CN110168033B - Photocatalyst coating set - Google Patents
Photocatalyst coating set Download PDFInfo
- Publication number
- CN110168033B CN110168033B CN201780082653.0A CN201780082653A CN110168033B CN 110168033 B CN110168033 B CN 110168033B CN 201780082653 A CN201780082653 A CN 201780082653A CN 110168033 B CN110168033 B CN 110168033B
- Authority
- CN
- China
- Prior art keywords
- photocatalyst
- compound
- protective layer
- group
- forming
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 216
- 239000011248 coating agent Substances 0.000 title claims abstract description 96
- 238000000576 coating method Methods 0.000 title claims abstract description 95
- 150000001875 compounds Chemical class 0.000 claims abstract description 62
- 239000000203 mixture Substances 0.000 claims abstract description 57
- 239000010410 layer Substances 0.000 claims abstract description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000000758 substrate Substances 0.000 claims abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000003609 titanium compounds Chemical class 0.000 claims abstract description 20
- 239000011254 layer-forming composition Substances 0.000 claims abstract description 16
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 230000001681 protective effect Effects 0.000 claims abstract description 13
- 239000011241 protective layer Substances 0.000 claims description 65
- 239000006185 dispersion Substances 0.000 claims description 60
- -1 isocyanate modified alkoxy silane compound Chemical class 0.000 claims description 38
- 239000010936 titanium Substances 0.000 claims description 28
- 229910052719 titanium Inorganic materials 0.000 claims description 28
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 23
- 229920000058 polyacrylate Polymers 0.000 claims description 21
- 229910000077 silane Inorganic materials 0.000 claims description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 16
- 239000013522 chelant Substances 0.000 claims description 14
- 239000003960 organic solvent Substances 0.000 claims description 14
- 239000012948 isocyanate Substances 0.000 claims description 13
- 239000000376 reactant Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 125000003368 amide group Chemical group 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical group CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000003606 oligomerizing effect Effects 0.000 claims description 3
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000003700 epoxy group Chemical group 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims 1
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- 230000001699 photocatalysis Effects 0.000 abstract description 37
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- 239000004593 Epoxy Substances 0.000 description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
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- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 8
- 125000003545 alkoxy group Chemical group 0.000 description 7
- 230000000845 anti-microbial effect Effects 0.000 description 7
- RTTZISZSHSCFRH-UHFFFAOYSA-N 1,3-bis(isocyanatomethyl)benzene Chemical class O=C=NCC1=CC=CC(CN=C=O)=C1 RTTZISZSHSCFRH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 230000003373 anti-fouling effect Effects 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
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- 125000000962 organic group Chemical group 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- 239000000843 powder Substances 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
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- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 4
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical group CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
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- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
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- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000001680 brushing effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
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- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 238000005096 rolling process Methods 0.000 description 3
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- 238000004383 yellowing Methods 0.000 description 3
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 2
- OVBFMUAFNIIQAL-UHFFFAOYSA-N 1,4-diisocyanatobutane Chemical compound O=C=NCCCCN=C=O OVBFMUAFNIIQAL-UHFFFAOYSA-N 0.000 description 2
- KQADPCKBFSKJHI-UHFFFAOYSA-N 1-ethoxysilylpropan-2-amine Chemical compound CCO[SiH2]CC(C)N KQADPCKBFSKJHI-UHFFFAOYSA-N 0.000 description 2
- KBRVQAUYZUFKAJ-UHFFFAOYSA-N 1-trimethoxysilylpropan-2-amine Chemical compound CO[Si](OC)(OC)CC(C)N KBRVQAUYZUFKAJ-UHFFFAOYSA-N 0.000 description 2
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- OZPCFHQGYPXBGG-UHFFFAOYSA-N 3-[2-carboxyethyl(carboxymethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CC(O)=O)CCC(O)=O OZPCFHQGYPXBGG-UHFFFAOYSA-N 0.000 description 2
- IWTIBPIVCKUAHK-UHFFFAOYSA-N 3-[bis(2-carboxyethyl)amino]propanoic acid Chemical compound OC(=O)CCN(CCC(O)=O)CCC(O)=O IWTIBPIVCKUAHK-UHFFFAOYSA-N 0.000 description 2
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 description 2
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- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 241000702217 Pseudomonas virus phi6 Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 229920004482 WACKER® Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- NOKSMMGULAYSTD-UHFFFAOYSA-N [SiH4].N=C=O Chemical class [SiH4].N=C=O NOKSMMGULAYSTD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-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
- 125000002344 aminooxy group Chemical group [H]N([H])O[*] 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- HIFVAOIJYDXIJG-UHFFFAOYSA-N benzylbenzene;isocyanic acid Chemical class N=C=O.N=C=O.C=1C=CC=CC=1CC1=CC=CC=C1 HIFVAOIJYDXIJG-UHFFFAOYSA-N 0.000 description 1
- JGCWKVKYRNXTMD-UHFFFAOYSA-N bicyclo[2.2.1]heptane;isocyanic acid Chemical compound N=C=O.N=C=O.C1CC2CCC1C2 JGCWKVKYRNXTMD-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- QYQADNCHXSEGJT-UHFFFAOYSA-N cyclohexane-1,1-dicarboxylate;hydron Chemical compound OC(=O)C1(C(O)=O)CCCCC1 QYQADNCHXSEGJT-UHFFFAOYSA-N 0.000 description 1
- PJIFJEUHCQYNHO-UHFFFAOYSA-N diethoxy-(3-isocyanatopropyl)-methylsilane Chemical compound CCO[Si](C)(OCC)CCCN=C=O PJIFJEUHCQYNHO-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- SLQTWNAJXFHMHM-UHFFFAOYSA-N dimethoxy-methyl-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](C)(OC)OC)CCC2OC21 SLQTWNAJXFHMHM-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000003475 lamination Methods 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
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- DBVCVJHNRMYMKN-UHFFFAOYSA-N methyl-[3-(oxiran-2-ylmethoxy)propyl]-di(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)CCCOCC1CO1 DBVCVJHNRMYMKN-UHFFFAOYSA-N 0.000 description 1
- 238000013008 moisture curing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- LIBWSLLLJZULCP-UHFFFAOYSA-N n-(3-triethoxysilylpropyl)aniline Chemical compound CCO[Si](OCC)(OCC)CCCNC1=CC=CC=C1 LIBWSLLLJZULCP-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- KSCKTBJJRVPGKM-UHFFFAOYSA-N octan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-].CCCCCCCC[O-] KSCKTBJJRVPGKM-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical class S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000009823 thermal lamination Methods 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 239000012463 white pigment Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- 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
- B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The photocatalyst coating kit of the present invention comprises: a composition for forming a photocatalyst layer, which contains a titanium oxide photocatalyst and an organic titanium compound; and a protective layer-forming composition containing a compound having a hydrolyzable group or a polymer thereof. According to the present invention, it is possible to coat a photocatalytic material exhibiting excellent adhesion to various substrates. Further, according to the present invention, it is possible to coat a photocatalytic material having excellent antibacterial performance and antiviral performance in addition to the above-described adhesiveness.
Description
Technical Field
The present invention relates to: a photocatalyst coating kit for supporting a photocatalytic substance on a substrate, a photocatalyst coating film and a photocatalyst carrier.
