JPH10159264A - Roofing material - Google Patents
Roofing materialInfo
- Publication number
- JPH10159264A JPH10159264A JP8335170A JP33517096A JPH10159264A JP H10159264 A JPH10159264 A JP H10159264A JP 8335170 A JP8335170 A JP 8335170A JP 33517096 A JP33517096 A JP 33517096A JP H10159264 A JPH10159264 A JP H10159264A
- Authority
- JP
- Japan
- Prior art keywords
- cobalt
- water
- photocatalyst
- repellent silicone
- photoexcitation
- 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
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 claims abstract description 44
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 35
- 239000005871 repellent Substances 0.000 claims abstract description 29
- 230000001443 photoexcitation Effects 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 21
- 239000002344 surface layer Substances 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 19
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 18
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 10
- 230000003628 erosive effect Effects 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 38
- 230000002940 repellent Effects 0.000 abstract 5
- 238000000576 coating method Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 125000000962 organic group Chemical group 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 8
- 150000004756 silanes Chemical class 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 239000008199 coating composition Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 229920003051 synthetic elastomer Polymers 0.000 description 6
- 239000005061 synthetic rubber Substances 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 238000001723 curing Methods 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229940011182 cobalt acetate Drugs 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- IQYVXTLKMOTJKI-UHFFFAOYSA-L cobalt(ii) chlorate Chemical compound [Co+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IQYVXTLKMOTJKI-UHFFFAOYSA-L 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 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
- 150000007514 bases Chemical class 0.000 description 2
- YSALUHGLIBYTET-UHFFFAOYSA-N benzyl(dibutoxy)silane Chemical compound CCCCO[SiH](OCCCC)CC1=CC=CC=C1 YSALUHGLIBYTET-UHFFFAOYSA-N 0.000 description 2
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- MGQFVQQCNPBJKC-UHFFFAOYSA-N dibutoxy(diethyl)silane Chemical compound CCCCO[Si](CC)(CC)OCCCC MGQFVQQCNPBJKC-UHFFFAOYSA-N 0.000 description 2
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 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
- VGWJKDPTLUDSJT-UHFFFAOYSA-N diethyl dimethyl silicate Chemical compound CCO[Si](OC)(OC)OCC VGWJKDPTLUDSJT-UHFFFAOYSA-N 0.000 description 2
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 2
- BZCJJERBERAQKQ-UHFFFAOYSA-N diethyl(dipropoxy)silane Chemical compound CCCO[Si](CC)(CC)OCCC BZCJJERBERAQKQ-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
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 2
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 2
- JQYGMRTZHJTQAC-UHFFFAOYSA-N methyl-phenyl-dipropoxysilane Chemical compound CCCO[Si](C)(OCCC)C1=CC=CC=C1 JQYGMRTZHJTQAC-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- -1 pH = 1) Chemical compound 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 2
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 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
- WAAWAIHPWOJHJJ-UHFFFAOYSA-N tributoxy(propyl)silane Chemical compound CCCCO[Si](CCC)(OCCCC)OCCCC WAAWAIHPWOJHJJ-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-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
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-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
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- VUWVDNLZJXLQPT-UHFFFAOYSA-N tripropoxy(propyl)silane Chemical compound CCCO[Si](CCC)(OCCC)OCCC VUWVDNLZJXLQPT-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- JXNKBTBWPCYTQC-UHFFFAOYSA-N [Si].C(CCCCC)N Chemical class [Si].C(CCCCC)N JXNKBTBWPCYTQC-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 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
- 230000001680 brushing effect Effects 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
- 239000002772 conduction electron Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 235000019645 odor Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Landscapes
- Roof Covering Using Slabs Or Stiff Sheets (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Laminated Bodies (AREA)
- Catalysts (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、着氷雪しにくい屋
根材に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a roofing material which is hardly iced and snowy.
【0002】[0002]
【従来の技術】屋根に氷雪が付着すると、放置しておけ
ば、その重みによって、屋根の変形等が生じるおそれが
ある。そのため、降雪地域では頻繁に雪おろしする必要
性が生じ、多大のコストと労力を要していた。2. Description of the Related Art If ice or snow adheres to a roof, the roof may be deformed due to its weight if left unattended. For this reason, in snowfall areas, it is necessary to frequently remove snow, which has required a great deal of cost and labor.
【0003】[0003]
【発明が解決しようとする課題】上記着氷雪を防止する
方法としては、屋根表面に撥水性を付与するとよいこと
が知られている。部材表面に撥水性を付与すると、部材
表面で水滴が動き回るようになる。このため水滴が付着
しにくくなり、水滴が付着しないため、雪や氷も付着し
にくくなる。As a method for preventing the formation of icing snow, it is known that it is preferable to impart water repellency to the roof surface. When water repellency is imparted to the member surface, water droplets move around on the member surface. As a result, water droplets are less likely to adhere, and snow and ice are less likely to adhere because water droplets do not adhere.
