WO2013077315A1 - 光触媒担持構造体 - Google Patents
光触媒担持構造体 Download PDFInfo
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- WO2013077315A1 WO2013077315A1 PCT/JP2012/080049 JP2012080049W WO2013077315A1 WO 2013077315 A1 WO2013077315 A1 WO 2013077315A1 JP 2012080049 W JP2012080049 W JP 2012080049W WO 2013077315 A1 WO2013077315 A1 WO 2013077315A1
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- Prior art keywords
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- photocatalyst
- poly
- meth
- silicone
- Prior art date
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- 239000000178 monomer Substances 0.000 claims abstract description 52
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 239000012790 adhesive layer Substances 0.000 claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 claims abstract description 36
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 36
- 239000011347 resin Substances 0.000 claims abstract description 32
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 14
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- 239000012736 aqueous medium Substances 0.000 claims abstract description 6
- -1 vinyl halide Chemical class 0.000 claims description 43
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 39
- 125000004432 carbon atom Chemical group C* 0.000 claims description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 28
- 229920001223 polyethylene glycol Polymers 0.000 claims description 22
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- 150000002148 esters Chemical class 0.000 claims description 14
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 13
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001346 alkyl aryl ethers Chemical class 0.000 claims description 6
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 6
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- 150000004692 metal hydroxides Chemical class 0.000 claims description 6
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- 125000000542 sulfonic acid group Chemical group 0.000 claims description 6
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- 229920000178 Acrylic resin Polymers 0.000 claims description 5
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- 125000003118 aryl group Chemical group 0.000 claims description 4
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- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
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- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 5
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- 125000001424 substituent group Chemical group 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- KVXNKFYSHAUJIA-UHFFFAOYSA-N acetic acid;ethoxyethane Chemical compound CC(O)=O.CCOCC KVXNKFYSHAUJIA-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000005791 algae growth Effects 0.000 description 1
- 125000005011 alkyl ether group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- YCITZMJNBYYMJO-UHFFFAOYSA-N chloro(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](Cl)C1=CC=CC=C1 YCITZMJNBYYMJO-UHFFFAOYSA-N 0.000 description 1
- DMZWVCJEOLBQCZ-UHFFFAOYSA-N chloro(ethenyl)silane Chemical compound Cl[SiH2]C=C DMZWVCJEOLBQCZ-UHFFFAOYSA-N 0.000 description 1
- YGZSVWMBUCGDCV-UHFFFAOYSA-N chloro(methyl)silane Chemical compound C[SiH2]Cl YGZSVWMBUCGDCV-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000004759 cyclic silanes Chemical class 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 description 1
- 125000003438 dodecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- HTDJPCNNEPUOOQ-UHFFFAOYSA-N hexamethylcyclotrisiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O1 HTDJPCNNEPUOOQ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- HMMGMWAXVFQUOA-UHFFFAOYSA-N octamethylcyclotetrasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 HMMGMWAXVFQUOA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 125000001325 propanoyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001846 repelling effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid group Chemical group C(CCC(=O)O)(=O)O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical group OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- XYJRNCYWTVGEEG-UHFFFAOYSA-N trimethoxy(2-methylpropyl)silane Chemical compound CO[Si](OC)(OC)CC(C)C XYJRNCYWTVGEEG-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical class OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/06—Homopolymers or copolymers containing elements other than carbon and hydrogen
- C09J157/10—Homopolymers or copolymers containing elements other than carbon and hydrogen containing oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/10—Block or graft copolymers containing polysiloxane sequences
Definitions
- the present invention relates to a photocatalyst carrying structure carrying a photocatalyst used for antifouling, water purification, deodorization, sterilization, wastewater treatment, water splitting, algal growth inhibition and various chemical reactions.
- An object of the present invention is to provide an adhesive layer for supporting a photocatalyst that does not contain a volatile organic compound as a solvent.
- the present invention relates to a photocatalyst carrying structure comprising a carrier and a photocatalyst layer carried on the carrier via an adhesive layer, wherein the adhesive layer comprises a photocatalyst carrying structure containing an aqueous silicone modified resin,
- the aqueous silicone-modified resin is preferably a resin obtained by emulsion-polymerizing a monomer in an aqueous medium in the presence of an emulsifier and further silicone-modified using a compound having a silicone structure.
- an aqueous silicone-modified (meth) acrylic resin is preferred.
- the monomer is a (meth) acrylate monomer selected from the group consisting of acrylic acid esters, methacrylic acid esters, and mixtures thereof, acrylamide monomers, methacrylamide monomers, vinyl monomers Selected from the group consisting of an ethylenically unsaturated monomer having a carboxylic acid group, vinyl cyanide, aromatic vinyl monomer, vinyl halide, butadiene and ethylene, and copolymerized with the (meth) acrylate monomer
- it is at least one possible comonomer, and in the monomer, the amount of the (meth) acrylate monomer is 90 to 100% by mass, and the amount of the comonomer is 0 to 10% by mass.
- the (meth) acrylate monomer is 5 to 12 carbon atoms of (meth) acrylic acid in an amount of 5% by mass or more based on the total mass of the monomer.
- the emulsifier is at least one selected from the group consisting of an ethylenically unsaturated monomer having a sulfonic acid group or a sulfonate group, an ethylenically unsaturated monomer having a sulfate ester group, and a mixture thereof.
