JP2021195462A - Antibacterial/antivirus paint - Google Patents
Antibacterial/antivirus paint Download PDFInfo
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- JP2021195462A JP2021195462A JP2020103414A JP2020103414A JP2021195462A JP 2021195462 A JP2021195462 A JP 2021195462A JP 2020103414 A JP2020103414 A JP 2020103414A JP 2020103414 A JP2020103414 A JP 2020103414A JP 2021195462 A JP2021195462 A JP 2021195462A
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- antibacterial
- antiviral
- paint
- quaternary ammonium
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 128
- 239000003973 paint Substances 0.000 title claims abstract description 87
- 230000002155 anti-virotic effect Effects 0.000 title abstract description 7
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 53
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 25
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 25
- 239000007787 solid Substances 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 5
- 230000000840 anti-viral effect Effects 0.000 claims description 105
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 claims description 11
- OQXBPCPZNLQMTK-UHFFFAOYSA-N 1-decylpyridin-1-ium-4-carboxamide;bromide Chemical compound [Br-].CCCCCCCCCC[N+]1=CC=C(C(N)=O)C=C1 OQXBPCPZNLQMTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- FGDLGJWCMASAHH-UHFFFAOYSA-N butane;dihydrobromide Chemical compound Br.Br.CCCC FGDLGJWCMASAHH-UHFFFAOYSA-N 0.000 claims description 6
- SPFVNQBOHYXSMM-UHFFFAOYSA-M 1-decylpyridin-1-ium;bromide Chemical compound [Br-].CCCCCCCCCC[N+]1=CC=CC=C1 SPFVNQBOHYXSMM-UHFFFAOYSA-M 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 abstract description 56
- 238000000576 coating method Methods 0.000 abstract description 55
- 239000000463 material Substances 0.000 abstract description 17
- 239000000126 substance Substances 0.000 abstract description 17
- 230000003373 anti-fouling effect Effects 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000003749 cleanliness Effects 0.000 abstract description 4
- 208000035874 Excoriation Diseases 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 66
- 239000010408 film Substances 0.000 description 50
- 239000003242 anti bacterial agent Substances 0.000 description 32
- 239000003443 antiviral agent Substances 0.000 description 23
- 238000005259 measurement Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229920000877 Melamine resin Polymers 0.000 description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 230000005856 abnormality Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 6
- -1 polyethylene terephthalate Polymers 0.000 description 6
- 150000003863 ammonium salts Chemical class 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000008199 coating composition Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 4
- 241000714201 Feline calicivirus Species 0.000 description 4
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 241000700605 Viruses Species 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 229920002635 polyurethane Polymers 0.000 description 4
- 239000004814 polyurethane Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 229940121375 antifungal agent Drugs 0.000 description 3
- UDSAIICHUKSCKT-UHFFFAOYSA-N bromophenol blue Chemical compound C1=C(Br)C(O)=C(Br)C=C1C1(C=2C=C(Br)C(O)=C(Br)C=2)C2=CC=CC=C2S(=O)(=O)O1 UDSAIICHUKSCKT-UHFFFAOYSA-N 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000005923 long-lasting effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- MFMBELVKZWEQOM-UHFFFAOYSA-N 1-decylpyridin-1-ium Chemical compound CCCCCCCCCC[N+]1=CC=CC=C1 MFMBELVKZWEQOM-UHFFFAOYSA-N 0.000 description 2
- 229940099451 3-iodo-2-propynylbutylcarbamate Drugs 0.000 description 2
- WYVVKGNFXHOCQV-UHFFFAOYSA-N 3-iodoprop-2-yn-1-yl butylcarbamate Chemical compound CCCCNC(=O)OCC#CI WYVVKGNFXHOCQV-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920000298 Cellophane Polymers 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 2
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 239000003429 antifungal agent Substances 0.000 description 2
- 210000004666 bacterial spore Anatomy 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 239000004210 ether based solvent Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 208000015181 infectious disease Diseases 0.000 description 2
- 230000002458 infectious effect Effects 0.000 description 2
- 208000037797 influenza A Diseases 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000007591 painting process Methods 0.000 description 2
- 239000013500 performance material Substances 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 2
- JLHMJWHSBYZWJJ-UHFFFAOYSA-N 1,2-thiazole 1-oxide Chemical compound O=S1C=CC=N1 JLHMJWHSBYZWJJ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 0 CCC(C)(CC(C)(CC)Oc(c(C)c1)cc*1N)OCc(cc1)c(C)c*1N Chemical compound CCC(C)(CC(C)(CC)Oc(c(C)c1)cc*1N)OCc(cc1)c(C)c*1N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000711573 Coronaviridae Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001343 alkyl silanes Chemical class 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
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000000834 fixative Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- CHHVJOKDGAOHMJ-UHFFFAOYSA-N methoxy(propyl)silane Chemical compound CCC[SiH2]OC CHHVJOKDGAOHMJ-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Abstract
Description
本発明は、既に形成されている塗膜を含め、多くの製品素材の表面に、室温下で、透明性（表面クリアー性）を有し、清潔感を付与することができるとともに、防汚性、耐薬品性、耐擦傷性などに優れた特性をも付与することができる抗菌／抗ウイルス塗料に関する。 INDUSTRIAL APPLICABILITY The present invention has transparency (surface clearness) on the surface of many product materials, including a coating film that has already been formed, at room temperature, can impart a feeling of cleanliness, and has antifouling properties. The present invention relates to an antibacterial / antiviral paint capable of imparting excellent properties such as chemical resistance and scratch resistance.
近年の新型コロナウイルス騒動の広まりに伴い、手指や人が触れる可能性がある多種多様な製品素材の表面を消毒するための抗菌／抗ウイルス剤の要求が増大している。これらの抗菌／抗ウイルス剤は定着性がないため、人が触れる可能性がある多種多様な製品素材の表面に抗菌／抗ウイルス性を有する塗料を塗布することにより、これらの表面に直接抗菌／抗ウイルス性を有する塗膜を形成することが行われている。 With the spread of the new coronavirus turmoil in recent years, there is an increasing demand for antibacterial / antiviral agents to disinfect the surface of a wide variety of product materials that can be touched by fingers and humans. Since these antibacterial / antiviral agents are not fixative, antibacterial / antiviral agents can be applied directly to the surfaces of a wide variety of product materials that may be touched by humans by applying antibacterial / antiviral paints. Forming a coating film having antiviral properties has been performed.
従来、製品素材の表面に抗菌性ないし抗ウイルス性を付与するための抗菌／抗ウイルス塗料として種々の組成のものが知られている。たとえば、下記特許文献１には、一般的なアクリル／メラミン系塗料、ポリエステル／メラミン系塗料、ポリウレタン系塗料やエポキシ塗料等からなる樹脂エマルジョン組成物と、光触媒型酸化チタンと、無機多孔質顔料と、を含む塗料組成物が開示されている。この塗料組成物では、無機多孔質顔料が塗膜に残留している添加剤や低分子オリゴマー等の残留物を吸着するため、光触媒がこれらの残留物を分解しにくくるので、塗膜形成直後でも光触媒機能の低下が少なくなって抗菌／抗ウイルス性が良好に発現されるようになるものである。 Conventionally, those having various compositions are known as antibacterial / antiviral paints for imparting antibacterial or antiviral properties to the surface of a product material. For example, Patent Document 1 below describes a resin emulsion composition composed of a general acrylic / melamine-based paint, polyester / melamine-based paint, polyurethane-based paint, epoxy paint, etc., a photocatalytic titanium oxide, and an inorganic porous pigment. , A coating composition comprising, is disclosed. In this coating composition, since the inorganic porous pigment adsorbs residues such as additives and small molecule oligomers remaining on the coating film, it is difficult for the photocatalyst to decompose these residues. However, the deterioration of the photocatalytic function is reduced and the antibacterial / antiviral property is well expressed.
また、下記特許文献２には、建築用塗料として多く用いられているアクリルメラミン塗料中に、抗菌／抗ウイルス性を発現するための有効成分である４級アンモニウム塩と、多価カルボン酸と、リン酸塩と、を含む、抗菌／抗ウイルス性コーティング剤が開示されている。このコーティング剤によれば、４級アンモニウム塩による塗膜の硬化不良が生じにくくなるとともに、水に接触しても４級アンモニウム塩が塗膜から溶出しにくくなり、しかも塗料中に沈殿物が生じにくくなるので、優れた外観を維持できる抗菌／抗ウイルス性塗膜を形成可能な抗菌／抗ウイルス性コーティング剤が得られるというものである。 Further, in Patent Document 2 below, a quaternary ammonium salt, which is an active ingredient for expressing antibacterial / antiviral properties, and a polyvalent carboxylic acid are described in acrylic melamine paint, which is often used as a building paint. Antibacterial / antiviral coatings, including phosphates, are disclosed. According to this coating agent, the quaternary ammonium salt is less likely to cause curing failure of the coating film, the quaternary ammonium salt is less likely to elute from the coating film even when it comes into contact with water, and a precipitate is formed in the coating material. Since it becomes difficult, an antibacterial / antiviral coating agent capable of forming an antibacterial / antiviral coating film capable of maintaining an excellent appearance can be obtained.
