O 5 , WO 3 , SnO 2 , Bi 2 O 3. NiO, Cu 2 O, SiC, SiO 2 , MoS 2 , InPb, RuO 2 , CeO 2 and the like.
A metal such as Pt, Rh, RuO 2 , Nb, Cu, Sn, Ni, Fe, or a metal oxide of these metals may be added to these photocatalysts.
Among these, from the viewpoint of durability, cost, and photocatalytic activity, those containing titanium oxide (TiO 2 ) as a main component are preferable, and anatase-type titanium oxide is particularly preferable.
Moreover, not only titanium oxide that shows catalytic activity with light containing a lot of ultraviolet rays such as sunlight, but also titanium oxide that shows catalytic activity even in room light with little ultraviolet rays by doping a noble metal or the like can be used.
光触媒は、粉末状、ゾル状、溶液状等いずれであってもよいが、ゾル状であって平均粒子径が５０ｎｍ以下、好ましくは２０ｎｍ以下のものは、光触媒層の透明性が向上し直線透過率が高くなるため、透明性を要求されるガラス基板やプラスチック成形体に塗布する場合に好ましい。 The photocatalyst may be in the form of powder, sol, solution, etc., but if it is sol and has an average particle size of 50 nm or less, preferably 20 nm or less, the transparency of the photocatalyst layer is improved and linear transmission is achieved. Since the rate becomes high, it is preferable when it is applied to a glass substrate or plastic molded body that requires transparency.
平均粒子径が５０ｎｍ以上では直線透過率が減少し、ヘイズ率が高くなる。ここで、ヘイズ率は、関係式：ヘイズ率＝（全光透過率−直線透過率）／全光透過率で求められる値である。例えば、トイレの窓ガラスは、トイレ内を明るくするために全光透過率の高いもので、かつ、内部がはっきりと見えないようにヘイズ率が高いものである必要がある。 When the average particle diameter is 50 nm or more, the linear transmittance decreases and the haze ratio increases. Here, the haze ratio is a value obtained by the relational expression: haze ratio = (total light transmittance−linear transmittance) / total light transmittance. For example, a window glass of a toilet needs to have a high total light transmittance in order to brighten the inside of the toilet and a high haze ratio so that the inside cannot be clearly seen.
前記光触媒複合体中の光触媒の含有量は、光触媒複合体全体に対して、酸化物に換算して５重量％〜６０重量％が好ましい。５重量％未満になると光触媒活性が著しく低下する。一方、６０重量％を越える場合には光触媒活性は高くなるものの、接着層との接着性が乏しくなる。 The content of the photocatalyst in the photocatalyst complex is preferably 5% by weight to 60% by weight in terms of oxide with respect to the entire photocatalyst complex. If it is less than 5% by weight, the photocatalytic activity is remarkably lowered. On the other hand, when it exceeds 60% by weight, the photocatalytic activity becomes high, but the adhesiveness with the adhesive layer becomes poor.
シリカとしては、球状コロイダルシリカ粒子が細長い鎖状に結合してなる鎖状コロイダルシリカ粒子であるのが好ましい。その形状は、球状コロイダルシリカ粒子をパールネックレスのパールにみたてると、パールネックレスの一部のような形状である。具体的には、球状コロイダルシリカ粒子を３個以上、好ましくは５個以上、更に好ましくは７個以上連結したものを例示することができる。 The silica is preferably a chain colloidal silica particle formed by binding spherical colloidal silica particles in an elongated chain shape. The shape is like a part of a pearl necklace when spherical colloidal silica particles are seen on the pearl of the pearl necklace. Specific examples include those in which 3 or more, preferably 5 or more, and more preferably 7 or more spherical colloidal silica particles are connected.
球状コロイダルシリカ粒子一つ一つの形状は明確である必要はなく、部分的に筒状に連続して細長い形状をしているものでもよい。また、球状コロイダルシリカ粒子は結合していなくてもよく、全体として細長い鎖状であればよい。 The shape of each of the spherical colloidal silica particles does not need to be clear, and may be partially elongated continuously in a cylindrical shape. Further, the spherical colloidal silica particles do not have to be bonded and may be long and slender as a whole.
球状コロイダルシリカ粒子の粒子径は、１０〜５０ｎｍであるのが好ましい。
鎖状コロイダルシリカ粒子の長さは、５０〜４００ｎｍであるのが好ましく、太さが１０〜５０ｎｍであるのが好ましく、全体にわたって太さが均一なものが好ましい。また、鎖状コロイダルシリカ粒子の細長い形状は、ある球状コロイダルシリカ粒子を起点に２次元方向に伸長しているのが好ましい。また、全体として細長い形状であれば、分岐構造を有するものでも構わない。
The particle diameter of the spherical colloidal silica particles is preferably 10 to 50 nm.