- the compound having the silicone structure is preferably represented by the following formula (I): (Wherein R 1 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 4 to 5 carbon atoms, an aralkyl group having 7 to 11 carbon atoms, Represents a cycloalkyl group having 5 to 6 carbon atoms, a vinyl group, or a (meth) acryloyloxyalkyl group having 1 to 10 carbon atoms, and R 2 represents an alkyl group having 1 to 8 carbon atoms, an acyl group, or a hydrogen atom.
- R 1 is a hydrogen atom, an aliphatic hydrocarbon group having 1 to 16 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heteroaryl group having 4 to 5 carbon atoms, an aralkyl group having 7 to 11 carbon atoms
- n is 1 or 2 represents, when n is 2, R 1 each other may be the same or different, also may be combined to form a ring with R 1 each other, R 2 And may be the same or different from each other.) It is preferable that at least one compound selected from the group of compounds represented by formula (1) or cyclic polysiloxane is used, and the compound having the silicone structure is represented by the formula (I) , Selected from the group consisting of compounds wherein n is 1 It is more preferable that at least one selected from the group consisting of compounds wherein n is 2, and in the compound having the silicone structure, n is 1 in the formula (I) More preferably, the ratio of at least one selected from the group consisting of a certain compound and at least one selected from the group consisting of a compound wherein n is 2 is 1/10 or more in terms of molar ratio.
- the photocatalyst layer is preferably composed of a photocatalyst particle composite containing 25 to 95% by mass of a metal oxide gel or metal hydroxide gel.
- the adhesive layer may further comprise (poly) ethylene glycol, (poly) ethylene glycol monoalkyl ether, (poly) ethylene glycol ester, (poly) ethylene glycol ether ester, (poly) propylene glycol, (poly) propylene glycol monoalkyl. It is preferable to contain at least one selected from the group consisting of ether, (poly) propylene glycol ester, and (poly) propylene glycol ether ester.
- the present invention relates to an adhesive layer forming composition
- an adhesive layer forming composition comprising an aqueous silicone-modified resin.
- the composition for forming an adhesive layer (poly) ethylene glycol, (poly) ethylene glycol monoalkyl ether, (poly) ethylene glycol ester, (poly) ethylene glycol ether ester, (poly) propylene glycol, (poly) propylene glycol It is preferable to contain at least one selected from the group consisting of monoalkyl ethers, (poly) propylene glycol esters and (poly) propylene glycol ether esters.
- an adhesive layer for supporting a photocatalyst that does not contain a volatile organic compound as a solvent is provided.
- the adhesive layer of the present invention can be used indoors or the like in terms of the working environment.
- the carrier is not particularly limited, and may be any shape such as a film shape, a plate shape, a tubular shape, a spherical shape, and a fibrous shape.
- the thickness (diameter) is preferably 10 ⁇ m or more.
- This invention is comprised from the contact bonding layer containing water-based silicone modified resin.
- the aqueous silicone modified resin is not particularly limited as long as it is a resin partially having a silicone bond in the molecule.
- the aqueous silicone modified (meth) acrylic resin, the aqueous silicone modified epoxy resin, and the aqueous silicone modified polyester are used. Resin etc. can be illustrated. More specifically, JP-A-2-150475, JP-A-6-25369, JP-A-6-3322052, JP-A-8-120085, JP-A-10-329427, JP-A-2001-2001.
- the water-based silicone resin described in 1991163 can be illustrated, A water-based silicone modified (meth) acrylic resin is especially preferable.
- the monomer used in the aqueous silicone-modified (meth) acrylic resin include alkyl esters of 1 to 18 carbon atoms of (meth) acrylic acid and hydroxy of 1 to 18 carbon atoms of (meth) acrylic acid.
- examples include alkyl esters, (poly) oxyalkylene mono (meth) acrylates having 1 to 100 alkylene oxide groups, and (poly) oxyalkylene di (meth) acrylates having 1 to 100 alkylene oxide groups. be able to.
- Hydroxyalkyl esters ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, tetraethylene glycol (meth) acrylate, methoxy (meth) Tetraethylene glycol acrylate, (Meth) acrylic acid propylene glycol, methoxy (meth) acrylic acid propylene glycol, (meth) acrylic acid dipropylene glycol, methoxy (meth) acrylic acid dipropylene glycol, (meth) acrylic acid tetrapropylene glycol, methoxy (meth) acrylic acid (Poly) oxyalkylene mono (meth) acrylate having 1 to 100 alkylene oxide groups such as tetrapropylene glycol, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, di (meth) acrylic acid (Poly) oxyalkylene di
- the monomer is a (meth) acrylate monomer selected from the group consisting of acrylic acid ester, methacrylic acid ester and a mixture thereof, (meth) acrylamide monomer, vinyl monomer, carboxylic acid Selected from the group consisting of an ethylenically unsaturated monomer having a group, vinyl cyanide, aromatic vinyl monomer, vinyl halide, butadiene and ethylene, and at least copolymerizable with the (meth) acrylate monomer
- One comonomer is preferred.
- comonomers include (meth) acrylamide monomers such as (meth) acrylamide, diacetone (meth) acrylamide, N-methylol (meth) acrylamide, and N-butoxymethyl (meth) acrylamide, vinyl acetate, and propion.
- Vinyl monomers such as vinyl acid, vinyl versatate, vinyl pyrrolidone and methyl vinyl ketone, vinyl cyanide such as acrylonitrile and methacrylonitrile, aromatic vinyl monomers such as vinyl toluene, styrene and ⁇ -methyl styrene, chloride
- vinyl halides such as vinyl and vinylidene chloride.