また、下記特許文献３には、２液型ポリウレタン樹脂塗料中に、汎用的な抗菌剤の添加量を、抗菌性が発現する範囲における抗菌剤の下限添加量よりも多くすることにより抗ウイルス機能をも発現させるようにした抗ウイルス用塗料組成物の発明が開示されている。さらに、下記特許文献４には、塗膜形成用塗料、紫外線硬化塗膜用塗料として使用可能な、アミノ基を有するポリビニルアルコールからなる抗菌／抗ウイルス性高分子化合物の発明が開示されている。 Further, in Patent Document 3 below, the antiviral function is obtained by increasing the amount of a general-purpose antibacterial agent added to the two-component polyurethane resin paint to be larger than the minimum amount of the antibacterial agent added in the range in which the antibacterial property is exhibited. The invention of an antiviral coating composition is disclosed. Further, Patent Document 4 below discloses an invention of an antibacterial / antiviral polymer compound composed of polyvinyl alcohol having an amino group, which can be used as a coating film forming coating film and a coating film for an ultraviolet curable coating film.
上記特許文献１に開示されている塗料組成物の発明によれば、光触媒の有する良好な抗菌性ないし抗ウイルス性により、一般のアクリル／メラミン系塗料やポリエステル／メラミン系塗料、ポリウレタン系塗料やエポキシ塗料等からなる樹脂エマルジョン組成物を用いても、優れた抗菌／抗ウイルス性を有する塗膜が得られるようになる。しかしながら、これらの塗料組成物は、平均粒径数μｍの粉末からなる光触媒や顔料を混錬したものからなるので、透明性に優れた高外観のクリアー塗膜を得ることができなかった。また、アクリル／メラミン系塗料やポリエステル／メラミン系塗料の塗装工程では１５０℃以上の焼付が必要となり、ポリウレタン系塗料やエポキシ塗料の塗装工程では、使用時に主剤と硬化剤を混合し、ポットライフの時間内に使用せねばならず、複雑な処理工程が必要である他、塗膜の性能上、１５〜２０μｍ以上の膜厚が必要であるという課題があった。 According to the invention of the coating composition disclosed in Patent Document 1, general acrylic / melamine-based paints, polyester / melamine-based paints, polyurethane-based paints and epoxys due to the good antibacterial or antiviral properties of the photocatalyst. Even if a resin emulsion composition composed of a paint or the like is used, a coating film having excellent antibacterial / antiviral properties can be obtained. However, since these coating compositions are obtained by kneading a photocatalyst or a pigment made of powder having an average particle size of several μm, it has not been possible to obtain a clear coating film having excellent transparency and high appearance. In addition, baking at 150 ° C or higher is required in the painting process of acrylic / melamine paints and polyester / melamine paints, and in the painting process of polyurethane paints and epoxy paints, the main agent and curing agent are mixed at the time of use to make pot life. It must be used within a certain period of time, requires a complicated treatment process, and has a problem that a film thickness of 15 to 20 μm or more is required in terms of the performance of the coating film.
また、上記特許文献２に開示されている抗菌／抗ウイルス性コーティング剤はアクリルメラミン系塗料を用いており、上記特許文献３に開示されている抗ウイルス用塗料組成物によれば２液型ポリウレタン樹脂塗料を用いているので、それぞれ上記特許文献１に開示されている発明と場合と同様の課題があった。 Further, the antibacterial / antiviral coating agent disclosed in Patent Document 2 uses an acrylic melamine-based paint, and according to the antiviral paint composition disclosed in Patent Document 3, two-component polyurethane. Since the resin paint is used, there are the same problems as the invention disclosed in Patent Document 1 above.
さらに、特許文献４に開示されている塗料によれば、抗菌／抗ウイルス性を発現する高分子化合物がアミノ基を有するポリビニルアルコールであるため、塗膜形成にはポリビニルアルコール、ポリビニルアセタール（ブチラール樹脂等）、セルロース類、アクリルウレタン樹脂、アクリル樹脂、ウレタン樹脂、塩化ビニル樹脂、塩化ビニリデン樹脂、ポリオレフィン樹脂、ポリエチレンテレフタレート、ポリエステル樹脂、ポリスチレン、ポリアミド樹脂、ポリカーボネート樹脂、ＡＢＳ樹脂等を用いる必要があり、防汚性、耐薬品性、耐擦傷性等に課題があった。 Further, according to the coating material disclosed in Patent Document 4, since the polymer compound exhibiting antibacterial / antiviral properties is polyvinyl alcohol having an amino group, polyvinyl alcohol and polyvinyl acetal (butyral resin) are used for forming a coating film. Etc.), cellulose, acrylic urethane resin, acrylic resin, urethane resin, vinyl chloride resin, vinylidene chloride resin, polyolefin resin, polyethylene terephthalate, polyester resin, polystyrene, polyamide resin, polycarbonate resin, ABS resin, etc. There were problems with stain resistance, chemical resistance, scratch resistance, and the like.
本発明は、上述のような従来技術の課題を解決すべくなされたものであり、既に形成されている塗膜を含め、多くの製品素材の表面に、室温下で、透明性（表面クリアー性）を有し、清潔感を付与することができるとともに、防汚性、耐薬品性、耐擦傷性などに優れた特性をも付与することができる抗菌／抗ウイルス塗料を提供することを目的とする。 The present invention has been made to solve the above-mentioned problems of the prior art, and is transparent (surface clearness) on the surface of many product materials including the already formed coating film at room temperature. ), And the purpose is to provide an antibacterial / anti-virus paint that can impart a feeling of cleanliness and also have excellent properties such as stain resistance, chemical resistance, and scratch resistance. do.
すなわち、本発明は、湿気硬化型の１液性シリコーンアルコキシオリゴマーをバインダーとし、抗菌／抗ウイルス性成分として第４アンモニウム塩を含む抗菌／抗ウイルス塗料であって、前記第４アンモニウム塩含有量は、前記シリコーンアルコキシオリゴマーを含む塗料固形分１００質量部に対して２〜１０質量部であることを特徴とする。 That is, the present invention is an antibacterial / antiviral paint containing a moisture-curable one-component silicone alkoxy oligomer as a binder and a fourth ammonium salt as an antibacterial / antiviral component, wherein the fourth ammonium salt content is It is characterized in that it is 2 to 10 parts by mass with respect to 100 parts by mass of the paint solid content containing the silicone alkoxy oligomer.
本発明の抗菌／抗ウイルス塗料によれば、塗膜形成成分としてのバインダーが湿気硬化型の１液性シリコーンアルコキシオリゴマーからなるので、加熱操作を必要とせずに室温下で塗膜形成することができ、しかも得られた塗膜は透明性が良好なガラス質の膜となるので、既に形成されている塗膜の表面や多くの製品素材の表面にそれぞれの意匠を生かしながら清潔感を付与することができるようになる。また、得られる塗膜は硬質であるので、既に形成されている塗膜の表面や多くの製品素材の表面に防汚性、耐薬品性、耐擦傷性をも付与することができる。加えて、本発明の抗菌／抗ウイルス塗料によれば、スプレー法、、刷毛による塗布法、ローラー法や拭き上げ法などで塗装でき、数μｍ以下の膜厚の抗菌／抗ウイルス性を有する透明薄膜を形成することができる。特に、拭き上げ法では、１μｍ以下の膜厚の超薄膜塗装も可能となる。 According to the antibacterial / antiviral paint of the present invention, since the binder as a coating film forming component is a moisture-curable one-component silicone alkoxy oligomer, the coating film can be formed at room temperature without the need for a heating operation. Since the resulting coating film is a vitreous film with good transparency, it gives a clean feeling to the surface of the already formed coating film and the surface of many product materials while making the best use of their respective designs. You will be able to. Further, since the obtained coating film is hard, it is possible to impart antifouling property, chemical resistance, and scratch resistance to the surface of the already formed coating film and the surface of many product materials. In addition, according to the antibacterial / antiviral paint of the present invention, it can be painted by a spray method, a brush coating method, a roller method, a wiping method, etc., and is transparent with an antibacterial / antiviral property having a film thickness of several μm or less. A thin film can be formed. In particular, the wiping method enables ultra-thin film coating with a film thickness of 1 μm or less.
しかも、本発明の抗菌／抗ウイルス塗料においては、膜形成成分としての湿気硬化型の１液性シリコーンアルコキシオリゴマーと抗菌／抗ウイルス性成分としての第４アンモニウム塩を互いに相容性の溶剤（例えばアルコール系溶剤、グリコールエーテル系溶剤等）に溶解させたものを用いることができ、互いの相容性も良好であるために均質に溶解させることができ、長期間に亘って優れた抗菌／抗ウイルス性を発揮できる塗膜が得られる。 Moreover, in the antibacterial / antiviral coating material of the present invention, a moisture-curable one-component silicone alkoxy oligomer as a film-forming component and a fourth ammonium salt as an antibacterial / antiviral component are compatible with each other (for example). It can be dissolved in alcohol-based solvent, glycol ether-based solvent, etc.), and since it has good compatibility with each other, it can be uniformly dissolved, and it has excellent antibacterial / antibacterial properties over a long period of time. A coating film capable of exhibiting virality can be obtained.