Background
Known are: titanium oxide (TiO) which functions as a catalyst by irradiation with light to remove harmful substances, purify air, deodorize, purify water, sterilize, antibacterial, antifouling, antifog, etc2) Tungsten oxide (WO)3) Photocatalytic substances such as zinc oxide (ZnO), cadmium sulfide (CdS), and the like. Among them, titanium oxide is widely used as a white pigment and an ultraviolet absorber as a raw material for paints, cosmetics, and the like, and is also an inexpensive and safe material which is recognized as a food additive.
The coating film containing the photocatalytic substance has functions of stain resistance, antibacterial, mold prevention, deodorization, air purification and the like. The coating film can be obtained as follows: the photocatalyst coating material containing an inorganic binder such as a titanium dioxide sol or an alkali metal silicate is directly applied to a substrate and then subjected to heat treatment. However, since the photocatalytic energy possessed by the coating film acts in all directions of the coating film, not only the coating film itself but also the substrate on which the coating film is formed is affected, and deterioration may occur. Therefore, for the purpose of protecting the substrate from photocatalytic energy and improving the adhesion of the photocatalytic substance, the following techniques are known: an organic layer called an adhesive layer or a protective layer is formed between a substrate and a coating film containing a photocatalytic substance to protect the substrate from photocatalytic energy (patent documents 1 to 4 and the like).
Silicon compounds, colloidal silica, and the like are generally used for the photocatalyst coating material and the adhesive layer or the protective layer.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2002-
Patent document 2: japanese patent laid-open No. 2001-323189
Patent document 3: japanese patent laid-open No. 2001-205102
Patent document 4: japanese laid-open patent publication No. 2000-280397
Disclosure of Invention
Problems to be solved by the invention
However, the present inventors have conducted studies and, as a result, have found that: for example, when the photocatalyst coating surface is touched with a finger, the photocatalytic material may adhere to the finger, or when the pressure-sensitive adhesive tape is peeled off after being attached to the photocatalyst coating surface without being peeled off by the finger, the photocatalytic material may be peeled off without being adhered to a large amount of the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape. Further, in order to enhance the adhesion of the photocatalytic material to the base material, when a large amount of a known adhesive is used as a conventional technique, the adhesive is coated around the photocatalyst, and thus there is a problem that the hydrophilic phenomenon is reduced or the antibacterial performance and the antiviral performance are remarkably reduced.
Accordingly, an object of the present invention is to provide: a kit for coating a photocatalytic material exhibiting excellent adhesion to various substrates.
Further, another object of the present invention is to provide: a kit for coating a photocatalytic material having excellent antibacterial and antiviral properties in addition to the above adhesiveness.
Another object of the present invention is to provide: a photocatalyst laminated coating film formed by using the set, a photocatalyst carrier with excellent adhesiveness to a substrate, a photocatalyst laminated coating film formed by using the set, and a photocatalyst carrier with excellent adhesiveness to a substrate.
Means for solving the problems
The gist of the present invention is as follows.
[1] A photocatalyst coating kit comprising: a composition for forming a photocatalyst layer, which contains a titanium oxide photocatalyst and an organic titanium compound; and a protective layer-forming composition containing a compound having a hydrolyzable group or a polymer thereof.
[2] The photocatalyst coating kit according to the above [1], wherein the composition for forming a protective layer further contains: an acrylic polymer having a number average molecular weight of 2 to 500 ten thousand and/or a reaction product of the acrylic polymer and a compound having a hydrolyzable group.
[3] The photocatalyst coating kit according to the above [1] or [2], wherein the organic titanium compound is: an alkoxytitanate compound having a phosphoric acid group, a phosphate group, an amino group, an amide group, a lactic acid group or a stearyl group, a titanium chelate compound, or a compound obtained by oligomerizing at least 1 compound selected from the group consisting of the alkoxytitanate compound and the titanium chelate compound.
[4] The photocatalyst coating kit according to any one of the above [1] to [3], wherein the hydrolyzable group of the hydrolyzable group-containing compound is an alkoxy group.
[5] The photocatalyst coating kit according to any one of the above [1] to [4], wherein the hydrolyzable group-containing compound is an isocyanate-modified alkoxysilane compound.
[6] The photocatalyst coating kit according to any one of the above [1] to [5], wherein the photocatalyst layer forming composition is a dispersion liquid.
[7] The photocatalyst coating kit according to the above [6], wherein the dispersion liquid contains water or an organic solvent.
[8] The photocatalyst coating kit according to the above [6] or [7], wherein the organic titanium compound is added in an amount of 0.01 to 30 wt% to the dispersion liquid.
[9] The photocatalyst coating kit according to any one of the above [5] to [8], wherein the isocyanate-modified alkoxysilane compound is at least 1 compound selected from the group consisting of an isocyanate, a reactant with a mercaptoalkoxysilane or an aminoalkoxysilane, and a polymer thereof.
[10] The photocatalyst coating kit according to any one of the above [1] to [9], wherein the protective layer forming composition contains a hydrophilic or non-hydrophilic organic solvent.
[11] The photocatalyst coating kit according to item [10], wherein the total solid content of the acrylic polymer having a number average molecular weight of 2 to 500 ten thousand and the reactant of the acrylic polymer and the hydrolyzable group-containing compound in the protective layer-forming composition is 3 to 40% by weight.
[12] The photocatalyst coating kit according to any one of the above [1] to [11], wherein the titanium oxide photocatalyst is anatase type titanium oxide or rutile type titanium oxide having a primary particle diameter of 10 to 500 nm.
[13] A photocatalyst laminated coating film formed by using the photocatalyst coating kit according to any one of the above [1] to [12], comprising: a protective layer formed from the protective layer-forming composition; and a photocatalyst layer formed on the protective layer and made of the composition for forming a photocatalyst layer.
[14] The photocatalyst laminated coating film according to the above [13], wherein the photocatalyst-forming composition in the photocatalyst layer and the protective layer-forming composition in the protective layer are cured.
[15] A photocatalyst carrier obtained by forming the photocatalyst laminated coating film according to the above [13] or [14] on a surface of a substrate.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the photocatalyst coating kit of the present invention, since the protective layer is formed on the surface of the substrate using the composition for forming a protective layer and the photocatalyst layer is formed on the surface of the protective layer using the composition for forming a photocatalyst layer, the surface of the substrate can be protected from photocatalytic energy as compared with the case where the photocatalyst layer is directly formed on the surface of the substrate. Further, since the protective layer and the photocatalyst layer are made of specific resins, respectively, the adhesion between the protective layer and the photocatalyst layer in the formed photocatalyst coating film is significantly improved, and thus, for example, the photocatalyst layer is touched with fingers, or the pressure-sensitive adhesive tape is further pulled up and peeled off, and the photocatalytic material is not easily peeled off.
In the present invention, particles of a photocatalytic substance (hereinafter also referred to as photocatalyst particles) are bonded by using an organic titanium compound having high electrical conductivity, thereby facilitating the movement of electrons, and a material that does not inhibit the movement of electrons is used for the protective layer, thereby achieving excellent balance among film-forming properties (adhesiveness), antibacterial properties, antiviral properties, and hydrophilicity.