- the comonomer is preferably an ethylenically unsaturated monomer having a carboxylic acid group, and acrylic acid, methacrylic acid, itaconic acid and its half ester, fumaric acid and its half ester, and maleic acid and It is preferably at least one selected from the group consisting of the half esters.
- the amount of the (meth) acrylate monomer is preferably 90 to 100% by mass, the amount of the comonomer is preferably 0 to 10% by mass, and the (meth) acrylate single amount
- the body preferably contains a cycloalkyl ester of 5 to 12 carbon atoms of (meth) acrylic acid in an amount of 5% by mass or more based on the total mass of the monomer.
- the cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, or a cyclododecyl group, and may have an alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or an epoxy group as a substituent.
- Specific examples of cycloalkyl esters of (meth) acrylic acid having 5 to 12 carbon atoms include cyclohexyl (meth) acrylate, 2-hydroxycyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, (meth) Examples include acrylic acid 2,3-cyclohexene oxide.
- the method for producing the aqueous silicone-modified resin is not particularly limited.
- the production method described in the patent publications exemplified above can be exemplified, but more specifically, the monomer is used as an emulsifier.
- an emulsion polymerization is carried out in an aqueous medium, and a method of silicone modification using a compound having a silicone structure can be preferably exemplified during or after the emulsion polymerization.
- the emulsifier to be used is not particularly limited as long as it has an emulsifying action, but a compound having an ethylenically unsaturated bond having a sulfonic acid group, a sulfonate group, or a sulfate group is preferable.
- the ethylenically unsaturated bond is preferably a radically polymerizable double bond
- the sulfonic acid group is preferably an ammonium salt or an alkali metal salt (ammonium sulfonate group or alkali metal sulfonate group).
- Examples of the compound having an ethylenically unsaturated bond include an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, an aryl group having 6 to 10 carbon atoms, and A compound having a substituent selected from the group consisting of succinic acid groups is preferable, and a vinyl sulfonate compound having a vinyl group as a substituent of the sulfonic acid group is more preferable.
- the compound having an ethylenically unsaturated bond include Eleminol (trademark) JS-2 manufactured by Sanyo Kasei Co., Ltd., Latemul (trademark) S-120, S-180A and S-180 manufactured by Kao Corporation.
- the compound having a silicone structure is represented by the following formula (I) Or a cyclic polysiloxane can be preferably used.
- R 1 specifically, carbon atoms such as hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, n-decyl group, etc.
- C6-C5 heteroaryl group such as 1-16 aliphatic hydrocarbon group, furanyl group, etc.
- C6-C11 aralkyl group such as benzyl group, phenethyl group, phenyl group, naphthyl group, etc.
- cycloalkyl group having 5 to 6 carbon atoms such as aryl group, cyclopentyl group, cyclohexyl group, etc., vinyl group, (meth) acryloyloxypropyl group, (meth) acryloyloxyethyl group, etc.
- Ten (meth) acryloyloxyalkyl groups can be exemplified.
- R 2 is an alkyl group having 1 to 8 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, isobutyl group, acetyl group, benzoyl group,
- An acyl group such as a propanoyl group or a hydrogen atom is represented.
- n represents 1 or 2
- R 1 each other may be the same or different, also may be combined to form a ring with R 1 each other, R 2 each other May be the same or different.
- Linear polysiloxanes (including oligomers) in which the silane compound represented by the formula (I) is partially or fully hydrolyzed and condensed can also be used.
- R 1 is preferably a methyl group, phenyl group, vinyl group, or ⁇ - (meth) acryloxypropyl group
- R 2 is a methyl group, ethyl group, n-propyl group, n -A butyl group, a 1-methoxyethyl group and a hydrogen atom are preferred.
- silane compound represented by the formula (I) examples include trimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, isobutyltrimethoxysilane, vinyltriethoxysilane, ⁇ -acrylic.
- cyclic silane specifically, octamethylcyclotetrasiloxane
- examples include octaphenylcyclosiloxane, hexamethylcyclotrisiloxane, decamethylcyclopentasiloxane, and tetramethyltetravinylcyclotetrasiloxane.
- n in the formula (I) such as monoalkoxysilane
- tetraalkoxysilane or monoalkoxysilane include triphenylethoxysilane, trimethylmethoxysilane, trimethylethoxysilane, tetraethoxysilane, and tetramethoxysilane.
- halogenosilanes can also be exemplified as silane compounds used in the present application.
- methylchlorosilane methyldichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, phenyltrichlorosilane, diphenylchlorosilane, vinylchlorosilane, ⁇ - ( And chlorosilanes such as (meth) acryloxypropyltrichlorosilane and ⁇ - (meth) acryloxypropyldichloromethylsilane.
- silane is hydrolyzed / condensed to form silicone in acrylate polymer emulsion particles.
- the monomer is first emulsion-polymerized in an aqueous medium in the presence of an emulsifier to disperse the seed latex.
- a pre-aqueous acrylate polymer emulsion is obtained (Step 1) and emulsified by adding monomer and emulsifier, optionally with an aqueous medium, to the pre-aqueous acrylate polymer emulsion obtained by Step 1.
- Polymerization is performed to obtain an aqueous acrylate polymer emulsion that is the final desired emulsion (step 2), and an aqueous silicone-modified acrylate that is silicone-modified with a compound having a silicone structure during or after emulsion polymerization
- a method for obtaining a polymer emulsion can be exemplified.