なお、無機抗菌剤として、光触媒以外にもゼオライト、ガラスやリン酸カルシウムなどに銀、銅あるいは亜鉛を担持させた製品が知られており、また、有機系抗菌剤としては、スルファミド系、ピリジン系、イソチアゾロン系、チアゾール系、イミダゾール系や第４アンモニウム塩系抗菌剤が知られている。しかしながら、無機系抗菌剤は、平均粒径が数μｍの粉末であるため、透明性に劣り、薄膜状態で高品質の外観を有する塗膜を得ることが困難である。有機系抗菌剤では、抗菌／抗ウイルス効果に優れ、溶剤への溶解性が良好で、安全性や耐久持続性などの点から第４アンモニウム塩系抗菌剤が好適である In addition to photocatalysts, products in which silver, copper, or zinc is supported on zeolite, glass, calcium phosphate, etc. are known as inorganic antibacterial agents, and sulfamide-based, pyridine-based, and isothiazolone-based organic antibacterial agents are known. System, thiazole type, imidazole type and quaternary ammonium salt type antibacterial agents are known. However, since the inorganic antibacterial agent is a powder having an average particle size of several μm, it is inferior in transparency and it is difficult to obtain a coating film having a high quality appearance in a thin film state. As an organic antibacterial agent, a quaternary ammonium salt-based antibacterial agent is suitable from the viewpoints of excellent antibacterial / antiviral effect, good solubility in a solvent, safety and durability.
なお、本発明の抗菌／抗ウイルス塗料は、少なくとも湿気硬化型の１液性シリコーンアルコキシオリゴマーと、アルコキシシランと、硬化触媒としての有機金属化合物を塗料固形分として含むものであり、以下の反応式に示すように、空気中の水分によりシラノール基が生成する脱アルコール縮合硬化タイプの塗料として周知のものである。
アルコキシシランは、架橋剤として、また密着改良剤（シランカップリング剤）として作用するものであり、メチルトリメトキシシラン、ジメチルシリメトキシシラン、エチルトリメトキシシランやn-プロピルメトキシシランなどのアルキルアルコキシシランやアルキル基以外の官能基（ビニル基、エポキシ基、アミノ基など）を有するシランカップリング剤を用いることができる。アルコキシシランの量は、シリコーンアルコキシオリゴマー１００質量部あたり５〜２０質量部が好ましい。なお、塗膜の可撓性付与のために、適宜量のオルガノポリシロキサンを添加してもよい。 Alkylsilane acts as a cross-linking agent and an adhesion improver (silane coupling agent), and is an alkylalkoxysilane such as methyltrimethoxysilane, dimethylsilimethoxysilane, ethyltrimethoxysilane and n-propylmethoxysilane. A silane coupling agent having a functional group (vinyl group, epoxy group, amino group, etc.) other than the alkyl group and the alkyl group can be used. The amount of alkoxysilane is preferably 5 to 20 parts by mass per 100 parts by mass of the silicone alkoxy oligomer. An appropriate amount of organopolysiloxane may be added to impart flexibility to the coating film.
硬化触媒は、金属脂肪酸塩や金属アルコラートであり、アミン化合物なども使用することができる。金属脂肪酸塩としてはスズ化合物やジルコニウム化合物、アルコラートとしてはチタン系化合物やアルミ系化合物が一般的である。 The curing catalyst is a metal fatty acid salt or a metal alcoholate, and an amine compound or the like can also be used. As the metal fatty acid salt, a tin compound or a zirconium compound is generally used, and as an alcoholate, a titanium-based compound or an aluminum-based compound is generally used.
なお、本発明の抗菌／抗ウイルス塗料においては、抗菌／抗ウイルス性成分としての第４アンモニウム塩含有量は、前記シリコーンアルコキシオリゴマーを含む塗料固形分１００質量部に対して２〜１０質量部とすることが必要である。第４アンモニウム塩含有量が塗料固形分１００質量部に対して２質量部未満であると抗菌／抗ウイルス性が低下するが、特に抗ウイルス性が激減する。同じく１０質量部を越えると、抗菌／抗ウイルス効果が飽和してしまうし、塗膜の硬度や耐擦傷性などの塗膜の強度が低下する他、低温時における塗料の保存性が低下する。 In the antibacterial / antiviral paint of the present invention, the content of the quaternary ammonium salt as an antibacterial / antiviral component is 2 to 10 parts by mass with respect to 100 parts by mass of the paint solid content containing the silicone alkoxy oligomer. It is necessary to. When the content of the quaternary ammonium salt is less than 2 parts by mass with respect to 100 parts by mass of the paint solid content, the antibacterial / antiviral property is lowered, but the antiviral property is particularly sharply reduced. Similarly, if it exceeds 10 parts by mass, the antibacterial / antiviral effect is saturated, the strength of the coating film such as the hardness and scratch resistance of the coating film is lowered, and the storage stability of the paint film at low temperature is lowered.
なお、本発明の抗菌／抗ウイルス塗料を用いて形成された塗膜の抗菌／抗ウイルス性の存在は、得られた塗膜の表面にブロモフェノールブルー（ＢＰＢ）を滴下すると、カチオン性の４級アンモニウムとカチオン性のＢＰＢとが結合して無色の状態から青色へと変色するので、確認することができる。 The presence of the antibacterial / antiviral property of the coating film formed by using the antibacterial / antiviral coating film of the present invention is 4 when bromophenol blue (BPB) is dropped on the surface of the obtained coating film. It can be confirmed because the quaternary ammonium and the cationic BPB combine to change the color from a colorless state to a blue color.
本発明の抗菌／抗ウイルス塗料においては、前記第４アンモニウム塩は、
４，４'−（テトラメチレンジカルボニルジアミノ）ビス（１−デシルピリジニウムブロマイド）、
Ｎ，Ｎ'−ヘキサメチレンビス（４−カルバモイル−１−デシルピリジニウムブロマイド、
１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド、
から選択された少なくとも１種のビス型構造のものであることが好ましい。
In the antibacterial / antiviral paint of the present invention, the quaternary ammonium salt is used.
4,4'-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide),
N, N'-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide,
1,4-Bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide,
It is preferable that it has at least one screw-type structure selected from the above.
第４アンモニウム塩は、抗菌／抗ウイルス剤として、種々のものが広く市販されていおり、入手が容易であり、一応良好な抗菌／抗ウイルス性を示す塗膜が得られる。これらの第４アンモニウム塩としては、ピリジニウム基を有するものが好ましく、ピリジニウム基を有するもののうちピリジン核にアンモニウム長鎖アルキル基のようなかさ高い置換基が導入されたものが好ましく、モノ型構造のものよりもビス型構造のものがさらに好ましい。なお、モノ型構造の第４アンモニウム塩は、微生物の表面疎水性に依存して様々なＭＩＣ（最小発育阻止濃度）が測定され、殺菌力に限界がある（上記非特許文献１参照）。それに対し、ビス型構造の第４アンモニウム塩は、ＭＩＣの比較で、多くの細菌に対して高い活性を示し、細菌芽胞に対して強い細胞破壊作用を有している。 Various quaternary ammonium salts are widely marketed as antibacterial / antiviral agents and are easily available, so that a coating film showing good antibacterial / antiviral properties can be obtained. As these quaternary ammonium salts, those having a pyridinium group are preferable, and those having a pyridinium group in which a bulky substituent such as an ammonium long-chain alkyl group is introduced into a pyridine nucleus are preferable, and those having a monotype structure are preferable. A screw-type structure is more preferable than that. The quaternary ammonium salt having a mono-type structure has various MICs (minimum inhibitory concentrations) measured depending on the surface hydrophobicity of microorganisms, and has a limited bactericidal activity (see Non-Patent Document 1 above). On the other hand, the quaternary ammonium salt having a bis-type structure shows high activity against many bacteria and has a strong cell-destroying action against bacterial spores in comparison with MIC.
なお、モノ型構造の第４アンモニウム塩(臭素塩)の化学構造式の例を下記化２に、ビス型構造の第４アンモニウム塩(臭素塩)の化学構造式の例を下記化３に、それぞれ示した。
また、本発明の抗菌／抗ウイルス塗料においては、さらに、第４アンモニウム塩とナノシリカとの複合体を含んでいてもよい。 Further, the antibacterial / antiviral paint of the present invention may further contain a complex of a quaternary ammonium salt and nanosilica.
第４アンモニウム塩とナノシリカとの複合体は、カチオン性の第４アンモニウム塩がナノシリカの表面の水酸基と結合したものと考えられる。これにより、第４アンモニウム塩がナノシリカの表面に強固に結合した状態となるので、抗菌／抗ウイルス性の耐久持続性に優れた抗菌／抗ウイルス塗膜が得られるようになる。なお、第４アンモニウム塩単体の場合と比較すると、第４アンモニウム塩とナノシリカとの複合体の方が、抗菌／抗ウイルス性の耐久持続性だけでなく、抗菌／抗ウイルス性も良好となる。 The complex of the quaternary ammonium salt and the nanosilica is considered to be a cationic quaternary ammonium salt bonded to a hydroxyl group on the surface of the nanosilica. As a result, the quaternary ammonium salt is firmly bonded to the surface of the nanosilica, so that an antibacterial / antiviral coating film having excellent antibacterial / antiviral durability and durability can be obtained. Compared with the case of the quaternary ammonium salt alone, the complex of the quaternary ammonium salt and the nanosilica has better antibacterial / antiviral properties as well as long-lasting antibacterial / antiviral properties.
係る場合の前記第４アンモニウム塩とナノシリカとの複合体の含有量は、前記第四アンモニウム塩に対して、ナノシリカが２０〜５０質量％であることが好ましい。ナノシリカの含有量が２０質量％未満では抗菌/抗ウイルス性の耐久持続性の向上効果が確認できず、５０質量％を超えると塗料安定性が低下し、沈殿や粒状異物を発生することがある。 In such a case, the content of the complex of the quaternary ammonium salt and the nanosilica is preferably 20 to 50% by mass of the nanosilica with respect to the quaternary ammonium salt. If the content of nanosilica is less than 20% by mass, the effect of improving the durability of antibacterial / antiviral properties cannot be confirmed, and if it exceeds 50% by mass, the paint stability is lowered and precipitation or granular foreign matter may be generated. ..