【0004】その一方法として、基材表面に撥水性シリ
コ−ンからなる表面層を形成する方法がある。しかしな
がら、この構成では経時的に汚れが付着することによっ
て水との接触角が70゜程度に低下し、撥水性の効果が
持続しない。そこで、上記課題を解決する他の方法とし
て、基材表面に光触媒と撥水性シリコ−ンとからなる表
面層を形成する方法がある。この方法によれば、光触媒
の酸化分解性に基づき、経時的に付着する汚れを分解で
きる。しかしながら、この構成では屋外で太陽光に晒す
と、光触媒の光励起によりシリコ−ンが親水化してしま
うため表面の撥水性を維持することができない。本発明
では、上記事情に鑑み、表面の撥水性を長期にわたり維
持しうる屋根材を提供し、以て屋根材への着氷雪を防止
することを目的とする。As one of the methods, there is a method of forming a surface layer made of a water-repellent silicone on a substrate surface. However, with this structure, the contact angle with water is reduced to about 70 ° due to the adhesion of dirt over time, and the effect of water repellency is not maintained. Therefore, as another method for solving the above-mentioned problem, there is a method of forming a surface layer comprising a photocatalyst and a water-repellent silicone on the surface of a substrate. According to this method, it is possible to decompose the adhered dirt over time based on the oxidative decomposability of the photocatalyst. However, in this configuration, when exposed to sunlight outdoors, the silicone is hydrophilized by photoexcitation of the photocatalyst, so that the water repellency of the surface cannot be maintained. In view of the above circumstances, an object of the present invention is to provide a roofing material that can maintain the water repellency of its surface for a long period of time, and to prevent icing and snow on the roofing material.
【0005】[0005]
【課題を解決するための手段】本発明では、上記課題を
解決すべく、基材表面に、光触媒粒子と、撥水性シリコ
−ンと、前記撥水性シリコ−ンの前記光触媒の光励起に
よる親水化を防止するための物質とを含有する表面層が
形成されている、或いは基材表面に、光触媒粒子と撥水
性シリコ−ンとを含有する層が形成され、さらにその層
表面の少なくとも一部には前記撥水性シリコ−ンの前記
光触媒の光励起による親水化を防止するための物質が固
定されていることを特徴とする屋根材を提供する。コバ
ルト又はコバルト化合物のような光触媒の光励起による
親水化を防止するための物質が表面層に含有されている
ようにすることにより、光触媒の光励起によりシリコ−
ンが親水化してしまうのを防止することができる。かつ
光触媒が含有されているので、光触媒の酸化分解性に基
づき、経時的に付着する汚れを分解できる。従って、表
面の撥水性を維持することができ、屋根材に氷雪が付着
するのを防止することができる。According to the present invention, in order to solve the above-mentioned problems, photocatalyst particles, water-repellent silicone, and hydrophilization of the water-repellent silicone by photoexcitation of the photocatalyst are provided on a substrate surface. Or a layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of the base material, and is further formed on at least a part of the surface of the layer. Provides a roofing material to which a substance for preventing the water-repellent silicone from being hydrophilized by photoexcitation of the photocatalyst is fixed. By making the surface layer contain a substance such as cobalt or a cobalt compound for preventing the photocatalyst from becoming hydrophilic due to photoexcitation, the silicon can be produced by photoexcitation of the photocatalyst.
Can be prevented from becoming hydrophilic. In addition, since the photocatalyst is contained, it is possible to decompose the dirt adhering with time based on the oxidative decomposability of the photocatalyst. Therefore, the water repellency of the surface can be maintained, and ice and snow can be prevented from attaching to the roofing material.
【0006】[0006]
【発明の実施の形態】図1は、屋根材の斜視図を示して
おり、本発明の一態様においては、図2に示すように、
基材の表面に光触媒粒子と、シリコ−ンと、コバルト又
はコバルト化合物等の光触媒の光励起による親水化を防
止するための物質を含む表面層が形成されている。本発
明の他の態様においては、図3に示すように、基材の表
面に光触媒粒子と撥水性シリコ−ンとを含有する層が形
成され、さらにその層表面の少なくとも一部にはコバル
ト又はコバルト化合物等の撥水性シリコ−ンの光触媒の
光励起による親水化を防止するための物質が固定されて
いる。FIG. 1 is a perspective view of a roofing material. In one embodiment of the present invention, as shown in FIG.
A surface layer containing a photocatalyst particle, silicon, and a substance for preventing hydrophilicity due to photoexcitation of a photocatalyst such as cobalt or a cobalt compound is formed on the surface of the base material. In another embodiment of the present invention, as shown in FIG. 3, a layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of the substrate, and at least a part of the surface of the layer is made of cobalt or A substance for preventing hydrophilicity due to photoexcitation of a photocatalyst of a water-repellent silicone such as a cobalt compound is fixed.
【0007】光触媒とは、その結晶の伝導帯と価電子帯
との間のエネルギ−ギャップよりも大きなエネルギ−
(すなわち短い波長)の光(励起光)を照射したとき
に、価電子帯中の電子の励起(光励起)が生じて、伝導
電子と正孔を生成しうる物質をいい、例えば、アナタ−
ゼ型酸化チタン、酸化亜鉛、酸化錫、酸化第二鉄、三酸
化二ビスマス、三酸化タングステン、チタン酸ストロン
チウム等の酸化物が好適に利用できる。光触媒の光励起
に用いる光源としては、日中は太陽光に晒されるので、
太陽光を利用できる。A photocatalyst has an energy greater than the energy gap between the conduction band and the valence band of the crystal.