- a compound having a silicone structure may be added, and silicone modification may be performed during emulsion polymerization, and the final desired emulsion, an aqueous acrylate polymer emulsion, is treated with a compound having a silicone structure, Silicone modification may be performed after emulsion polymerization.
- the monomer and the emulsifier used in Step 1 and Step 2 may be the same or different.
- the silicon content in the aqueous silicone-modified resin is preferably 1 to 10% by mass in terms of oxide.
- a curing catalyst at the time of forming the adhesive layer for example, organic acids such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin diacetate, tin octylate, tin laurate, iron octylate, lead octylate, and tetrabutyl titanate Amine compounds such as n-hexylamine, 1,8-diazabicyclo [5,4,0] -7-undecene can be added to the aqueous silicone-modified acrylate polymer emulsion.
- these curing catalysts are not water-soluble, it is desirable to emulsify with a surfactant and water before use.
- Aqueous silicone-modified resins such as aqueous silicone-modified acrylate polymer emulsions have a pH of 5 to 10 using amines such as ammonia, sodium hydroxide, potassium hydroxide and dimethylaminoethanol in order to maintain long-term dispersion stability of the emulsion. It is preferable that the range is adjusted.
- the aqueous silicone-modified acrylate polymer emulsion preferably has an average particle size of the dispersoid of 10 to 1000 nm.
- water-based silicone-modified acrylate polymer emulsion components that are usually added to and blended with water-based paints, such as film forming aids, thickeners, antifoaming agents, pigments, dispersants, dyes, preservatives, etc. are optionally added. Can be blended.
- aqueous silicone-modified resin used in the present invention examples include Polydurex (trademarks) G627S and G620 manufactured by Asahi Kasei Chemicals Corporation.
- the composition for forming an adhesive layer is composed of the above-described aqueous solution containing an aqueous silicone-modified resin, and can be constituted by adding a film-forming auxiliary or an organic solvent as necessary.
- the aqueous silicone-modified resin is preferably used in the range of 5 to 30% by mass, and more preferably in the range of 10 to 20% by mass as the solid content.
- the film-forming aid is not particularly limited as long as it can improve the film-forming property of the emulsion.
- the film-forming aid is specifically represented by the general formula: HO— (CH 2 CH 2 O) m—R 5 (wherein R 5 is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, m is an integer of 1 to 5), and is represented by (poly) ethylene glycol or (poly) ethylene glycol mono Alkyl ether, general formula: R 7 CO—O— (CH 2 CH 2 O) q —R 6 (wherein R 6 is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, (poly) ethylene glycol ester or (poly) ethylene glycol ether ester represented by the following formula: q is an integer of 1 to 5, and R 7 represents a linear or branched alkyl group having 1 to 10 carbon atoms.
- esters or (poly) propylene glycol ether esters More specifically, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve; diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monoisobutyl ether, diethylene glycol Propylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monoisobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monoi Ethers such as butyl ether; ethyl cellosolve acetate, but
- an organic solvent in combination.
- the type of organic solvent is preferably a water-soluble solvent, specifically, lower alcohols, and more specifically, methanol, ethanol, isopropanol, n-propanol, n-butanol and the like.
- the amount of the solvent used is preferably in the range of 10 to 40% by mass, more preferably in the range of 20 to 30% by mass in the composition for forming an adhesive layer. If the amount of ethanol added is small, repelling may occur when applied, and a good coating film may not be formed. On the other hand, if the amount of ethanol added is large, the undercoat layer may be scraped off when the adhesive layer forming composition is overcoated.
- the photocatalyst layer is composed of a photocatalyst particle composite containing a metal oxide gel or a metal hydroxide gel.
- the metal oxide gel or metal hydroxide gel in the photocatalyst layer has an effect of fixing the photocatalyst powder and firmly adhering to the adhesive layer. Since the metal oxide gel or metal hydroxide gel is porous, it has adsorptivity and also has an effect of enhancing photocatalytic activity.
- the content of the metal oxide gel or metal hydroxide gel in the photocatalyst layer is preferably 25 to 95% by mass.
- the thickness of the adhesive layer is preferably 0.5 to 5 ⁇ m, more preferably 1 to 3 ⁇ m.
- Example 1 As an adhesive layer forming composition, 43.5 parts by mass of an aqueous silicone-modified acrylate polymer emulsion (trade name: Polydurex G627S, manufactured by Asahi Kasei Chemicals Corporation, solid content 46% by mass), 30 parts by mass of ethanol and dipropylene glycol -2.6 parts by mass of n-butyl ether and the remainder were mixed with water to prepare 100 parts by mass of the composition.
- Vistrator 360C manufactured by Nippon Soda Co., Ltd.
- the adhesive layer forming composition is applied once by brush painting to the coated surface of an aluminum coated plate (undercoat (sealer): Esco (white), topcoat: lettan PG80 (white), 65 mm ⁇ 150 mm) as a carrier, It was dried at room temperature for 2 hours to form an adhesive layer, and a photocatalyst layer forming solution was further applied by brush painting to form a photocatalyst layer to produce a photocatalyst-supporting structure.
- undercoat (sealer): Esco (white), topcoat: lettan PG80 (white), 65 mm ⁇ 150 mm as a carrier
- Example 2 A photocatalyst-supporting structure was prepared in the same manner as in Example 1 except that an aqueous silicone-modified acrylate polymer emulsion (trade name: Polydurex G620, manufactured by Asahi Kasei Chemicals Corporation, solid content 46% by mass) was used as the adhesive layer forming composition. Produced.