さらに、係る態様の抗菌／抗ウイルス塗料においては、前記第４アンモニウム塩とナノシリカとの複合体を構成するナノシリカの平均粒径を１０〜５０ｎｍとすることが好ましい。ナノシリカの平均粒径が小さいほど得られる抗菌／抗ウイルス塗膜の透明性及び表面平滑性が良好となるが、平均粒径が１０nm未満のナノシリカは製造しがたい。また、ナノシリカの平均粒径が５０ｎｍを越えると、得られる抗菌／抗ウイルス塗膜の透明性及び表面平滑性が低下するほか、膜厚の薄い抗菌／抗ウイルス性塗膜を形成しがたくなる。 Further, in the antibacterial / antiviral paint of such an embodiment, it is preferable that the average particle size of the nanosilica constituting the complex of the quaternary ammonium salt and the nanosilica is 10 to 50 nm. The smaller the average particle size of the nanosilica, the better the transparency and surface smoothness of the obtained antibacterial / antiviral coating film, but it is difficult to produce nanosilica with an average particle size of less than 10 nm. Further, when the average particle size of nanosilica exceeds 50 nm, the transparency and surface smoothness of the obtained antibacterial / antiviral coating film are lowered, and it becomes difficult to form a thin antibacterial / antiviral coating film. ..
以上述べたように、本発明によれば、既に形成されている塗膜を含め、多くの製品素材の表面に、室温下で、透明性（表面クリアー性）を有し、清潔感を付与することができるとともに、防汚性、耐薬品性、耐擦傷性などに優れた特性をも付与することができる抗菌／抗ウイルス塗料が提供される。 As described above, according to the present invention, the surface of many product materials, including the already formed coating film, has transparency (surface clearness) at room temperature and imparts a feeling of cleanliness. Provided is an antibacterial / antiviral paint capable of imparting excellent properties such as antifouling property, chemical resistance, and scratch resistance.
以下、本発明に係る抗菌／抗ウイルス塗料について、各種実施例及び比較例を用いて詳細に説明する。ただし、以下に示す各種実施例は、本発明の技術思想を具体化するための例を示すものであって、本発明をこれらの実施例に示したものに特定することを意図するものではない。本発明は特許請求の範囲に含まれるその他の実施形態のものにも等しく適用し得るものである。 Hereinafter, the antibacterial / antiviral coating material according to the present invention will be described in detail with reference to various examples and comparative examples. However, the various examples shown below show examples for embodying the technical idea of the present invention, and are not intended to specify the present invention as those shown in these examples. .. The present invention is equally applicable to other embodiments included in the claims.
［実施例１］
湿気硬化型の１液性シリコーンアルコキシオリゴマーとしてメトキシ基を２８％含有するメチル系シリコーンアルコキシオリゴマー（ＫＲ−５００、信越化学工業(株)製）を８０質量部、アルコキシシランとしての３−グリシドキシプロピルトリメトキシシラン（ＸＩＡＭＥＴＥＲ ＯＦＳ−６０４０、ダウ・東レ(株)製）１０質量部、硬化触媒としてのジオクチルスズラウレート２質量部を、イソプロピルアルコール４０質量部及びノルマルプロピルアルコール４０質量部からなる混合溶剤に均一に撹拌・混合して塗料を調整した。
[Example 1]
80 parts by mass of a methyl silicone alkoxy oligomer (KR-500, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) containing 28% of methoxy group as a moisture-curable one-component silicone alkoxy oligomer, 3-glycidoxy as an alkoxysilane A mixture of 10 parts by mass of propyltrimethoxysilane (XIAMETER OFS-6040, manufactured by Dow Toray Co., Ltd.), 2 parts by mass of dioctyltin laurate as a curing catalyst, and 40 parts by mass of isopropyl alcohol and 40 parts by mass of normal propyl alcohol. The paint was adjusted by uniformly stirring and mixing with the solvent.
次に抗菌／抗ウイルス剤として、ビス型構造であるＮ，Ｎ'−ヘキサメチレンビス（４−カルバモイル−１−デシルピリジニウムブロマイド(N,N'-Hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide))（ダイマー３８、イヌイ(株)製）をノルマルプロピルアルコールに溶解して、前記塗料固形分中１００質量部に対し、抗菌／抗ウイルス剤固形分３．５質量部となるように添加混合し、透明の実施例１の抗菌／抗ウイルス塗料を得た。 Next, as an antibacterial / antiviral agent, N, N'-hexamethylene bis (4-carbamoyl-1-decylpyridinium bromide), which has a bis-type structure, is N, N'-Hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide). (Dimer 38, manufactured by Inui Co., Ltd.) was dissolved in normal propyl alcohol, and added and mixed so as to have an antibacterial / antiviral agent solid content of 3.5 parts by mass with respect to 100 parts by mass of the paint solid content. A transparent antibacterial / antiviral paint of Example 1 was obtained.
実施例１の抗菌／抗ウイルス塗料を透明ポリカーボネート板にスプレー法により３〜５μｍとなるよう塗装して、常温下で５日間放置して硬化乾燥させて実施例１の試験片を調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。 The antibacterial / antiviral paint of Example 1 was applied to a transparent polycarbonate plate by a spray method to a size of 3 to 5 μm, left at room temperature for 5 days to cure and dry, and the test piece of Example 1 was prepared. It was subjected to the antibacterial / antiviral test shown in. The results are summarized in Table 1.
［実施例２］
湿気硬化型の１液性シリコーンアルコキシオリゴマーとしてメトキシ基を３５％含有するメチル系シリコーンアルコキシオリゴマー（ＸＲ３１−Ｂ１４１０、モメンティブパフォーマンスマテリアルズジャパン合同会社製）６５質量部、可撓性付与成分としてメトキシ基１２％のオルガノポリシロキサン（Ｘ−４０−９２４６、信越化学工業(株)製）１５質量部、アルコキシシランとして３−グリシドキシプロピルトリメトキシシラン１０質量部、硬化触媒としてジブチルスズジアセテート２質量部を、イソプロピルアルコール４５質量部及びノルマルプロピルアルコール４５質量部からなる混合溶剤に均一に撹拌・混合して塗料を調整した。
[Example 2]
Methyl-based silicone alkoxy oligomer containing 35% methoxy group as a moisture-curable one-component silicone alkoxy oligomer (XR31-B1410, manufactured by Momentive Performance Materials Japan LLC) 65 parts by mass, methoxy group 12 as a flexibility-imparting component % Organopolysiloxane (X-40-9246, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 15 parts by mass, 10 parts by mass of 3-glycidoxypropyltrimethoxysilane as an alkoxysilane, and 2 parts by mass of dibutyltin diacetate as a curing catalyst. , 45 parts by mass of isopropyl alcohol and 45 parts by mass of normal propyl alcohol were uniformly stirred and mixed with a mixed solvent to prepare a coating material.
次に抗菌／抗ウイルス剤として、ビス型構造である１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド〔1,4'-bis[3,3'-(1-decylpyridinium)methyloxy]butandibromide)〕（ハイジェニアＳ−１００、タマ化学工業（株）製）をノルマルプロピルアルコールに溶解し、前記塗料固形分１００質量部に対し、抗菌／抗ウイルス剤固形分４．８質量部となるように添加混合し、透明の実施例２の抗菌／抗ウイルス塗料を得た。 Next, as an antibacterial / antiviral agent, 1,4-bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide [1,4'-bis [3,3'- (1-decylpyridinium) methyloxy] butandibromide)] (Hygenia S-100, manufactured by Tama Chemical Industry Co., Ltd.) was dissolved in normal propyl alcohol, and the antibacterial / antiviral agent solid content was 4 with respect to 100 parts by mass of the paint solid content. It was added and mixed so as to have an amount of 8.8 parts by mass to obtain a transparent antibacterial / antiviral paint of Example 2.
実施例２の抗菌／抗ウイルス塗料を用い、実施例１の場合と同様にして実施例２の試験片を調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。 Using the antibacterial / antiviral paint of Example 2, a test piece of Example 2 was prepared in the same manner as in the case of Example 1 and subjected to the antibacterial / antiviral test shown below. The results are summarized in Table 1.
［実施例３］
〈第４アンモニウム塩／ナノシリカ複合体の調整〉
平均粒子径１０〜１５μｍのナノシリカ液（ＩＰＡ−ＳＴ、ＳｉＯ３０％、日産化学工業（株）製）をノルマルプロピルアルコールで希釈して、シリカ固形分を２０％に調整した（ナノシリカ２０％液）。このナノシリカ２０％液を１００ｇガラスビーカーに取り、撹拌機で撹拌しながら液温をヒーターで３０〜４０℃に保持した。
[Example 3]
<Preparation of quaternary ammonium salt / nanosilica complex>
A nanosilica solution (IPA-ST, SiO30%, manufactured by Nissan Chemical Industry Co., Ltd.) having an average particle diameter of 10 to 15 μm was diluted with normal propyl alcohol to adjust the silica solid content to 20% (nanosilica 20% solution). This 20% nanosilica liquid was placed in a 100 g glass beaker, and the liquid temperature was maintained at 30 to 40 ° C. with a heater while stirring with a stirrer.
