JP2004346202A - Aqueous coating composition, antibacterial member and method for forming coating film - Google Patents
Aqueous coating composition, antibacterial member and method for forming coating film Download PDFInfo
- Publication number
- JP2004346202A JP2004346202A JP2003145022A JP2003145022A JP2004346202A JP 2004346202 A JP2004346202 A JP 2004346202A JP 2003145022 A JP2003145022 A JP 2003145022A JP 2003145022 A JP2003145022 A JP 2003145022A JP 2004346202 A JP2004346202 A JP 2004346202A
- Authority
- JP
- Japan
- Prior art keywords
- component
- coating composition
- antibacterial
- weight
- coating film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 115
- 239000011248 coating agent Substances 0.000 title claims abstract description 104
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 96
- 239000008199 coating composition Substances 0.000 title claims abstract description 75
- 238000000034 method Methods 0.000 title claims description 13
- 239000002245 particle Substances 0.000 claims abstract description 97
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 93
- 239000000049 pigment Substances 0.000 claims abstract description 53
- 239000007787 solid Substances 0.000 claims abstract description 43
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000178 monomer Substances 0.000 claims abstract description 26
- -1 alkyl methacrylate Chemical compound 0.000 claims abstract description 25
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 14
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 14
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- 239000011941 photocatalyst Substances 0.000 claims description 26
- 239000010419 fine particle Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000011347 resin Substances 0.000 claims description 17
- 239000000758 substrate Substances 0.000 claims description 17
- 239000004599 antimicrobial Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000004568 cement Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 2
- 210000003298 dental enamel Anatomy 0.000 claims description 2
- 239000010440 gypsum Substances 0.000 claims description 2
- 229910052602 gypsum Inorganic materials 0.000 claims description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 238000010297 mechanical methods and process Methods 0.000 claims 1
- 230000005226 mechanical processes and functions Effects 0.000 claims 1
- 229910052573 porcelain Inorganic materials 0.000 claims 1
- 239000003242 anti bacterial agent Substances 0.000 abstract description 40
- 238000002845 discoloration Methods 0.000 abstract description 20
- 238000004040 coloring Methods 0.000 abstract description 15
- 238000013461 design Methods 0.000 abstract description 4
- 125000005250 alkyl acrylate group Chemical group 0.000 abstract 1
- 239000004615 ingredient Substances 0.000 abstract 1
- 230000007774 longterm Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 72
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 27
- 239000008119 colloidal silica Substances 0.000 description 27
- 239000003973 paint Substances 0.000 description 27
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 23
- 239000004606 Fillers/Extenders Substances 0.000 description 22
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 18
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 15
- 229910052709 silver Inorganic materials 0.000 description 15
- 239000004332 silver Substances 0.000 description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229910052623 talc Inorganic materials 0.000 description 11
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
- 229910021536 Zeolite Inorganic materials 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000011282 treatment Methods 0.000 description 8
- 239000010457 zeolite Substances 0.000 description 8
- 239000002585 base Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 239000002344 surface layer Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000002296 dynamic light scattering Methods 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000845 anti-microbial effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical group CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 239000011211 glass fiber reinforced concrete Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000000682 scanning probe acoustic microscopy Methods 0.000 description 2
- 229920002050 silicone resin Polymers 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 235000014692 zinc oxide Nutrition 0.000 description 2
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000035473 Communicable disease Diseases 0.000 description 1
- 241001448862 Croton Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 1
- 206010016952 Food poisoning Diseases 0.000 description 1
- 208000019331 Foodborne disease Diseases 0.000 description 1
- 101000610557 Homo sapiens U4/U6 small nuclear ribonucleoprotein Prp31 Proteins 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- RJQXTJLFIWVMTO-TYNCELHUSA-N Methicillin Chemical compound COC1=CC=CC(OC)=C1C(=O)N[C@@H]1C(=O)N2[C@@H](C(O)=O)C(C)(C)S[C@@H]21 RJQXTJLFIWVMTO-TYNCELHUSA-N 0.000 description 1
- 206010029803 Nosocomial infection Diseases 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 101001109965 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L7-A Proteins 0.000 description 1
- 101001109960 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) 60S ribosomal protein L7-B Proteins 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 241000295644 Staphylococcaceae Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 102100040118 U4/U6 small nuclear ribonucleoprotein Prp31 Human genes 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 108010059993 Vancomycin Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 239000007798 antifreeze agent Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000011381 foam concrete 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000002054 inoculum Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- GWVMLCQWXVFZCN-UHFFFAOYSA-N isoindoline Chemical compound C1=CC=C2CNCC2=C1 GWVMLCQWXVFZCN-UHFFFAOYSA-N 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229960003085 meticillin Drugs 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007591 painting process Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000045 pyrolysis gas chromatography Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 238000001004 secondary ion mass spectrometry Methods 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 208000015891 sexual disease Diseases 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 239000010454 slate Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
- MYPYJXKWCTUITO-LYRMYLQWSA-N vancomycin Chemical compound O([C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=C2C=C3C=C1OC1=CC=C(C=C1Cl)[C@@H](O)[C@H](C(N[C@@H](CC(N)=O)C(=O)N[C@H]3C(=O)N[C@H]1C(=O)N[C@H](C(N[C@@H](C3=CC(O)=CC(O)=C3C=3C(O)=CC=C1C=3)C(O)=O)=O)[C@H](O)C1=CC=C(C(=C1)Cl)O2)=O)NC(=O)[C@@H](CC(C)C)NC)[C@H]1C[C@](C)(N)[C@H](O)[C@H](C)O1 MYPYJXKWCTUITO-LYRMYLQWSA-N 0.000 description 1
- 229960003165 vancomycin Drugs 0.000 description 1
- MYPYJXKWCTUITO-UHFFFAOYSA-N vancomycin Natural products O1C(C(=C2)Cl)=CC=C2C(O)C(C(NC(C2=CC(O)=CC(O)=C2C=2C(O)=CC=C3C=2)C(O)=O)=O)NC(=O)C3NC(=O)C2NC(=O)C(CC(N)=O)NC(=O)C(NC(=O)C(CC(C)C)NC)C(O)C(C=C3Cl)=CC=C3OC3=CC2=CC1=C3OC1OC(CO)C(O)C(O)C1OC1CC(C)(N)C(O)C(C)O1 MYPYJXKWCTUITO-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