The length of the chain colloidal silica particles is preferably 50 to 400 nm, preferably 10 to 50 nm in thickness, and preferably has a uniform thickness throughout. The elongated shape of the chain colloidal silica particles preferably extends in a two-dimensional direction starting from a certain spherical colloidal silica particle. Further, as long as it has an elongated shape as a whole, it may have a branched structure.
以上のような特性を有する鎖状コロイダルシリカ粒子として、具体的には、動的光散乱法による測定粒子径（Ｄ１）が４０〜３００ｎｍであり、Ｄ１と窒素ガス吸着法による測定粒子径（Ｄ２）の比（Ｄ１／Ｄ２）が５以上であって、電子顕微鏡観察による５〜２０ｎｍの範囲内の一様な太さで一平面内のみの伸長を有する非晶質コロイダルシリカ粒子を例示することができる。 Specifically, as the chain colloidal silica particles having the above characteristics, the measured particle diameter (D1) by the dynamic light scattering method is 40 to 300 nm, and the measured particle diameter (D2) by D1 and the nitrogen gas adsorption method. ) A ratio (D1 / D2) of 5 or more, and an amorphous colloidal silica particle having a uniform thickness within a range of 5 to 20 nm by electron microscope observation and extending only in one plane Can do.
このような鎖状コロイダルシリカ粒子が分散したゾルの製造方法として、特開平１−３１７１１５号公報、特開平７−１１８００８号公報に記載されている方法を例示することができる。
シリカの含有量は特に制限されないが、光触媒複合体全体に対して、５〜５０重量％であるのが好ましい。
Examples of a method for producing a sol in which such chain colloidal silica particles are dispersed include the methods described in JP-A-1-317115 and JP-A-7-118008.
The content of silica is not particularly limited, but is preferably 5 to 50% by weight with respect to the entire photocatalyst complex.
本発明に用いられるジルコニウム化合物は、光触媒複合体の耐アルカリ性を向上させる目的で添加される。
ジルコニウム化合物としては、ジルコニウムの、酸化物、酸化水酸化物、水酸化物、硝酸塩、オキシ硝酸塩、炭酸塩、オキシ炭酸塩、蓚酸塩、オキシ蓚酸塩、酢酸塩、オキシ酢酸塩、炭素数１〜６のアルコキシド、及び炭素数１〜６のアルコキシドの加水分解生成物からなる群から選ばれる１種又は２種以上の混合物が挙げられる。これらの中でも、ジルコニウムの、酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド及び該アルコキシドの加水分解生成物からなる群から選ばれる１種又は２種以上の混合物が好ましい。
The zirconium compound used in the present invention is added for the purpose of improving the alkali resistance of the photocatalyst complex.
Zirconium compounds include zirconium oxide, oxide hydroxide, hydroxide, nitrate, oxynitrate, carbonate, oxycarbonate, oxalate, oxysuccinate, acetate, oxyacetate, carbon number 1 to 1 type, or 2 or more types of mixtures chosen from the group which consists of a hydrolysis product of 6 alkoxides and C1-C6 alkoxides are mentioned. Among these, one selected from the group consisting of oxides, oxide hydroxides, hydroxides, oxynitrates, oxycarbonates, alkoxides having 1 to 4 carbon atoms, and hydrolysis products of the alkoxides of zirconium. A mixture of two or more is preferred.
ジルコニウムの化合物の好ましい具体例としては、酸化ジルコニウム、オキシ硝酸ジルコニウム、オキシ塩化ジルコニウム、水和酸化ジルコニウム、オキシ水酸化ジルコニウム、水和硝酸ジルコニウム、水和オキシ塩化ジルコニウム、蓚酸ジルコニウム、酢酸ジルコニウム、ジルコニウムテトライソプロポキシド、ジルコニウムテトラブトキシド、ジルコニウムジブトキシドアセチルアセトナート、ジルコニウムジブトキシドラクテート、ジルコニウムブトキシドの加水分解生成物、ジルコニウムイソプロポキシドの加水分解生成物等が挙げられる。 Preferred examples of the zirconium compound include zirconium oxide, zirconium oxynitrate, zirconium oxychloride, hydrated zirconium oxide, zirconium oxyhydroxide, hydrated zirconium nitrate, hydrated zirconium oxychloride, zirconium oxalate, zirconium acetate, zirconium tetra Examples thereof include isopropoxide, zirconium tetrabutoxide, zirconium dibutoxide acetylacetonate, zirconium dibutoxide lactate, a hydrolysis product of zirconium butoxide, a hydrolysis product of zirconium isopropoxide, and the like.