- an aqueous silicone-modified acrylate polymer emulsion (trade name: Polydurex G620, manufactured by Asahi Kasei Chemicals Corporation, solid content 46% by mass) was used as the adhesive layer forming composition.
- Example 3 A photocatalyst carrying structure was produced in the same manner as in Example 1 except that the adhesive phase forming composition was applied twice (overcoated) at an interval of 10 minutes to the painted surface of the aluminum coated plate.
- Example 4 A photocatalyst carrying structure was prepared in the same manner as in Example 2 except that the adhesive layer forming composition was applied twice (overcoated) at an interval of 10 minutes to the painted surface of the aluminum coated plate.
- Test Example 1 Accelerated weathering test using a sunshine carbon arc weather meter
- the sunshine carbon arc weather specified in JIS K5400
- the accelerated weather resistance test using a meter was performed under the conditions of a test time of 1000 hours, a black panel temperature of 63 ° C., a 120-minute cycle, and a rain of 18 minutes using Suga Model S80.
- the results are shown in Table 1. Each evaluation item was measured as follows.
- L 0 is the initial brightness
- L n represents the brightness at the time of measurement
- a 0 and b 0 represent the initial chromaticity
- a n and b n are the chromaticity at the time of measurement To express.
- an adhesive layer for supporting a photocatalyst that does not contain a volatile organic compound as a solvent is provided.
- the adhesive layer of the present invention can be used indoors or the like in terms of the working environment. From the above, the present invention is extremely useful industrially.
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Abstract
Description
本願は、2011年11月25日に、日本に出願された特願2011-257834号に基づき優先権を主張し、その内容をここに援用する。
本願発明は、溶媒として揮発性有機化合物を含まない光触媒担持用の接着層を提供することを目的とする。
即ち、本発明は、担体と、接着層を介して前記担体に担持された光触媒層とを備えた光触媒担持構造体であって、前記接着層は水性シリコーン変性樹脂を含む光触媒担持構造体に関し、前記水性シリコーン変性樹脂が、単量体を乳化剤の存在下、水性媒体中において乳化重合し、さらにシリコーン構造を有する化合物を用いてシリコーン変性された樹脂であるのが好ましく、前記水性シリコーン変性樹脂が、水性シリコーン変性(メタ)アクリル樹脂であるのが好ましい。
また、前記単量体が、アクリル酸エステル、メタクリル酸エステルおよびそれらの混合物よりなる群より選択される(メタ)アクリレート単量体と、アクリルアミド単量体、メタクリルアミド単量体、ビニル単量体、カルボン酸基を有するエチレン性不飽和単量体、シアン化ビニル、芳香族ビニル単量体、ハロゲン化ビニル、ブタジエンおよびエチレンからなる群より選択され、前記(メタ)アクリレート単量体と共重合可能な少なくとも1種のコモノマーであるのが好ましく、前記単量体中、前記(メタ)アクリレート単量体の量が90~100質量%であり、前記コモノマーの量が0~10質量%であり、かつ、前記(メタ)アクリレート単量体が、前記単量体の全質量に対して5質量%以上の量の(メタ)アクリル酸の炭素数5~12のシクロアルキルエステル、あるいはそれらの混合物を含むのが好ましい。
また、前記乳化剤が、スルホン酸基またはスルホネート基を有するエチレン性不飽和単量体、硫酸エステル基を有するエチレン性不飽和単量体およびそれらの混合物からなる群より選択される少なくとも1種であるのが好ましく、前記シリコーン構造を有する化合物が、下記式(I)