- 229940043810 zinc pyrithione Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- PICXIOQBANWBIZ-UHFFFAOYSA-N zinc;1-oxidopyridine-2-thione Chemical compound [Zn+2].[O-]N1C=CC=CC1=S.[O-]N1C=CC=CC1=S PICXIOQBANWBIZ-UHFFFAOYSA-N 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Landscapes
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、水性塗料組成物に関わるものであり、詳しくは優れた抗菌作用が長期に渡り効果的に発現し、さらに湿度や光に対する優れた耐変退色性と耐候性を併せ持つ水性塗料組成物、該組成物により形成した塗膜で一部または全体が覆われた被覆物、および、該被覆物の形成方法に関するものである。
【０００２】
【従来の技術】
近年、構造物や建造物の表面を被覆する塗膜には、基材を外気から遮断し保護する目的や着色等により基材が本来持つものとは異なる意匠を付与する目的以外に、さまざまな機能を付与することが提案され、実用化されている。戸建・集合住宅の屋内環境では、省エネルギー対応の観点から内空間の気密性が大きく向上し、その結果、熱・湿気の逃げ場が無く、細菌などの微生物が繁殖しやすい環境になりやすく、アレルギー性疾患や感染症の遠因となっている。病院ではメチシリン耐性ブドウ球菌やバンコマイシン耐性腸球菌などの耐性菌が猛威を振るい院内感染が問題視されるようになってきた。学校や老健施設の給食施設、食品工場などでも、黄色ブドウ球菌や大腸菌などに起因した食中毒が毎年発生しており、一向に減少する傾向にない。構造物や建造物の内装空間における微生物に対する安全性は年々重要になっている。
【０００３】
抗菌性を発現する水性塗料組成物に関する従来技術としては、以下のものが挙げられる。
▲１▼ 微生物繁殖に効果がある有機薬剤類を配合した塗料
▲２▼ 銀イオン担持ゼオライトを配合した塗料
▲３▼ 銀イオン担持無機系抗菌剤と変色防止剤を配合した塗料
▲４▼ 銀イオン担持光触媒と結晶性層状リン酸化合物を配合した塗料
▲５▼ 樹脂成分と水性コロイダルシリカと抗菌剤を配合した塗料
【０００４】
従来技術▲１▼に関しては、有機薬剤としてフェノール系薬剤、ブロム系薬剤、ヨウド系薬剤などを含有した塗料があるが、塗膜形成後、これら有機薬剤が溶出しつつ抗菌性が発揮されるため、その持続性に課題がある。
【０００５】
従来技術▲２▼に関しては、銀イオン担持ゼオライトを配合した塗料が開示されている（例えば、特許文献１参照）。特許文献１では１μｍ程度のゼオライトを用いており、ゼオライトは塗膜中に均一に分散していると考えられる。また、ゼオライトの添加量も塗料中に１〜５％とやや多めであり、塗膜が変色する可能性が考えられる。また、銀イオン担持ゼオライトを外気と接する状態に露出させるために、ポーラスな塗膜構造となり、そこに汚れが充填され取れなくなったり、清掃時に抗菌性を発揮する成分が溶出する可能性が考えられる。
【０００６】
従来技術▲３▼に関しては、銀イオン担持無機系抗菌剤と変色防止剤を配合した塗料が開示されている（例えば、特許文献２参照）。この場合も、変色は抑制されているものの、無機系抗菌剤の添加量は比較的多く、また有機系の変色防止剤の添加は室内用塗料としては好ましくない。
【０００７】
従来技術▲４▼に関しては、従来技術▲２▼と同様の理由で、抗菌性能が劣化する。また、塗膜中での抗菌剤である銀担持酸化チタンの分散、分布状態に別段工夫がなされていないため、酸化チタンの光触媒反応によって、徐々に有機樹脂が分解されることによる塗膜自体の劣化も危惧される。
【０００８】
従来技術▲５▼に関しては、エチレン性不飽和モノマーとメルカプト基および親水性極性基含有ウレタンプレポリマーとをラジカル重合によって結合した自己乳化性共重合体を含有する樹脂成分及び水性コロイダルシリカからなる水性無機塗料に抗菌剤を添加した塗料が開示されている（例えば、特許文献３参照）。特許文献３に記載されている塗料はアクリル−ウレタンの共重合体であり、コロイダルシリカを多く含有するものである。このような塗料では、塗膜の組成は傾斜しておらず均一である。従って抗菌性を得るために、多量の抗菌剤を添加する必要があり、塗膜の変色などの課題がある。
【０００９】
【特許文献１】特開昭６０−２０２１６２号公報
【特許文献２】特開平６−１４９７９号公報
【特許文献３】特開２００１−４０２７２号公報
【００１０】
【発明が解決しようとする課題】
本発明は従来技術における課題を解決するためになされたもので、その課題は、所望の抗菌活性をより少ない抗菌剤添加量で長期に渡って発現し、耐変色性および耐候性に優れる塗膜を一回の塗布にて形成でき、さらに着色顔料などにより基材が本来持つ意匠とは異なる意匠を付与できる水性塗料組成物、および抗菌部材を提供することである。
【００１１】
【課題を解決するための手段】
本発明では、上記課題を解決すべく、（ａ）アクリル系樹脂エマルジョンと、（ｂ）シリカ微粒子と、（ｃ）抗菌剤粒子と、（ｄ）水と、（ｅ）顔料と、を少なくとも含んだ水性塗料組成物であって、前記（ａ）成分中に分散してエマルジョン粒子はＣ２からＣ７のアルキルアクリレート、Ｃ２からＣ７のアルキルメタクリレートから選択される少なくとも１種類以上のモノマーを重合させたものであり、（ｂ）成分の平均粒子径が５０ｎｍ以下であり、（ｃ）成分の平均粒子径が５０ｎｍ以下であり、さらに（ｂ）成分が全固形分の１０〜７０重量％であることを特徴とする水性塗料組成物を提供する。
【００１２】
（ｂ）成分の平均粒子径は、３０ｎｍ以下であれば更に好ましい。
【００１３】
（ｃ）成分の平均粒子径は、４０ｎｍ以下であれば更に好ましい。
【００１４】
また、前記水性塗料組成物を基材上に塗布し、乾燥して形成した塗膜で被覆された部材であって、（ｂ）成分および（ｃ）成分が外気に接する塗膜表面近傍に多く分布するように濃度勾配を有する塗膜で被覆された抗菌性部材を提供する。
【００１５】
本発明に係る水性塗料組成物を基材に塗布して得られた塗膜構造を図１に模式的に示す。本発明では、（ａ）成分のモノマー組成と、（ｂ）、（ｃ）各成分の粒子径を最適化することで、前記水性塗料組成物を塗布した後の乾燥過程で（ｂ）成分、および（ｃ）成分が塗膜の表面側で多くなるような濃度勾配が達成される。
【００１６】
（ｃ）成分が外気に接する塗膜表面近傍に多く分布するように濃度勾配を有するため、塗料構成材料が均一に分布した塗膜に比べて、所望の抗菌性能をより少ない抗菌剤配合量で得ることができる。その結果、銀などの抗菌金属に起因した変色も抑制できる。
【００１７】
逆に、基材と密着する下層部分には（ａ）成分が多く分布するように濃度勾配を有するため、密着性に優れた塗膜を形成できる。
【００１８】
このような傾斜組成を達成するのに、２液を用いることなく１液で施工できるため、塗装工程は簡便である。
【００１９】
また、（ｃ）成分とともに（ｂ）成分も同様に分布するため、（ｃ）成分が抗菌金属担持光触媒の場合でも、樹脂との直接的な接触を防ぎ、樹脂が光触媒によって酸化分解されること無く、優れた耐候性を有する抗菌性塗膜を得ることができる。さらに、（ｂ）成分や（ｃ）成分のような無機微粒子材料が塗膜表面近傍に多く分布するように濃度勾配を有するため、親水撥油性が発揮され、水中でのオレイン酸の接触角は６０°を大きく上回り、組成によっては１００°を上回る。このような親水撥油表面は油汚れが落としやすい易洗浄性表面になる。また、基材の種類に依らず、帯電半減期は５０秒以下に短くすることができ、その結果、抗菌性を効果的に発現するだけでなく、ホコリが付着しにくく、油汚れが落としやすい表面を持つ部材を提供することが可能となる。
【００２０】
本発明の塗料から得られる塗膜は、（ｃ）成分が塗膜表層に多く分布するように濃度勾配を有するため、（ｃ）成分の添加量が少なくても、充分な抗菌性を発揮する。具体的には、大腸菌を用いたＪＩＳ Ｚ ２８０１記載の試験で接触時間３時間後に生菌数が０となる。また、銀による着色も小さい。具体的には、相対湿度１００％、紫外線強度１ｍＷ／ｃｍ２ の環境下に１ヶ月放置しても変色色差は２に達することはない。
【００２１】
本発明において、（ｂ）成分の固形分量が全固形分の１０〜７０重量％である。このような水性塗料組成物を塗布して形成した塗膜では、外気に接する塗膜表層が、親水性を示す（ｂ）成分でほぼ覆われ、簡単な拭き掃除で抗菌性発現を妨害する汚れの蓄積を防ぐことができる。
【００２２】
本発明の好ましい態様においては、（ａ）成分の固形分量が全固形分の１０重量％以上である。（ａ）成分の固形分量が全固形分の１０重量％以上であれば、水性エマルジョン中の樹脂の硬化により、基材もしくは下塗り材との密着性が得られ、耐久性に優れた塗膜を得ることができる。より好ましい（ａ）成分の固形分量は全固形分の２０重量％以上である。
【００２３】
本発明の好ましい態様においては、（ｃ）成分が抗菌金属担持光触媒である。光の当たる場所では、担持した抗菌金属の作用と、担体の光触媒作用が相乗的に作用して、優れた抗菌性を持続的に発揮することが可能となる。
【００２４】
本発明の好ましい態様においては、（ｃ）成分が抗菌金属担持光触媒であって、その固形分が（ｂ）成分に対して、１〜５０重量％であるようにする。この範囲であれば、塗膜を形成したときに（ｂ）成分、（ｃ）成分が塗膜表面近傍に多くなるような濃度勾配を持たせることができ、（ｃ）成分による抗菌性が充分得られ、かつ（ｃ）成分と（ａ）成分の直接の接触を防ぐため、光触媒機能を有するにもかかわらず、十分な耐候性が得られるのである。
【００２５】
本発明の好ましい態様においては、（ｃ）成分の抗菌金属担持光触媒に用いる抗菌金属が、銀、銅のいずれかを１種類以上含む。これらの金属類は優れた抗菌性を発揮すると共に、光触媒に担持することで抗菌性能の持続性、光触媒機能の向上に寄与する。
【００２６】
本発明の好ましい態様においては、（ｃ）成分が抗菌金属担持光触媒であって、抗菌金属の光触媒に対する担持率が０．１〜１０重量％であるようにする。塗膜表面近傍に抗菌剤成分が多くなるように濃度勾配を持たせることで、塗膜の変色を抑制しつつ所望の抗菌性を発揮できる。
【００２７】
本発明の好ましい態様においては、（ｅ）成分の平均粒径が１００ｎｍ以上になるようにする。その結果、（ｅ）成分は塗膜と基材との界面側に多く分布するように濃度勾配を有するため、密着性の向上に貢献する。
【００２８】
本発明の好ましい態様においては、（ｂ）成分と（ｃ）成分の固形分の合計の（ｅ）成分の固形分に対する比率が０．４以上であるようにする。さらに好ましくは０．６以上であるようにする。そうすることで、表面への（ｅ）成分の露出を抑制でき、（ｂ）成分と（ｃ）成分を効率よく塗膜表面に多く存在するようにさせることができる。
【００２９】
本発明の好ましい態様においては、水性塗料組成物の固形分濃度が２０重量％以上であるようにする。さらに好ましくは３５重量％以上になるようにする。そうすることで、通常の建築物の塗装工程である、下塗り１回、上塗り２回の作業で、膜厚１μｍ〜２００μｍで十分な隠蔽性を有する塗膜を得ることができる。
【００３０】
【発明の実施の形態】以下に本発明に基づき、実施の形態を説明する。
まず、以下に本発明で用いる語について説明する。
【００３１】
本発明において、（ａ）成分の「アクリル系樹脂エマルジョン」は、ビニル系単量体としてアルキル（メタ）アクリレート類を主成分とするビニル共重合体であり、さらに、ビニル系単量体としてクロトン酸アルキル類、不飽和二塩基酸ジアルキル類、モノカルボン酸ビニルエステル類もしくは芳香族ビニル系単量体類のような、各種の非官能性の単量体類、３級アミノ基、酸基、中和された酸基、アミド基、シアノ基、水酸基、エポキシ基、加水分解性シリル基の如き官能基を有する各種のビニル系単量体、さらに１分子あたり２個以上の重合性二重結合を有する多官能のビニル系単量体類を使用することができる。エマルジョンの平均粒子径は１４０ｎｍ以上が好ましく、１４５ｎｍ以上がさらに好ましい．
【００３２】
更に、上記アクリル系樹脂エマルジョンに架橋剤を加えた、架橋性タイプのもの、自己架橋タイプのものや、非架橋性タイプのもの等の各種乾燥（硬化）タイプのもの、一つのエマルジョン粒子中にシェル部と芯部からなるコアシェルタイプのもの、多段乳化重合法によりエマルジョン芯部より殻部へ段階的にモノマー組成を変えたタイプを利用することができる。
【００３３】
本発明において（ｂ）成分の「シリカ微粒子」には、粒子径が５０ｎｍ以下であれば、ガラス状シリカ、石英、無定型シリカ、シリカゲル、シリカ粉末、シリカゾルや、シリカ表面をアルミ等で被覆した各種被覆シリカ微粒子、及び樹脂粒子や金属酸化物ゾル等の表面をシリカで被覆したシリカ被覆微粒子、球状シリカ微粒子、棒状シリカ微粒子、球状シリカが連結したネックレス状シリカ微粒子、等が利用できる。また、粒子径が前記範囲よりも大きい場合は、粉砕等の工程によって微細化した後に利用することもできる。これらの材料は、日産化学工業（株）製のスノーテックスのような市販品を用いても良いし、ゾルゲル法に代表される各種合成方法に従って調製した物を用いることもできる。
【００３４】
本発明において（ｃ）成分の「抗菌剤粒子」には、抗菌金属担持ゼオライト、抗菌金属担持アパタイトなど平均粒子径が５０ｎｍ以下であり、前記アクリル系樹脂エマルジョンやシリカ微粒子と混合して、分散性が悪化しない抗菌剤であれば、任意に利用できる。各種合成法に従い調製した材料以外に市販品を利用することもできる。例えば、アルミナシリカに銀を担持した触媒化成工業（株）製のアトミーボールＵＡなどがこれに該当する。なお、抗菌金属とは、銀、銅のように、イオンや酸化物の状態で抗菌性を発揮し得る金属種のことを示す。
【００３５】
本発明において（ｃ）成分として抗菌金属担持光触媒粒子を利用することができる。抗菌金属は単独あるいは２種類以上を組み合わせて利用することができる。
【００３６】
抗菌金属担持光触媒は触媒化成工業（株）製のアトミーボールＬのような、平均粒子径５０ｎｍ以下の市販商品を用いることができるし、ゾルゲル法に代表される各種合成方法に従って調製したものを用いることもできる。
【００３７】
前記光触媒には、アナターゼ型酸化チタン、ルチル型酸化チタン、ブルッカイト型酸化チタン、チタン酸ストロンチウム、酸化タンタル、酸化ニオブ、酸化スズ、酸化亜鉛から選ばれる少なくとも一種を利用することができる。特に光触媒活性が高いアナターゼ型酸化チタンが好ましい。酸化チタンは石原産業（株）、昭和電工（株）、多木化学（株）の製品などの市販品を用いることができるし、調製した物を用いることもできる。近年、可視光に応答する酸化チタン光触媒が、住友化学（株）、豊田中央研究所（株）、エコデバイス（株）、昭和電工（株）、石原産業（株）などより発表されているが、これらの材料も平均粒子径を５０ｎｍ以下に微細化できれば、利用可能である。このような光触媒材料への抗菌金属の担持には光触媒活性を利用した光還元電着法、含浸法などを利用することができる。
【００３８】
本発明の水性塗料組成物においては、シリカ微粒子と併用することのできる（ｅ）成分「顔料」として、水性エマルジョン塗料に一般的に用いられている無機着色顔料、有機着色顔料、無機体質顔料が利用できる。無機着色顔料としては、酸化チタン白、チタンイエロー、スピネルグリーン、亜鉛華、ベンガラ、酸化クロム、コバルトブルー、鉄黒などの金属酸化物系、アルミナホワイト、黄色酸化鉄などの金属水酸化物系、紺青などのフェロシアン化合物系、黄鉛、ジンクロメート、モリブデンレッドなどのクロム酸鉛系、硫化亜鉛、朱、カドミウムイエロー、カドミウムレッドなどの硫化物、セレン化合物系、バライト、沈降性硫酸バリウムなどの硫酸塩系、重質炭酸カルシウム、沈降性炭酸カルシウムなどの炭酸塩系、含水珪酸塩、クレー、群青などの珪酸塩系、カーボンブラックなどの炭素系、アルミニウム粉、ブロンズ粉、亜鉛粉末などの金属粉系、雲母・酸化チタン系などのパール顔料系などが挙げられる。また、有機顔料としてはアントラキノン系、キナクドリン系、ペリレン系、イソインドリン系等のキノン系顔料、アゾ顔料、フタロシアニン顔料などが挙げられる。また、無機体質顔料としては、酸化チタンウィスカー、炭酸カルシウムウィスカー、チタン酸カリウムウィスカー、ホウ酸アルミニウムウィスカー、マイカ、タルク、硫酸バリウム、炭酸カリウム、珪砂、珪藻土、カオリン、クレー、セピオライト、陶土、炭酸バリウム等が好適である。これらの顔料はそれぞれ単独で使用しても、或いは２種以上を併用してもよく、例えば各種着色顔料及び／又は各種体質顔料とを併用することも可能である。
【００３９】
水性塗料組成物中でのこれらの顔料の配合量については、（ｂ）成分「シリカ粒子」、（ｃ）成分「抗菌剤粒子」、（ｅ）成分「顔料」を合わせたＰＷＣが３０〜９０、好ましくは４０〜８０となるように配合することが好ましい。