アルミニウムの化合物は、光触媒複合体の耐アルカリ性をさらに向上させ、ヘイズ率を下げる目的で添加される。
アルミニウム化合物としては、アルミニウムの、酸化物、酸化水酸化物、水酸化物、硝酸塩、オキシ硝酸塩、炭酸塩、オキシ炭酸塩、蓚酸塩、オキシ蓚酸塩、酢酸塩、オキシ酢酸塩、炭素数１〜６のアルコキシド及び該アルコキシドの加水分解生成物からなる群から選ばれた１種又は２種以上の混合物が挙げられる。これらの中でも、アルミニウムの、酸化物、酸化水酸化物、水酸化物、オキシ硝酸塩、オキシ炭酸塩、炭素数１〜４のアルコキシド及び該アルコキシドの加水分解生成物からなる群から選ばれた１種又は２種以上の混合物が好ましい。
The aluminum compound is added for the purpose of further improving the alkali resistance of the photocatalyst complex and lowering the haze ratio.
As aluminum compounds, aluminum oxide, oxide hydroxide, hydroxide, nitrate, oxynitrate, carbonate, oxycarbonate, oxalate, oxysuccinate, acetate, oxyacetate, carbon number 1 to Examples thereof include one or a mixture of two or more selected from the group consisting of 6 alkoxides and hydrolysis products of the alkoxides. Among these, aluminum is one selected from the group consisting of oxides, oxide hydroxides, hydroxides, oxynitrates, oxycarbonates, alkoxides having 1 to 4 carbon atoms, and hydrolysis products of the alkoxides. Or the mixture of 2 or more types is preferable.
アルミニウムの化合物の好ましい具体例としては、酸化アルミニウム、酸化水酸化アルミニウム、水酸化アルミニウム、水和酸化アルミニウム、ベーマイト、硝酸アルミニウム、オキシ硝酸アルミニウム、炭酸アルミニウム、オキシ炭酸アルミニウム、蓚酸アルミニウム、オキシ蓚酸アルミニウム、酢酸アルミニウム、オキシ酢酸アルミニウム、アルミニウムトリイソプロポキシド、アルミニウムトリブトキシド、アルミニウムブトキシドアセチルアセトナート、アルミニウムブトキシドラクテート、アルミニウムブトキシドの加水分解生成物、アルミニウムイソプロポキシドの加水分解生成物等が挙げられる。 Preferred specific examples of the aluminum compound include aluminum oxide, aluminum oxide hydroxide, aluminum hydroxide, hydrated aluminum oxide, boehmite, aluminum nitrate, aluminum oxynitrate, aluminum carbonate, aluminum oxycarbonate, aluminum oxalate, aluminum oxyoxalate, Examples thereof include aluminum acetate, aluminum oxyacetate, aluminum triisopropoxide, aluminum tributoxide, aluminum butoxide acetylacetonate, aluminum butoxide lactate, aluminum butoxide hydrolysis product, and aluminum isopropoxide hydrolysis product.
ジルコニウム化合物及びアルミニウム化合物はゾルの形で用いるのが好ましい。ゾルの形で用いる場合には、安定化のために光触媒複合体中に酸やアルカリの解膠剤を添加してもよい。また、接着性や操作性を良くする目的で、光触媒に対して５重量％以下の界面活性剤等を添加することもできる。 The zirconium compound and the aluminum compound are preferably used in the form of a sol. When used in the form of a sol, an acid or alkali peptizer may be added to the photocatalyst complex for stabilization. Further, for the purpose of improving adhesiveness and operability, 5% by weight or less of a surfactant or the like can be added to the photocatalyst.
ジルコニウム化合物又はアルミニウム化合物のゾルは、平均粒子径が２ｎｍ〜５０ｎｍ、好ましくは２ｎｍ〜２０ｎｍであるのが好ましい。
この範囲の粒子径のものを使用すると、光触媒層の透明性が向上し、直線透過率が高くなるため、特に透明性を要求されるガラス基板やプラスチック成形体に塗布する場合に好ましい。透明な光触媒層は、下地の担体に色や模様が印刷されたものの場合に、下地の色や柄を損なうことがなく好ましい。平均粒子径が５０ｎｍ以上のものを用いると、直線透過率が減少し、ヘイズ率が高くなる。
The zirconium compound or aluminum compound sol preferably has an average particle size of 2 nm to 50 nm, preferably 2 nm to 20 nm.
Use of a particle having a particle size in this range improves the transparency of the photocatalyst layer and increases the linear transmittance, and is therefore particularly preferable when applied to a glass substrate or plastic molded product that requires transparency. A transparent photocatalyst layer is preferable because it does not impair the color or pattern of the base when the base carrier is printed with a color or pattern. When the average particle diameter is 50 nm or more, the linear transmittance is reduced and the haze ratio is increased.
前記光触媒複合体中のジルコニウム化合物又はアルミニウム化合物は、１５０℃で乾燥後の比表面積が１００ｍ２／ｇ以上の多孔質ゲルであるのが好ましい。多孔質ゲルは吸着性を有しており、光触媒活性を高める効果を有する。 The zirconium compound or aluminum compound in the photocatalyst complex is preferably a porous gel having a specific surface area after drying at 150 ° C. of 100 m 2 / g or more. The porous gel has adsorptivity and has an effect of enhancing photocatalytic activity.