Therefore, in the photocatalyst carrier obtained by forming a photocatalyst coating film on the surface of various members such as members used in a living environment by using the photocatalyst coating kit of the present invention, it is possible to impart effects such as removal of harmful substances, air purification, deodorization, water purification, sterilization, antibacterial, antifouling, antifogging, and the like to these substrates. The photocatalyst carrier may be used alone, or may be applied to various members by an adhesive, or thermal lamination, if necessary, and is developed in a wide range of applications.
Detailed Description
(photocatalyst coating set)
The photocatalyst coating kit of the present invention (hereinafter, the kit of the present invention) is characterized by comprising: a composition for forming a photocatalyst layer, which contains a titanium oxide photocatalyst and an organic titanium compound; and a protective layer-forming composition containing a compound having a hydrolyzable group or a polymer thereof.
In the present invention, the composition for forming a photocatalyst layer is a composition for forming a layer containing a photocatalyst (photocatalyst layer) on the surface of the protective layer.
The titanium oxide photocatalyst contained in the composition for forming a photocatalyst layer may be a titanium oxide photocatalyst having ultraviolet-ray responsiveness or visible-ray responsiveness. The titanium oxide of the titanium oxide photocatalyst may contain a completely crystalline state or an incompletely crystalline state, that is, an amorphous state. The crystal form of titanium oxide may be any single phase of anatase, rutile, and brookite, or 2 or more kinds of them may be mixed. In order to exhibit high photocatalytic activity, the titanium oxide is preferably an anatase single phase, a rutile single phase, or a mixed phase thereof.
Specific examples of the titanium oxide-based photocatalyst include anatase-type or rutile-type crystalline titanium dioxide, crystalline titanium dioxide on which a metal such as platinum, copper, or iron is supported, peroxotitanium, peroxotitanic acid, and a metal titanate. These may be used in the form of a powder or a dispersion of a powder, and particularly in the form of a dispersion using water, ethanol or the like as a dispersion medium. As the powder, those having a primary particle diameter in the range of 10 to 500nm as determined by an electron microscope (SEM, TEM) can be suitably used.
Commercially available materials for the powder or dispersion of the titanium oxide-based photocatalyst include ST-21, ST-41, STS-21, MPT-623 (trade names), Showa Denko K.K. FP6, and LUMI-RESH (registered trademark) series, all of which are available from Shigaku K.K.
The content of the titanium oxide photocatalyst in the composition for forming a photocatalyst layer is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, from the viewpoint of efficiently exhibiting photocatalytic activity.
The organic titanium compound contained in the composition for forming a photocatalyst layer is a titanium compound containing an organic group, and examples thereof include an alkanol titanium compound, a titanium chelate compound, a titanium acylate compound, and a titanium oligomer compound.
Examples of the titanium alkoxide compound include
A substance represented by the general formula (1):
Ti(OR1)4 (1)
[ in the formula, R1Independently represent the same or different alkyl groups. And (c) a temperature sensor.
As R in the above general formula (1)1The alkyl group shown is as follows: examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and 2-ethylhexyl.
As the titanium alkoxide compound represented by the above general formula (1), for example, there can be used: tetramethoxytitanate, tetraethoxytitanate, tetrapropoxytitanate, tetraisopropyltitanate, tetrabutoxytitanate, tetra-n-butyltitanate, tetraoctyltitanate, and the like.
Examples of commercially available products of the titanium alkoxide compound include "organo" series manufactured by MATSUMOTO FINE CHEMICAL co.
The titanium alkoxide compound may be an alkoxy titanate compound having a phosphoric acid group, a phosphate group, an amino group, an amide group, a lactic acid group, or a stearyl group. Commercially available products of the titanium alkoxide compound having the above-mentioned group include titanate-based coupling agents "pleact" series manufactured by Ajinomoto Fine-Techno Co., Inc.
The titanium chelate compound may be a titanium compound containing a chelating agent having the ability to coordinate to a titanium atom, and examples thereof include polycarboxylic acids such as phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, malic acid, hydroxypolycarboxylic acids such as citric acid, ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, and nitrogen-containing polycarboxylic acids such as methoxyethyliminodiacetic acid.
Examples of commercially available titanium chelate compounds include "organo" series manufactured by MATSUMOTO FINE CHEMICAL co.
The titanium acylate compound is a titanium compound having an acylate group as a substituent. Examples of the acylate group include tetraacylate groups such as lactate and stearate, polycarboxylic acid compounds such as phthalic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, fumaric acid, cyclohexanedicarboxylic acid or anhydrides thereof, nitrogen-containing polycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotripropionic acid, carboxyiminodiacetic acid, carboxymethyliminodipropionic acid, diethylenetriaminopentaacetic acid, triethylenetetraminehexaacetic acid, iminodiacetic acid, hydroxyethyliminodiacetic acid, and methoxyethyliminodiacetic acid. The amino group includes aniline, phenylamine, diphenylamine and the like, and is preferably at least 1 selected from these compounds, and more preferably 1 or 2. Further, diisopropoxybis acetylacetone containing 2 kinds of these substituents, and (triethanolamine) isopropanol may be mentioned. The alkoxy group and the acylate group are preferably aliphatic from the viewpoint of polymerization activity.
Examples of the titanium acyl compound include titanium isostearate.
Examples of commercially available titanium chelate compounds include "organo" series manufactured by MATSUMOTO FINE CHEMICAL co.
The organic titanium compound may be one obtained by oligomerizing at least 1 compound selected from the group consisting of the alkylol titanium compound, the alkoxytitanate compound, and the titanium acylate compound. Specifically, the oligomer may be one obtained by reacting the 1 or more compounds.
These organic titanium compounds can be used alone or in a mixture of 2 or more.
The content of the organic titanium compound in the composition for forming a photocatalyst layer is preferably 0.01 to 30% by weight, more preferably 0.01 to 10% by weight, from the viewpoint of hydrophilicity, antibacterial and antiviral properties.
Examples of the solvent of the composition for forming a photocatalyst layer include water, an organic solvent, a water-containing organic solvent, and the like. Examples of the organic solvent include methanol, ethanol, and isopropanol. The ratio of water to the organic solvent in the aqueous organic solvent is not particularly limited. Among them, water is preferred as the solvent from the viewpoint of improving the dispersibility of the photocatalyst.
The content of the solvent in the composition for forming a photocatalyst layer is preferably 50 to 95% by weight, more preferably 70 to 95% by weight, from the viewpoint of improving the dispersibility of the photocatalyst and from the viewpoint of drying property.
The composition for forming a photocatalyst layer may contain any component such as a silicon compound, a reactive silicon compound, colloidal silica, aluminum, a zirconium alkoxysilane compound, a filler, a sealing agent, and a dispersant, as required.
The composition for forming a photocatalyst layer can be produced by mixing the titanium oxide photocatalyst, the organic titanium compound, a solvent, and, if necessary, the optional components described above.
Further, the composition for forming a photocatalyst layer can be oligomerized by heating at a predetermined temperature by reacting the titanium alkoxide compound, the alkoxytitanate compound, the titanium acylate compound, and the like contained as the organic titanium compound.
In the present invention, the composition for forming a protective layer refers to the following composition: a protective layer for preventing deterioration of the base material due to photocatalytic energy is formed between the photocatalyst layer and the base material.
The composition for forming a protective layer contains: a compound containing a hydrolyzable group or a polymer thereof.