【００４０】
ここで、ＰＷＣとはＰｉｇｍｅｎｔ Ｗｅｉｇｈｔ Ｃｏｎｃｅｎｔｒａｔｉｏｎ （顔料重量濃度）のことであり、下記の式により算出される。
ＰＷＣ＝［（含有顔料重量％）／（全塗料固形分重量％）］×１００
ＰＷＣが３０未満である場合には、抗菌性が十分に発揮されず、汚れの清掃性も悪化する。逆に９０を越えると成膜性が低下し、塗膜に割れ、剥離等が発生する傾向があるので好ましくない。
【００４１】
本発明の水性塗料組成物において、（ｂ）成分「シリカ微粒子」と（ｃ）成分「抗菌剤粒子」の合計配合量はその他の顔料との合計配合量の１０〜８５重量％を占めることが好ましい。配合量が合計配合量の１０重量％未満である場合には耐候性や抗菌性が十分には発揮されない。逆に配合量が合計配合量の８５重量％を越える場合には成膜性が低下し、塗膜に割れ、剥離等が発生する傾向があるので好ましくない。
【００４２】
本発明の水性塗料組成物には一般に防かび剤などに用いられる有機薬剤、たとえばジンクピリチオンやイミダゾール系薬剤、チアゾールやイソチアゾール系薬剤を添加しても良い。
【００４３】
本発明の水性塗料組成物は、以上に説明したアクリル系樹脂エマルジョン、シリカ微粒子、抗菌剤粒子、水、及び顔料を必須成分として含有し、その上に、必要に応じて、メタノール、エタノール、メチルセロソルブ、エチレングリコール等の各種親水性有機溶剤、中和剤、増粘剤、分散剤、消泡剤、造膜助剤、防腐剤、凍結防止剤、造膜助剤、紫外線吸収剤等の各種添加剤を含有することもできる。しかし、塗料に関しては、近年、作業環境、周辺への影響、臭いなどの観点から、溶剤系塗料よりも水系塗料（水性塗料）を用いる傾向が高まりつつある。つまり、造膜助剤などの溶剤、特に揮発性有機溶剤を含有しないことが好ましい。
【００４４】
本発明の水性塗料組成物の混合、分散処理には、サンドミル、ホモジナイザー、ボールミル、ロールミル、ペイントシェーカー、超音波分散機、羽根式攪拌機、マグネチックスターラー、高速分散機、乳化機、自転公転プロペラレス混和機などを用いることができる。
【００４５】
本発明の塗料組成物で被覆可能な基材としては、金属、プラスチック、ガラス、タイル、ホーロー、陶磁器、木材、セメント、目地、コンクリート、窯業系無機質板、石膏ボード、または、それらの複合体、それらの積層体、それらの塗装体、それらの表面に有機または無機の皮膜やフィルムを有するもの等である。窯業系無機質板とは、繊維強化セメント板、珪酸カルシウム板、スレート板、パーライトセメント板、軽量起泡コンクリート（ＡＬＣ）、ガラス繊維強化コンクリート（ＧＲＣ）、窯業系サイディング等の基材であり、特に限定されない。プラスチック基材とは、繊維強化プラスチック、アクリル樹脂、ポリカーボネート樹脂、ポリエチレンテレフタレート（ＰＥＴ）樹脂、ポリブチレンテレフタレート（ＰＢＴ）樹脂、ポリプロピレン（ＰＰ）、アクリルブタジレンスチレン共重合体樹脂（ＡＢＳ）樹脂、塩化ビニル樹脂、エポキシ樹脂、フェノール樹脂等の成形体およびフィルム状にしたものが挙げられ、特に限定されない。塗装体に関しては、有機被膜としては、エポキシ樹脂、フェノール樹脂、不飽和ポリエステル樹脂、ユリア樹脂、フッ素樹脂、シリコーン樹脂、アクリルシリコーン樹脂、メタクリレート樹脂、ポリウレタン樹脂、メラミン樹脂等の被膜が挙げられ、無機被膜としては、アルカリシリケート系、りん酸系、ほう酸系等の被膜が挙げられるが、特に限定されない。
【００４６】
本発明の塗料組成物を塗布する前に、適宜、各種基材に適した下塗り材を塗装することも可能である。塗膜に接して下塗り材によって形成されるアンダーコート層としては、ウレタン樹脂、アクリル樹脂、アクリルウレタン樹脂、アクリルシリコン樹脂、エポキシ樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、フタル酸樹脂、アルキド樹脂、シリコンアルキド樹脂などの有機樹脂系塗膜に加えて無機系塗膜なども用いることができる。
【００４７】
本発明の塗料組成物は抗菌性が期待される物品に適用される。このような物品としては、建築物や構造物や車輌の外装や内装などが挙げられ、より具体的には、屋根材、瓦、カラートタン、カラー鉄板、窯業系建材、サイディング材、セメント壁、アルミサイディング、カーテンウォール、塗装鋼板、石材、ＡＬＣ、タイル、ガラスブロック、サッシ、ビルサッシ、網戸、雨戸、門扉、窓枠、ベランダ、ベランダ手すり、屋根樋、エアコン室外機、店舗看板、サイン、広告塔、冷蔵・冷凍ショーケース、シャッター、屋外ベンチ、自動販売機、プラント外壁、プラント内壁、石油貯蔵タンク、テント、キッチン設備部材、浴室設備部材、陶磁器、浴槽、洗面台、台所用品、食器乾燥器、流し、キッチンフード、換気扇、などが挙げられる。
【００４８】
本発明による抗菌性部材は、基材の表面に本発明の塗料組成物が塗布され、その後乾燥または硬化されて塗膜を形成されたものである。
【００４９】
ここで塗料組成物を塗布する手段はとくに限定されず、刷毛塗り、スポンジ塗り、ロールコーティング、フローコーティング、スピンコーティング、ディップコーティングなどの方法が挙げられる。
【００５０】
ここで塗膜の乾燥または硬化は、１〜８０℃までの常温乾燥、強制乾燥、加熱、紫外線照射等によって実施することができる。
【００５１】
また、本発明の塗料組成物が適用される基材表面は清浄であることが好ましい。特に建築物の内壁や外壁等、既設の基材に塗布する場合には、予め洗浄剤の使用など、公知の方法にて洗浄することが望ましい。
【００５２】
各種エマルジョンを構成するモノマーの組成は、熱分解ＧＣ／ＭＳを用いて分析評価できる。
【００５３】
平均粒子径とは、ＭＡＬＶＥＲＮ社のＺＥＴＡＳＩＺＥＲ ３０００ＨＳ を用いて光子相関分光法（ＰＣＳ）により測定した体積平均粒子径である。
【００５４】
塗膜の基材密着部分から外気に接する表層部分までの構造・組成解析は、走査型電子顕微鏡、透過型電子顕微鏡による直接観察、塗膜断面のエネルギー拡散Ｘ線（ＥＤＸ）分析あるいはＸ線マイクロアナリシス（ＥＰＭＡ）分析、または表面からの深さ方向の組成分析として、オージェ電子分光法（ＡＥＳ）、Ｘ線光電子分光法（ＸＰＳ）、二次イオン質量分析法（ＳＩＭＳ）などの方法を利用することができる。また塗膜表面から機械的、多段階的に削り取った成分の組成分析、観察を行なっても良い。
【００５５】
本発明に係る水性塗料組成物は、５０ｎｍ以下の（ｂ）成分「シリカ微粒子」、（ｃ）成分「抗菌剤粒子」の小粒子径成分と、１００ｎｍよりも大きく、モノマーがＣ２からＣ７の（ａ）成分「アクリル系樹脂エマルジョン」、（ｅ）成分「顔料」の大粒子径成分と（ｄ）成分「水」で構成される。水分量はＴＧ−ＤＴＡ等の熱分析にて評価ができる。小粒径成分と大粒形成分は、孔径５０ｎｍから１００ｎｍのフィルターを用いて分離でき各種評価法を用いて定性、定量が可能である。例えば光子相関分光法などにより粒子径の情報が得られる。分離後の再分散が困難な場合は走査型電子顕微鏡や透過型電子顕微鏡のような直接観察によって用いた材料の粒子径評価を実施することもできる。蛍光Ｘ線分析などによれば組成の解析ができる。
【００５６】
本発明に係る抗菌金属担持光触媒の抗菌金属担持率は、担体である光触媒の量に対する抗菌金属の担持量の割合を示すものであって、分離した小粒径成分を乾燥させ、蛍光Ｘ線分析や酸やアルカリに溶解して原子吸光分析やＩＣＰ発光分析にて定量、評価できる。
【００５７】
塗膜の厚さは走査型電子顕微鏡による断面観察で測定できる。
【００５８】
帯電半減期は、気温２５℃、相対湿度２０％に調整された環境下で、シシド静電気（株）製ＳＴＡＴＩＣ ＨＯＮＥＳＴＭＥＴＥＲを用いて測定した。印加電圧１０ｋＶとし、塗膜表面が飽和帯電電位に達した後に、帯電電位がその１／２まで減衰するのに必要とした時間である。
【００５９】
紫外線強度はＭＩＮＯＬＴＡ（株）製紫外線強度計ＵＭ−１０（受光部ＵＭ−３６０）で計測した。
【００６０】
高湿度、紫外線照射環境下に放置した後の塗膜の変色色差は下記の式に従って算出する。
色差△Ｅ＊＝｛（Ｌ＊ １Ｌ＊ ０）２＋（ａ＊ １ａ＊ ０）２＋（ｂ＊ １ｂ＊ ０）２｝１／２
ここで、（Ｌ＊ ０，ａ＊ ０，ｂ＊ ０）： ＪＩＳ Ｚ ８７２９記載のＬ＊ａ＊ｂ＊表色系に基づく放置前のサンプル表面の色値、（Ｌ＊ １，ａ＊ １，ｂ＊ １）：放置後のサンプル表面の色値である。尚、色値測定はＭＩＮＯＬＴＡ（株）製分光測色計ＣＭ−３７００ｄにて測定した。
【００６１】
塗膜の抗菌性評価は、基本的にＪＩＳ Ｚ ２８０１に記載の方法に従って実施した。ただし、菌の塗装面への接触時間は、任意に変化させた。
【００６２】
＜銀担持酸化チタンの作製＞
表１に記載の条件に従って、酸化チタン分散液に硝酸銀を溶解し、紫外線照射を行なって酸化チタン表面に銀を光電着した。
【００６３】
【表１】
表２に用いた市販抗菌剤を記載する。
【００６５】
【表２】
表１および表２に記載の平均粒子径は、ＭＡＬＶＥＲＮ社のＺＥＴＡＳＩＺＥＲ３０００ＨＳ を用いて光子相関分光法（ＰＣＳ）により測定した体積平均粒子径である。
【００６７】
＜塗料組成物＞
実施例１
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）９重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）２９．９８重量部、表１記載の抗菌剤Ａ（銀担持酸化チタン：平均粒子径３５ｎｍ）０．２重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２９重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２０重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）８重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００６８】
実施例２
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）１０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＳ、平均粒子径５．４ｎｍ）２９．９５重量部、表２記載の抗菌剤Ｃ（Ａ社銀担持酸化チタン：平均粒子径３．５ｎｍ）０．０５重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２４重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２０重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）１０重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）６重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００６９】
実施例３
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）８重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）２９．６４重量部、表２記載の抗菌剤Ｄ（Ａ社銀担持酸化チタン：平均粒子径１３．８ｎｍ）０．０６重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２９重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）１９．６重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）９．６重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４．１重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００７０】
実施例４
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）１０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）２９．９６５重量部、表２記載の抗菌剤Ｅ（Ａ社銀担持酸化チタン：平均粒子径１５．８ｎｍ）０．０３５重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２３重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２４重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）９重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００７１】
実施例５
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）８．２重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）１０重量部、コロイダル（日産化学株式会社製、商品名スノーテックスＳ、平均粒子径５．４ｎｍ）２０重量部、表２記載の抗菌剤Ｇ（Ｃ社銀担持酸化チタン：平均粒子径３２．１ｎｍ）０．２重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２８重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２０．１重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）９．６重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４．１重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００７２】
実施例６
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＸＬ、平均粒子径５２．１ｎｍ）８重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）１０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＳ、平均粒子径５．４ｎｍ）２０重量部、表２記載の抗菌剤Ｈ（Ｃ社銅担持酸化チタン：平均粒子径３０．８ｎｍ）０．２重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２８重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２１．６重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）９．６重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４．１重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＣｕＯ量は１１．２５ｐｐｍであった。
【００７３】
比較例１
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）９重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）２９．９８重量部、表１記載の抗菌剤Ｂ（銀担持酸化チタン：平均粒子径１５３．６ｎｍ）０．２重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２９重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２０重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）８重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００７４】
比較例２
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）１０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）１０重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＳ、平均粒子径５．４ｎｍ）２０重量部、表２記載の抗菌剤Ｆ（銀担持ゼオライト：平均粒子径４５８．３ｎｍ）０．２重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２６重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２０．３重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）９．６重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４．１重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００７５】