A substance capable of generating conduction electrons and holes by excitation of electrons in the valence band (photoexcitation) when irradiated with light (excitation light) having a short wavelength (excitation light).
Oxides such as zeta-type titanium oxide, zinc oxide, tin oxide, ferric oxide, bismuth trioxide, tungsten trioxide and strontium titanate can be suitably used. As a light source used for photoexcitation of the photocatalyst, it is exposed to sunlight during the day,
Sunlight is available.
【0008】シリコ−ンには、平均組成式 RpSiO(4-p)/2 (式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、pは0<p<2を満足する数
である)で表される樹脂が利用できる。The silicone has an average composition formula R p SiO (4-p) / 2 (where R is a functional group comprising one or more monovalent organic groups, or a monovalent organic group) A resin represented by the following formula: X is an alkoxy group or a halogen atom, and p is a number satisfying 0 <p <2. Is available.
【0009】コバルト化合物には、コバルト合金、酸化
コバルト、塩化コバルト、硫酸コバルト、ヨウ化コバル
ト、臭化コバルト、酢酸コバルト、塩素酸コバルト、硝
酸コバルト等が好適に利用できる。As the cobalt compound, cobalt alloy, cobalt oxide, cobalt chloride, cobalt sulfate, cobalt iodide, cobalt bromide, cobalt acetate, cobalt chlorate, cobalt nitrate and the like can be suitably used.
【0010】表面層の膜厚は、0.4μm以下にするの
が好ましい。そうすれば、光の乱反射による白濁を防止
することができ、表面層は実質的に透明となる。さら
に、表面層の膜厚を、0.2μm以下にすると一層好ま
しい。そうすれば、光の干渉による表面層の発色を防止
することができる。また、表面層が薄ければ薄いほどそ
の透明度は向上する。更に、膜厚を薄くすれば、表面層
の耐摩耗性が向上する。The thickness of the surface layer is preferably set to 0.4 μm or less. Then, cloudiness due to irregular reflection of light can be prevented, and the surface layer becomes substantially transparent. Further, it is more preferable that the thickness of the surface layer be 0.2 μm or less. Then, it is possible to prevent the surface layer from being colored by light interference. Also, the thinner the surface layer, the better its transparency. Further, when the film thickness is reduced, the wear resistance of the surface layer is improved.
【0011】表面層には、Ag、Cu、Znのような金
属を添加することができる。前記金属を添加した表面層
は、表面に付着した細菌や黴を暗所でも死滅させること
ができる。A metal such as Ag, Cu and Zn can be added to the surface layer. The surface layer to which the metal is added can kill bacteria and fungi attached to the surface even in a dark place.
【0012】表面層にはPt、Pd、Ru、Rh、I
r、Osのような白金族金属を添加することができる。
前記金属を添加した表面層は、光触媒の酸化還元活性を
増強でき、有機物汚れの分解性、有害気体や悪臭の分解
性を向上させることができる。Pt, Pd, Ru, Rh, I
A platinum group metal such as r or Os can be added.
The surface layer to which the metal is added can enhance the redox activity of the photocatalyst, and can improve the decomposability of organic contaminants and the decomposability of harmful gases and odors.
【0013】次に、基材表面に、光触媒粒子と、撥水性
シリコ−ンと、前記撥水性シリコ−ンの前記光触媒の光
励起による親水化を防止するための物質とを含有する表
面層が形成されている撥水性部材の製法について説明す
る。この場合の製法は、基本的には、基材表面にコ−テ
ィング組成物を塗布し、硬化させることによる。Next, a surface layer containing photocatalyst particles, water-repellent silicone, and a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst is formed on the surface of the substrate. The method of manufacturing the water-repellent member described above will be described. The production method in this case is basically based on applying a coating composition on the surface of a substrate and curing the coating composition.
【0014】ここでコ−ティング組成物は、光触媒粒
子、コバルト又はコバルト化合物等の光触媒の光励起に
よる親水化を防止するための物質にシリコ−ンの前駆体
を必須構成要件とし、その他に水、エタノ−ル、プロパ
ノ−ル等の溶媒や、塩酸、硝酸、硫酸、酢酸、マレイン
酸等のシリコ−ンの前駆体の加水分解を促進する触媒
や、トリブチルアミン、ヘキシルアミンなどの塩基性化
合物類、アルミニウムトリイソプロポキシド、テトライ
ソプロピルチタネ−トなどの酸性化合物類等のシリコ−
ンの前駆体を硬化させる触媒や、シランカップリング剤
等のコ−ティング液の分散性を向上させる界面活性剤な
どを添加してもよい。Here, the coating composition contains a precursor of silicon as an essential component of a substance for preventing photocatalytic particles, cobalt or a cobalt compound or the like from becoming hydrophilic by photoexcitation of a photocatalyst. Solvents such as ethanol and propanol, catalysts that promote hydrolysis of silicone precursors such as hydrochloric acid, nitric acid, sulfuric acid, acetic acid and maleic acid, and basic compounds such as tributylamine and hexylamine Silicon compounds such as acidic compounds such as aluminum, aluminum triisopropoxide and tetraisopropyl titanate;
And a surfactant for improving the dispersibility of the coating liquid such as a silane coupling agent.