第４アンモニウム塩として、実施例２で使用したのと同様の１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド粉末４０ｇを６０分かけて少しずつ添加した。混合液は、無色透明から淡褐色透明の粘調な複合体溶液に変化した。これは、カチオン性の第４アンモニウム塩がナノリシカ表面の−ＯＨ基と結合したものと考えられる。 As the quaternary ammonium salt, 40 g of 1,4-bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide powder similar to that used in Example 2 was added little by little over 60 minutes. .. The mixture changed from a colorless transparent to a light brown transparent viscous complex solution. It is considered that this is because the cationic quaternary ammonium salt is bonded to the -OH group on the surface of nanolyrica.
（抗菌／抗ウイルス塗料の調製)
実施例２で調製した塗料の塗料固形分１００質量部に対し、上述のようにして調製した第４アンモニウム塩／ナノシリカ複合体溶液を固形分７．０質量部（第４アンモニウム塩４質量部、ナノシリカ３質量部）となるように添加混合し、透明の実施例３の抗菌／抗ウイルス塗料を得た。
(Preparation of antibacterial / antiviral paint)
The quaternary ammonium salt / nanosilica complex solution prepared as described above was added to a solid content of 7.0 parts by mass (4 parts by mass of the quaternary ammonium salt, 4 parts by mass) with respect to 100 parts by mass of the paint solid content of the paint prepared in Example 2. 3 parts by mass of nanosilica) was added and mixed to obtain a transparent antibacterial / antiviral paint of Example 3.
実施例３の抗菌／抗ウイルス塗料を用い、実施例１の場合と同様にして実施例３の試験片を調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。 Using the antibacterial / antiviral paint of Example 3, a test piece of Example 3 was prepared in the same manner as in Example 1 and subjected to the antibacterial / antiviral test shown below. The results are summarized in Table 1.
［比較例］
実施例２の場合と同様にして調製した塗料の塗料固形分１００質量部に対し、ヨウ素系抗菌／抗ウイルス剤（ヨードプロピニルブチルカルバメート、Iodopropynylbutylcarbamate（Ｏｍａｃｉｄｅ ＩＰＢＣ１００、ロンザジャパン(株)製）をノルマルプロピルアルコールに溶解した溶液を、抗菌／抗ウイルス剤固形分３質量部となるように添加混合し、透明の比較例の抗菌／抗ウイルス塗料を得た。
[Comparison example]
An iodine-based antibacterial / antiviral agent (iodopropynylbutylcarbamate (Omacide IPBC100, manufactured by Lonza Japan Co., Ltd.)) was added to 100 parts by mass of the paint solid content of the paint prepared in the same manner as in Example 2. The solution dissolved in alcohol was added and mixed so as to have an antibacterial / antiviral agent solid content of 3 parts by mass to obtain a transparent antibacterial / antiviral paint of Comparative Example.
比較例の抗菌／抗ウイルス塗料を用い、実施例１の場合と同様にして比較例の試験片を調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。 Using the antibacterial / antiviral paint of Comparative Example, a test piece of Comparative Example was prepared in the same manner as in Example 1 and subjected to the antibacterial / antiviral test shown below. The results are summarized in Table 1.
なお、表１における各試験項目は以下のようにして測定されたものである。
抗菌活性値（Ｒ）：無加工試験片（薬剤無添加）の２４時間培養後の菌数の対数値（Ｕｔ）と加工試験片（抗菌剤添加）の２４時間培養後の菌数の対数値（Ａｔ）の差（Ｒ＝Ｕｔ−Ａｔ）を示す。Ｒが２以上で合格と判定される。
抗ウイルス活性値（Ｒ）：無加工試験片（薬剤無添加）の２４時間後のウイルス感染価（Ｕｔ）と加工試験片（抗菌剤添加）の２４時間後のウイルス感染価（Ａｔ）の対数値の差（Ｒ＝Ｕｔ−Ａｔ）を示す。Ｒが２以上で合格とされる。
Each test item in Table 1 was measured as follows.
Antibacterial activity value (R): logarithmic value (Ut) of the number of bacteria after 24-hour culture of the unprocessed test piece (no drug added) and the logarithmic value of the number of bacteria after 24-hour culture of the processed test piece (added antibacterial agent) The difference (R = Ut-At) of (At) is shown. If R is 2 or more, it is judged to pass.
Antiviral activity value (R): Pair of virus infectious titer (Ut) 24 hours after unprocessed test piece (no drug added) and virus infectious titer (At) 24 hours after processed test piece (added antibacterial agent) The difference between the numerical values (R = Ut-At) is shown. If R is 2 or more, it is passed.
表１に示した結果によれば、実施例１〜３及び比較例の試験片とも、緑膿菌及び大腸菌（Ｏ１５７）に関する抗菌活性値（Ｒ）は一応良好な結果が得られている。それに対し、Ａ型インフルエンザ及びネコカリシウイルスに関する抗ウイルス活性値（Ｒ）は、実施例１〜３の試験片では良好な結果が得られているが、比較例の試験片では合格値に達しなかった。元々比較例で用いたヨードプロピニルブチルカルバメートは、抗真菌剤および抗菌剤として広く使用されている剤であって、抗ウイルス剤としてはほとんど使用されていない剤であるので、妥当な結果であると思われる。 According to the results shown in Table 1, the antibacterial activity values (R) for Pseudomonas aeruginosa and Escherichia coli (O157) were tentatively good in both the test pieces of Examples 1 to 3 and Comparative Examples. On the other hand, the antiviral activity values (R) for influenza A and feline calicivirus were good results in the test pieces of Examples 1 to 3, but did not reach the passing values in the test pieces of the comparative examples. rice field. The iodinepropynylbutylcarbamate originally used in the comparative example is an agent widely used as an antifungal agent and an antibacterial agent, and is rarely used as an antiviral agent, so that it is a reasonable result. Seem.
［耐湿性試験］
ここでは、抗菌／抗ウイルス試験で良好な結果が得られた実施例２及び３の試験片を用いて、抗菌／抗ウイルス性がどの程度の時間にわたって維持できるかを調べるため、耐湿試験を行った。なお、耐湿試験は、実施例２と実施例３の試験片を用い、それぞれの試験片を５０℃×９８％ＲＨの条件下に１００時間暴露を行い、上記と同様にしてネコカリシウイルスに対する抗ウイルス活性値（Ｒ）を測定した。結果を纏めて表２に示した。
[Moisture resistance test]
Here, a moisture resistance test is performed to investigate how long the antibacterial / antiviral property can be maintained by using the test pieces of Examples 2 and 3 that have obtained good results in the antibacterial / antiviral test. rice field. In the moisture resistance test, the test pieces of Example 2 and Example 3 were used, and each test piece was exposed under the condition of 50 ° C. × 98% RH for 100 hours, and the antiviral resistance against feline calicivirus was carried out in the same manner as above. The virus activity value (R) was measured. The results are summarized in Table 2.
表２に示した結果によれば、実施例２の試験片では暴露試験後の抗ウイルス活性値（Ｒ）が「２」以下となっており、合格値よりも低くなっている。それに対し、実施例３の試験片では暴露試験後でも高い抗ウイルス活性値（Ｒ）を維持していた。実施例２の試験片と実施例３の試験片との構成の差異は、抗菌／抗ウイルス性塗膜中に第４アンモニウム塩／ナノシリカ複合体として添加されている抗菌／抗ウイルス剤を含まない（実施例２）か、あるいは含む（実施例３）かであるから、抗菌／抗ウイルス剤としての４級アンモニウム塩を第４アンモニウム塩／ナノシリカ複合体の形で添加する方が、第４アンモニウム塩がナノシリカに担持された形となり、持続耐久性に優れるようになることが分かる。 According to the results shown in Table 2, in the test piece of Example 2, the antiviral activity value (R) after the exposure test was "2" or less, which was lower than the passing value. On the other hand, the test piece of Example 3 maintained a high antiviral activity value (R) even after the exposure test. The difference in composition between the test piece of Example 2 and the test piece of Example 3 does not include the antibacterial / antiviral agent added as the quaternary ammonium salt / nanosilica complex in the antibacterial / antiviral coating film. Since it is either (Example 2) or (Example 3), it is better to add the quaternary ammonium salt as an antibacterial / antiviral agent in the form of a quaternary ammonium salt / nanosilica complex. It can be seen that the salt is supported on nanosilica and has excellent long-lasting durability.
［塗膜の各種性能の測定］
実験例１〜３で調製した抗菌／抗ウイルス塗料を用い、素材としてボンデ鋼板の表面にスプレー法によってそれぞれ膜厚：４〜６μｍとなるように塗布し、常温下で５日間放置することにより硬化させて各種性能の測定用試料を得た。この測定試料を用い、目視により、硬度、付着性試験、耐衝撃性試験、耐酸試験、耐溶剤性、耐湿試験、耐汚染性試験を行った。なお、結果は、実験例１〜３で調製した抗菌／抗ウイルス塗料の何れを用いても同様の結果となったので、下記表３にはその結果のみを纏めて示した。
[Measurement of various performances of coating film]
Using the antibacterial / anti-virus paint prepared in Experimental Examples 1 to 3, the surface of the bonded steel sheet was coated with a spray method so that the film thickness was 4 to 6 μm, and the film was cured by leaving it at room temperature for 5 days. Then, samples for measuring various performances were obtained. Using this measurement sample, hardness, adhesion test, impact resistance test, acid resistance test, solvent resistance, moisture resistance test, and stain resistance test were visually performed. The results were the same regardless of which of the antibacterial / antiviral paints prepared in Experimental Examples 1 to 3 was used. Therefore, only the results are summarized in Table 3 below.