比較例３
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）９重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０、平均粒子径１４．９ｎｍ）２９．９８重量部、表１記載の抗菌剤Ａ（銀担持酸化チタン：平均粒子径３５ｎｍ）０．２重量部、アクリル系エマルジョン（モノマー：アクリル酸２エチルヘキシル、メタクリル酸オクチル平均粒子径１３０ｎｍ）２９重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）２０重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）８重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。本塗料組成物中のＡｇ２Ｏ量は１１．２５ｐｐｍであった。
【００７６】
比較例４
市販の抗菌塗料を比較例４とした。
【００７７】
参考例１
コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＺＬ、平均粒子径１２４．７ｎｍ）９．６重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックスＳ、平均粒子径５．４ｎｍ）３２．９重量部、アクリル系エマルジョン（モノマー：アクリル酸ブチル、メタクリル酸ブチル 平均粒子径１５０ｎｍ）２３．２重量部、着色顔料（大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５）１９．６重量部、体質顔料（日本タルク株式会社、商品名 Ｐ−３）１０．６重量部、体質顔料（大塚化学株式会社製、商品名 ＭＴＷ−５００）４．１重量部（以上固形分で表示）、の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１２７重量部であった。
【００７８】
＜基材への塗布方法＞
５０ｍｍ×５０ｍｍに裁断したポリカーボネイト板（ＪＩＳ Ｋ ６７３５に準拠したもの）に微弾性下塗り剤（ジャパンハイドロテクトコーティングス、商品名ＲＰ１１）をローラー塗布し、室温で２４時間乾燥させた。
続いて、前記で調製した実施例１の塗料組成物をローラー塗りした。
実施例２〜６および、比較例１〜３、参考例１の塗料組成物についても、本塗布方法にしたがい塗布を行った。
最後に、上記被塗装物を室温で７日間乾燥させて試験片１から９を得た。
また市販の抗菌塗料（比較例４）についても同様に塗布し、試験片１０を得た。
【００７９】
試験片１： 実施例１に記載の塗料組成物を塗布
試験片２： 実施例２に記載の塗料組成物を塗布
試験片３： 実施例３に記載の塗料組成物を塗布
試験片４： 実施例４に記載の塗料組成物を塗布
試験片５： 実施例５に記載の塗料組成物を塗布
試験片６： 実施例６に記載の塗料組成物を塗布
試験片７： 比較例１に記載の塗料組成物を塗布
試験片８： 比較例２に記載の塗料組成物を塗布
試験片９： 比較例３に記載の塗料組成物を塗布
試験片１０： 比較例４に記載の市販の抗菌塗料を塗布
試験片１１： 参考例１に記載の塗料組成物を塗布
【００８０】
＜評価▲１▼ 抗菌性能＞
ＪＩＳ Ｚ ２８０１記載の抗菌性試験方法に従い、菌種に大腸菌を用いて各試験片の抗菌性能の評価を行なった。表３に抗菌試験結果をまとめる。なお、表３に記載の「判定」は抗菌活性Ｒに依る。Ｒ＜２を判定×、Ｒ≧２を判定○とした。
【００８１】
抗菌活性値Ｒは２４時間接触後の非抗菌試験片に対する各試験片の生菌数の減少桁数で表す。（ＪＩＳ Ｚ ２８０１記載）
Ｒ＝Ｌｏｇ１０（Ｂ２４／Ｃ２４）
Ｂ２４： 非抗菌試験片の２４時間後の生菌数
Ｃ２４： 各試験片の２４時間後の生菌数
【００８２】
表３、４、及び５において抗菌速度ｋは、２時間接触後の生菌数から求めた１時間当たりの菌の減少桁数とする。
ｋ＝（Ｌｏｇ１０（Ｃ０／Ｃ２））／２
なお、Ｃ０： 初期の接種菌数、Ｃ２： ２時間接触後の生菌数である。
【００８３】
表３に記載のように、実施例１から実施例６で平均粒子径が５０ｎｍ以下の抗菌剤を使用した場合、優れた抗菌性が得られるのに対して、比較例１と比較例２で平均粒子径が５０ｎｍ以上の抗菌剤を使用した場合、全く抗菌性が得られなかった。本試験結果は粒径に依存して、塗膜中の抗菌剤分布が異なっていることを支持している。比較例３は、抗菌剤の平均粒径は５０ｎｍ以下であるが、用いたアクリル系樹脂エマルジョンがＣ７よりも大きいモノマーを含み構成されるため、塗布後の乾燥過程で抗菌剤成分やシリカ微粒子の塗膜表面近傍への濃度勾配が阻害された。その結果、抗菌活性値Ｒ＜２となり、抗菌性判定は「×」となった。
【００８４】
【表３】
＜評価▲２▼ ＳＥＭ観察＞
日立走査型電子顕微鏡Ｓ−８００にて試験片１（実施例１）および試験片７（比較例１）、試験片９（比較例３）の表面構造の観察を行なった。観察結果を図２に示す。
【００８６】
図２に示すように、試験片１および試験片７は、５０ｎｍ以下の微小粒子が塗膜表面に充填された表面構造をとる。一方、試験片９は塗料組成物を構成する各材料がランダムに露出した均一構造を示す。
【００８７】
試験片１と試験片７を比較したとき、両者は同様の表面構造をとるにもかかわらず、抗菌性には大きく差が現れた。試験片７に用いた抗菌剤の平均粒子径は１５３．６ｎｍであるが、観察結果からは、その露出を確認できなかった。
【００８８】
試験片１で優れた抗菌活性が得られたのは、微小な抗菌剤Ａが、同様に微小なコロイダルシリカとともに塗膜表層で多くなるような濃度勾配を持つためと考えられる。試験片７で抗菌性が得られなかったのは、抗菌剤Ｂの粒子径が比較的大きいため、塗膜表面で多くなるような濃度勾配を持たず、微小なコロイダルシリカが緻密に充填した表層で覆われてしまった結果と考えられる。
【００８９】
試験片１と同量の抗菌剤を含有するにもかかわらず、試験片９の抗菌活性は大きく劣っていた。図２のＳＥＭ像が示すように、試験片９は各材料が均一に分布した塗膜構造をもつ。エマルジョンがＣ７よりも大きなモノマーを含み構成される（表３）ため、乾燥過程で微小なシリカ成分と抗菌剤成分の塗膜表面近傍に多くなるような濃度勾配を持たなかったためと考えられる。試験片１と試験片９の結果は、塗膜の深さ方向で抗菌剤が濃度勾配を持つ傾斜構造をとることによって、所望の抗菌活性をより少量の抗菌剤で実現できることを示唆している。
【００９０】
＜抗菌性能の持続性＞
社団法人日本住宅設備システム協会規定の「住宅設備機器における抗菌性能試験方法・表示及び判定基準」に記載の
処理▲１▼水浸漬試験： 塗装面を５０℃の温水に１６時間浸漬する。
処理▲２▼耐洗剤試験： 塗装面に一般清掃用洗剤１６時間接触する。
塗装面が汚れていく過程を想定して、
処理▲３▼汚染−洗浄サイクル試験： 汚れを模したカーボンブラックを分散したオレイン酸を塗装面に塗布し、水拭きを２０回繰り返す。
を実施した。
【００９１】
上記の方法によって、試験片６（実施例６）、試験片９（比較例３）、試験片１０（比較例４）に処理▲１▼〜▲３▼を施して、抗菌性能の実用的な持続性を評価した。抗菌試験は前述した方法に従って行なった。
【００９２】
表４に処理▲１▼から処理▲３▼を施した試験片と無処理の試験片での評価結果をまとめる。
【００９３】
【表４】
表４に示すように、試験片６のみが高い抗菌速度を▲１▼〜▲３▼の各処理後にも維持した。試験片６は塗装面の帯電半減期が５０未満。一方、試験片９と試験片１０では５０秒以上であった。また、オレイン酸の水中接触角は試験片６は７０°以上を示したのに対して、試験片９と試験片１０では３０°を下回った。試験片６は易洗浄性を有するため抗菌性が長期に渡って効果的に発揮されるのに対して、試験片９および試験片１０では汚れを除去しにくいため、抗菌性が大きく劣化したと考えられる。
【００９５】
＜評価３ 耐候性＞
サンシャインウェザーメーターを用いて、試験片１（実施例１）と試験片９（比較例３）の耐候性を評価した。耐候性試験方法はＪＩＳ Ｋ ５６００ ７−７
に記載の方法に従った。
【００９６】
図３に示す写真のように、試験片１は上記耐候性試験で塗膜表面にクラックや白化を生じないのに対して、試験片９はクラックや白化が生じた。
【００９７】
試験片１では、抗菌剤Ａが微小シリカ粒子とともに塗膜表層部に多く分布するように濃度勾配を有するため、抗菌剤中の酸化チタン光触媒によるエマルジョンの分解を抑制できたと考えられる。一方、試験片９では、抗菌剤が均一に塗膜中に分散するため、前記光触媒によってエマルジョンが侵され、その結果クラックや白化が発生したと考えられる。
【００９８】
＜評価４ 耐変退色性＞
一般に銀系抗菌剤を使った抗菌塗料は、抗菌スペクトルが広く多くの菌種に対して効果を発揮するが、一方で、多量添加すると湿度や光による銀の価数変化のために、塗料自体が褐色を帯びてくる。
【００９９】
試験片１（実施例１）と試験片１０（比較例４）について、耐変退色性の評価を行なった。各試験片を相対湿度１００％、気温２５℃、紫外線強度１ｍＷ／ｃｍ２の条件下に１ヶ月放置し、銀の価数変化に伴う塗膜の変色度を評価した。変色度は、高湿度下・紫外線照射前後の色差ΔＥ＊で評価した。表５に各サンプルの抗菌試験結果とともに、色差ΔＥ＊をまとめた。
【０１００】
【表５】
表５に示したように、実施例は比較例に比べて、抗菌速度が３倍優れているにもかかわらず、変色度が小さく耐変退色性に優れている。
【０１０２】
＜評価５ 塗膜断面のシリカ分布＞
実施例および比較例に記載した組成物中抗菌金属担持酸化チタンの固形分量は非常に少ないため、代用としてシリカの塗膜断面での分布を評価した。塗膜断面分析用試料、試験片１１の塗膜表面及び試験片１１を破断してサンプリングした破断面に白金を約５０Åの厚さでコーティングして塗膜断面の分析用試料を作製した。
【０１０３】
塗膜断面の観察、分析塗膜断面をＳＥＭ（日立製作所社製、Ｓ８００）、ＥＤＸ（堀場製作所社製、ＥＭＡＸ−２７７０）により分析した。分析視野の光触媒性塗膜の膜厚は４０μｍであった。次いで、分析視野中央部、塗膜最表面から基材側界面まで線上にＥＤＸ分析を行った。シリコン（Ｓｉ）について検出した塗膜最表面から基材側界面までのＸ線強度の変化を図４に示す。
【０１０４】
図４に示すように、ＳｉＯ２に由来するＳｉ成分が塗膜表層側に多く分布するようにな濃度勾配を有していることが分かる。また図２に示した試験片１の塗膜表面写真では平均粒子径１０ｎｍ程度の微小な粒子が確認できた。これらの結果は、平均粒子径が小さなシリカ微粒子が塗膜表面近傍に多く分布するように濃度勾配を有することを示唆している。
【０１０５】
抗菌金属担持光触媒の添加量は微量であるため、ＥＤＸによる濃度勾配の判定は難しいが、同程度の粒子径のシリカ粒子が塗膜表面に傾斜充填していること、粒子径が小さい場合に限り抗菌性が発現することなどの結果から、抗菌金属担持光触媒も塗膜面近傍に多く分布するように濃度勾配を有すると考えられる。
【０１０６】
また、シリカ微粒子や抗菌剤粒子が塗膜表層近傍に多く分布するように濃度勾配を有するため、必然的にアクリル系樹脂は基材あるいは下塗り材と接する界面付近に多く分布するように濃度勾配を有すると考えられる。
【０１０７】
【発明の効果】
本発明では、塗料に添加するシリカ微粒子と抗菌剤粒子の大きさとエマルジョンのモノマーの種類を規定することにより、塗装後の塗膜構造を制御して、シリカ微粒子と抗菌剤粒子が塗膜表面近傍に多くなるように濃度勾配を持たせる。その結果、均一に充填した時に比べて、所望の抗菌性能をより少ない抗菌剤添加量で得ることができる。その結果、コスト的に安価な塗料を作製できる上、塗料の安定性、塗膜の耐変退色性も大きく改善できる。また、抗菌剤に抗菌金属担持光触媒を用いた場合でも、抗菌金属担持光触媒はシリカ微粒子とともに塗膜表面近傍で多くなるように濃度勾配ができるため、フッ素系樹脂やシリコン系樹脂に比べて耐候性が劣るアクリル系樹脂でも、光触媒によるエマルジョンの酸化分解を抑制できる。
本発明に依れば、耐候性・耐変退色性を損なうことなく、優れた抗菌性を示し、長期に渡って持続させることが可能な水性塗料組成物、抗菌性部材が得られる。
【図面の簡単な説明】
【図１】本発明に係る水性塗料組成物を各種基材に塗布して形成する塗膜の形態の模式図。
【図２】実施例１、比較例１、比較例３の水性塗料組成物を塗装して得られる試験片の走査型電子顕微鏡（ＳＥＭ）写真。
【図３】実施例１及び比較例３に記載の水性塗料組成物を塗装して得られる試験片はサンシャインウェザーメーターで処理した後の塗装表面写真。
【図４】参考例１に記載の水性塗料組成物を塗装して得られる塗膜の断面のＳＥＭ−ＥＤＸ分析によって、得られたＳｉの深さ方向の分布。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a water-based coating composition, and more specifically, an excellent antibacterial effect is effectively exhibited over a long period of time, and furthermore, an aqueous coating composition having excellent resistance to discoloration and discoloration against humidity and light and weather resistance. The present invention relates to a coating partly or wholly covered with a coating film formed by the composition, and a method for forming the coating.
[0002]
[Prior art]
In recent years, coatings that coat the surface of structures and buildings have various purposes besides the purpose of shielding and protecting the base material from the outside air and the purpose of giving a design different from that originally possessed by coloring etc. It has been proposed to add a function and has been put to practical use. In the indoor environment of a detached house or apartment house, the airtightness of the interior space is greatly improved from the viewpoint of energy saving, and as a result, there is no escape place for heat and moisture, and it is easy for bacteria and other microorganisms to propagate, and allergies are likely to occur. It is a distant cause of sexual and infectious diseases. In hospitals, resistant bacteria such as methicillin-resistant staphylococci and vancomycin-resistant enterococci are rampant and hospital-acquired infections have become a problem. Food poisoning caused by Staphylococcus aureus, Escherichia coli and the like also occurs in schools, school lunch facilities, food factories, etc., and does not tend to decrease at all. The safety against microorganisms in the interior space of structures and buildings has become important year by year.