(式中、R1は水素原子、炭素数1~16の脂肪族炭化水素基、炭素数6~10のアリール基、炭素数4~5のヘテロアリール基、炭素数7~11のアラルキル基、炭素数5~6のシクロアルキル基、ビニル基、または炭素数1~10の(メタ)アクロイルオキシアルキル基を表し、R2は、炭素数1~8のアルキル基、アシル基または水素原子を表し、nは、1または2を表し、nが2の場合、R1同士は、同一でも相異なっていてもよく、また、R1同士で結合して環を形成してもよく、R2同士は、同一でも相異なっていてもよい。)で表される化合物群から選択される少なくとも1種、または環状ポリシロキサンであるのが好ましく、前記シリコーン構造を有する化合物が、式(I)中、nが1である化合物からなる群から選択される少なくとも1種と、nが2である化合物からなる群から選択される少なくとも1種との混合物であるのがさらに好ましく、前記シリコーン構造を有する化合物において、式(I)中、nが1である化合物からなる群から選択される少なくとも1種と、nが2である化合物からなる群から選択される少なくとも1種との比率が、モル比で1/10以上であるのが、さらに好ましい。
また、前記光触媒層は、金属酸化物ゲルまたは金属水酸化物ゲルを25~95質量%含有する光触媒粒子複合体からなるのが好ましい。
また前記接着層が更に、(ポリ)エチレングリコール、(ポリ)エチレングリコールモノアルキルエーテル、(ポリ)エチレングリコールエステル、(ポリ)エチレングリコールエーテルエステル、(ポリ)プロピレングリコール、(ポリ)プロピレングリコールモノアルキルエーテル、(ポリ)プロピレングリコールエステルおよび(ポリ)プロピレングリコールエーテルエステルからなる群から選択される少なくとも1種を含有することが好ましい。
更に本発明は、水性シリコーン変性樹脂を含有することを特徴とする接着層形成用組成物に関する。前記接着層形成用組成物において、(ポリ)エチレングリコール、(ポリ)エチレングリコールモノアルキルエーテル、(ポリ)エチレングリコールエステル、(ポリ)エチレングリコールエーテルエステル、(ポリ)プロピレングリコール、(ポリ)プロピレングリコールモノアルキルエーテル、(ポリ)プロピレングリコールエステルおよび(ポリ)プロピレングリコールエーテルエステルからなる群から選択される少なくとも1種を含有することが好ましい。
担体の形状は、特に限定されるものではなく、フィルム状、板状、管状、球状、繊維状など、いかなる形状であってもよい。光触媒層を強固に担持するためには、その厚さ(直径)は10μm以上であることが好ましい。
水性シリコーン変性樹脂は、部分的にシリコーン結合を分子内に有する樹脂であれば、特に制限されないが、具体的には、水性シリコーン変性(メタ)アクリル樹脂、水性シリコーン変性エポキシ樹脂、水性シリコーン変性ポリエステル樹脂等を例示することができる。より具体的には、特開平2-150475号公報、特開平6-25369号公報、特開平6-3322052号公報、特開平8-120085号公報、特開平10-329427号公報、特開2001-199163号公報に記載されている水性シリコーン樹脂を例示することができ、中でも水性シリコーン変性(メタ)アクリル樹脂が好ましい。
より具体的には、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n-ブチル、(メタ)アクリル酸イソブチル、(メタ)アクリル酸2-エチルヘキシル、(メタ)アクリル酸ドデシル等の(メタ)アクリル酸の炭素数1~18のアルキルエステル、(メタ)アクリル酸2-ヒドロキシエチル、(メタ)アクリル酸2-ヒドロキシプロピル等の(メタ)アクリル酸の炭素数1~18のヒドロキシアルキルエステル、(メタ)アクリル酸エチレングリコール、メトキシ(メタ)アクリル酸エチレングリコール、(メタ)アクリル酸ジエチレングリコール、メトキシ(メタ)アクリル酸ジエチレングリコール、(メタ)アクリル酸テトラエチレングリコール、メトキシ(メタ)アクリル酸テトラエチレングリコール、(メタ)アクリル酸プロピレングリコール、メトキシ(メタ)アクリル酸プロピレングリコール、(メタ)アクリル酸ジプロピレングリコール、メトキシ(メタ)アクリル酸ジプロピレングリコール、(メタ)アクリル酸テトラプロピレングリコール、メトキシ(メタ)アクリル酸テトラプロピレングリコール等のアルキレンオキサイド基の数が1~100個の(ポリ)オキシアルキレンモノ(メタ)アクリレート、 ジ(メタ)アクリル酸エチレングリコール、ジ(メタ)アクリル酸ジエチレングリコール、ジ(メタ)アクリル酸トリエチレングリコール、ジ(メタ)アクリル酸テトラエチレングリコール等のアルキレンオキサイド基の数が1~100個の(ポリ)オキシアルキレンジ(メタ)アクリレート、(メタ)アクリル酸グリシジル、トリメチロールプロパントリ(メタ)アクリレート等を例示することができる。
コモノマーとして、具体的には、(メタ)アクリルアミド、ダイアセトン(メタ)アクリルアミド、N-メチロール(メタ)アクリルアミド、N-ブトキシメチル(メタ)アクリルアミド等の(メタ)アクリルアミド単量体、酢酸ビニル、プロピオン酸ビニル、バーサチック酸ビニル、ビニルピロリドン、メチルビニルケトン等のビニル単量体、アクリロニトリル、メタクリロニトリル等のシアン化ビニル、ビニルトルエン、スチレン、α-メチルスチレン等の芳香族ビニル単量体、塩化ビニル、塩化ビニリデン等のハロゲン化ビニル等を例示することができる。
前記単量体中、前記(メタ)アクリレート単量体の量が90~100質量%であり、前記コモノマーの量が0~10質量%であるのが好ましく、また、前記(メタ)アクリレート単量体が、前記単量体の全質量に対して5質量%以上の量の(メタ)アクリル酸の炭素数5~12のシクロアルキルエステルを含むのが好ましい。
水性シリコーン変性樹脂の製造方法は、特に限定されないが、具体的には、上記例示した特許公報に記載の製造方法等を例示することができるが、さらに具体的には、単量体を、乳化剤の存在下、水性媒体中において乳化重合し、その乳化重合中または乳化重合後に、シリコーン構造を有する化合物を用いてシリコーン変性する方法を好ましく例示することができる。