なお、硬度は、三菱鉛筆製の「ユニ」（商品名）の鉛筆硬度Ｈ及び２Ｈのものを用い、測定用試料の表面をなぞった際に傷が付くか付かないかを目視により確認した。何れの測定用試料であっても全く傷が付かないことが確認できた。 As the hardness, pencil hardness H and 2H of "Uni" (trade name) manufactured by Mitsubishi Pencil were used, and it was visually confirmed whether or not the surface of the measurement sample was scratched or scratched. It was confirmed that no scratches were made on any of the measurement samples.
付着性試験は、測定用試料として、ボンデ鋼板の表面に２ｍｍ方眼の塗膜を１００個作成し、市販のセロハンテープを貼り付けた後、セロハンテープを剥離し、目視によって塗膜が剥がれなかった個数を計数した。何れの測定用試料においても全く剥がれが生じなかった。 In the adhesion test, 100 2 mm grid coating films were prepared on the surface of the bonde steel sheet as a measurement sample, a commercially available cellophane tape was attached, and then the cellophane tape was peeled off, and the coating film did not peel off visually. The number was counted. No peeling occurred in any of the measurement samples.
耐衝撃試験は、直径２５．４ｍｍ、３００ｇの落下球を用い、ＪＩＳ Ｋ ５６００−５−３ 落球試験に準ずる方法によって、５００ｍｍの高さから測定用試料の表面に落下させた際に傷が付くか付かないかを目視により確認した。何れの測定用試料においても全く異常は生じなかった。 The impact resistance test uses a falling ball with a diameter of 25.4 mm and 300 g, and is scratched when dropped from a height of 500 mm onto the surface of the measurement sample by a method similar to the JIS K 5600-5-3 falling ball test. It was visually confirmed whether or not it was attached. No abnormality occurred in any of the measurement samples.
耐酸試験は、５％硫酸水溶液スポットテストとして測定用試料の表面に滴下し、２３℃×６時間経過後の表面の状態を目視により確認した。何れの測定用試料においても全く異常は生じなかった。 The acid resistance test was dropped on the surface of the measurement sample as a 5% sulfuric acid aqueous solution spot test, and the state of the surface after the lapse of 23 ° C. × 6 hours was visually confirmed. No abnormality occurred in any of the measurement samples.
耐溶剤性試験は、溶剤としてエタノール、トルエン及びメチルエチルケトンの３種類についてそれぞれ単独で布製のラビング剤に含浸させ、測定用試料の表面を５００ｇの荷重をを印加しつつ１０往復ラビングし、表面に何等かの異常が生じるか否かを目視により確認した。何れの測定用試料においても、何れの溶剤を用いた場合でも、全く異常は生じなかった。 In the solvent resistance test, three types of solvents, ethanol, toluene and methyl ethyl ketone, were individually impregnated with a cloth rubbing agent, and the surface of the measurement sample was rubbed 10 times back and forth while applying a load of 500 g. It was visually confirmed whether or not the abnormality occurred. No abnormality occurred in any of the measurement samples, regardless of which solvent was used.
耐湿試験は、測定試料を５０℃×９８％ＲＨの条件下に１００時間暴露し、表面に何等かの異常状態が生じるか否かを目視により確認した。何れの測定用試料においても全く異常は生じなかった。 In the moisture resistance test, the measurement sample was exposed to the condition of 50 ° C. × 98% RH for 100 hours, and it was visually confirmed whether or not any abnormal state occurred on the surface. No abnormality occurred in any of the measurement samples.
耐汚染性試験は、測定試料の表面に黒及び赤の油性マジックを塗布し、エタノールを含浸した布により拭き取った際に異常が生じるか否かを目視により確認した。何れの測定用試料においても全く異常は生じなかった。 In the stain resistance test, black and red oil-based magic was applied to the surface of the measurement sample, and it was visually confirmed whether or not any abnormality occurred when the sample was wiped with a cloth impregnated with ethanol. No abnormality occurred in any of the measurement samples.
以上の表３に示した結果から、本発明による抗菌／抗ウイルス塗料により得られた塗膜は、防汚性、耐薬品性、耐擦傷性などに優れた特性を有していることが確認できた。 From the results shown in Table 3 above, it was confirmed that the coating film obtained by the antibacterial / antiviral paint according to the present invention has excellent properties such as antifouling property, chemical resistance, and scratch resistance. did it.
すなわち、本発明は、湿気硬化型の１液性シリコーンアルコキシオリゴマーをバインダーとし、抗菌／抗ウイルス性成分として第４アンモニウム塩を含む抗菌／抗ウイルス塗料であって、
前記第４アンモニウム塩は、
４，４'−（テトラメチレンジカルボニルジアミノ）ビス（１−デシルピリジニウムブロマイド）、
Ｎ，Ｎ'−ヘキサメチレンビス（４−カルバモイル−１−デシルピリジニウムブロマイド、
１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド、
から選択された少なくとも１種のビス型構造のものであって、ナノシリカとの複合体を形成しており、
前記第４アンモニウム塩含有量は、前記シリコーンアルコキシオリゴマーを含む塗料固形分１００質量部に対して２〜１０質量部であることを特徴とする。
That is, the present invention is an antibacterial / antiviral paint containing a moisture-curable one-component silicone alkoxy oligomer as a binder and a quaternary ammonium salt as an antibacterial / antiviral component.
The quaternary ammonium salt is
4,4'-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide),
N, N'-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide,
1,4-Bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide,
It has at least one screw-type structure selected from the above, and forms a complex with nanosilica.
The content of the quaternary ammonium salt is 2 to 10 parts by mass with respect to 100 parts by mass of the paint solid content containing the silicone alkoxy oligomer.
しかも、本発明の抗菌／抗ウイルス塗料においては、膜形成成分としての湿気硬化型の１液性シリコーンアルコキシオリゴマーと抗菌／抗ウイルス性成分としての、４，４'−（テトラメチレンジカルボニルジアミノ）ビス（１−デシルピリジニウムブロマイド）、Ｎ，Ｎ'−ヘキサメチレンビス（４−カルバモイル−１−デシルピリジニウムブロマイド、１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド、から選択された少なくとも１種のビス型構造のものであって、ナノシリカとの複合体を形成しているものを互いに相容性の溶剤（例えばアルコール系溶剤、グリコールエーテル系溶剤等）に溶解させたものを用いることができ、互いの相容性も良好であるために均質に溶解させることができ、長期間に亘って優れた抗菌／抗ウイルス性を発揮できる塗膜が得られる。
Moreover, in the antibacterial / antiviral coating material of the present invention, a moisture-curable one-component silicone alkoxy oligomer as a film-forming component and 4,4'-(tetramethylenedicarbonyldiamino) as an antibacterial / antiviral component. Bis (1-decylpyridinium bromide), N, N'-hexamethylene bis (4-carbamoyl-1-decylpyridinium bromide, 1,4-bis [3,3'-(1-decylpyridinium) methyloxy] butanji At least one virus-type structure selected from bromide, which forms a complex with nanosilica, is used as a solvent compatible with each other (for example, alcohol-based solvent, glycol ether-based solvent, etc.). A melted product can be used, and since it has good compatibility with each other, it can be uniformly dissolved, and a coating film capable of exhibiting excellent antibacterial / antiviral properties over a long period of time can be obtained.
本発明の抗菌／抗ウイルス塗料においては、前記第４アンモニウム塩としては、
４，４'−（テトラメチレンジカルボニルジアミノ）ビス（１−デシルピリジニウムブロマイド）、
Ｎ，Ｎ'−ヘキサメチレンビス（４−カルバモイル−１−デシルピリジニウムブロマイド、
１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド、
から選択された少なくとも１種のビス型構造のものが用いられる。
In the antibacterial / antiviral paint of the present invention, the quaternary ammonium salt is used as the quaternary ammonium salt.
4,4'-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide),
N, N'-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide,
1,4-Bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide,
At least one of the screw type structures selected from the above is used.
第４アンモニウム塩は、抗菌／抗ウイルス剤として、種々のものが広く市販されていおり、入手が容易であり、一応良好な抗菌／抗ウイルス性を示す塗膜が得られる。しかしながら、モノ型構造の第４アンモニウム塩は、微生物の表面疎水性に依存して様々なＭＩＣ（最小発育阻止濃度）が測定され、殺菌力に限界がある（上記非特許文献１参照）。それに対し、ビス型構造の第４アンモニウム塩は、ＭＩＣの比較で、多くの細菌に対して高い活性を示し、細菌芽胞に対して強い細胞破壊作用を有している。
Various quaternary ammonium salts are widely marketed as antibacterial / antiviral agents and are easily available, so that a coating film showing good antibacterial / antiviral properties can be obtained. However, the quaternary ammonium salt having a mono-type structure has various MICs (minimum inhibitory concentration) measured depending on the surface hydrophobicity of microorganisms, and has a limited bactericidal activity (see Non-Patent Document 1 above). On the other hand, the quaternary ammonium salt having a bis-type structure shows high activity against many bacteria and has a strong cell-destroying action against bacterial spores in comparison with MIC.
また、本発明の抗菌／抗ウイルス塗料においては、第４アンモニウム塩はナノシリカとの複合体からなっている。
Further, in the antibacterial / antiviral paint of the present invention , the quaternary ammonium salt is composed of a complex with nanosilica .