前記光触媒複合体中のジルコニウム化合物の含有量は、光触媒複合体全体に対して、酸化物に換算して５〜４０重量％であるのが好ましい。５重量％未満では得られる光触媒層の耐アルカリ性に乏しくなる。一方、４０重量％を越えると得られる光触媒層の透明性が悪くなる。 The content of the zirconium compound in the photocatalyst complex is preferably 5 to 40% by weight in terms of oxide with respect to the entire photocatalyst complex. If it is less than 5% by weight, the alkali resistance of the resulting photocatalyst layer becomes poor. On the other hand, if it exceeds 40% by weight, the transparency of the resulting photocatalyst layer becomes poor.
前記光触媒複合体中のアルミニウム化合物の含有量は、光触媒複合体全体に対して、酸化物に換算して２０〜９０重量％であるのが好ましい。２０重量％未満では得られる光触媒層のヘイズ率の上昇を抑制する効果及び耐アルカリ性を高める効果に乏しくなる。一方、添加量が９０重量％を越えると光触媒活性が低下する。 The content of the aluminum compound in the photocatalyst complex is preferably 20 to 90% by weight in terms of oxide with respect to the entire photocatalyst complex. If it is less than 20% by weight, the effect of suppressing an increase in the haze ratio of the resulting photocatalyst layer and the effect of increasing the alkali resistance are poor. On the other hand, when the addition amount exceeds 90% by weight, the photocatalytic activity decreases.
前記光触媒複合体中のジルコニウム化合物及びアルミニウム化合物の総含有量は、これらの酸化物に換算して４０〜９５重量％であるのが好ましい。４０重量％未満では光触媒層と接着層との接着が不十分となる。一方、９５重量％を越えると、添加できる光触媒の量が減少するため光触媒活性の低下が著しい。 The total content of the zirconium compound and the aluminum compound in the photocatalyst complex is preferably 40 to 95% by weight in terms of these oxides. If it is less than 40% by weight, the adhesion between the photocatalyst layer and the adhesive layer becomes insufficient. On the other hand, if it exceeds 95% by weight, the amount of the photocatalyst that can be added decreases, so the photocatalytic activity is remarkably lowered.
光触媒層は、光触媒層形成用組成物を担体上に形成された接着層上に塗布し、乾燥・硬化することにより形成することができる。
光触媒層形成用組成物は、例えば、前記光触媒、鎖状コロイダルシリカ粒子、ジルコニウム化合物及び／又はアルミニウム化合物等を溶媒中に均一に懸濁又は分散させて製造することができる。
The photocatalyst layer can be formed by applying a composition for forming a photocatalyst layer onto an adhesive layer formed on a carrier, followed by drying and curing.
The composition for forming a photocatalyst layer can be produced, for example, by uniformly suspending or dispersing the photocatalyst, chain colloidal silica particles, zirconium compound and / or aluminum compound in a solvent.
具体的には、（ａ）光触媒、鎖状コロイダルシリカゾル、ジルコニウム化合物及び／又はアルミニウム化合物のゾル溶液を混合する方法、（ｂ）ジルコニウム化合物及び／又はアルミニウム化合物のゾルの前駆体溶液に、光触媒と鎖状コロイダルシリカゾルを混合する方法、（ｃ）ジルコニウム化合物及び／又はアルミニウム化合物のゾルの前駆体溶液中に、光触媒粒子又はゾル、及び鎖状コロイダルシリカゾル等を分散し、塗布する際に加水分解又は中和分解してゾル化させる方法等によって製造することができる。 Specifically, (a) a method of mixing a photocatalyst, a chain colloidal silica sol, a zirconium compound and / or an aluminum compound sol solution, (b) a precursor solution of the zirconium compound and / or aluminum compound sol, A method of mixing a chain colloidal silica sol, (c) a photocatalyst particle or sol, a chain colloidal silica sol, etc. are dispersed in a precursor solution of a zirconium compound and / or aluminum compound sol; It can be produced by a method of neutralization and decomposition to sol.
用いる溶媒としては、例えば、水；メタノール、エタノール、プロピルアルコール、イソプロピルアルコール、ブタノール、ｔ−ブタノール等のアルコール類；アセトン、メチルエチルケトン、メチルイソブチルケトン、アセチルアセトン、シクロヘキサノン等のケトン類；ジエチルエーテル、メチルセルソルブ、テトラヒドロフラン等のエーテル類；ベンゼン、トルエン、キシレン等の芳香族炭化水素；ジクロロメタン、クロロホルム等のハロゲン化炭化水素；酢酸エチル、酢酸プロピル、酢酸ブチル等のエステル類；ペンタン、ヘキサン、シクロヘキサン等の飽和炭化水素；等を挙げることができる。
これらは１種単独で、あるいは２種以上を混合して用いることができる。これらの中でも、水−アルコール系溶媒の使用が特に好ましい。
Examples of the solvent used include water; alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, and t-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, and cyclohexanone; diethyl ether and methyl cell. Ethers such as sorb and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, propyl acetate and butyl acetate; pentane, hexane and cyclohexane Saturated hydrocarbons; and the like.