【0015】コバルト又はコバルト化合物としては、水
溶性のコバルト化合物を用いるのが好ましい。水溶性の
コバルト化合物としては、例えば、塩化コバルト、硫酸
コバルト、ヨウ化コバルト、臭化コバルト、酢酸コバル
ト、塩素酸コバルト、硝酸コバルト等が好適に利用でき
る。As cobalt or a cobalt compound, a water-soluble cobalt compound is preferably used. As the water-soluble cobalt compound, for example, cobalt chloride, cobalt sulfate, cobalt iodide, cobalt bromide, cobalt acetate, cobalt chlorate, cobalt nitrate and the like can be suitably used.
【0016】ここでシリコ−ンの前駆体としては、平均
組成式 RpSiXqO(4-p-q)/2 (式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、p及びqは0<p<2、0<
q<4を満足する数である)で表されるシロキサンから
なる塗膜形成要素、又は一般式 RpSiX4-p (式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、pは1または2である)で表
される加水分解性シラン誘導体からなる塗膜形成要素、
が好適に利用できる。[0016] Here silicone - The precursor emissions in the average composition formula R p SiX q O (4- pq) / 2 ( wherein, R consists of one or more organic groups monovalent functional X or a functional group comprising two or more selected from a monovalent organic group and a hydrogen group, X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <
a film-forming element composed of a siloxane represented by the following formula: q <4) or a general formula R p SiX 4-p (where R is one or more monovalent organic groups) Wherein X is an alkoxy group or a halogen atom, and p is 1 or 2. A film-forming element comprising a hydrolyzable silane derivative to be
Can be suitably used.
【0017】ここで上記加水分解性シラン誘導体からな
る塗膜形成要素としては、メチルトリメトキシシラン、
メチルトリエトキシシラン、メチルトリプロポキシシラ
ン、メチルトリブトキシシラン、エチルトリメトキシシ
ラン、エチルトリエトキシシラン、エチルトリプロポキ
シシラン、エチルトリブトキシシラン、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、
ジメチルジメトキシシラン、ジメチルジエトキシシラ
ン、ジメチルジプロポキシシラン、ジメチルジブトキシ
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、ジエチルジプロポキシシラン、ジエチルジブ
トキシシラン、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、フェニルメチルジプロポ
キシシラン、フェニルメチルジブトキシシラン、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、n−プロ
ピルトリブトキシシラン、γ−グリコキシドキシプロピ
ルトリメトキシシラン、γ−アクリロキシプロピルトリ
メトキシシラン等が好適に利用できる。Here, as the coating film forming element comprising the hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.
【0018】また、上記シロキサンからなる塗膜形成要
素としては、上記加水分解性シラン誘導体の部分加水分
解及び脱水縮重合、又は上記加水分解性シラン誘導体の
部分加水分解物と、テトラメトキシシラン、テトラエト
キシシラン、テトラプロポキシシラン、テトラブトキシ
シラン、ジエトキシジメトキシシラン等の部分加水分解
物との脱水縮重合等で作製することができる。The film-forming element composed of the siloxane includes partial hydrolysis and dehydration-condensation polymerization of the hydrolyzable silane derivative, or partial hydrolyzate of the hydrolyzable silane derivative, tetramethoxysilane, tetramethoxysilane, It can be produced by dehydration polycondensation with a partial hydrolyzate such as ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.
【0019】上記コ−ティング組成物の塗布方法として
は、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、刷毛塗り、スポンジ塗り等の方法
が好適に利用できる。硬化方法としては、熱処理、室温
放置、紫外線照射等により重合させて行うことができ
る。The coating method of the coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.
【0020】次に、基材表面に、光触媒粒子と撥水性シ
リコ−ンとを含有する層が形成され、さらにその層表面
の少なくとも一部には前記撥水性シリコ−ンの前記光触
媒の光励起による親水化を防止するための物質が固定さ
れている撥水性部材の製法について説明する。この場合
の製法は、基本的には、光触媒粒子と撥水性シリコ−ン
の前駆体とを含有するコ−ティング組成物を塗布し、硬
化させた後、コバルト又はコバルト化合物等の光触媒の
光励起による親水化を防止するための物質を含有する溶
液を塗布し、表面に固定することによる。Next, a layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of the base material, and at least a part of the surface of the layer is formed by photoexcitation of the photocatalyst by the water-repellent silicone. A method for manufacturing a water-repellent member to which a substance for preventing hydrophilicity is fixed will be described. The production method in this case is basically based on the photo-excitation of a photocatalyst such as cobalt or a cobalt compound after coating and curing a coating composition containing photocatalyst particles and a water-repellent silicone precursor. By applying a solution containing a substance for preventing hydrophilization and fixing the solution to the surface.