で表される化合物、または、環状ポリシロキサンを好ましく用いることができる。
式中、R1として、具体的には、水素原子、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、s-ブチル基、イソブチル基、n-デシル基等の炭素数1~16の脂肪族炭化水素基、フラニル基等の炭素数4~5のヘテロアリール基、ベンジル基、フェネチル基等の炭素数7~11のアラルキル基、フェニル基、ナフチル基等の炭素数6~10のアリール基、シクロペンチル基、シクロヘキシル基等の炭素数5~6のシクロアルキル基、ビニル基、または(メタ)アクロイルオキシプロピル基、(メタ)アクロイルオキシエチル基等の炭素数1~10の(メタ)アクロイルオキシアルキル基を例示することができる。
式中、R2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、s-ブチル基、イソブチル基等の炭素数1~8のアルキル基、アセチル基、ベンゾイル基、プロパノイル基等のアシル基または水素原子を表す。
nは、1または2を表し、nが2の場合、R1同士は、同一でも相異なっていてもよく、また、R1同士で結合して環を形成してもよく、R2同士は、同一でも相異なっていてもよい。
式(I)で表されるシラン化合物が部分または全部加水分解、及び縮合した線状のポリシロキサン(オリゴマーを含む)を用いることもできる。
また、ステップ1とステップ2で用いる単量体、及び乳化剤は、同一でも相異なっていてもよい。
なお、これらの硬化触媒が水溶性でない場合には、その使用に際して、界面活性剤と水を用いてエマルジョン化しておくことが望ましい。
また、水性シリコーン変性アクリレート重合体エマルジョンは、分散質の平均粒子径が10~1000nmであることが好ましい。
接着層形成用組成物中、水性シリコーン変性樹脂は、固形分として、5~30質量%の範囲で用いるのが好ましく、10~20質量%の範囲で用いるのがより好ましい。水性シリコーン変性樹脂の量が少ないと、接着層形成用組成物を担体に塗工した際、ハジキが発生し、良好な塗膜を形成することができない。一方、多すぎると、塗膜に刷毛筋が生じる。
光触媒層中の金属酸化物ゲルまたは金属水酸化物ゲルは、光触媒粉末を固着し、接着層と強固に接着させる効果を有している。
金属酸化物ゲルまたは金属水酸化物ゲルは、多孔質であることから、吸着性を有し、光触媒活性を高める効果もある。
光触媒層中の金属酸化物ゲルまたは金属水酸化物ゲルの含有量は、25~95質量%であることが好ましい。
接着層の厚さは、0.5~5μmが好ましく、1~3μmがより好ましい。
接着層形成用組成物として、水性シリコーン変性アクリレート重合体エマルジョン(商品名:ポリデュレックスG627S、旭化成ケミカルズ社製、固形分46質量%)を43.5質量部、エタノールを30質量部およびジプロピレングリコール-n-ブチルエーテルを2.6質量部、残部が水を混合して、組成物100質量部を調製した。
光触媒層形成用組成物としては、ビストレーター360C(日本曹達社製)を用いた。
担体としてのアルミ塗装板(下塗り(シーラー):エスコ(白)、上塗り:レタンPG80(白)、65mm×150mm)の塗装面に、刷毛塗装により、接着層形成用組成物を1回塗布し、室温で2時間乾燥させて、接着層を形成し、さらに光触媒層形成溶液を刷毛塗装により塗布し、光触媒層を形成し、光触媒担持構造体を作製した。
接着層形成用組成物として、水性シリコーン変性アクリレート重合体エマルジョン(商品名:ポリデュレックスG620、旭化成ケミカルズ社製、固形分46質量%)を用いる以外、実施1と同様に行い、光触媒担持構造体を作製した。
アルミ塗装板の塗装面に、接着相形成用組成物を10分間隔で2回塗布(重ね塗り)した以外は、実施例1と同様にして、光触媒担持構造体を作製した。
アルミ塗装板の塗装面に、接着層形成用組成物を10分間隔で2回塗布(重ね塗り)した以外は、実施例2と同様にして、光触媒担持構造体を作製した。
シリコーン含有量3重量%のアクリル-シリコーン樹脂(ガラス転移温度20℃)、テトラメトキシシランの部分加水分解生成物であり、重合度が3~6であるオリゴマーを固形分重量比65:35に混合し、エチルアルコール-酢酸エチル混合溶媒で固形分濃度が10質量%になるように希釈し、接着層形成用組成物を調製した。
実施例1と同様の基板を用い、上記した接着層形成用組成物を用いて光触媒担持構造体を作製した。なお、光触媒層の形成も実施例1と同様に行った。
実施例1~4及び比較例1でアルミ塗装板の塗装面に形成した光触媒担持構造体について、JIS K5400に規定されたサンシャインカーボンアークウェザーメーターによる促進耐候性試験を、スガ試験機社製S80型を用いて、試験時間1000時間、ブラックパネル温度63℃、120分サイクル、18分間降雨の条件で行った。
その結果を表1に示す。
なお、各評価項目を以下のように測定した。
日本電色工業社製、分光色彩計、SD5000で試験前後の明度、色度(L*a*b*)を測定し、その差を取り、下記式により求めた。
村上色材研究所社製、グロスメーター、GMX-202(60°)で測定した。
初期光沢度に対する試験後光沢度の割合で求めた。
協和界面科学社製、DropMaster700を用い、液滴0.4μLを滴下し、3sec後に測定し、3点平均値として求めた。
Claims (13)
- 担体と、接着層を介して前記担体に担持された光触媒層とを備えた光触媒担持構造体であって、
前記接着層は、水性シリコーン変性樹脂を含む光触媒担持構造体。 - 前記水性シリコーン変性樹脂が、単量体を乳化剤の存在下、水性媒体中において乳化重合し、さらにシリコーン構造を有する化合物を用いてシリコーン変性された樹脂である請求項1に記載の光触媒担持構造体。
- 前記水性シリコーン変性樹脂が、水性シリコーン変性(メタ)アクリル樹脂である請求項1または2に記載の光触媒担持構造体。