These may be used alone or in combination of two or more. Among these, the use of a water-alcohol solvent is particularly preferable.
光触媒層形成用組成物に含まれる各成分量は、組成物全体に対して、固形分として酸化物換算で、球状コロイダルシリカ粒子が細長い形状に結合した鎖状コロイダルシリカ粒子が分散したシリカゾルが０．３〜５重量％、光触媒粒子及び／又はゾルを固形分として０．３〜６重量％、ジルコニウム化合物が０．３〜５重量％、アルミニウム化合物が１〜９重量％であるのがそれぞれ好ましい。 The amount of each component contained in the composition for forming a photocatalyst layer is 0% of a silica sol in which chain colloidal silica particles in which spherical colloidal silica particles are bonded in an elongated shape are dispersed as an oxide as a solid content with respect to the entire composition. 3 to 5% by weight, 0.3 to 6% by weight of photocatalyst particles and / or sol as solid content, 0.3 to 5% by weight of zirconium compound, and 1 to 9% by weight of aluminum compound are preferable, respectively. .
前記光触媒層形成用組成物を接着層表面に塗布する方法としては、印刷法、シート成形法、スプレー吹き付け法、ディップコーティング法、スピンコーティング法等が挙げられる。
乾燥・硬化する温度は、担体材質及び接着層中の樹脂材質によるが、通常５０℃〜３００℃である。
Examples of the method for applying the photocatalyst layer forming composition to the surface of the adhesive layer include a printing method, a sheet forming method, a spray spraying method, a dip coating method, and a spin coating method.
The drying / curing temperature depends on the carrier material and the resin material in the adhesive layer, but is usually 50 ° C to 300 ° C.
光触媒層の厚みは特に制限されないが、０．１μｍ〜２０μｍであるのが好ましい。光触媒層の厚みは厚い方が光触媒活性は高くなるが、２０μｍを越えると光触媒活性は飽和し、塗布加工が困難となる場合が多く、また光触媒層の光透過率が低下する。一方、光触媒層の厚さが０．１μｍ未満になると、透光性は良くなるものの、光触媒が利用する紫外線をも透過してしまうために高い活性は望めない。 The thickness of the photocatalyst layer is not particularly limited, but is preferably 0.1 μm to 20 μm. The photocatalytic activity becomes higher as the photocatalyst layer is thicker, but if it exceeds 20 μm, the photocatalytic activity is saturated, and coating processing is often difficult, and the light transmittance of the photocatalyst layer is lowered. On the other hand, when the thickness of the photocatalyst layer is less than 0.1 μm, the translucency is improved, but the ultraviolet ray used by the photocatalyst is also transmitted, so that high activity cannot be expected.
以上のようにして得られる本発明の光触媒担持構造体は、前記接着層と光触媒層とを合計した、波長５５０ｎｍの光の全光線透過率が７０％以上である。 The photocatalyst carrying structure of the present invention obtained as described above has a total light transmittance of 70% or more of light having a wavelength of 550 nm, which is the sum of the adhesive layer and the photocatalyst layer.
また、紫外線強度３ｍＷ／ｃｍ２のブラックライトの光を、温度４０℃、相対湿度９０％の下で５００時間照射した後でのＪＩＳ Ｋ５４００に規定された碁盤目テープ法による付着性の評価点数が、６点以上である。 Moreover, the evaluation score of adhesiveness by the cross-cut tape method defined in JIS K5400 after irradiating light of black light with an ultraviolet intensity of 3 mW / cm 2 at a temperature of 40 ° C. and a relative humidity of 90% for 500 hours is , 6 points or more.
例えば、光触媒層の厚さを０．１μｍ〜２０μｍとし、平均粒子が５０ｎｍ以下の光触媒粒子、及びアルミニウムの酸化物もしくは水酸化物のゲルを用いることにより、光触媒層と接着層の合計の波長５５０ｎｍの全光線透過率は８０％以上で、ヘイズ率が２％以下のものを得ることができる。かかる光触媒担持構造体は、透明な担体を用いる場合、透過した可視光線を照明として利用でき、また担体が不透明な場合でも、担体上の色や柄を損なうことがないので装飾性の上でも優れたものとなる。 For example, when the photocatalyst layer has a thickness of 0.1 μm to 20 μm, and photocatalyst particles having an average particle size of 50 nm or less, and an aluminum oxide or hydroxide gel, the total wavelength of the photocatalyst layer and the adhesive layer is 550 nm. Can have a total light transmittance of 80% or more and a haze ratio of 2% or less. Such a photocatalyst-supporting structure can be used for illumination of transmitted visible light when a transparent carrier is used, and even if the carrier is opaque, it does not impair the color or pattern on the carrier, so it is excellent in terms of decorativeness. It will be.