【0021】ここでコ−ティング組成物は、光触媒粒子
と、撥水性シリコ−ンの前駆体を必須構成要件とし、そ
の他に水、エタノ−ル、プロパノ−ル等の溶媒や、塩
酸、硝酸、硫酸、酢酸、マレイン酸等のシリカの前駆体
の加水分解を促進する触媒や、トリブチルアミン、ヘキ
シルアミンなどの塩基性化合物類、アルミニウムトリイ
ソプロポキシド、テトライソプロピルチタネ−トなどの
酸性化合物類等のシリカの前駆体を硬化させる触媒や、
シランカップリング剤等のコ−ティング液の分散性を向
上させる界面活性剤などを添加してもよい。Here, the coating composition has photocatalyst particles and a precursor of a water-repellent silicone as essential components, and in addition, a solvent such as water, ethanol, propanol, hydrochloric acid, nitric acid, and the like. Catalysts that promote the hydrolysis of silica precursors such as sulfuric acid, acetic acid and maleic acid, basic compounds such as tributylamine and hexylamine, and acidic compounds such as aluminum triisopropoxide and tetraisopropyl titanate Such as a catalyst for curing a precursor of silica,
A surfactant such as a silane coupling agent for improving the dispersibility of the coating liquid may be added.
【0022】ここでシリコ−ンの前駆体としては、平均
組成式 RpSiXqO(4-p-q)/2 (式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、p及びqは0<p<2、0<
q<4を満足する数である)で表されるシロキサンから
なる塗膜形成要素、又は一般式 RpSiX4-p (式中、Rは一価の有機基の1種若しくは2種以上から
なる官能基、又は、一価の有機基と水素基から選ばれた
2種以上からなる官能基であり、Xはアルコキシ基、又
は、ハロゲン原子であり、pは1または2である)で表
される加水分解性シラン誘導体からなる塗膜形成要素、
が好適に利用できる。[0022] Here silicone - The precursor emissions in the average composition formula R p SiX q O (4- pq) / 2 ( wherein, R consists of one or more organic groups monovalent functional X or a functional group comprising two or more selected from a monovalent organic group and a hydrogen group, X is an alkoxy group or a halogen atom, and p and q are 0 <p <2, 0 <
a film-forming element composed of a siloxane represented by the following formula: q <4) or a general formula R p SiX 4-p (where R is one or more monovalent organic groups) Wherein X is an alkoxy group or a halogen atom, and p is 1 or 2. A film-forming element comprising a hydrolyzable silane derivative to be
Can be suitably used.
【0023】ここで上記加水分解性シラン誘導体からな
る塗膜形成要素としては、メチルトリメトキシシラン、
メチルトリエトキシシラン、メチルトリプロポキシシラ
ン、メチルトリブトキシシラン、エチルトリメトキシシ
ラン、エチルトリエトキシシラン、エチルトリプロポキ
シシラン、エチルトリブトキシシラン、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、
ジメチルジメトキシシラン、ジメチルジエトキシシラ
ン、ジメチルジプロポキシシラン、ジメチルジブトキシ
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、ジエチルジプロポキシシラン、ジエチルジブ
トキシシラン、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、フェニルメチルジプロポ
キシシラン、フェニルメチルジブトキシシラン、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、n−プロ
ピルトリブトキシシラン、γ−グリコキシドキシプロピ
ルトリメトキシシラン、γ−アクリロキシプロピルトリ
メトキシシラン等が好適に利用できる。Here, as the coating film forming element comprising the hydrolyzable silane derivative, methyltrimethoxysilane,
Methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltripropoxysilane, ethyltributoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltripropoxysilane, Phenyltributoxysilane,
Dimethyldimethoxysilane, dimethyldiethoxysilane, dimethyldipropoxysilane, dimethyldibutoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldipropoxysilane, diethyldibutoxysilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, phenyl Methyldipropoxysilane, phenylmethyldibutoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-propyltripropoxysilane, n-propyltributoxysilane, γ-glycoxydoxypropyltrimethoxysilane, γ -Acryloxypropyltrimethoxysilane and the like can be suitably used.
【0024】また、上記シロキサンからなる塗膜形成要
素としては、上記加水分解性シラン誘導体の部分加水分
解及び脱水縮重合、又は上記加水分解性シラン誘導体の
部分加水分解物と、テトラメトキシシラン、テトラエト
キシシラン、テトラプロポキシシラン、テトラブトキシ
シラン、ジエトキシジメトキシシラン等の部分加水分解
物との脱水縮重合等で作製することができる。The film-forming element composed of the siloxane includes partial hydrolysis and dehydration-condensation polymerization of the hydrolyzable silane derivative, or a partial hydrolyzate of the hydrolyzable silane derivative, tetramethoxysilane, tetramethoxysilane and tetramethoxysilane. It can be produced by dehydration polycondensation with a partial hydrolyzate such as ethoxysilane, tetrapropoxysilane, tetrabutoxysilane, diethoxydimethoxysilane and the like.
【0025】上記コ−ティング組成物の塗布方法として
は、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、刷毛塗り、スポンジ塗り等の方法
が好適に利用できる。硬化方法としては、熱処理、室温
放置、紫外線照射等により重合させて行うことができ
る。The coating method of the above coating composition includes spray coating, dip coating, flow coating, spin coating, roll coating, brush coating, and sponge. A method such as coating can be suitably used. As a curing method, it can be carried out by polymerizing by heat treatment, standing at room temperature, ultraviolet irradiation, or the like.