Examples of the hydrolyzable group in the hydrolyzable group-containing compound include an alkoxy group, a ketoxime group, an alkenyloxy group, an aryloxy group, a mercapto group, an acyloxy group, an amino group, an aminoxy group, an amide group, an isocyanate group, and a halogen. Among these hydrolyzable groups, alkoxy groups, alkenyloxy groups, acyloxy groups, and halogens are preferably highly active, and alkoxy groups such as methoxy groups and ethoxy groups are more preferred in view of stable hydrolyzability and easy handling.
Examples of the hydrolyzable group-containing compound include isocyanate-modified alkoxysilane compounds, amino-modified alkoxysilane compounds, mercapto-modified alkoxysilane compounds, and the like.
Among them, isocyanate-modified alkoxysilane compounds are preferred from the viewpoint of stable hydrolyzability and easy handling. The isocyanate-modified alkoxysilane compound is a reaction product of an isocyanate and an alkoxysilane.
The isocyanate is not particularly limited as long as it is a crosslinking agent containing an isocyanate group, and examples thereof include polyisocyanates which are free from yellowing or hardly yellowed, aliphatic isocyanates, and alicyclic isocyanates.
Examples of the non-yellowing or non-yellowing polyisocyanate include aromatic polyisocyanates such as tolylene diisocyanate, 4' -diphenylmethane diisocyanate, xylylene diisocyanate, and tolidine diisocyanate, and examples of commercially available polyisocyanates include "XDI system", "IPDI system", and "HDI system" manufactured by mitsui chemical co.
Examples of the aliphatic isocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, Hexamethylene Diisocyanate (HDI), 2, 4-trimethylhexamethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, and 2-methyl-1, 5-pentamethylene diisocyanate (MPDI), and examples of commercially available products include "TAKENATE" series manufactured by mitsui chemical co.
Examples of the alicyclic isocyanate include isophorone diisocyanate (IPDI), hydrogenated toluene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, 1, 3-cyclohexane diisocyanate, methyl-2, 4-cyclohexane diisocyanate, methyl-2, 6-cyclohexane diisocyanate, 1, 3-bis (isocyanatomethyl) cyclohexane, and norbornane diisocyanate.
Examples of the alkoxysilane used in the isocyanate-modified alkoxysilane compound include: mercaptoalkoxysilanes having a mercapto group such as γ -mercaptopropylmethyldiethoxysilane, γ -mercaptopropyltrimethoxysilane, γ -mercaptopropylmethyldimethoxysilane, γ -mercaptopropyltriethoxysilane, and the like; aminoalkoxysilanes having primary and secondary amino groups, e.g. gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, N- (. beta. -aminoethyl) -N' - (gamma-trimethoxysilylpropyl) -ethylenediamine, N- (. beta. -aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (. beta. -aminoethyl) -gamma-aminopropylmethyldiethoxysilane, N- (. beta. -aminoethyl) -gamma-aminopropylmethyldimethoxysilane, N- (. beta. -aminoethyl) -gamma-aminopropyltriethoxysilane, N- (. beta. -aminopropyl-trimethoxysilane, N- (beta. -aminoethyl) -gamma-methyldimethoxysilane, N- (beta-aminopropyl-trimethoxysilane, N- (beta. -aminopropyl-triethoxysilane, N- (beta. -aminopropyl-trimethoxysilane, N-gamma-methyldimethoxysilane, N- (beta-aminoethyl) -gamma-aminopropyl-trimethoxysilane, N- (gamma-ethoxysilane, N- (beta-aminopropyl-trimethoxysilane, N- (beta-ethoxysilane, N- (beta-aminopropyl-ethoxysilane) and N- (beta-aminopropyl-ethoxysilane) compounds, 1, 3-diaminoisopropyltrimethoxysilane, γ -N-phenylaminopropyltrimethoxysilane, γ -N-phenylaminopropyltriethoxysilane, bis (trimethoxysilylpropyl) amine, etc.; alkoxysilanes having an epoxy group such as γ -glycidoxypropyltrimethoxysilane, γ -glycidoxypropylmethyldimethoxysilane, 3, 4-epoxycyclohexylethyltrimethoxysilane, 3, 4-epoxycyclohexylethylmethyldimethoxysilane, γ -glycidoxypropylmethyldiisopropyloxysilane and the like; alkoxysilanes having an isocyanate group such as γ -isocyanatopropylmethyldiethoxysilane, γ -isocyanatopropylmethyldimethoxysilane, γ -isocyanatopropyltrimethoxysilane, γ -isocyanatopropyltriethoxysilane and the like.
The polymerization degree of the polymer of the isocyanate-modified alkoxysilane compounds is not particularly limited.
As the isocyanate-modified alkoxysilane compound or a polymer thereof, 1 or more compounds selected from the group consisting of isocyanates, reactants with mercaptoalkoxysilanes or aminoalkoxysilanes, and polymers thereof are preferably used from the viewpoint of weather resistance and radical resistance.
In addition, the composition for forming a protective layer may further contain: an acrylic polymer having a number average molecular weight of 2 to 500 ten thousand and/or a reaction product of the acrylic polymer and a compound having a hydrolyzable group. The inclusion of these compounds has an advantage of optimizing weather resistance, radical resistance, and the like.
The acrylic polymer is a polymer of an acrylic ester or a methacrylic ester as long as it is used for the coating agent.
The number average molecular weight of the acrylic polymer is 2 to 500 ten thousand, and from the viewpoint of workability and film-forming properties, 2 to 50 ten thousand is preferable, and 5 to 30 ten thousand is more preferable.
As the acrylic polymer having a number average molecular weight of 2 to 500 ten thousand, commercially available products can be used. For example, "Dianal BR" series manufactured by Mitsubishi Rayon Co. Ltd. can be used.
Examples of the reactant of the acrylic polymer and the hydrolyzable group-containing compound include: the acrylic polymer having a number average molecular weight of 2 to 500 ten thousand is reacted with an alkoxy group-containing silane coupling agent in an organic solvent.
Examples of the alkoxy group-containing silane coupling agent include acrylic silanes, amino silanes, epoxy silanes, isocyanate silanes, mercapto silanes, and the like. The degree of the reaction is not particularly limited as long as it is a partial reaction.
The total solid content of the hydrolyzable group-containing compound, the polymer thereof, the acrylic polymer having a number average molecular weight of 2 to 500 ten thousand, and the reactant of the acrylic polymer and the hydrolyzable group-containing compound in the protective layer-forming composition is preferably 3 to 40% by weight, more preferably 3 to 20% by weight, from the viewpoint of antibacterial/antiviral properties and film-forming properties.
Examples of the solvent of the composition for forming a protective layer include hydrophilic or non-hydrophilic organic solvents. Examples of the hydrophilic organic solvent include an alcohol-based organic solvent. Examples of the non-hydrophilic organic solvent include ethyl acetate and butyl acetate.
The content of the solvent in the protective layer forming composition is preferably 70 to 95% by weight from the viewpoint of workability and the like.
The protective layer forming composition may contain any component such as a silane coupling agent and a dispersant as needed.
The composition for forming a protective layer can be prepared as follows: the mixture can be prepared by mixing the hydrolyzable group-containing compound or the polymer thereof, an acrylic polymer having a number average molecular weight of 2 to 500 ten thousand as required, and/or a reaction product of the acrylic polymer and the hydrolyzable group-containing compound, and further the optional components in the solvent.
Among them, the composition for forming a photocatalyst layer is preferably a dispersion liquid from the viewpoint of workability.