[0003]
Conventional techniques relating to an aqueous coating composition exhibiting antibacterial properties include the following.
(1) Paint containing organic drugs that are effective for microbial propagation
(2) Paint containing zeolite carrying silver ions
(3) A paint containing a silver ion-carrying inorganic antibacterial agent and a discoloration inhibitor
(4) Paint containing a silver ion-supported photocatalyst and a crystalline layered phosphoric acid compound
(5) Paint containing resin component, aqueous colloidal silica and antibacterial agent
[0004]
Regarding the prior art (1), there is a paint containing a phenolic agent, a bromide agent, an iodine agent, etc. as an organic agent. However, after the coating film is formed, these organic agents elute and exhibit antibacterial properties. There is a problem with its sustainability.
[0005]
Regarding the prior art (2), a paint containing a silver ion-supported zeolite is disclosed (for example, see Patent Document 1). In
[0006]
With regard to the prior art (3), a paint containing a silver ion-carrying inorganic antibacterial agent and a discoloration inhibitor is disclosed (for example, see Patent Document 2). In this case as well, although the discoloration is suppressed, the amount of the inorganic antibacterial agent added is relatively large, and the addition of the organic discoloration inhibitor is not preferable as an indoor paint.
[0007]
Regarding the prior art (4), the antibacterial performance is deteriorated for the same reason as in the prior art (2). In addition, since the dispersion and distribution of silver-supported titanium oxide, which is an antibacterial agent in the coating film, have not been specifically devised, the organic resin is gradually decomposed by the photocatalytic reaction of titanium oxide, and the coating film itself is degraded. Deterioration is also a concern.
[0008]
With respect to the prior art (5), a water component comprising a resin component containing a self-emulsifiable copolymer in which an ethylenically unsaturated monomer and a urethane prepolymer containing a mercapto group and a hydrophilic polar group are bonded by radical polymerization, and aqueous colloidal silica A paint in which an antibacterial agent is added to an inorganic paint is disclosed (for example, see Patent Document 3). The paint described in Patent Document 3 is an acryl-urethane copolymer and contains a large amount of colloidal silica. In such a paint, the composition of the coating film is not inclined but uniform. Therefore, in order to obtain antibacterial properties, it is necessary to add a large amount of an antibacterial agent, and there are problems such as discoloration of the coating film.
[0009]
[Patent Document 1] JP-A-60-202162
[Patent Document 2] JP-A-6-14979
[Patent Document 3] Japanese Patent Application Laid-Open No. 2001-40272
[0010]
[Problems to be solved by the invention]
The present invention has been made to solve the problems in the prior art, and the problem is that a desired antibacterial activity is exhibited over a long period of time with a smaller amount of an antibacterial agent added, and a coating film excellent in discoloration resistance and weather resistance is provided. The present invention provides an aqueous coating composition and an antibacterial member which can be formed by a single application, and which can impart a design different from the original design of the base material with a coloring pigment or the like.
[0011]
[Means for Solving the Problems]
In order to solve the above problems, the present invention includes at least (a) an acrylic resin emulsion, (b) silica fine particles, (c) an antibacterial agent particle, (d) water, and (e) a pigment. An aqueous coating composition, wherein the emulsion particles dispersed in the component (a) are obtained by polymerizing at least one or more monomers selected from C2 to C7 alkyl acrylates and C2 to C7 alkyl methacrylates. The average particle diameter of the component (b) is 50 nm or less, the average particle diameter of the component (c) is 50 nm or less, and the component (b) is 10 to 70% by weight of the total solids. An aqueous coating composition is provided.
[0012]
The average particle diameter of the component (b) is more preferably 30 nm or less.
[0013]
The average particle diameter of the component (c) is more preferably 40 nm or less.
[0014]
Further, a member coated with a coating film formed by applying the aqueous coating composition on a substrate and drying the coating material, wherein the component (b) and the component (c) are mostly present near the surface of the coating film in contact with the outside air. An antimicrobial member coated with a coating having a concentration gradient so as to be distributed is provided.
[0015]
FIG. 1 schematically shows a coating film structure obtained by applying the aqueous coating composition according to the present invention to a substrate. In the present invention, by optimizing the monomer composition of the component (a) and the particle diameter of each of the components (b) and (c), the component (b) is dried in the drying process after the application of the aqueous coating composition. And a concentration gradient such that the component (c) increases on the surface side of the coating film.
[0016]
Since the component (c) has a concentration gradient such that the component is distributed more near the surface of the coating film in contact with the outside air, the desired antibacterial performance can be reduced with a smaller amount of the antibacterial agent compared to a coating film in which the coating material is uniformly distributed. Obtainable. As a result, discoloration caused by an antibacterial metal such as silver can be suppressed.
[0017]
Conversely, since the lower layer portion in close contact with the substrate has a concentration gradient such that the component (a) is distributed in a large amount, a coating film having excellent adhesion can be formed.
[0018]
In order to achieve such a gradient composition, since one liquid can be used without using two liquids, the coating process is simple.
[0019]
In addition, since the component (b) is similarly distributed together with the component (c), even when the component (c) is an antibacterial metal-supported photocatalyst, direct contact with the resin is prevented, and the resin is oxidized and decomposed by the photocatalyst. Thus, an antibacterial coating film having excellent weather resistance can be obtained. Furthermore, since the inorganic fine particle material such as the component (b) or the component (c) has a concentration gradient so as to be distributed in the vicinity of the surface of the coating film, hydrophilic oil repellency is exhibited, and the contact angle of oleic acid in water is reduced. It greatly exceeds 60 °, and in some compositions, exceeds 100 °. Such a hydrophilic oil-repellent surface is an easily washable surface from which oil stains are easily removed. Also, regardless of the type of the base material, the charging half-life can be shortened to 50 seconds or less. As a result, not only does the antibacterial property appear effectively, but also dust hardly adheres and oil stains are easily removed. It is possible to provide a member having a surface.
[0020]
Since the coating film obtained from the coating material of the present invention has a concentration gradient such that the component (c) is distributed in a large amount on the surface layer of the coating film, sufficient antibacterial properties are exhibited even when the addition amount of the component (c) is small. . Specifically, in the test described in JIS Z 2801 using Escherichia coli, the viable cell count becomes 0 after a contact time of 3 hours. In addition, coloring by silver is small. Specifically, the relative humidity is 100%, the ultraviolet intensity is 1 mW / cm.2 The discolored color difference does not reach 2 even if left for one month in the environment.
[0021]
In the present invention, the solid content of the component (b) is 10 to 70% by weight of the total solid. In the coating film formed by applying such an aqueous coating composition, the surface layer of the coating film which is in contact with the outside air is almost covered with the component (b) exhibiting hydrophilicity, and a stain which hinders the development of antibacterial properties by simple wiping. Accumulation can be prevented.
[0022]
In a preferred embodiment of the present invention, the solid content of the component (a) is at least 10% by weight of the total solids. When the solid content of the component (a) is 10% by weight or more of the total solid content, the resin in the aqueous emulsion is cured, whereby adhesion to the base material or the undercoat material is obtained, and a coating film having excellent durability is obtained. Obtainable. More preferably, the solid content of the component (a) is at least 20% by weight of the total solids.
[0023]
In a preferred embodiment of the present invention, the component (c) is an antibacterial metal-supported photocatalyst. In a place exposed to light, the action of the supported antibacterial metal and the photocatalytic action of the carrier act synergistically, and it is possible to continuously exhibit excellent antibacterial properties.
[0024]
In a preferred embodiment of the present invention, the component (c) is an antibacterial metal-supported photocatalyst, and its solid content is 1 to 50% by weight based on the component (b). Within this range, it is possible to give a concentration gradient such that the component (b) and the component (c) increase near the surface of the coating film when the coating film is formed, and the antibacterial property of the component (c) is sufficient. In order to prevent direct contact between the component (c) and the component (a), sufficient weather resistance is obtained despite having a photocatalytic function.
[0025]
In a preferred embodiment of the present invention, the antibacterial metal used for the antibacterial metal-supported photocatalyst of the component (c) contains at least one of silver and copper. These metals exhibit excellent antibacterial properties, and contribute to the sustainability of antibacterial performance and the improvement of the photocatalytic function by being supported on the photocatalyst.
[0026]
In a preferred embodiment of the present invention, the component (c) is an antibacterial metal-supported photocatalyst, and the loading of the antibacterial metal on the photocatalyst is 0.1 to 10% by weight. By imparting a concentration gradient so that the antibacterial agent component increases near the surface of the coating film, desired antibacterial properties can be exhibited while suppressing discoloration of the coating film.
[0027]
In a preferred embodiment of the present invention, the component (e) has an average particle diameter of 100 nm or more. As a result, the component (e) has a concentration gradient such that the component (e) is distributed more on the interface side between the coating film and the substrate, which contributes to the improvement of the adhesion.
[0028]
In a preferred embodiment of the present invention, the ratio of the total solid content of the components (b) and (c) to the solid content of the component (e) is 0.4 or more. More preferably, it is set to 0.6 or more. By doing so, the exposure of the component (e) to the surface can be suppressed, and the components (b) and (c) can be efficiently present in large amounts on the coating film surface.
[0029]
In a preferred embodiment of the present invention, the solid content concentration of the aqueous coating composition is 20% by weight or more. More preferably, the content is 35% by weight or more. By doing so, it is possible to obtain a coating film having a film thickness of 1 μm to 200 μm and a sufficient concealing property by the operation of once undercoating and twice overcoating, which are the usual painting processes for buildings.
[0030]
Embodiments of the present invention will be described below based on the present invention.
First, words used in the present invention will be described below.
[0031]
In the present invention, the “acrylic resin emulsion” of the component (a) is a vinyl copolymer containing alkyl (meth) acrylates as a vinyl monomer as a main component, and further has croton as a vinyl monomer. Various non-functional monomers such as alkyl acid, unsaturated dibasic dialkyl, vinyl monocarboxylate or vinyl aromatic monomer, tertiary amino group, acid group, Various vinyl monomers having functional groups such as neutralized acid groups, amide groups, cyano groups, hydroxyl groups, epoxy groups, hydrolyzable silyl groups, and two or more polymerizable double bonds per molecule Can be used. The average particle size of the emulsion is preferably 140 nm or more, more preferably 145 nm or more.
[0032]
Further, various drying (curing) types such as a cross-linking type, a self-cross-linking type, and a non-cross-linking type obtained by adding a cross-linking agent to the acrylic resin emulsion, and one emulsion particle A core-shell type having a shell portion and a core portion, and a type in which a monomer composition is changed stepwise from an emulsion core portion to a shell portion by a multi-stage emulsion polymerization method can be used.
[0033]
In the present invention, the “silica fine particles” of the component (b) may be glassy silica, quartz, amorphous silica, silica gel, silica powder, silica sol, or a silica surface coated with aluminum or the like if the particle diameter is 50 nm or less. Various types of coated silica fine particles, silica-coated fine particles in which the surfaces of resin particles, metal oxide sols and the like are coated with silica, spherical silica fine particles, rod-shaped silica fine particles, necklace-shaped silica fine particles in which spherical silica is connected, and the like can be used. When the particle diameter is larger than the above range, it can be used after being refined by a process such as pulverization. As these materials, commercially available products such as Snowtex manufactured by Nissan Chemical Industries, Ltd. may be used, or those prepared according to various synthesis methods represented by the sol-gel method may be used.
[0034]
In the present invention, the “antibacterial agent particles” of the component (c) have an average particle diameter of 50 nm or less, such as zeolite carrying antibacterial metal and apatite carrying antibacterial metal. Any antibacterial agent that does not worsen can be used. In addition to materials prepared according to various synthetic methods, commercially available products can also be used. For example, Atomie Ball UA manufactured by Catalyst Kasei Kogyo Co., Ltd. having silver supported on alumina silica corresponds to this. The antibacterial metal refers to a metal species that can exhibit antibacterial properties in the form of ions or oxides, such as silver and copper.
[0035]
In the present invention, antibacterial metal-supported photocatalyst particles can be used as the component (c). Antibacterial metals can be used alone or in combination of two or more.
[0036]
As the antibacterial metal-supported photocatalyst, commercially available products having an average particle diameter of 50 nm or less, such as Atomie Ball L manufactured by Kasei Kagaku Kogyo Co., Ltd., and those prepared according to various synthesis methods represented by the sol-gel method can be used. It can also be used.