【0026】コバルト又はコバルト化合物等の光触媒の
光励起による親水化を防止するための物質を含有する溶
液を塗布し、表面に固定する方法は、例えば、塩化コバ
ルト、硫酸コバルト、ヨウ化コバルト、臭化コバルト、
酢酸コバルト、塩素酸コバルト、硝酸コバルト等の水溶
性のコバルト化合物を、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、刷毛塗り、スポ
ンジ塗り等の方法で塗布し、光還元、熱処理、アルコ−
ル等の犠牲酸化剤を併用する還元等の方法で固定するこ
とにより行う。The method of applying a solution containing a substance for preventing the photocatalyst such as cobalt or a cobalt compound from being hydrophilized by photoexcitation and fixing it on the surface includes, for example, cobalt chloride, cobalt sulfate, cobalt iodide, bromide, and the like. cobalt,
Spray coating method, dip coating method, flow coating method, spin coating method, roll coating method, brushing water-soluble cobalt compounds such as cobalt acetate, cobalt chlorate and cobalt nitrate Coating, sponge coating, etc., photoreduction, heat treatment, alcohol
This is performed by fixing by a method such as reduction using a sacrificial oxidizing agent such as toluene.
【0027】[0027]
参考例.アナタ−ゼ型酸化チタンゾル(日産化学、TA
−15、硝酸解膠型、pH=1)と、シリカゾル(日本
合成ゴム、グラスカA液、pH=4)と、メチルトリメ
トキシシラン(日本合成ゴム、グラスカB液)とエタノ
−ルを混合し、2〜3時間撹拌して得たコ−ティング液
を、スプレ−コ−ティング法にて5×10cm角の施釉
タイル基材(東陶機器、AB02E11)上に塗布し、
200℃で15分熱処理して、アナタ−ゼ型酸化チタン
粒子11重量部、シリカ6重量部、シリコ−ン5重量部
からなる表面層を形成した#1試料を得た。#1試料の
水との接触角は92゜であった。ここで水との接触角は
接触角測定器(協和界面科学、CA−X150)を用
い、マイクロシリンジから水滴を滴下した後30秒後の
水との接触角で評価した。次いで#1試料表面に、紫外
線光源(三共電気、ブラックライトブル−(BLB)蛍
光灯)を用いて0.3mW/cm2の紫外線照度で1日
照射し、#2試料を得た。その結果、#2試料の水との
接触角は0゜まで親水化された。次に、#1試料と、#
1試料に水銀灯を22.8mW/cm2の紫外線照度で
2時間照射して得た#3試料夫々の試料表面をラマン分
光分析した。その結果、#1試料表面で認められたメチ
ル基のピ−クが#3試料では認められず、代わりに水酸
基のブロ−ドなピ−クが認められた。以上のことから、
光触媒であるアナタ−ゼ型酸化チタンの光励起により被
膜の表面のシリコ−ン分子中のケイ素原子に結合した有
機基は、水酸基に置換されること、及び親水化されるこ
とがわかる。Reference example. Anatase type titanium oxide sol (Nissan Chemical, TA
-15, nitric acid peptized type, pH = 1), silica sol (Nippon Synthetic Rubber, Glasca A solution, pH = 4), methyltrimethoxysilane (Nippon Synthetic Rubber, Glasca B solution) and ethanol are mixed. The coating liquid obtained by stirring for 2 to 3 hours was applied on a 5 × 10 cm square glazed tile base material (TOTOKIKI, AB02E11) by spray coating.
A heat treatment was performed at 200 ° C. for 15 minutes to obtain a # 1 sample having a surface layer formed of 11 parts by weight of anatase type titanium oxide particles, 6 parts by weight of silica, and 5 parts by weight of silicone. The contact angle of the # 1 sample with water was 92 °. Here, the contact angle with water was evaluated using a contact angle measuring device (Kyowa Interface Science, CA-X150) by the contact angle with water 30 seconds after a water droplet was dropped from the micro syringe. Next, the surface of the # 1 sample was irradiated for one day with an ultraviolet illuminance of 0.3 mW / cm 2 using an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp) to obtain a # 2 sample. As a result, the contact angle with water of the # 2 sample was hydrophilized to 0 °. Next, # 1 sample and #
One sample was irradiated with a mercury lamp at an ultraviolet irradiance of 22.8 mW / cm 2 for 2 hours, and the surface of each of the # 3 samples obtained was subjected to Raman spectroscopic analysis. As a result, a peak of methyl group observed on the surface of sample # 1 was not observed in sample # 3, but a peak of hydroxyl group was observed instead. From the above,
It can be seen that the organic group bonded to the silicon atom in the silicon molecule on the surface of the film by the photoexcitation of the anatase type titanium oxide which is a photocatalyst is replaced by a hydroxyl group and becomes hydrophilic.