The amounts of the photocatalyst layer-forming composition and the protective layer-forming composition in the kit of the present invention are not particularly limited as long as they are appropriately determined according to the surface area of the substrate for forming the coating film and the desired thickness of each layer.
(photocatalyst laminated coating film)
The photocatalyst laminated coating film of the present invention is a coating film formed using the photocatalyst coating kit, and includes: a protective layer formed from the protective layer-forming composition; and a photocatalyst layer formed on the protective layer and made of the composition for forming a photocatalyst layer.
As a method for forming the photocatalyst laminated coating film, a coating film having a protective layer and a photocatalyst layer integrated with each other can be formed by molding the composition for forming a protective layer contained in the kit into a film form, applying the composition for forming a photocatalyst layer on the surface of the film, and drying and reacting the composition.
When the composition for forming a protective layer is formed into a film shape, the composition for forming a protective layer may be applied to the surface of a substrate to a predetermined thickness, for example. As the substrate, a substrate formed of a synthetic resin film, a synthetic resin sheet, glass, woven fabric, nonwoven fabric, paper, plastic, stone, metal, tile, gypsum board, wood, or the like can be suitably used.
The coating may be carried out by a known method such as air spraying, brushing, or rolling.
In addition, it is preferable that the composition for a photocatalyst in the photocatalyst layer and the composition for a protective layer in the protective layer undergo a curing reaction.
The curing reaction is carried out, for example, at 20 to 80 ℃, preferably 20 to 40 ℃, for 0.1 to 24 hours, preferably 0.5 to 24 hours.
(photocatalyst carrier)
The photocatalyst support of the present invention is a photocatalyst support having the photocatalyst layered coating film formed on the surface of a substrate.
More specifically, the present invention is a photocatalyst carrier obtained by coating a photocatalyst on the surface of a substrate using the photocatalyst coating kit,
the coating composition is obtained by adhering the composition for forming a protective layer to the surface of the substrate, adhering the composition for forming a photocatalyst layer to the surface of the composition for forming a protective layer, and carrying out a curing reaction.
As the substrate, a substrate formed of a synthetic resin film, a synthetic resin sheet, glass, woven fabric, nonwoven fabric, paper, plastic, stone, metal, tile, gypsum board, wood, or the like can be suitably used.
As a method for adhering the composition for forming a protective layer to the surface of the substrate, known methods such as air spraying, brushing, and rolling can be used.
As described above, the protective layer can be formed by drying the protective layer forming composition attached to the surface of the substrate. The drying conditions may be such that the solvent disappears to such an extent that the composition for forming the protective layer does not flow, and may be, for example, 20 to 40 ℃.
As a method for adhering the composition for forming a photocatalyst layer to the surface of the composition for forming a protective layer, known methods such as air spraying, brushing, and rolling can be used.
Examples of the method for curing the photocatalyst-forming composition include moisture curing, moist heat curing and the like.
The photocatalyst carrier obtained as described above can be used alone, and can be applied to various members by being bonded to the members with an adhesive, heat lamination, or the like as needed, and thus can be used in a wide range of applications.
The present invention will be described in further detail with reference to examples below, which, however, do not limit the scope of the present invention.
Examples
Example 1 ultraviolet light type 1
To 200g (concentration: 10%) of an aqueous dispersion of ultraviolet titanium oxide "ST-21" (having a primary particle diameter of 20nm as measured by electron microscopy (SEM, TEM), a titanate-based coupling agent "Plenoct 44" (Ajinomoto Fine-Techno Co., Inc.) was added in an amount of 1g, and the mixture was uniformly mixed.
Next, 0.5g of a titanium chelate compound "organic TC-310" (titanium lactate, manufactured by MATSUMOTO FINE CHEMICAL CO. LTD.) was added and dispersed.
Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of the alkoxytitanate to partially oligomerize the alkoxide, thereby preparing a photocatalyst dispersion (composition for forming a photocatalyst layer).
Subsequently, a protective agent was produced in the following manner.
10g of trimethylolpropane hydrogenated XDI compound (manufactured by Mitsui chemical Co., Ltd. "TAKENATE (registered trademark) D-120N") as an aliphatic isocyanate compound was reacted with 8g of mercaptoalkoxysilane "KBM 803" (3-mercaptopropyltrimethoxysilane, manufactured by shin-Etsu chemical Co., Ltd.) at 80 ℃ for 24 hours in 200g of ethyl acetate. The reaction is completed as the end of the reaction by disappearance of NCO%.
Next, 0.5g of epoxysilane "KBM 402" (3-glycidoxypropylmethyldiethoxysilane, product of shin-Etsu chemical Co., Ltd.) was added to the above reaction solution.
Further, 40g each of a 10% ethyl acetate solution of an acrylic resin "Dianal (registered trademark) BR 80" (manufactured by Mitsubishi Rayon Co. Ltd., weight average molecular weight 95000) dissolved and partially reacted in advance and an acrylic alkoxy partial reactant solution (obtained by reacting 0.5g of acrylic silane "KBM 503" (3-methacryloxypropyltrimethoxysilane, manufactured by shin-Etsu chemical Co., Ltd.) in a 10% ethyl acetate acrylic resin solution at 50 ℃ for 24 hours) was added to the reaction solution to complete a protective agent (composition for forming a protective layer).
Next, using the obtained photocatalyst dispersion and the protective agent, a test piece having a coating film containing a photocatalyst was produced in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours and reacted to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The photocatalytic performance of the test article obtained under ultraviolet irradiation was evaluated in accordance with the following procedure.
Ultraviolet irradiation with a metal halide lamp 80mw/cm2After 4 hours, the contact angle of the water drop was measured by a contact angle tester manufactured by Coulter's interfacial science for 10 seconds.
As a result of the test, it was found that the contact angle was 10 ° or less, which was a practical level for antifouling property and antifogging property.
In addition, in order to evaluate the adhesive strength of the photocatalyst in the test piece, finger touch and tape peeling were performed.
With respect to the finger-touch property, the photocatalyst-coated surface of the test piece was pressed with the entire hand, and as a result, the photocatalyst particles did not adhere to the hand. Further, when a test was carried out in which a transparent adhesive tape was adhered to the photocatalyst-coated surface and then peeled off so that the tape angle became 90 ° or more, no significant (visible) adhesion of the photocatalyst particles was observed on the tape adhesive surface, and it was found that the adhesive strength was at a practical level.
Example 2 ultraviolet light type 2
To 200g of an aqueous dispersion of ultraviolet titanium oxide "ST-21", 0.5g of a titanate-based coupling agent "Plectant 46B" (manufactured by Ajinomoto Fine-Techno Co., Inc.) and 0.5g of a titanium chelate compound "OrgatixTC-401" (manufactured by triethanolamine, MATSUMOTO FINE CHEMICAL CO. LTD.) were added, and the mixture was uniformly mixed and dispersed.
Subsequently, the obtained dispersion was left in an oven at 50 ℃ for 3 days to react a part of the alkoxytitanate to oligomerize it, thereby preparing a photocatalyst dispersion.
Subsequently, a protective agent was produced in the following manner.