本発明の光触媒担持構造体は、建築用資材、壁紙、窓ガラス、ブラインド、カーテン、カーペット、照明器具、照明灯、道路灯、トンネル照明灯、高速道や新幹線の遮音壁、ブラックライト、船底・漁網防汚資材、水処理用充填剤、農ビフィルム、防草シート、包装資材等に使用できる。特に高温多湿の環境下や屋外の環境下で使用される場合に、その優れた耐候性や透明性などの特性を発揮する。 The photocatalyst carrying structure of the present invention includes building materials, wallpaper, window glass, blinds, curtains, carpets, lighting fixtures, lighting lights, road lights, tunnel lighting lights, sound barriers for expressways and bullet trains, black lights, ship bottoms and fishing nets. It can be used for antifouling materials, water treatment fillers, agricultural film, grass protection sheets, packaging materials, and the like. In particular, when used in a hot and humid environment or an outdoor environment, it exhibits excellent properties such as weather resistance and transparency.
次に、実施例および比較例により本発明をさらに詳細に説明するが、本発明は、以下の実施例に限定されるものでない。 EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to a following example.
１）光触媒担持構造体の製造
下記のようにして、第１表に示すような構成を有する実施例１〜７、および比較例１、２の光触媒担持構造体を製造した。
1) Manufacture of photocatalyst carrying structure The photocatalyst carrying structure of Examples 1-7 which have a structure as shown in Table 1 and Comparative Examples 1 and 2 were manufactured as follows.
（１）担体
（ＴＡ）ソーダライムガラス板を用いた。
（２）接着層
・シリコン変性樹脂等（ＰＳ−１、ＰＳ−２）を樹脂溶液（Ｊ−１、Ｊ−２）に含有させたものを用いた。
（ＰＳ−１）コルコート製ポリエトキシシロキサン商品名エチルシリケート４０
（ＰＳ−２）コルコート製ポリメトキシシロキサン商品名メチルシリケート５６
（Ｊ−１）シリコン含有量３重量％のアクリルシリコン樹脂キシレン溶液
（Ｊ−２）シリコン含有量１０重量％のアクリルシリコン樹脂のキシレンイソプロパノール溶液
なお、シリコン含有量は樹脂固形分中のＳｉＯ２に換算して表示した。
(1) Carrier (TA) Soda lime glass plate was used.
(2) Adhesive layer / silicon modified resin (PS-1, PS-2) contained in resin solution (J-1, J-2) was used.
(PS-1) Colcoat polyethoxysiloxane product name ethyl silicate 40
(PS-2) Colcoat polymethoxysiloxane trade name Methyl silicate 56
(J-1) Acrylic silicon resin xylene solution having a silicon content of 3% by weight (J-2) Xylene isopropanol solution of an acrylic silicon resin having a silicon content of 10% by weight Note that the silicon content is the SiO 2 in the resin solids. Converted and displayed.
・シランカップリング剤としては次のものを使用した。
（ＳＣ−１）シランカップリング剤（日本ユニカー（株）製、Ａ−１１２０）
シリコン変性樹脂等の樹脂溶液を混合し、濃度調整し、シランカップリング剤を３重量％添加混合して接着層形成用組成物を得た。接着層は、担体上に接着層塗布液をディッピング法で塗布し、１２０℃で乾燥することにより、厚み２μｍで形成した。
-The following silane coupling agents were used.
(SC-1) Silane coupling agent (Nihon Unicar Co., Ltd., A-1120)
A resin solution such as a silicon-modified resin was mixed, the concentration was adjusted, and 3% by weight of a silane coupling agent was added and mixed to obtain an adhesive layer forming composition. The adhesive layer was formed to have a thickness of 2 μm by applying an adhesive layer coating solution onto the carrier by dipping and drying at 120 ° C.
（３）光触媒層
光触媒は次のものを使用した。
（Ｔ−１）硝酸酸性酸化チタンゾル（結晶粒子径８ｎｍ）
シリカゾルは次のものを使用した。
（Ｓ−１）ネックレス状コロイダルシリカ（日産化学（株）製、スノーテックスＰＳ）
アルミニウム化合物は次のものを使用した。
（Ａ−１）酸化水酸化アルミニウム（ベーマイト）微粒子（川研ファインケミカル（株）製、アルミゾル１０）
ジルコニウム化合物は次のものを使用した。
（Ｚ−１）オキシ硝酸ジルコニウム６水和物（和光純薬（株）製、試薬特級）を水に溶解して１０％水溶液とした後、１２時間加熱して半量の水を常圧で留去して得られた液をオキシ硝酸ジルコニウム液として使用した。
(3) Photocatalyst layer The following was used for the photocatalyst.