【0028】実施例1.アナタ−ゼ型酸化チタンゾル
(日産化学、TA−15、硝酸解膠型、pH=1)と、
シリカゾル(日本合成ゴム、グラスカA液、pH=4)
と、メチルトリメトキシシラン(日本合成ゴム、グラス
カB液)と、塩化コバルト六水和物と、エタノ−ルを混
合し、2〜3時間撹拌して得たコ−ティング液を、スプ
レ−コ−ティング法にてスレ−ト基材上に塗布し、15
0℃で15分熱処理して、アナタ−ゼ型酸化チタン粒子
11重量部、シリカ6重量部、シリコ−ン5重量部、コ
バルト0.2重量部からなる表面層を形成した#4試料
を得た。#4試料の水との接触角は97゜であった。こ
こで水との接触角は接触角測定器(協和界面科学、CA
−X150)を用い、マイクロシリンジから水滴を滴下
した後30秒後の水との接触角で評価した。次いで#4
試料表面に、紫外線光源(三共電気、ブラックライトブ
ル−(BLB)蛍光灯)を用いて0.3mW/cm2の
紫外線照度で1日照射し、#5試料を得た。その結果、
#5試料の水との接触角は依然95゜と撥水性を維持し
た。従って、以上のことから、光触媒であるアナタ−ゼ
型酸化チタンの光励起による被膜の表面のシリコ−ンの
親水化が、コバルトにより阻害されることがわかる。こ
れは、被膜の表面のシリコ−ン分子中のケイ素原子に結
合した有機基の水酸基への置換がコバルトにより阻害さ
れるためと考えられる。Embodiment 1 FIG. Anatase type titanium oxide sol (Nissan Chemical, TA-15, peptized nitrate, pH = 1),
Silica sol (Nippon Synthetic Rubber, Glasca A solution, pH = 4)
And methyltrimethoxysilane (Nippon Synthetic Rubber, Glasca B solution), cobalt chloride hexahydrate, and ethanol, and stirred for 2-3 hours. -Applied on a slat base material by the
Heat-treated at 0 ° C. for 15 minutes to obtain a # 4 sample having a surface layer formed of 11 parts by weight of anatase type titanium oxide particles, 6 parts by weight of silica, 5 parts by weight of silicone, and 0.2 parts by weight of cobalt. Was. The contact angle of the # 4 sample with water was 97 °. Here, the contact angle with water is measured using a contact angle measuring instrument (Kyowa Interface Science, CA
-X150), and evaluated by the contact angle with water 30 seconds after a water drop was dropped from the micro syringe. Then # 4
The sample surface was irradiated with ultraviolet light of 0.3 mW / cm 2 for one day using an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp) to obtain a # 5 sample. as a result,
The contact angle with water of the # 5 sample was still 95 °, maintaining water repellency. Therefore, it can be understood from the above that the hydrophilicity of the silicon on the surface of the coating film due to the photoexcitation of the anatase type titanium oxide as a photocatalyst is inhibited by cobalt. This is considered because the substitution of the hydroxyl group for the organic group bonded to the silicon atom in the silicon molecule on the surface of the coating is inhibited by cobalt.
【0029】実施例2.アナタ−ゼ型酸化チタンゾル
(日産化学、TA−15、硝酸解膠型、pH=1)と、
シリカゾル(日本合成ゴム、グラスカA液、pH=4)
と、メチルトリメトキシシラン(日本合成ゴム、グラス
カB液)と、エタノ−ルを混合し、2〜3時間撹拌して
得たコ−ティング液を、スプレ−コ−ティング法にてス
レ−ト基材上に塗布し、150℃で15分熱処理して、
アナタ−ゼ型酸化チタン粒子11重量部、シリカ6重量
部、シリコ−ン5重量部からなる表面層を形成した。さ
らにその上にコバルト金属濃度50μmol/gの塩化
コバルト六水和物水溶液を0.3g塗布後、紫外線光源
(三共電気、ブラックライトブル−(BLB)蛍光灯)
を用いて紫外線照度0.4mW/cm2の紫外線を10
分照射して基材上にコバルトを固定して#6試料を得
た。#6試料の水との接触角は96゜であった。ここで
水との接触角は接触角測定器(協和界面科学、CA−X
150)を用い、マイクロシリンジから水滴を滴下した
後30秒後の水との接触角で評価した。次いで#6試料
表面に、紫外線光源(三共電気、ブラックライトブル−
(BLB)蛍光灯)を用いて0.3mW/cm2の紫外
線照度で1日照射し、#7試料を得た。その結果、#7
試料の水との接触角は依然94゜と撥水性を維持した。
従って、以上のことから、光触媒であるアナタ−ゼ型酸
化チタンの光励起による被膜の表面のシリコ−ンの親水
化が、コバルトにより阻害されることがわかる。これ
は、被膜の表面のシリコ−ン分子中のケイ素原子に結合
した有機基の水酸基への置換がコバルトにより阻害され
るためと考えられる。Embodiment 2 FIG. Anatase type titanium oxide sol (Nissan Chemical, TA-15, peptized nitrate, pH = 1),
Silica sol (Nippon Synthetic Rubber, Glasca A solution, pH = 4)
, Methyltrimethoxysilane (Nippon Synthetic Rubber, Glasca B Solution) and ethanol were mixed, and the mixture was stirred for 2 to 3 hours. Coated on a substrate, heat treated at 150 ° C for 15 minutes,
A surface layer comprising 11 parts by weight of anatase type titanium oxide particles, 6 parts by weight of silica and 5 parts by weight of silicone was formed. Furthermore, after applying 0.3 g of an aqueous solution of cobalt chloride hexahydrate having a cobalt metal concentration of 50 μmol / g thereon, an ultraviolet light source (Sankyo Electric, Black Light Blue (BLB) fluorescent lamp) was applied.