10g of trimethylolpropane hydrogenated XDI compound as an aliphatic isocyanate compound was reacted with 8g of mercaptoalkoxysilane "KBM 802" (3-mercaptopropylmethyldimethoxysilane, manufactured by shin-Etsu chemical Co., Ltd.) at 80 ℃ for 24 hours in a solution of 200g of ethyl acetate. Further, 0.5g of epoxy silane "KBM 403" (3-glycidoxypropyltrimethoxysilane, available from shin-Etsu chemical Co., Ltd.) was added. To the reaction solution were added 40g each of a 10% ethyl acetate solution of an acrylic resin "Dianal (registered trademark) BR 85" (manufactured by Mitsubishi Rayon co. ltd., having a weight average molecular weight of 280000) dissolved and partially reacted in advance and an acrylic alkoxy partial reactant solution (obtained by reacting 0.5g of an acrylic silane "KBM 503" in a 10% ethyl acetate acrylic resin solution at 50 ℃ for 24 hours), thereby completing a protecting agent.
Next, using the obtained photocatalyst dispersion and the protective agent, a test piece having a coating film containing a photocatalyst was produced in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The obtained test piece was evaluated for the photocatalytic performance under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test piece in the same manner as in example 1.
As a result of the test, it was found that the contact angle was 10 ° or less, which was a practical level for antifouling property and antifogging property.
Further, regarding the film forming property, it is known that the adhesive strength of the tape is a practical level because no significant (visible) adhesion of the photocatalyst particles is observed on the tape adhesive surface as a result of a test in which the photocatalyst particles are not adhered to the hands in the finger touch property, and the transparent adhesive tape is peeled off so that the tape angle becomes 90 ° or more.
Example 3 ultraviolet light type 3
To 200g of an aqueous dispersion of ultraviolet titanium oxide "ST-21", 0.5g of a titanate coupling agent "Pleacta 44" was added and uniformly mixed, followed by compounding and dispersing 0.5g of a titanium chelate compound "Orgatix TC-310". Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of the alkoxytitanate to oligomerize it, thereby preparing a photocatalyst dispersion.
Subsequently, a protective agent was produced in the following manner.
10g of trimethylolpropane IPDI compound (manufactured by Mitsui chemical Co., Ltd. "TAKENATE (registered trademark) D140N") as an aliphatic isocyanate compound was reacted with 8g of mercaptoalkoxysilane "KBM 803" in 200g of ethyl acetate at 80 ℃ for 24 hours. Further, 1g of epoxy silane "KBM 403" was added. To the reaction solution were added 40g each of a 10% ethyl acetate solution of an acrylic resin "Dianal (registered trademark) BR 85" dissolved and partially reacted in advance and an acrylic alkoxy partial reaction product solution (obtained by reacting 0.5g of an acrylic silane "KBM 503" in a 10% ethyl acetate acrylic resin solution at 50 ℃ for 24 hours), thereby completing a protecting agent.
Next, using the obtained photocatalyst dispersion and the protective agent, a test piece having a coating film containing a photocatalyst was produced in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The obtained test piece was evaluated for the photocatalytic performance under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test piece in the same manner as in example 1.
As a result of the test, it was found that the contact angle was 10 ° or less, which was a practical level for antifouling property and antifogging property. Further, regarding the film forming property, in a test in which the transparent adhesive tape was peeled off so that the tape angle became 90 ° or more after the photocatalyst particles did not adhere to the surface of the transparent adhesive tape in the finger touch property, no significant (visual) adhesion of the photocatalyst particles was observed on the tape adhesive surface, and the adhesive strength was known as a practical level.
Comparative example 1 ultraviolet light type 4)
To 200g of an aqueous dispersion of ultraviolet titanium oxide "ST-21", 1g of a methyl Silicone resin emulsion "SILRES (registered trademark) BS 45" (manufactured by Wacker Asahikasei Silicone Co., Ltd.) was added and mixed uniformly, and then 0.5g each of aminosilane "KBM 603" (manufactured by N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, shin-Etsu chemical Co., Ltd.) and acrylic silane "KBM 503" was added and dispersed to prepare a dispersion. Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of alkoxysilane to oligomerize it, thereby preparing a photocatalyst dispersion.
Next, using the protective agent prepared in example 1, a test piece on which a coating film containing a photocatalyst was formed was prepared in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The obtained test piece was evaluated for the photocatalytic performance under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test piece in the same manner as in example 1.
As a result of the test, it was confirmed that the contact angle was 60 °, and the contact angle was not practical for stain resistance and antifogging property.
On the other hand, regarding the film forming property, it was found that in the test in which the photocatalyst particles were not adhered to the hands and the transparent adhesive tape was adhered to the surface and peeled at 90 ° or more, no significant (visual) adhesion of the photocatalyst particles was observed on the tape adhesive surface, and the film forming property was found to be a practical level.
Comparative example 2 ultraviolet light type 5)
To 200g of an aqueous dispersion of ultraviolet titanium oxide "ST-21", 1g of silicone emulsion "IE-7170" (manufactured by Dow Corning Toray Co., Ltd.) was added and uniformly mixed, and then, 0.5g of epoxy silane "KBM 403" and mercaptoalkoxysilane "KBM 803" were added and dispersed. Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of alkoxysilane to oligomerize it, thereby preparing a photocatalyst dispersion.
Next, using the protective agent prepared in example 2, a test piece on which a coating film containing a photocatalyst was formed was prepared in accordance with the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The obtained test piece was evaluated for the photocatalytic performance under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test piece in the same manner as in example 1.
As a result of the test, it was confirmed that the contact angle was 30 ° and the coating could not be used for stain resistance and antifogging property, and was not practical.
In the finger-touch property, it was confirmed that the photocatalyst particles were attached to the hand. In addition, in the test in which the transparent adhesive tape was adhered to the surface and peeled at 90 ° or more, the adhesion (visually observable) of the photocatalyst particles was also observed on the tape adhesive surface, and it was confirmed that the adhesive strength was not a practical level.
Comparative example 3 ultraviolet light type 6)
200g of an aqueous dispersion of ultraviolet titanium oxide "ST-21" was prepared.
Next, using the protective agent prepared in example 1, a test piece on which a coating film containing a photocatalyst was formed was prepared in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The obtained test piece was evaluated for the photocatalytic performance under ultraviolet irradiation and the adhesive strength of the photocatalyst in the test piece in the same manner as in example 1.
As a result of the test, it was found that the contact angle was 10 ° or less, which was a practical level for antifouling property and antifogging property.
On the other hand, in the finger-touch property, the photocatalyst particles were attached to the hand and also significantly attached in the scotch tape adhesion test, and it was confirmed that the adhesive strength was not a practical level.
The results of the contact angle, the tape releasability, and the finger-touch property in examples 1 to 3 and comparative examples 1 to 3 are shown in table 1.
The evaluation criteria for tape releasability and finger-touch ability are as follows.
[ with peelability ]
O: the photocatalyst material was hardly visually confirmed on the tape-peeled surface.
And (delta): the photocatalyst material was visually confirmed on the tape-peeled surface. The adhesion rate was less than 50% of the release tape surface.
X: the photocatalyst material was visually confirmed on the tape-peeled surface. The adhesion rate is 50% or more of the surface of the release tape.
[ touchability ]
O: the photocatalyst material was substantially not visually confirmed on a finger.
And (delta): the photocatalyst material was visually confirmed on a finger. The attachment area is less than 70%.
X: the photocatalyst material was visually confirmed on a finger. The attachment area is 70% or more.