(T-1) Nitric acid acidic titanium oxide sol (crystal particle diameter: 8 nm)
The following silica sol was used.
(S-1) Necklace-shaped colloidal silica (manufactured by Nissan Chemical Co., Ltd., Snowtex PS)
The following aluminum compounds were used.
(A-1) Aluminum oxide hydroxide (boehmite) fine particles (Aluminum sol 10 manufactured by Kawaken Fine Chemical Co., Ltd.)
The following zirconium compounds were used.
(Z-1) Zirconium oxynitrate hexahydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) was dissolved in water to make a 10% aqueous solution, and then heated for 12 hours to distill half of the water at normal pressure. The liquid obtained was used as the zirconium oxynitrate liquid.
上記光触媒、シリカゾル、アルミニウム化合物及びジルコニウム化合物を、ｐＨ１．５〜９の適当な範囲に調製して混合し、所定量の界面活性剤を加えて光触媒複合体溶液（光触媒層形成用組成物）を得た。
得られた光触媒複合体溶液をディッピング法で、上記接着層上に塗工形成した。光触媒層は、接着層を乾燥するのと同じ温度で乾燥して、厚み１μｍで形成した。
The photocatalyst, silica sol, aluminum compound and zirconium compound are prepared in an appropriate range of pH 1.5 to 9, mixed, a predetermined amount of a surfactant is added, and a photocatalyst complex solution (photocatalyst layer forming composition) is prepared. Obtained.
The obtained photocatalyst complex solution was applied and formed on the adhesive layer by dipping. The photocatalyst layer was formed at a thickness of 1 μm by drying at the same temperature as that for drying the adhesive layer.
２）光触媒担持構造体の性能試験
上記１）で得られた光触媒担持構造体を用いて、以下の性能試験を行った。
（１）光触媒活性の評価試験
上記１）で得られた光触媒担持構造体を、大きさ７０ｍｍ×７０ｍｍに切り出し、試料として用いた。
各試料を容量４リットルのパイレックス（登録商標）製ガラス容器中に設置した。この容器中に空気とアルデヒドの混合ガスを、アルデヒド濃度が２００ｐｐｍとなるように加えた。次いで、試料に紫外線強度２ｍＷ／ｃｍ２のブラックライト（ＦＬ１５ＢＬＢ、東芝ライテック製）の光を３時間照射後、容器内部のアルデヒドガス濃度をガスクロマトグラフィーにより測定したところ、優れた光触媒活性を有していた。
2) Performance test of photocatalyst carrying structure The following performance test was conducted using the photocatalyst carrying structure obtained in 1) above.
(1) Photocatalytic activity evaluation test The photocatalyst-supporting structure obtained in 1) above was cut into a size of 70 mm x 70 mm and used as a sample.
Each sample was placed in a 4-liter Pyrex (registered trademark) glass container. A mixed gas of air and aldehyde was added to the container so that the aldehyde concentration was 200 ppm. Next, the sample was irradiated with light from a black light (FL15BLB, manufactured by Toshiba Lighting & Technology) with an ultraviolet intensity of 2 mW / cm 2 for 3 hours, and the aldehyde gas concentration inside the container was measured by gas chromatography. It was.
（２）ヘイズ率の測定
接着層及び光触媒層を担持する前の担体をリファレンスとして、各試料の、波長５５０ｎｍの全光線透過率、及びヘイズ率を自記分光光度計（日立製作所（株）製Ｕ−４０００型）で測定した。測定結果を下記第２表に示す。
（３）テープ剥離試験
各試料表面に、切り傷によって２ｍｍの間隔で２５個のマス目を形成し、ＪＩＳ Ｋ５４００に規定する碁盤目テープ法試験により付着性の評価を行った。剥離しなかったものを○、少しでも剥離したものを×として評価した。評価結果を下記第２表に示す。
(2) Measurement of haze ratio Using the carrier before supporting the adhesive layer and the photocatalyst layer as a reference, the total light transmittance at a wavelength of 550 nm and the haze ratio of each sample were recorded by a self-recording spectrophotometer (U manufactured by Hitachi, Ltd.). -4000 type). The measurement results are shown in Table 2 below.
(3) Tape peeling test On the surface of each sample, 25 squares were formed at intervals of 2 mm by cuts, and adhesion was evaluated by a cross-cut tape method test defined in JIS K5400. Evaluation was made as ○ for those that did not peel, and × for those that did not peel. The evaluation results are shown in Table 2 below.