- 前記単量体が、アクリル酸エステル、メタクリル酸エステルおよびそれらの混合物よりなる群より選択される(メタ)アクリレート単量体と、アクリルアミド単量体、メタクリルアミド単量体、ビニル単量体、カルボン酸基を有するエチレン性不飽和単量体、シアン化ビニル、芳香族ビニル単量体、ハロゲン化ビニル、ブタジエンおよびエチレンからなる群より選択され、前記(メタ)アクリレート単量体と共重合可能な少なくとも1種のコモノマーである請求項2または3に記載の光触媒担持構造体。
- 前記単量体中、前記(メタ)アクリレート単量体の量が90~100質量%であり、前記(メタ)アクリレート単量体および前記コモノマーの合計質量に対して、前記コモノマーの量が0~10質量%であり、かつ、前記(メタ)アクリレート単量体が、前記単量体の全質量に対して5質量%以上の量のアクリル酸またはメタクリル酸の炭素数5~12のシクロアルキルエステル、あるいはそれらの混合物を含む請求項2~4のいずれかに記載の光触媒担持構造体。
- 前記乳化剤が、スルホン酸基またはスルホネート基を有するエチレン性不飽和単量体、硫酸エステル基を有するエチレン性不飽和単量体およびそれらの混合物からなる群より選択される少なくとも1種である請求項2~5のいずれかに記載の光触媒担持構造体。
- 前記シリコーン構造を有する化合物が、下記式(I)
(式中、R1は水素原子、炭素数1~16の脂肪族炭化水素基、炭素数6~10のアリール基、炭素数4~5のヘテロアリール基、炭素数7~11のアラルキル基、炭素数5~6のシクロアルキル基、ビニル基、または炭素数1~10の(メタ)アクロイルオキシアルキル基を表し、R2は、炭素数1~8のアルキル基、アシル基または水素原子を表し、nは、1または2を表し、nが2の場合、R1同士は、同一でも相異なっていてもよく、また、R1同士で結合して環を形成してもよく、R2同士は、同一でも相異なっていてもよい。)で表される化合物群から選択される少なくとも1種、または環状ポリシロキサンである請求項2~6のいずれかに記載の光触媒担持構造体。 - 前記シリコーン構造を有する化合物が、式(I)中、nが1である化合物からなる群から選択される少なくとも1種と、nが2である化合物からなる群から選択される少なくとも1種との混合物である請求項7に記載の光触媒担持構造体。
- 前記シリコーン構造を有する化合物において、式(I)中、nが1である化合物からなる群から選択される少なくとも1種と、nが2である化合物からなる群から選択される少なくとも1種との比率が、モル比で1/10以上である請求項8に記載の光触媒担持構造体。
- 前記光触媒層は、金属酸化物ゲルまたは金属水酸化物ゲルを25~95質量%含有する光触媒粒子複合体からなる請求項1~9のいずれかに記載の光触媒担持構造体。
- 前記接着層が更に、(ポリ)エチレングリコール、(ポリ)エチレングリコールモノアルキルエーテル、(ポリ)エチレングリコールエステル、(ポリ)エチレングリコールエーテルエステル、(ポリ)プロピレングリコール、(ポリ)プロピレングリコールモノアルキルエーテル、(ポリ)プロピレングリコールエステルおよび(ポリ)プロピレングリコールエーテルエステルからなる群から選択される少なくとも1種を含有することを特徴とする請求項1~10のいずれかに記載の光触媒担持構造体。
- 水性シリコーン変性樹脂を含有することを特徴とする接着層形成用組成物。
- 更に(ポリ)エチレングリコール、(ポリ)エチレングリコールモノアルキルエーテル、(ポリ)エチレングリコールエステル、(ポリ)エチレングリコールエーテルエステル、(ポリ)プロピレングリコール、(ポリ)プロピレングリコールモノアルキルエーテル、(ポリ)プロピレングリコールエステルおよび(ポリ)プロピレングリコールエーテルエステルからなる群から選択される少なくとも1種を含有することを特徴とする請求項12に記載の接着層形成用組成物。
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JPWO2016157841A1 (ja) * | 2015-03-31 | 2018-01-11 | 日本曹達株式会社 | 光触媒担持構造体及び接着層形成用組成物 |
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CN103958181B (zh) | 2016-06-15 |
KR20140084203A (ko) | 2014-07-04 |
US9925531B2 (en) | 2018-03-27 |
MY185541A (en) | 2021-05-19 |
BR112014012117B1 (pt) | 2020-07-28 |
US20140323290A1 (en) | 2014-10-30 |
TWI483777B (zh) | 2015-05-11 |
JP5801902B2 (ja) | 2015-10-28 |
KR20160035605A (ko) | 2016-03-31 |
US9919301B2 (en) | 2018-03-20 |
PH12014501126B1 (en) | 2014-08-04 |
TW201338865A (zh) | 2013-10-01 |
KR101700075B1 (ko) | 2017-01-26 |
BR112014012117A2 (pt) | 2017-06-13 |
BR112014012117B8 (pt) | 2020-09-01 |
PH12014501126A1 (en) | 2014-08-04 |
EP2783845A1 (en) | 2014-10-01 |
JPWO2013077315A1 (ja) | 2015-04-27 |
BR112014012117A8 (pt) | 2017-06-20 |
CN103958181A (zh) | 2014-07-30 |
US20170128926A1 (en) | 2017-05-11 |
SG11201402471SA (en) | 2014-08-28 |
EP2783845A4 (en) | 2015-11-25 |
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