[0037]
As the photocatalyst, at least one selected from anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, strontium titanate, tantalum oxide, niobium oxide, tin oxide, and zinc oxide can be used. Particularly, anatase type titanium oxide having high photocatalytic activity is preferable. As the titanium oxide, commercially available products such as products of Ishihara Sangyo Co., Ltd., Showa Denko KK, and Taki Kagaku Co., Ltd. can be used, and prepared products can also be used. In recent years, titanium oxide photocatalysts that respond to visible light have been announced by Sumitomo Chemical Co., Ltd., Toyota Central R & D Labs., Eco Devices Co., Ltd., Showa Denko Co., Ltd., Ishihara Sangyo Co., Ltd., etc. These materials can be used if the average particle diameter can be reduced to 50 nm or less. For carrying the antibacterial metal on such a photocatalytic material, a photoreduction electrodeposition method utilizing photocatalytic activity, an impregnation method, or the like can be used.
[0038]
In the aqueous coating composition of the present invention, as the component (e) which can be used in combination with the silica fine particles, inorganic pigments, organic coloring pigments, and inorganic pigments generally used in aqueous emulsion coatings are included. Available. As inorganic coloring pigments, metal oxides such as titanium oxide white, titanium yellow, spinel green, zinc white, red iron oxide, chromium oxide, cobalt blue, iron black, alumina hydroxide, metal hydroxides such as yellow iron oxide, Ferrocyanide compounds such as navy blue, lead chromate such as lead, zinc chromate, molybdenum red, sulfides such as zinc sulfide, vermilion, cadmium yellow, cadmium red, selenium compounds, barite, precipitated barium sulfate, etc. Carbonates such as sulfate, heavy calcium carbonate and precipitated calcium carbonate; silicates such as hydrous silicate, clay and ultramarine blue; carbons such as carbon black; metals such as aluminum powder, bronze powder and zinc powder And pearl pigments such as powder, mica and titanium oxide. Examples of the organic pigment include quinone pigments such as anthraquinone, quinacdrine, perylene, and isoindoline pigments, azo pigments, and phthalocyanine pigments. Inorganic extender pigments include titanium oxide whiskers, calcium carbonate whiskers, potassium titanate whiskers, aluminum borate whiskers, mica, talc, barium sulfate, potassium carbonate, silica sand, diatomaceous earth, kaolin, clay, sepiolite, porcelain clay, barium carbonate. Etc. are preferred. Each of these pigments may be used alone, or two or more of these may be used in combination. For example, various pigments and / or various extenders may be used in combination.
[0039]
Regarding the compounding amount of these pigments in the water-based coating composition, the PWC including the component (b) “silica particles”, the component (c) “antibacterial particles” and the component (e) “pigment” is 30 to 90. , Preferably 40 to 80.
[0040]
Here, PWC means Pigment Weight Concentration (pigment weight concentration), which is calculated by the following equation.
PWC = [(weight% of pigment contained) / (weight% of total solid content of paint)] × 100
When the PWC is less than 30, the antibacterial properties are not sufficiently exhibited, and the dirt cleaning property is also deteriorated. Conversely, if it exceeds 90, the film-forming properties decrease, and the coating film tends to crack, peel off, etc., which is not preferable.
[0041]
In the aqueous coating composition of the present invention, the total amount of the component (b) “fine silica particles” and the component (c) “antimicrobial particles” may account for 10 to 85% by weight of the total amount of the other pigments. preferable. When the compounding amount is less than 10% by weight of the total compounding amount, the weather resistance and the antibacterial property are not sufficiently exhibited. Conversely, if the compounding amount exceeds 85% by weight of the total compounding amount, the film-forming properties are lowered, and the coating film tends to be cracked or peeled off, which is not preferable.
[0042]
The aqueous coating composition of the present invention may contain an organic agent generally used as a fungicide, such as zinc pyrithione or an imidazole agent, or a thiazole or isothiazole agent.
[0043]
The aqueous coating composition of the present invention contains the above-described acrylic resin emulsion, silica fine particles, antibacterial agent particles, water, and a pigment as essential components, and further, if necessary, methanol, ethanol, and methyl. Various hydrophilic organic solvents such as cellosolve, ethylene glycol, etc., neutralizers, thickeners, dispersants, defoamers, film forming aids, preservatives, antifreeze agents, film forming aids, ultraviolet absorbers, etc. Additives may also be included. However, with respect to paints, in recent years, there has been an increasing tendency to use water-based paints (water-based paints) rather than solvent-based paints from the viewpoints of working environment, influence on surroundings, and odor. That is, it is preferable not to contain a solvent such as a film-forming auxiliary, particularly a volatile organic solvent.
[0044]
The mixing and dispersion treatment of the aqueous coating composition of the present invention includes a sand mill, a homogenizer, a ball mill, a roll mill, a paint shaker, an ultrasonic disperser, a blade type stirrer, a magnetic stirrer, a high-speed disperser, an emulsifier, and a revolution propellerless. A pulverizer or the like can be used.
[0045]
Examples of the substrate that can be coated with the coating composition of the present invention include metals, plastics, glass, tiles, enamels, ceramics, wood, cement, joints, concrete, ceramic inorganic plates, gypsum boards, or composites thereof. These laminates, their painted bodies, and those having an organic or inorganic film or film on their surface, etc. The ceramic-based inorganic board is a base material such as fiber-reinforced cement board, calcium silicate board, slate board, perlite cement board, lightweight foamed concrete (ALC), glass fiber reinforced concrete (GRC), and ceramic-based siding. Not limited. The plastic substrate includes fiber reinforced plastic, acrylic resin, polycarbonate resin, polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polypropylene (PP), acrylic butadiene styrene copolymer resin (ABS) resin, chloride Examples thereof include a molded product such as a vinyl resin, an epoxy resin, and a phenol resin, and a film-shaped product, and are not particularly limited. Regarding the painted body, examples of the organic film include a film of an epoxy resin, a phenol resin, an unsaturated polyester resin, a urea resin, a fluororesin, a silicone resin, an acrylic silicone resin, a methacrylate resin, a polyurethane resin, a melamine resin, and the like. Examples of the film include alkali silicate, phosphoric acid, and boric acid films, but are not particularly limited.
[0046]
Before applying the coating composition of the present invention, it is also possible to appropriately coat an undercoat material suitable for various substrates. As an undercoat layer formed by an undercoat material in contact with the coating film, urethane resin, acrylic resin, acrylic urethane resin, acrylic silicon resin, epoxy resin, vinyl chloride resin, vinyl acetate resin, phthalic acid resin, alkyd resin, silicon In addition to organic resin-based coatings such as alkyd resins, inorganic coatings and the like can be used.
[0047]
The coating composition of the present invention is applied to articles expected to have antibacterial properties. Examples of such articles include exteriors and interiors of buildings and structures and vehicles, and more specifically, roofing materials, tiles, colored tins, colored iron plates, ceramic building materials, siding materials, cement walls, Aluminum siding, curtain walls, painted steel plates, stone materials, ALC, tiles, glass blocks, sashes, building sashes, screen doors, shutters, gates, window frames, verandas, veranda railings, roof gutters, outdoor air conditioners, store signs, signs, advertising towers , Refrigerated and frozen showcases, shutters, outdoor benches, vending machines, plant outer walls, plant inner walls, oil storage tanks, tents, kitchen equipment, bathroom equipment, ceramics, bathtubs, wash basins, kitchenware, dish dryers, Sinks, kitchen hoods, ventilation fans, and the like.
[0048]
The antibacterial member according to the present invention is a member in which the coating composition of the present invention is applied to the surface of a substrate and then dried or cured to form a coating film.
[0049]
Here, the means for applying the coating composition is not particularly limited, and examples thereof include brush coating, sponge coating, roll coating, flow coating, spin coating, and dip coating.
[0050]
Here, drying or curing of the coating film can be carried out by drying at room temperature to 1 to 80 ° C., forced drying, heating, irradiation with ultraviolet rays, or the like.
[0051]
Further, the surface of the substrate to which the coating composition of the present invention is applied is preferably clean. In particular, when applying the composition to an existing base material such as an inner wall or an outer wall of a building, it is preferable to wash the material by a known method such as using a cleaning agent in advance.
[0052]
The composition of the monomers constituting the various emulsions can be analyzed and evaluated using pyrolysis GC / MS.
[0053]
The average particle diameter is a volume average particle diameter measured by photon correlation spectroscopy (PCS) using ZETASIZER 3000HS manufactured by MALVERN.
[0054]
The structure and composition analysis of the coating film from the substrate contacting part to the surface layer in contact with the outside air can be directly observed with a scanning electron microscope or transmission electron microscope, energy diffusion X-ray (EDX) analysis of the coating film cross section or X-ray micro As an analysis (EPMA) analysis or a composition analysis in a depth direction from a surface, a method such as Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and secondary ion mass spectrometry (SIMS) is used. be able to. Also, the composition analysis and observation of the components mechanically and multi-stepped off from the coating film surface may be performed.
[0055]
The aqueous coating composition according to the present invention has a small particle size component of (b) component “silica fine particles” of 50 nm or less and component (c) “antibacterial agent particles” and a particle size larger than 100 nm and a monomer having C2 to C7 ( It is composed of a component (a) "acrylic resin emulsion", component (e) a large particle size component "pigment", and component (d) component "water". The water content can be evaluated by thermal analysis such as TG-DTA. The small particle size component and the large particle formation component can be separated using a filter having a pore size of 50 nm to 100 nm, and qualitative and quantitative determinations can be made using various evaluation methods. For example, particle size information can be obtained by photon correlation spectroscopy. When re-dispersion after separation is difficult, the particle size of the used material can be evaluated by direct observation using a scanning electron microscope or a transmission electron microscope. The composition can be analyzed by X-ray fluorescence analysis or the like.
[0056]
The antibacterial metal loading of the antibacterial metal-supported photocatalyst according to the present invention indicates the ratio of the amount of the antibacterial metal supported to the amount of the photocatalyst as a carrier. It can be quantified and evaluated by atomic absorption analysis or ICP emission analysis after dissolving in water or acid or alkali.
[0057]
The thickness of the coating film can be measured by cross-sectional observation using a scanning electron microscope.
[0058]
The charging half-life was measured using STATIC HONESTMETER manufactured by Shisido Electrostatic Co., Ltd. in an environment adjusted to a temperature of 25 ° C. and a relative humidity of 20%. After applying the applied voltage of 10 kV and reaching the saturated charging potential on the surface of the coating film, this is the time required for the charging potential to attenuate to half of that.
[0059]
The ultraviolet intensity was measured with an ultraviolet intensity meter UM-10 (light receiving unit UM-360) manufactured by MINOLTA.
[0060]
The discoloration and color difference of the coating film after being left in a high humidity, ultraviolet irradiation environment is calculated according to the following formula.
Color difference ΔE*= ｛(L* 1L* 0)2+ (A* 1a* 0)2+ (B* 1b* 0)2｝1/2
Here, (L* 0, A* 0, B* 0): Color value of sample surface before standing based on L * a * b * color system described in JIS Z 8729, (L* 1, A* 1, B* 1): Color value of the sample surface after standing. The color value was measured with a spectrophotometer CM-3700d manufactured by MINOLTA.
[0061]
The antibacterial evaluation of the coating film was basically performed according to the method described in JIS Z2801. However, the contact time of the bacteria on the painted surface was arbitrarily changed.
[0062]
<Preparation of silver-supported titanium oxide>
According to the conditions described in Table 1, silver nitrate was dissolved in the titanium oxide dispersion and irradiated with ultraviolet rays to silver electro-deposit silver on the titanium oxide surface.
[0063]
[Table 1]
Table 2 lists the commercial antimicrobial agents used.
[0065]
[Table 2]
The average particle diameter described in Tables 1 and 2 is a volume average particle diameter measured by photon correlation spectroscopy (PCS) using Zeltizer 3000HS manufactured by MALVERN.
[0067]
<Coating composition>
Example 1
9 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL, average particle diameter: 124.7 nm), colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name:
[0068]
Example 2
20 parts by weight of colloidal silica (trade name: Snowtex ZL, manufactured by Nissan Chemical Co., average particle diameter: 124.7 nm); colloidal silica (trade name: Snowtex S, manufactured by Nissan Chemical Co., Ltd., average particle diameter: 5.4 nm) 95 parts by weight, 0.05 parts by weight of antibacterial agent C shown in Table 2 (A company silver-supported titanium oxide: average particle diameter 3.5 nm), acrylic emulsion (monomer: butyl acrylate, butyl methacrylate average particle diameter 150 nm) 24 parts by weight, 20 parts by weight of a coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF Color MF5765), 10 parts by weight of an extender pigment (Nippon Talc Co., Ltd., trade name: P-3), and an extender pigment (Otsuka Chemical Co., Ltd.) Co., Ltd., 6 parts by weight (expressed in terms of solid content) of a coating composition (MTW-500). The water content at this time was 127 parts by weight with respect to the total of 100 parts by weight of the solid content. Ag in the present coating composition2The O content was 11.25 ppm.