[ Table 1]
From the results shown in table 1, the coating films produced in examples 1 to 3 all exhibited excellent photocatalytic ability because the contact angles were 10 ° or less, and were not peeled off only by touching the surface of the coating film with a finger, and further, when the adhesive tape was adhered, the peeling of the photocatalyst was not visually confirmed, and thus, it was found that the adhesive strength of the photocatalyst was high.
Example 4 visible light type 1
To 200g of an aqueous dispersion of a copper-supported visible light-responsive photocatalyst "LUMI-RESH (registered trademark)" (manufactured by Showa Denko K.K.), 1g of a titanate compound "Plenoct 44" was added and uniformly mixed, and then 0.5g of a titanium chelate compound "Orgatix TC-310" was dispersed. Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of the alkoxytitanate to oligomerize it, thereby obtaining a photocatalyst dispersion.
Subsequently, a protective agent was produced in the following manner.
10g of trimethylolpropane hydrogenated XDI compound "TAKENATE (registered trademark) D-120N" was reacted with 8g of mercaptoalkoxysilane "KBM 803" at 80 ℃ for 24 hours in 200g of ethyl acetate. The reaction is completed as the end of the reaction by disappearance of NCO%.
Next, 0.5g of epoxy silane "KBM 402" was added to the above reaction solution. Further, 40g each of a 10% ethyl acetate solution of acrylic resin "Dianal (registered trademark) BR 80" and an acrylic alkoxy partial reactant solution (obtained by reacting 0.5g of acrylic silane "KBM 503" in a 10% ethyl acetate acrylic resin solution at 50 ℃ C. for 24 hours) dissolved and partially reacted in advance were added to the above reaction solution to complete the protecting agent.
Next, a test piece having a coating film containing a photocatalyst was prepared by using the above protective agent in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The obtained test piece was evaluated for its photocatalytic ability under visible light irradiation, and its antibacterial and antiviral properties were evaluated.
The antibacterial and antiviral properties were evaluated according to JIS R1702 and 1756. Specifically, the irradiation time of the bacteria and the irradiation time of the virus were 8 hours and 4 hours, respectively, under a fluorescent lamp illumination of 1000LUX (sharp cut) of 400nm or less. As test bacteria, multidrug-resistant Staphylococcus aureus (MRSA) and multidrug-resistant Pseudomonas aeruginosa (MDRP) were used, and as test viruses, phage QB and phage φ 6 were used. The higher the value of the measured antibacterial activity value and the antiviral activity value, the stronger the activity.
As a result of the test, the antimicrobial activity was 3 to 4, the antiviral activity was 4 to 5, and the activity exceeded the "2" which is a standard requirement (99% of bacteria and viruses were killed), and the antimicrobial and antiviral properties were high, and were confirmed to be practical.
Further, the adhesion strength of the photocatalyst in the obtained test piece was evaluated in the same manner as in example 1, and as a result, in a test in which the photocatalyst particles were not adhered to the hand in the finger touch property, the transparent tape was adhered to the surface, and peeling was performed at 90 ° or more, no significant (visual) adhesion of the photocatalyst particles was observed on the tape-adhered surface, and the adhesion strength was found to be a practical level.
Example 5 visible light type 2
To 200g of an aqueous dispersion of a copper-supported visible light-responsive photocatalyst "LUMI-RESH (registered trademark)", 0.5g of a titanate-based coupling agent "Plenoct 46B" and 0.5g of a titanium chelate compound "OrgatixTC-410" were added and uniformly mixed to form a dispersion. Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of the alkoxytitanate to oligomerize it, thereby preparing a photocatalyst dispersion.
Subsequently, a protective agent was produced in the following manner.
10g of trimethylolpropane hydrogenated XDI compound "TAKENATE (registered trademark) D-120N" was reacted with 8g of mercaptoalkoxysilane "KBM 802" at 80 ℃ for 24 hours in 200g of ethyl acetate. Further, 0.5g of epoxy silane "KBM 403" was added, and 40g each of a 10% ethyl acetate solution of an acrylic resin "Dianal (registered trademark) BR 85" dissolved and partially reacted in advance and an acrylic alkoxy partial reactant solution (obtained by reacting 0.5g of acrylic silane "KBM 503" in a 10% ethyl acetate acrylic resin solution at 50 ℃ for 24 hours) was added to the above reaction solution to complete the protective agent.
Next, a test piece having a coating film containing a photocatalyst was prepared by using the above protective agent in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The photocatalytic ability and the photocatalytic adhesion strength under visible light irradiation of the test bodies obtained were evaluated in the same manner as in example 4.
As a result of the test, the antimicrobial activity was 3 to 4, and the antiviral activity was 4 to 5, which exceeded the "2" which is usually required (99% of bacteria and viruses were killed), and the antimicrobial and antiviral properties were high, and were confirmed to be practical.
In addition, in the finger touch test, the photocatalyst particles were not adhered to the hands, the transparent adhesive tape was adhered to the surface, and the peeling was performed at 90 ° or more, and no significant (visual) adhesion of the photocatalyst particles was observed on the tape adhesive surface, and it was found that the adhesive strength was also a practical level.
(example 6: visible light type 3)
To 200g of an aqueous dispersion of a copper-supported visible light-responsive photocatalyst "LUMI-RESH (registered trademark)", 0.5g of a titanate compound "Plenoct 44" was added and uniformly mixed, and then 0.5g of a titanium chelate compound "Orgatix TC-310" was added to form a dispersion. Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of the alkoxytitanate to oligomerize it, thereby preparing a photocatalyst dispersion.
Subsequently, a protective agent was produced in the following manner.
10g of trimethylolpropane IPDI compound "TAKENATE (registered trademark) D140N" was reacted with 8g of mercaptoalkoxysilane "KBM 803" at 80 ℃ for 24 hours in 200g of ethyl acetate. Further, 1g of epoxy silane "KBM 403" was added. To the reaction solution were added 40g each of a 10% ethyl acetate solution of an acrylic resin "Dianal (registered trademark) BR 85" dissolved and partially reacted in advance and an acrylic alkoxy partial reactant (obtained by reacting 0.5g of an acrylic silane "KBM 503" in a 10% ethyl acetate acrylic resin solution at 50 ℃ for 24 hours) solution, thereby completing a protecting agent.
Next, a test piece having a coating film containing a photocatalyst was prepared by using the above protective agent in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The photocatalytic ability and the photocatalytic adhesion strength under visible light irradiation of the test bodies obtained were evaluated in the same manner as in example 4.
As a result of the test, it was confirmed that the antimicrobial activity was 3 to 4 and the antiviral activity was 4 to 5, which were more than 2 (99% of bacteria and viruses were killed) which was generally required, and that the antimicrobial and antiviral properties were high, and thus the level of practical use was high.
In addition, in the test in which the transparent adhesive tape was peeled at 90 ° or more with the photocatalyst particles not adhering to the hands in the finger touch property, no significant (visual) adhesion of the photocatalyst particles was observed on the tape adhesive surface, and it was found that the adhesive strength was at a practical level.
Comparative example 4 visible light type 4
To 200g of an aqueous dispersion of a copper-supported visible light-responsive photocatalyst "LUMI-RESH (registered trademark)", 1g of a methyl silicone resin emulsion "SILRES (registered trademark) BS 45" was added and uniformly mixed, and then 0.5g each of an aminosilane "KBM 603", an acrylic silane "KBM 503" was blended and dispersed. Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of alkoxysilane to oligomerize it, thereby preparing a photocatalyst dispersion.