係る場合の前記第４アンモニウム塩とナノシリカとの複合体の含有量は、前記第４アンモニウム塩に対して、ナノシリカが２０〜５０質量％であることが好ましい。ナノシリカの含有量が２０質量％未満では抗菌/抗ウイルス性の耐久持続性の向上効果が確認できず、５０質量％を超えると塗料安定性が低下し、沈殿や粒状異物を発生することがある。
The content of the complex with the quaternary ammonium salt and nanosilica when according, to the said quaternary ammonium salt is preferably nanosilica is 20 to 50 mass%. If the content of nanosilica is less than 20% by mass, the effect of improving the durability of antibacterial / antiviral properties cannot be confirmed, and if it exceeds 50% by mass, the paint stability is lowered and precipitation or granular foreign matter may be generated. ..
以下、本発明に係る抗菌／抗ウイルス塗料について、各種実験例及び比較例を用いて詳細に説明する。ただし、以下に示す各種実験例は、本発明の技術思想を具体化するための例を示すものであって、本発明をこれらの実験例に示したものに特定することを意図するものではない。本発明は特許請求の範囲に含まれるその他の実施形態のものにも等しく適用し得るものである。
Hereinafter, the antibacterial / antiviral coating material according to the present invention will be described in detail with reference to various experimental examples and comparative examples. However, the various experimental examples shown below show examples for embodying the technical idea of the present invention, and are not intended to specify the present invention as those shown in these experimental examples. .. The present invention is equally applicable to other embodiments included in the claims.
［実験例１］
湿気硬化型の１液性シリコーンアルコキシオリゴマーとしてメトキシ基を２８％含有するメチル系シリコーンアルコキシオリゴマー（ＫＲ−５００、信越化学工業(株)製）を８０質量部、アルコキシシランとしての３−グリシドキシプロピルトリメトキシシラン（ＸＩＡＭＥＴＥＲ ＯＦＳ−６０４０、ダウ・東レ(株)製）１０質量部、硬化触媒としてのジオクチルスズラウレート２質量部を、イソプロピルアルコール４０質量部及びノルマルプロピルアルコール４０質量部からなる混合溶剤に均一に撹拌・混合して塗料を調整した。
[ Experimental Example 1]
80 parts by mass of a methyl silicone alkoxy oligomer (KR-500, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) containing 28% of methoxy group as a moisture-curable one-component silicone alkoxy oligomer, 3-glycidoxy as an alkoxysilane A mixture of 10 parts by mass of propyltrimethoxysilane (XIAMETER OFS-6040, manufactured by Dow Toray Co., Ltd.), 2 parts by mass of dioctyltin laurate as a curing catalyst, and 40 parts by mass of isopropyl alcohol and 40 parts by mass of normal propyl alcohol. The paint was adjusted by uniformly stirring and mixing with the solvent.
次に抗菌／抗ウイルス剤として、ビス型構造であるＮ，Ｎ'−ヘキサメチレンビス（４−カルバモイル−１−デシルピリジニウムブロマイド(N,N'-Hexamethylenebis(4-carbamoyl-1-decylpyridinium bromide))（ダイマー３８、イヌイ(株)製）をノルマルプロピルアルコールに溶解して、前記塗料固形分中１００質量部に対し、抗菌／抗ウイルス剤固形分３．５質量部となるように添加混合し、透明の実験例１の抗菌／抗ウイルス塗料を得た。
Next, as an antibacterial / antiviral agent, N, N'-hexamethylene bis (4-carbamoyl-1-decylpyridinium bromide), which has a bis-type structure, is N, N'-Hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide). (Dimer 38, manufactured by Inui Co., Ltd.) was dissolved in normal propyl alcohol, and added and mixed so as to have an antibacterial / antiviral agent solid content of 3.5 parts by mass with respect to 100 parts by mass of the paint solid content. A transparent antibacterial / antiviral paint of Experimental Example 1 was obtained.
実験例１の抗菌／抗ウイルス塗料を透明ポリカーボネート板にスプレー法により３〜５μｍとなるよう塗装して、常温下で５日間放置して硬化乾燥させて実験例１の試験片を調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。
The antibacterial / anti-virus paint of Experimental Example 1 was applied to a transparent polycarbonate plate by a spray method to a size of 3 to 5 μm, left at room temperature for 5 days to cure and dry, and the test piece of Experimental Example 1 was prepared. It was subjected to the antibacterial / antiviral test shown in. The results are summarized in Table 1.
［実験例２］
湿気硬化型の１液性シリコーンアルコキシオリゴマーとしてメトキシ基を３５％含有するメチル系シリコーンアルコキシオリゴマー（ＸＲ３１−Ｂ１４１０、モメンティブパフォーマンスマテリアルズジャパン合同会社製）６５質量部、可撓性付与成分としてメトキシ基１２％のオルガノポリシロキサン（Ｘ−４０−９２４６、信越化学工業(株)製）１５質量部、アルコキシシランとして３−グリシドキシプロピルトリメトキシシラン１０質量部、硬化触媒としてジブチルスズジアセテート２質量部を、イソプロピルアルコール４５質量部及びノルマルプロピルアルコール４５質量部からなる混合溶剤に均一に撹拌・混合して塗料を調整した。
[ Experimental Example 2]
Methyl-based silicone alkoxy oligomer containing 35% methoxy group as a moisture-curable one-component silicone alkoxy oligomer (XR31-B1410, manufactured by Momentive Performance Materials Japan LLC) 65 parts by mass, methoxy group 12 as a flexibility-imparting component % Organopolysiloxane (X-40-9246, manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 15 parts by mass, 10 parts by mass of 3-glycidoxypropyltrimethoxysilane as an alkoxysilane, and 2 parts by mass of dibutyltin diacetate as a curing catalyst. , 45 parts by mass of isopropyl alcohol and 45 parts by mass of normal propyl alcohol were uniformly stirred and mixed with a mixed solvent to prepare a coating material.
次に抗菌／抗ウイルス剤として、ビス型構造である１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド〔1,4'-bis[3,3'-(1-decylpyridinium)methyloxy]butandibromide)〕（ハイジェニアＳ−１００、タマ化学工業（株）製）をノルマルプロピルアルコールに溶解し、前記塗料固形分１００質量部に対し、抗菌／抗ウイルス剤固形分４．８質量部となるように添加混合し、透明の実験例２の抗菌／抗ウイルス塗料を得た。
Next, as an antibacterial / antiviral agent, 1,4-bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide [1,4'-bis [3,3'- (1-decylpyridinium) methyloxy] butandibromide)] (Hygenia S-100, manufactured by Tama Chemical Industry Co., Ltd.) was dissolved in normal propyl alcohol, and the antibacterial / antiviral agent solid content was 4 with respect to 100 parts by mass of the paint solid content. The mixture was added and mixed so as to have an amount of 8.8 parts by mass to obtain a transparent antibacterial / antiviral paint of Experimental Example 2.
実験例２の抗菌／抗ウイルス塗料を用い、実験例１の場合と同様にして実験例２の試験片を調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。
Using the antibacterial / antiviral paint of Experimental Example 2, a test piece of Experimental Example 2 was prepared in the same manner as in the case of Experimental Example 1 and subjected to the antibacterial / antiviral test shown below. The results are summarized in Table 1.
［実験例３］
〈第４アンモニウム塩／ナノシリカ複合体の調整〉
平均粒子径１０〜１５μｍのナノシリカ液（ＩＰＡ−ＳＴ、ＳｉＯ３０％、日産化学工業（株）製）をノルマルプロピルアルコールで希釈して、シリカ固形分を２０％に調整した（ナノシリカ２０％液）。このナノシリカ２０％液を１００ｇガラスビーカーに取り、撹拌機で撹拌しながら液温をヒーターで３０〜４０℃に保持した。
[ Experimental Example 3]
<Preparation of quaternary ammonium salt / nanosilica complex>
A nanosilica solution (IPA-ST, SiO30%, manufactured by Nissan Chemical Industry Co., Ltd.) having an average particle diameter of 10 to 15 μm was diluted with normal propyl alcohol to adjust the silica solid content to 20% (nanosilica 20% solution). This 20% nanosilica liquid was placed in a 100 g glass beaker, and the liquid temperature was maintained at 30 to 40 ° C. with a heater while stirring with a stirrer.
第４アンモニウム塩として、実験例２で使用したのと同様の１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド粉末４０ｇを６０分かけて少しずつ添加した。混合液は、無色透明から淡褐色透明の粘調な複合体溶液に変化した。これは、カチオン性の第４アンモニウム塩がナノリシカ表面の−ＯＨ基と結合したものと考えられる。
As the quaternary ammonium salt, 40 g of 1,4-bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide powder similar to that used in Experimental Example 2 was added little by little over 60 minutes. .. The mixture changed from a colorless transparent to a light brown transparent viscous complex solution. It is considered that this is because the cationic quaternary ammonium salt is bonded to the -OH group on the surface of nanolyrica.
（抗菌／抗ウイルス塗料の調製)
実験例２で調製した塗料の塗料固形分１００質量部に対し、上述のようにして調製した第４アンモニウム塩／ナノシリカ複合体溶液を固形分７．０質量部（第４アンモニウム塩４質量部、ナノシリカ３質量部）となるように添加混合し、透明の実験例３の抗菌／抗ウイルス塗料を得た。
(Preparation of antibacterial / antiviral paint)
The quaternary ammonium salt / nanosilica complex solution prepared as described above was added to the coating solid content of 100 parts by mass in Experimental Example 2 by 7.0 parts by mass (4 parts by mass of the quaternary ammonium salt). 3 parts by mass of nanosilica) was added and mixed to obtain a transparent antibacterial / antiviral paint of Experimental Example 3.