[0069]
Example 3
8 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL, average particle diameter: 124.7 nm), colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name:
[0070]
Example 4
20 parts by weight of colloidal silica (trade name: Snowtex ZL, manufactured by Nissan Chemical Co., average particle diameter: 124.7 nm); colloidal silica (trade name:
[0071]
Example 5
8.2 parts by weight of colloidal silica (trade name Snowtex ZL, average particle size 124.7 nm, manufactured by Nissan Chemical Co., Ltd.), colloidal silica (
[0072]
Example 6
8 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name Snowtex XL, average particle diameter 52.1 nm), 10 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name:
[0073]
Comparative Example 1
9 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL, average particle diameter: 124.7 nm), colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name:
[0074]
Comparative Example 2
10 parts by weight of colloidal silica (manufactured by Nissan Chemical Industries, trade name Snowtex ZL, average particle diameter 124.7 nm), 10 parts by weight of colloidal silica (manufactured by Nissan Chemical Industries,
[0075]
Comparative Example 3
9 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL, average particle diameter: 124.7 nm), colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name:
[0076]
Comparative Example 4
A commercially available antibacterial paint was used as Comparative Example 4.
[0077]
Reference Example 1
9.6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex ZL, average particle diameter: 124.7 nm), colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex S, average particle diameter: 5.4 nm) 32.9 parts by weight, acrylic emulsion (monomer: butyl acrylate, butyl methacrylate average particle diameter 150 nm) 23.2 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF Color MF5765) 19.6 Parts by weight, extender pigment (Nippon Talc Co., Ltd., trade name: P-3) 10.6 parts by weight, extender pigment (manufactured by Otsuka Chemical Co., Ltd., trade name: MTW-500) 4.1 parts by weight (displayed as solid content) Was prepared. The water content at this time was 127 parts by weight with respect to the total of 100 parts by weight of the solid content.
[0078]
<Coating method to substrate>
A slightly elastic primer (Japan Hydrotec Coatings, trade name: RP11) was roller-coated on a polycarbonate plate (conforming to JIS K 6735) cut to 50 mm x 50 mm, and dried at room temperature for 24 hours.
Subsequently, the coating composition of Example 1 prepared above was applied by roller.
The coating compositions of Examples 2 to 6, Comparative Examples 1 to 3, and Reference Example 1 were also coated according to the present coating method.
Finally, the object to be coated was dried at room temperature for 7 days to obtain
In addition, a commercially available antibacterial paint (Comparative Example 4) was similarly applied to obtain a
[0079]
Test piece 1: Applying the coating composition described in Example 1
Test piece 2: The coating composition described in Example 2 was applied.
Test piece 3: The coating composition described in Example 3 was applied.
Test piece 4: The coating composition described in Example 4 was applied.
Test piece 5: Coating the coating composition described in Example 5
Test piece 6: Coating the coating composition described in Example 6
Test piece 7: Coating the coating composition described in Comparative Example 1
Test piece 8: Coating the coating composition described in Comparative Example 2
Test piece 9: The coating composition described in Comparative Example 3 was applied.
Test piece 10: The commercially available antibacterial paint described in Comparative Example 4 was applied.
Test piece 11: The coating composition described in Reference Example 1 was applied.
[0080]
<Evaluation (1) Antibacterial performance>
According to the antibacterial test method described in JIS Z 2801, the antibacterial performance of each test piece was evaluated using Escherichia coli as the bacterial species. Table 3 summarizes the results of the antibacterial test. The “judgment” in Table 3 depends on the antibacterial activity R. R <2 was evaluated as x, and R ≧ 2 was evaluated as ○.
[0081]
The antimicrobial activity value R is represented by the number of orders of decrease in the viable cell count of each test piece relative to the non-antibacterial test piece after 24 hours of contact. (Described in JIS Z 2801)
R = Log10(B24 / C24)
B24: Viable cell count of the non-antibacterial test piece after 24 hours
C24: Viable count of each test specimen after 24 hours
[0082]
In Tables 3, 4, and 5, the antibacterial speed k is the number of digits of bacterial reduction per hour obtained from the number of viable bacteria after 2 hours of contact.
k = (Log10(C0 / C2)) / 2
C0: initial inoculum count, C2: viable count after 2 hours of contact.
[0083]
As shown in Table 3, when an antibacterial agent having an average particle diameter of 50 nm or less was used in Examples 1 to 6, excellent antibacterial properties were obtained, whereas in Comparative Examples 1 and 2, When an antibacterial agent having an average particle diameter of 50 nm or more was used, no antibacterial property was obtained. The test results support different distributions of antimicrobial agents in the coatings, depending on the particle size. In Comparative Example 3, although the average particle size of the antibacterial agent was 50 nm or less, the acrylic resin emulsion used contained a monomer larger than C7. The concentration gradient near the coating film surface was inhibited. As a result, the antibacterial activity value R <2, and the antibacterial property judgment was “x”.
[0084]
[Table 3]
<Evaluation 2> SEM observation>
The surface structures of the test piece 1 (Example 1), the test piece 7 (Comparative Example 1), and the test piece 9 (Comparative Example 3) were observed with a Hitachi scanning electron microscope S-800. FIG. 2 shows the observation results.
[0086]
As shown in FIG. 2, the
[0087]
When the
[0088]
It is considered that the reason why the excellent antibacterial activity was obtained in the
[0089]
Despite containing the same amount of antibacterial agent as
[0090]
<Durability of antibacterial performance>
It is described in the "Method, Labeling and Judgment Criteria for Testing Antibacterial Performance of Housing Equipment" prescribed by the Japan Housing Equipment System Association.
Treatment (1) Water immersion test: The painted surface is immersed in warm water of 50 ° C. for 16 hours.
Treatment (2) Detergent test: The painted surface is brought into contact with a general cleaning detergent for 16 hours.
Assuming that the painted surface gets dirty,
Treatment (3) Contamination-washing cycle test: Oleic acid in which carbon black simulating dirt is dispersed is applied to the painted surface, and water wiping is repeated 20 times.
Was carried out.
[0091]
According to the above-described method, the test pieces 6 (Example 6), the test piece 9 (Comparative Example 3), and the test piece 10 (Comparative Example 4) were subjected to the treatments (1) to (3) to obtain a practical antibacterial performance. Sustainability was assessed. The antibacterial test was performed according to the method described above.
[0092]
Table 4 summarizes the evaluation results of the test pieces subjected to the treatments (1) to (3) and the untreated test pieces.
[0093]
[Table 4]
As shown in Table 4, only the test piece 6 maintained the high antibacterial rate even after each of the treatments (1) to (3). Test piece 6 has a charged half life of less than 50 on the painted surface. On the other hand, the
[0095]
<Evaluation 3 Weather resistance>
The weather resistance of the test piece 1 (Example 1) and the test piece 9 (Comparative Example 3) were evaluated using a sunshine weather meter. The weather resistance test method is JIS K 5600 7-7.
The method described in the above was followed.
[0096]
As shown in the photograph shown in FIG. 3, the
[0097]
It is considered that the
[0098]
<Evaluation 4 Discoloration resistance>
In general, antibacterial paints using silver-based antibacterial agents have a broad antibacterial spectrum and are effective against many types of bacteria. Comes brown.
[0099]
The test piece 1 (Example 1) and the test piece 10 (Comparative Example 4) were evaluated for resistance to discoloration and fading. Each test piece was subjected to a relative humidity of 100%, a temperature of 25 ° C., and an ultraviolet intensity of 1 mW / cm.2Was allowed to stand for one month, and the degree of discoloration of the coating film accompanying a change in the valence of silver was evaluated. The degree of discoloration was evaluated by a color difference ΔE * before and after irradiation with ultraviolet light under high humidity. Table 5 summarizes the color difference ΔE * together with the antibacterial test results of each sample.
[0100]
[Table 5]
As shown in Table 5, the Example has a small degree of discoloration and is excellent in resistance to discoloration and fading, although the antibacterial speed is three times better than the Comparative Example.
[0102]
<Evaluation 5: Silica distribution in coating film cross section>
Since the solid content of the antibacterial metal-supported titanium oxide in the compositions described in Examples and Comparative Examples was very small, the distribution of silica in the cross section of the coating film was evaluated as a substitute. A sample for analyzing the coating film cross section, the coating surface of the test piece 11 and the sampled broken surface of the test piece 11 were coated with platinum at a thickness of about 50 ° to obtain a sample for analyzing the coating film cross section.
[0103]
Observation and analysis of the cross section of the coating film The cross section of the coating film was analyzed by SEM (S800, manufactured by Hitachi, Ltd.) and EDX (EMAX-2770, manufactured by Horiba, Ltd.). The thickness of the photocatalytic coating film in the analysis visual field was 40 μm. Next, EDX analysis was performed on the line from the center of the analysis visual field, from the outermost surface of the coating film to the interface on the substrate side. FIG. 4 shows a change in X-ray intensity detected from silicon (Si) from the outermost surface of the coating film to the interface on the substrate side.
[0104]
As shown in FIG.2It can be seen that there is a concentration gradient such that a large amount of the Si component originating from is distributed on the surface layer side of the coating film. In the photograph of the coating film surface of the
[0105]
The addition amount of the antibacterial metal-supported photocatalyst is very small, so it is difficult to determine the concentration gradient by EDX, but only if silica particles of similar particle size are inclinedly filled on the coating film surface and the particle size is small. From the results such as the manifestation of antibacterial properties, it is considered that the antibacterial metal-supported photocatalyst also has a concentration gradient such that the photocatalyst is distributed more near the coating film surface.
[0106]
In addition, since the silica fine particles and the antibacterial agent particles have a concentration gradient so as to be distributed more near the surface of the coating film, the acrylic resin necessarily has a concentration gradient so that it is more distributed near the interface in contact with the base material or the undercoat material. It is thought to have.
[0107]
【The invention's effect】
In the present invention, the size of the silica fine particles and the antimicrobial agent particles to be added to the paint and the type of the monomer of the emulsion are controlled to control the coating film structure after coating, and the silica fine particles and the antimicrobial agent particles are in the vicinity of the coating surface Have a concentration gradient so that As a result, a desired antibacterial performance can be obtained with a smaller amount of an antibacterial agent added than when uniformly filled. As a result, inexpensive paints can be produced at low cost, and the stability of paints and the resistance to discoloration and fading of coating films can be greatly improved. Even when an antibacterial metal-supported photocatalyst is used as the antibacterial agent, the antibacterial metal-supported photocatalyst together with the silica fine particles can have a concentration gradient such that it increases near the surface of the coating film. Even if the acrylic resin is inferior, the oxidative decomposition of the emulsion by the photocatalyst can be suppressed.
According to the present invention, an aqueous coating composition and an antibacterial member which exhibit excellent antibacterial properties and can be maintained for a long period of time without impairing weather resistance and discoloration resistance are obtained.
[Brief description of the drawings]
FIG. 1 is a schematic view of a form of a coating film formed by applying an aqueous coating composition according to the present invention to various substrates.
FIG. 2 is a scanning electron microscope (SEM) photograph of a test piece obtained by applying the aqueous coating composition of Example 1, Comparative Example 1, and Comparative Example 3.
FIG. 3 is a photograph of a coated surface of a test piece obtained by applying the aqueous coating composition described in Example 1 and Comparative Example 3 after treatment with a sunshine weather meter.
FIG. 4 shows the distribution in the depth direction of Si obtained by SEM-EDX analysis of a cross section of a coating film obtained by applying the aqueous coating composition described in Reference Example 1.