（４）指摩擦試験
試料表面を、指で摩擦し、剥離しなかったものを○、少しでも剥離したものを×として評価した。評価結果を下記第２表に示す。
（５）耐久性試験
試料表面に、ブラックライトで紫外線強度３ｍＷ／ｃｍ２の光を、温度４０℃、相対湿度９０％の恒温恒湿槽内で１５００時間照射後、テープ剥離試験及び指摩擦試験をして、耐久性の評価とした。評価結果を下記第２表に示す。
(4) Finger Friction Test The sample surface was evaluated as ◯ when the surface of the sample was rubbed with a finger and not peeled off, and x when peeled off even a little. The evaluation results are shown in Table 2 below.
(5) Durability test The sample surface was irradiated with black light with UV intensity of 3 mW / cm 2 in a constant temperature and humidity chamber at a temperature of 40 ° C. and a relative humidity of 90% for 1500 hours, and then a tape peeling test and a finger friction test. The durability was evaluated. The evaluation results are shown in Table 2 below.
第２表より、実施例１〜７の光触媒担持構造体は、促進耐候性試験においても、優れた耐久性を有していた。それに比して、シランカップリング剤を添加しない接着層形成用組成物から形成された接着層を有する比較例１の光触媒担持構造体は、テープ剥離試験および指摩擦試験において、初期から密着性に乏しい結果が得られた。また、シランカップリング剤を添加しているが、Ｓｉ含有量が、ＳｉＯ２に換算して５５重量％未満である接着層形成用組成物から形成された接着層を有する比較例２の光触媒担持構造体は、促進耐候性試験の結果、耐候性に劣る結果であった。
From Table 2, the photocatalyst carrying structures of Examples 1 to 7 had excellent durability even in the accelerated weather resistance test. In contrast, the photocatalyst-supporting structure of Comparative Example 1 having an adhesive layer formed from the composition for forming an adhesive layer to which no silane coupling agent is added has improved adhesiveness from the beginning in the tape peeling test and the finger friction test. Poor results were obtained. Further, although the addition of a silane coupling agent, Si content, the comparative example 2 having an adhesive layer formed from the adhesive layer forming composition in terms of less than 55% by weight SiO 2 photocatalyst carrying As a result of the accelerated weather resistance test, the structure was inferior in weather resistance.
Claims (21)
（ａ）シリコン変性樹脂、及び／又は
（ｂ）式（１）
(A) silicon modified resin and / or (b) formula (1)
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| JP2007085118A (en) * | 2005-09-26 | 2007-04-05 | Matsushita Electric Works Ltd | Interior finish member |
| JP2008262416A (en) * | 2007-04-12 | 2008-10-30 | Olympus Imaging Corp | Image reproduction device, image reproduction program, recording medium and image reproduction method |
| JP2008308511A (en) * | 2007-06-12 | 2008-12-25 | Toho Titanium Co Ltd | Composition for forming adhesive layer for photocatalyst film, adhesive layer for photocatalyst film, method of forming adhesive layer for photocatalyst film and photocatalyst structure |
| JP2009039687A (en) * | 2007-08-10 | 2009-02-26 | Nippon Soda Co Ltd | Composition for forming photocatalyst layer |
| JP2010005611A (en) * | 2008-05-27 | 2010-01-14 | Toto Ltd | Article coated with photocatalyst |
| JP2010099647A (en) * | 2008-03-28 | 2010-05-06 | Toto Ltd | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP2014188416A (en) * | 2013-03-26 | 2014-10-06 | Panahome Corp | Photocatalyst body |
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| JP2002080751A (en) * | 2000-09-08 | 2002-03-19 | Nippon Soda Co Ltd | Method for forming photocatalyst layer |
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| JP2007085118A (en) * | 2005-09-26 | 2007-04-05 | Matsushita Electric Works Ltd | Interior finish member |
| JP2008262416A (en) * | 2007-04-12 | 2008-10-30 | Olympus Imaging Corp | Image reproduction device, image reproduction program, recording medium and image reproduction method |
| JP2008308511A (en) * | 2007-06-12 | 2008-12-25 | Toho Titanium Co Ltd | Composition for forming adhesive layer for photocatalyst film, adhesive layer for photocatalyst film, method of forming adhesive layer for photocatalyst film and photocatalyst structure |
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| JP2010099647A (en) * | 2008-03-28 | 2010-05-06 | Toto Ltd | Photocatalyst-coated body and photocatalytic coating liquid for the same |
| JP2010005611A (en) * | 2008-05-27 | 2010-01-14 | Toto Ltd | Article coated with photocatalyst |
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| WO2016082658A1 (en) * | 2014-11-25 | 2016-06-02 | 江苏合志锂硫电池技术有限公司 | Composite binder, positive electrode of lithium rechargeable battery applying composite binder, and method for preparing same |
| CN105435764A (en) * | 2015-11-19 | 2016-03-30 | 上海应用技术学院 | Compound mesoporous photocatalyst and preparation method thereof |
| CN105435764B (en) * | 2015-11-19 | 2017-09-29 | 上海应用技术学院 | A kind of compound mesoporous photocatalytic agent and preparation method thereof |
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