UV light of 0.4 mW / cm 2 with 10 UV light
The sample was irradiated for 10 minutes to fix cobalt on the substrate to obtain a # 6 sample. The contact angle of the # 6 sample with water was 96 °. Here, the contact angle with water is measured using a contact angle measuring device (Kyowa Interface Science, CA-X).
150), the contact angle with water was evaluated 30 seconds after a water drop was dropped from the micro syringe. Next, an ultraviolet light source (Sankyo Electric, Black Light Blue-
(BLB) fluorescent light) for 1 day at an ultraviolet illuminance of 0.3 mW / cm 2 to obtain a # 7 sample. As a result, # 7
The contact angle of the sample with water was still 94 °, maintaining water repellency.
Therefore, it can be understood from the above that the hydrophilicity of the silicon on the surface of the coating film due to the photoexcitation of the anatase type titanium oxide as a photocatalyst is inhibited by cobalt. This is considered because the substitution of the hydroxyl group for the organic group bonded to the silicon atom in the silicon molecule on the surface of the coating is inhibited by cobalt.
【0030】実施例3.45゜に傾斜させた#5試料、
#7試料、及びスレ−ト板材にシャワ−を使って水をか
けた。その結果、スレ−ト板上には水滴が残留したのに
対し、#5試料、#7試料では水滴は転げ落ちた。Example 3. # 5 sample inclined at 45 °,
Water was applied to the # 7 sample and the slate plate using a shower. As a result, while water droplets remained on the slat plate, the water droplets rolled down in the # 5 and # 7 samples.
【0031】[0031]
【発明の効果】本発明では、屋根材において、基材表面
に、光触媒粒子と、撥水性シリコ−ンと、前記撥水性シ
リコ−ンの前記光触媒の光励起による親水化を防止する
ための物質とを含有する表面層が形成されているように
する、或いは基材表面に、光触媒粒子と撥水性シリコ−
ンとを含有する層が形成され、さらにその層表面の少な
くとも一部には前記撥水性シリコ−ンの前記光触媒の光
励起による親水化を防止するための物質が固定されてい
るようにすることにより、部材表面は長期にわたり撥水
性を維持可能となり、以て屋根材への着氷雪が防止され
る。According to the present invention, in a roofing material, a photocatalyst particle, a water-repellent silicone, and a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst are provided on the surface of the base material. Or a photocatalyst particle and a water-repellent silicone on the surface of the substrate.
And a substance for preventing hydrophilicity of the water-repellent silicone by photoexcitation of the photocatalyst is fixed to at least a part of the surface of the layer. In addition, the surface of the member can maintain water repellency for a long period of time, thereby preventing icing and snow on the roofing material.
【図1】屋根材の斜視図。FIG. 1 is a perspective view of a roofing material.
【図2】本発明に係る屋根材の表面構造を示す図。FIG. 2 is a diagram showing a surface structure of a roofing material according to the present invention.
【図3】本発明に係る屋根材の他の表面構造を示す図。FIG. 3 is a diagram showing another surface structure of the roofing material according to the present invention.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 FI B05D 7/24 303 B32B 33/00 B32B 33/00 E04D 1/28 A E04D 1/28 3/35 T 3/35 B B01J 23/74 311M ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI B05D 7/24 303 B32B 33/00 B32B 33/00 E04D 1/28 A E04D 1/28 3/35 T 3/35 B B01J 23 / 74 311M
Claims (3)
コ−ンと、前記撥水性シリコ−ンの前記光触媒の光励起
による親水化を防止するための物質とを含有する表面層
が形成されていることを特徴とする屋根材。1. A surface layer containing photocatalyst particles, water-repellent silicone, and a substance for preventing the water-repellent silicone from becoming hydrophilic by photoexcitation of the photocatalyst is formed on the surface of a substrate. Roofing material characterized by being.
−ンとを含有する層が形成され、さらにその層表面の少
なくとも一部には前記撥水性シリコ−ンの前記光触媒の
光励起による親水化を防止するための物質が固定されて
いることを特徴とする屋根材。2. A layer containing photocatalyst particles and a water-repellent silicone is formed on the surface of a base material, and at least a part of the surface of the layer is made hydrophilic by the photoexcitation of the photocatalyst of the water-repellent silicone. A roofing material, on which a substance for preventing erosion is fixed.
するための物質は、コバルト又はコバルト化合物である
ことを特徴とする請求項1、2に記載の屋根材。3. The roofing material according to claim 1, wherein the substance for preventing the photocatalyst from becoming hydrophilic by photoexcitation is cobalt or a cobalt compound.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8335170A JPH10159264A (en) | 1996-11-29 | 1996-11-29 | Roofing material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8335170A JPH10159264A (en) | 1996-11-29 | 1996-11-29 | Roofing material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10159264A true JPH10159264A (en) | 1998-06-16 |
Family
ID=18285547
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8335170A Pending JPH10159264A (en) | 1996-11-29 | 1996-11-29 | Roofing material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH10159264A (en) |
-
1996
- 1996-11-29 JP JP8335170A patent/JPH10159264A/en active Pending
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