Claims (16)
（ｂ）シリカ微粒子と、
（ｃ）抗菌剤粒子と、
（ｄ）水と、
（ｅ）顔料と、
を少なくとも含んだ水性塗料組成物であって、
前記（ａ）成分はＣ２からＣ７のアルキルアクリレート、Ｃ２からＣ７のアルキルメタクリレートから選択される少なくとも１種以上のモノマーを重合させたものであり、かつ（ｂ）成分の平均粒子径が５０ｎｍ以下であり、（ｃ）成分の平均粒子径が５０ｎｍ以下であり、さらに（ｂ）成分が全固形分の１０〜７０重量％であることを特徴とする水性塗料組成物。(A) an acrylic resin emulsion;
(B) silica fine particles;
(C) antimicrobial agent particles,
(D) water,
(E) a pigment;
An aqueous coating composition containing at least
The component (a) is obtained by polymerizing at least one or more monomers selected from C2 to C7 alkyl acrylates and C2 to C7 alkyl methacrylates, and the component (b) has an average particle diameter of 50 nm or less. An aqueous coating composition, wherein component (c) has an average particle size of 50 nm or less, and component (b) is 10 to 70% by weight of the total solids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003145022A JP4517384B2 (en) | 2003-05-22 | 2003-05-22 | Water-based paint composition, antibacterial member and coating film forming method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003145022A JP4517384B2 (en) | 2003-05-22 | 2003-05-22 | Water-based paint composition, antibacterial member and coating film forming method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004346202A true JP2004346202A (en) | 2004-12-09 |
| JP4517384B2 JP4517384B2 (en) | 2010-08-04 |
Family
ID=33532323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003145022A Expired - Fee Related JP4517384B2 (en) | 2003-05-22 | 2003-05-22 | Water-based paint composition, antibacterial member and coating film forming method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4517384B2 (en) |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2427139A (en) * | 2005-06-16 | 2006-12-20 | Ici Plc | Anti-microbial paint films comprising anti-microbial metal/metal compound deposited on particulate inorganic material |
| JP2007262150A (en) * | 2006-03-27 | 2007-10-11 | Ohbayashi Corp | Photocatalyst coating agent and photocatalyst carrier |
| JP2008093905A (en) * | 2006-10-10 | 2008-04-24 | Furukawa Sky Kk | Aluminum-coated plate and precoated aluminum fin material using the plate |
| JP2008223003A (en) * | 2006-12-28 | 2008-09-25 | Toto Ltd | Self-cleaning member and coating composition |
| JP2008229498A (en) * | 2007-03-20 | 2008-10-02 | Nichiha Corp | Construction plate |
| JP2009501697A (en) * | 2005-05-25 | 2009-01-22 | ポスコ | Silver-containing solution, antibacterial resin composition containing the same, and steel sheet coated with the resin composition |
| JP2010105329A (en) * | 2008-10-31 | 2010-05-13 | Furukawa-Sky Aluminum Corp | Aluminum-coated plate |
| JP2012166195A (en) * | 2012-03-27 | 2012-09-06 | Asahi Kasei Chemicals Corp | Method for forming stain-proof layer |
| US8512855B2 (en) | 2009-06-01 | 2013-08-20 | Toto Ltd. | Self-cleaning member and coating composition |
| CN103756489A (en) * | 2013-12-13 | 2014-04-30 | 张家港市双林制墨涂装有限公司 | Antibacterial interior wall emulsion paint, and preparation method thereof |
| CN104830185A (en) * | 2015-05-21 | 2015-08-12 | 田福东 | Environment-friendly aqueous interior wall coating for removing formaldehyde |
| CN106583168A (en) * | 2016-11-10 | 2017-04-26 | 刘志徽 | Production device of double-color camouflage type colorful stone coated steel tile and application thereof |
| CN108191378A (en) * | 2017-04-27 | 2018-06-22 | 钟建军 | A kind of inorganic compounding diatom ooze coating |
| JP2019196440A (en) * | 2018-05-09 | 2019-11-14 | 旭化成株式会社 | Coated film and aqueous composition |
| CN110684413A (en) * | 2018-07-05 | 2020-01-14 | 河北瀚宇建材有限公司 | Paint for preventing sand return of wall surface |
| CN113622792A (en) * | 2021-10-11 | 2021-11-09 | 南通海鹰木业股份有限公司 | Intelligent aluminum-wood door and window with heat preservation and purification functions |
| JP2021178954A (en) * | 2020-05-13 | 2021-11-18 | 新福光塗裝工程股▲分▼有限公司 | Antimicrobial coating material, method for producing antimicrobial coating material, antimicrobial coating, and antivirus tape |
| CN114717876A (en) * | 2022-04-06 | 2022-07-08 | 金东纸业（江苏）股份有限公司 | Preparation method of antibacterial paper and antibacterial paper |
| CN115074031A (en) * | 2022-06-29 | 2022-09-20 | 吉力水性新材料科技（珠海）有限公司 | Water-based antibacterial and antistatic coating and preparation method thereof |
| WO2022210560A1 (en) * | 2021-03-29 | 2022-10-06 | 富士フイルム株式会社 | Antibacterial film, touch panel, and copier |
| CN115466535A (en) * | 2022-08-10 | 2022-12-13 | 雅士利涂料（苏州）有限公司 | Novel composite antibacterial coating and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101053202B1 (en) * | 2011-03-07 | 2011-08-03 | 주식회사무영아멕스건축사사무소 | A helthy paint composition for antibacterial function and deodorization |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0925437A (en) * | 1995-07-12 | 1997-01-28 | Matsushita Electric Works Ltd | Antimicrobial inorganic coating material |
| JPH0987615A (en) * | 1995-09-21 | 1997-03-31 | Mitsubishi Chem Mkv Co | Antifogging agent composition |
| JPH11116885A (en) * | 1997-10-21 | 1999-04-27 | Nippon Paint Co Ltd | Low-fouling water-based coating material composition |
| JP2000095976A (en) * | 1998-09-22 | 2000-04-04 | Toto Ltd | Antibacterial photocatalytic aqueous coating material and antibacterial photocatalytic member |
| JP2000095979A (en) * | 1998-09-21 | 2000-04-04 | Kansai Paint Co Ltd | Room pollution remedy water paint |
| JP2001064583A (en) * | 1999-08-31 | 2001-03-13 | Toto Ltd | Photocatalyst coating composition, photocatalytic coating film, article covered therewith, and method for forming the coating film |
| JP2002249712A (en) * | 2001-02-26 | 2002-09-06 | Nisshin Steel Co Ltd | Photocatalytic coating composition |
| JP2003041181A (en) * | 2001-07-25 | 2003-02-13 | Toto Ltd | Hydrophilic coating composition |
-
2003
- 2003-05-22 JP JP2003145022A patent/JP4517384B2/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0925437A (en) * | 1995-07-12 | 1997-01-28 | Matsushita Electric Works Ltd | Antimicrobial inorganic coating material |
| JPH0987615A (en) * | 1995-09-21 | 1997-03-31 | Mitsubishi Chem Mkv Co | Antifogging agent composition |
| JPH11116885A (en) * | 1997-10-21 | 1999-04-27 | Nippon Paint Co Ltd | Low-fouling water-based coating material composition |
| JP2000095979A (en) * | 1998-09-21 | 2000-04-04 | Kansai Paint Co Ltd | Room pollution remedy water paint |
| JP2000095976A (en) * | 1998-09-22 | 2000-04-04 | Toto Ltd | Antibacterial photocatalytic aqueous coating material and antibacterial photocatalytic member |
| JP2001064583A (en) * | 1999-08-31 | 2001-03-13 | Toto Ltd | Photocatalyst coating composition, photocatalytic coating film, article covered therewith, and method for forming the coating film |
| JP2002249712A (en) * | 2001-02-26 | 2002-09-06 | Nisshin Steel Co Ltd | Photocatalytic coating composition |
| JP2003041181A (en) * | 2001-07-25 | 2003-02-13 | Toto Ltd | Hydrophilic coating composition |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009501697A (en) * | 2005-05-25 | 2009-01-22 | ポスコ | Silver-containing solution, antibacterial resin composition containing the same, and steel sheet coated with the resin composition |
| JP4740322B2 (en) * | 2005-05-25 | 2011-08-03 | ポスコ | Antibacterial resin composition containing silver-containing solution and steel sheet coated with resin composition |
| EP1888698A4 (en) * | 2005-05-25 | 2010-02-24 | Posco Co Ltd | Ag-containing solution, antibacterial resin composition comprising the solution and antibacterial resin coated steel plate |
| GB2427139B (en) * | 2005-06-16 | 2010-05-19 | Ici Plc | Anti-microbial paint films |
| GB2427139A (en) * | 2005-06-16 | 2006-12-20 | Ici Plc | Anti-microbial paint films comprising anti-microbial metal/metal compound deposited on particulate inorganic material |
| JP2007262150A (en) * | 2006-03-27 | 2007-10-11 | Ohbayashi Corp | Photocatalyst coating agent and photocatalyst carrier |
| JP2008093905A (en) * | 2006-10-10 | 2008-04-24 | Furukawa Sky Kk | Aluminum-coated plate and precoated aluminum fin material using the plate |
| JP2008280542A (en) * | 2006-12-28 | 2008-11-20 | Toto Ltd | Self-cleaning coating composition |
| JP2008223003A (en) * | 2006-12-28 | 2008-09-25 | Toto Ltd | Self-cleaning member and coating composition |
| JP2008229498A (en) * | 2007-03-20 | 2008-10-02 | Nichiha Corp | Construction plate |
| JP2010105329A (en) * | 2008-10-31 | 2010-05-13 | Furukawa-Sky Aluminum Corp | Aluminum-coated plate |
| US8512855B2 (en) | 2009-06-01 | 2013-08-20 | Toto Ltd. | Self-cleaning member and coating composition |
| JP2012166195A (en) * | 2012-03-27 | 2012-09-06 | Asahi Kasei Chemicals Corp | Method for forming stain-proof layer |
| CN103756489A (en) * | 2013-12-13 | 2014-04-30 | 张家港市双林制墨涂装有限公司 | Antibacterial interior wall emulsion paint, and preparation method thereof |
| CN104830185A (en) * | 2015-05-21 | 2015-08-12 | 田福东 | Environment-friendly aqueous interior wall coating for removing formaldehyde |
| CN106583168A (en) * | 2016-11-10 | 2017-04-26 | 刘志徽 | Production device of double-color camouflage type colorful stone coated steel tile and application thereof |
| CN108191378A (en) * | 2017-04-27 | 2018-06-22 | 钟建军 | A kind of inorganic compounding diatom ooze coating |
| JP2019196440A (en) * | 2018-05-09 | 2019-11-14 | 旭化成株式会社 | Coated film and aqueous composition |
| JP7074556B2 (en) | 2018-05-09 | 2022-05-24 | 旭化成株式会社 | Coating film and water-based composition |
| CN110684413A (en) * | 2018-07-05 | 2020-01-14 | 河北瀚宇建材有限公司 | Paint for preventing sand return of wall surface |
| JP7269670B2 (en) | 2020-05-13 | 2023-05-09 | 新福光塗裝工程股▲分▼有限公司 | Method for producing antibacterial paint |
| JP2021178954A (en) * | 2020-05-13 | 2021-11-18 | 新福光塗裝工程股▲分▼有限公司 | Antimicrobial coating material, method for producing antimicrobial coating material, antimicrobial coating, and antivirus tape |
| WO2022210560A1 (en) * | 2021-03-29 | 2022-10-06 | 富士フイルム株式会社 | Antibacterial film, touch panel, and copier |
| CN113622792B (en) * | 2021-10-11 | 2021-12-03 | 南通海鹰木业股份有限公司 | Intelligent aluminum-wood door and window with heat preservation and purification functions |
| CN113622792A (en) * | 2021-10-11 | 2021-11-09 | 南通海鹰木业股份有限公司 | Intelligent aluminum-wood door and window with heat preservation and purification functions |
| CN114717876A (en) * | 2022-04-06 | 2022-07-08 | 金东纸业（江苏）股份有限公司 | Preparation method of antibacterial paper and antibacterial paper |
| CN115074031A (en) * | 2022-06-29 | 2022-09-20 | 吉力水性新材料科技（珠海）有限公司 | Water-based antibacterial and antistatic coating and preparation method thereof |
| CN115466535A (en) * | 2022-08-10 | 2022-12-13 | 雅士利涂料（苏州）有限公司 | Novel composite antibacterial coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4517384B2 (en) | 2010-08-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4395886B2 (en) | Water-based paint composition, antibacterial member and coating film forming method | |
| JP4517384B2 (en) | Water-based paint composition, antibacterial member and coating film forming method | |
| JP7092475B2 (en) | Veneer | |
| TWI440505B (en) | Photocatalyst coating | |
| WO2003102091A1 (en) | Photocatalytic coating material, photocatalytic composite material and process for producing the same, self-cleaning water-based coating compositions, and self-cleaning member | |
| JP4092434B1 (en) | Photocatalyst-coated body and photocatalyst coating liquid therefor | |
| JP2004331969A (en) | Protective autologous decontamination or autologous cleaning coating against deleterious biological pathogen and toxic chemical | |
| JP2000129172A (en) | Heat-shielding coating and its coating method | |
| JP2007016558A (en) | Construction material board and manufacturing method therefor | |
| JP2012177062A (en) | Antifouling coating composition and method of forming antifouling coating | |
| JP6046436B2 (en) | Method for forming antifouling coating film and antifouling paint | |
| KR101801857B1 (en) | Building panels with excellent heat insulation and antifouling properties | |
| JP2001064583A (en) | Photocatalyst coating composition, photocatalytic coating film, article covered therewith, and method for forming the coating film | |
| JP2004143452A (en) | Self-cleaning aqueous coating composition and self- cleaning member | |
| JP2010042414A (en) | Photocatalyst-coated body and photocatalyst coating liquid therefor | |
| JP2003342526A (en) | Self-cleaning aqueous coating composition and self- cleaning member | |
| JP2003080078A (en) | Photoactive compound and its use | |
| JP2006233072A (en) | Photocatalytic coating, and indoor interior article and wallpaper each coated with the same | |
| JP2023035717A (en) | Coated body, coating composition and method for producing coated body | |
| JP2004300345A (en) | Water-based coating composition, stainproof member and method for forming coating film | |
| JP6797511B2 (en) | Aqueous infrared / ultraviolet shielding coating agent and infrared / ultraviolet shielding treatment method using this | |
| JP2024008136A (en) | Active energy ray-curable composition and coated body | |
| JP2001031907A (en) | Water-base coating composition and coating film thereof | |
| JP7121356B2 (en) | Antibacterial/antiviral coating composition | |
| JP2003206416A (en) | Stain-resisting coating liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060414 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090914 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091113 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091214 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100122 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100426 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100509 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130528 Year of fee payment: 3 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 4517384 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130528 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140528 Year of fee payment: 4 |
|
| LAPS | Cancellation because of no payment of annual fees |