実験例３の抗菌／抗ウイルス塗料を用い、実験例１の場合と同様にして実験例３の試験片を調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。
Using the antibacterial / antiviral paint of Experimental Example 3, a test piece of Experimental Example 3 was prepared in the same manner as in the case of Experimental Example 1 and subjected to the antibacterial / antiviral test shown below. The results are summarized in Table 1.
［比較例］
実験例２の場合と同様にして調製した塗料の塗料固形分１００質量部に対し、ヨウ素系抗菌／抗ウイルス剤（ヨードプロピニルブチルカルバメート、Iodopropynylbutylcarbamate（Ｏｍａｃｉｄｅ ＩＰＢＣ１００、ロンザジャパン(株)製）をノルマルプロピルアルコールに溶解した溶液を、抗菌／抗ウイルス剤固形分３質量部となるように添加混合し、透明の比較例の抗菌／抗ウイルス塗料を得た。
[Comparison example]
Iodine-based antibacterial / antiviral agents (iodopropynylbutylcarbamate (Omacide IPBC100, manufactured by Lonza Japan Co., Ltd.)) were added to 100 parts by mass of the paint solid content of the paint prepared in the same manner as in Experimental Example 2. The solution dissolved in alcohol was added and mixed so as to have an antibacterial / antiviral agent solid content of 3 parts by mass to obtain a transparent antibacterial / antiviral paint of Comparative Example.
比較例の抗菌／抗ウイルス塗料を用い、実験例１の場合と同様にして比較例の試験片を
調製し、以下に示す抗菌／抗ウイルス性試験に供した。結果を纏めて表１に示した。
Using the antibacterial / antiviral paint of Comparative Example, a test piece of Comparative Example was prepared in the same manner as in Experimental Example 1 and subjected to the antibacterial / antiviral test shown below. The results are summarized in Table 1.
表１に示した結果によれば、実験例１〜３及び比較例の試験片とも、緑膿菌及び大腸菌（Ｏ１５７）に関する抗菌活性値（Ｒ）は一応良好な結果が得られている。それに対し、Ａ型インフルエンザ及びネコカリシウイルスに関する抗ウイルス活性値（Ｒ）は、実験例１〜３の試験片では良好な結果が得られているが、比較例の試験片では合格値に達しなかった。元々比較例で用いたヨードプロピニルブチルカルバメートは、抗真菌剤および抗菌剤として広く使用されている剤であって、抗ウイルス剤としてはほとんど使用されていない剤であるので、妥当な結果であると思われる。
According to the results shown in Table 1, the antibacterial activity values (R) for Pseudomonas aeruginosa and Escherichia coli (O157) were tentatively good in both the test pieces of Experimental Examples 1 to 3 and Comparative Examples. On the other hand, the antiviral activity value (R) for influenza A and feline calicivirus was good in the test pieces of Experimental Examples 1 to 3, but did not reach the passing value in the test pieces of Comparative Examples. rice field. The iodinepropynylbutylcarbamate originally used in the comparative example is an agent widely used as an antifungal agent and an antibacterial agent, and is rarely used as an antiviral agent, so that it is a reasonable result. Seem.
［耐湿性試験］
ここでは、抗菌／抗ウイルス試験で良好な結果が得られた実験例２及び３の試験片を用いて、抗菌／抗ウイルス性がどの程度の時間にわたって維持できるかを調べるため、耐湿試験を行った。なお、耐湿試験は、実験例２と実験例３の試験片を用い、それぞれの試験片を５０℃×９８％ＲＨの条件下に１００時間暴露を行い、上記と同様にしてネコカリシウイルスに対する抗ウイルス活性値（Ｒ）を測定した。結果を纏めて表２に示した。
[Moisture resistance test]
Here, a moisture resistance test is performed to investigate how long the antibacterial / antiviral property can be maintained by using the test pieces of Experimental Examples 2 and 3 in which good results were obtained in the antibacterial / antiviral test. rice field. In the moisture resistance test, the test pieces of Experimental Example 2 and Experimental Example 3 were used, and each test piece was exposed under the condition of 50 ° C. × 98% RH for 100 hours, and the resistance against feline calicivirus was carried out in the same manner as above. The virus activity value (R) was measured. The results are summarized in Table 2.
表２に示した結果によれば、実験例２の試験片では暴露試験後の抗ウイルス活性値（Ｒ
）が「２」以下となっており、合格値よりも低くなっている。それに対し、実験例３の試験片では暴露試験後でも高い抗ウイルス活性値（Ｒ）を維持していた。実験例２の試験片と実験例３の試験片との構成の差異は、抗菌／抗ウイルス性塗膜中に第４アンモニウム塩／ナノシリカ複合体として添加されている抗菌／抗ウイルス剤を含まない（実験例２）か、あるいは含む（実験例３）かであるから、抗菌／抗ウイルス剤としての第４アンモニウム塩を第４アンモニウム塩／ナノシリカ複合体の形で添加する方が、第４アンモニウム塩がナノシリカに担持された形となり、持続耐久性に優れるようになることが分かる。
According to the results shown in Table 2, the test piece of Experimental Example 2 has an antiviral activity value (R) after the exposure test.
) Is "2" or less, which is lower than the passing value. On the other hand, the test piece of Experimental Example 3 maintained a high antiviral activity value (R) even after the exposure test. The difference in composition between the test piece of Experimental Example 2 and the test piece of Experimental Example 3 does not include the antibacterial / antiviral agent added as the quaternary ammonium salt / nanosilica complex in the antibacterial / antiviral coating film. (experimental example 2) or, alternatively because it (experimental example 3) or, better to add a quaternary ammonium salt as an antimicrobial / antiviral agent in the form of quaternary ammonium salt / nanosilica complexes, quaternary ammonium It can be seen that the salt is supported on nanosilica and has excellent long-lasting durability.
Claims (5)
前記第４アンモニウム塩含有量は、前記シリコーンアルコキシオリゴマーを含む塗料固形分１００質量部に対して２〜１０質量部であることを特徴とする抗菌／抗ウイルス塗料。 An antibacterial / antiviral paint containing a quaternary ammonium salt as an antibacterial / antiviral component using a moisture-curable one-component silicone alkoxy oligomer as a binder.
The quaternary ammonium salt content is 2 to 10 parts by mass with respect to 100 parts by mass of the paint solid content containing the silicone alkoxy oligomer.
４，４'−（テトラメチレンジカルボニルジアミノ）ビス（１−デシルピリジニウムブロマイド）、
Ｎ，Ｎ'−ヘキサメチレンビス（４−カルバモイル−１−デシルピリジニウムブロマイド、
１，４−ビス［３，３'−（１−デシルピリジニウム）メチルオキシ］ブタンジブロマイド,
から選択された少なくとも１種のビス型構造のものであることを特徴とする、請求項１に記載の抗菌／抗ウイルス塗料。 The quaternary ammonium salt is
4,4'-(tetramethylenedicarbonyldiamino) bis (1-decylpyridinium bromide),
N, N'-hexamethylenebis (4-carbamoyl-1-decylpyridinium bromide,
1,4-Bis [3,3'-(1-decylpyridinium) methyloxy] butane dibromide,
The antibacterial / antiviral paint according to claim 1, wherein the paint has at least one screw-type structure selected from the above.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49115136A (en) * | 1973-02-20 | 1974-11-02 | ||
| JPH1095773A (en) * | 1996-09-19 | 1998-04-14 | Inui Kk | Bisquaternary ammonium salt compound having antimicrobial activity and its production |
| JP2003277686A (en) * | 2002-03-27 | 2003-10-02 | Osaka Gas Co Ltd | Sustained release antibacterial coating material composition |
| JP2006022217A (en) * | 2004-07-08 | 2006-01-26 | Hiroki Koma | Antibacterial or mildew-proofing resin composition |
| JP2010031135A (en) * | 2008-07-29 | 2010-02-12 | Sogo Giken:Kk | Abrasion-proof wear-resistant cohesive coating member, method for producing the same, and abrasion-proof wear-resistant cohesive product |
| WO2018042804A1 (en) * | 2016-08-29 | 2018-03-08 | 信越化学工業株式会社 | Photocatalyst laminate |
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2020
- 2020-06-15 JP JP2020103414A patent/JP6792896B1/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49115136A (en) * | 1973-02-20 | 1974-11-02 | ||
| JPH1095773A (en) * | 1996-09-19 | 1998-04-14 | Inui Kk | Bisquaternary ammonium salt compound having antimicrobial activity and its production |
| JP2003277686A (en) * | 2002-03-27 | 2003-10-02 | Osaka Gas Co Ltd | Sustained release antibacterial coating material composition |
| JP2006022217A (en) * | 2004-07-08 | 2006-01-26 | Hiroki Koma | Antibacterial or mildew-proofing resin composition |
| JP2010031135A (en) * | 2008-07-29 | 2010-02-12 | Sogo Giken:Kk | Abrasion-proof wear-resistant cohesive coating member, method for producing the same, and abrasion-proof wear-resistant cohesive product |
| WO2018042804A1 (en) * | 2016-08-29 | 2018-03-08 | 信越化学工業株式会社 | Photocatalyst laminate |
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