Next, using the protective agent prepared in example 1, a test piece on which a coating film containing a photocatalyst was formed was prepared in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The photocatalytic ability and the photocatalytic adhesion strength under visible light irradiation of the test bodies obtained were evaluated in the same manner as in example 4.
As a result, it was found that the tape peeling and the finger touch properties were at a practical level for the film forming property, but the antibacterial and antiviral properties were low and not at a practical level.
Comparative example 5 visible light type 5
1g of a silicone emulsion "IE-7170" was added to 200g of an aqueous dispersion of a copper-supported visible light-responsive photocatalyst "LUMI-RESH (registered trademark)", and uniformly mixed, and then 0.5g each of an epoxy silane "KBM 403" and a mercaptoalkoxysilane "KBM 803" was compounded and dispersed. Subsequently, the dispersion was left in an oven at 50 ℃ for 3 days to react a part of alkoxysilane to oligomerize it, thereby preparing a photocatalyst dispersion.
Next, a test piece was prepared using the protective agent prepared in example 2.
A protective agent was applied to a PET film (Toyobo) having a thickness of 100 μm by an air spray gun to form a uniform film, the film was dried at room temperature for 30 minutes, then the photocatalyst dispersion was applied by an air spray gun to form a uniform film, and the film was dried at 50 ℃ for 24 hours to carry out a curing reaction to form a film. Evaluation of antibacterial and antiviral properties, tape peeling, and finger touch properties were evaluated in the same manner as in example 1. The results of the measurement show that the antibacterial and antiviral properties were low in the anti-activity value, and that neither of the film-forming properties, the adhesion of visible photocatalyst particles in tape peeling, and the finger-touch properties, the adhesion of photocatalyst particles to the hand, nor the judged amphoteric properties were practical levels.
(comparative example 6: visible light type 6)
200g of an aqueous dispersion of a copper-loaded visible light-responsive photocatalyst "LUMI-RESH (registered trademark)" was prepared.
Next, using the protective agent prepared in example 1, a test piece on which a coating film containing a photocatalyst was formed was prepared in the following procedure.
A PET film (Toyo Boseki Co., Ltd.) having a thickness of 100 μm was coated with a protective agent by an air spray gun to be uniform, dried at room temperature for 30 minutes, then coated with the photocatalyst dispersion by an air spray gun to be uniform, dried at 50 ℃ for 24 hours, and subjected to a curing reaction to form a film.
The thickness of the protective layer in the coating film formed on the PET film is about 1 to 10 μm, and the thickness of the photocatalyst layer formed on the protective layer is about 1 μm.
The photocatalytic ability and the photocatalytic adhesion strength under visible light irradiation of the test bodies obtained were evaluated in the same manner as in example 4.
As a result, the antibacterial and antiviral properties obtained high antimicrobial activity values in the measured results, but it was found that tape peeling and finger touch properties were not practical levels for film forming properties.
The results of evaluation of antibacterial activity, antiviral activity, tape releasability, and finger-touch ability in examples 4 to 6 and comparative examples 4, 5, and 6 are shown in table 2.
[ Table 2]
From the results shown in table 2, it is understood that the coating films produced in examples 4 to 6 have high antibacterial activity and antiviral activity, and that the photocatalyst is not peeled off even when the coating films are touched with a finger or a pressure-sensitive adhesive tape is further stuck, and thus the adhesive strength of the photocatalyst is excellent.
Claims (12)
1. A photocatalyst coating kit comprising: a composition for forming a photocatalyst layer, which contains a titanium oxide photocatalyst and an organic titanium compound; and a protective layer-forming composition containing a compound having a hydrolyzable group or a polymer thereof,
the compound containing a hydrolyzable group is an isocyanate-modified alkoxysilane compound,
the isocyanate modified alkoxy silane compound is a reactant of isocyanate and mercaptoalkoxy silane, amino alkoxy silane or alkoxy silane with epoxy group,
the composition for forming a protective layer further contains: an acrylic polymer having a number average molecular weight of 2 to 500 ten thousand and a reaction product of the acrylic polymer and a compound having a hydrolyzable group,
the acrylic polymer is a polymer of an acrylate or methacrylate,
the photocatalyst coating kit is used for coating a PET substrate.
2. The photocatalyst coating kit according to claim 1, wherein the acrylic polymer has a number average molecular weight of 5 to 30 ten thousand.
3. The photocatalyst coating kit according to claim 1 or 2, wherein the organic titanium compound is: an alkoxy titanate compound having a phosphoric group, a phosphate group, an amino group, an amide group, a lactic acid group or a stearyl group, a titanium chelate compound, or a compound obtained by oligomerizing 1 or more compounds selected from the group consisting of the alkoxy titanate compound and the titanium chelate compound.
4. The photocatalyst coating kit according to claim 1 or 2, wherein the photocatalyst layer forming composition is a dispersion liquid.
5. The photocatalyst coating kit according to claim 4, wherein the dispersion liquid contains water or an organic solvent.
6. The photocatalyst coating kit according to claim 4, wherein the organic titanium compound is contained in an amount of 0.01 to 30 wt% in the dispersion liquid.
7. The photocatalyst coating kit according to claim 1 or 2, wherein the protective layer forming composition contains a hydrophilic or non-hydrophilic organic solvent.
8. The photocatalyst coating kit according to claim 7, wherein the total of the acrylic polymer having a number average molecular weight of 2 to 500 ten thousand and the solid content of the reactant of the acrylic polymer and the hydrolyzable group-containing compound in the protective layer-forming composition is 3 to 40% by weight.
9. The photocatalyst coating kit according to claim 1 or 2, wherein the titanium oxide photocatalyst is anatase type titanium oxide or rutile type titanium oxide having a primary particle diameter of 10 to 500 nm.
10. A photocatalyst laminated coating film formed by using the photocatalyst coating kit according to any one of claims 1 to 9, comprising: a protective layer formed from the protective layer-forming composition; and a photocatalyst layer formed on the protective layer and formed of the composition for forming a photocatalyst layer.
11. The photocatalyst laminated coating film according to claim 10, wherein the photocatalyst-forming composition in the photocatalyst layer and the protective layer-forming composition in the protective layer are cured.
12. A photocatalyst carrier obtained by forming the photocatalyst layered coating film according to claim 10 or 11 on the surface of a PET substrate.
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| PCT/JP2017/001956 WO2018134972A1 (en) | 2017-01-20 | 2017-01-20 | Photocatalyst coating set |
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| CN103554168A (en) * | 2007-03-09 | 2014-02-05 | 莫门蒂夫性能材料股份有限公司 | Epoxysilanes, processes for their manufacture and curable compositions containing same |
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| JP4324775B2 (en) * | 2003-10-08 | 2009-09-02 | Ｊｓｒ株式会社 | Coating composition and structure for undercoating containing photocatalyst coating film |
| JP2006068685A (en) * | 2004-09-03 | 2006-03-16 | Jsr Corp | Laminated body having visible light-active photocatalyst layer and coating film of visible light-active photocatalyst |
| JP4869578B2 (en) * | 2004-10-13 | 2012-02-08 | 宇部日東化成株式会社 | Film forming coating composition for snow sliding, snow coating film and snow sliding member |
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