JP2019136655A - Antibacterial porous material and antibacterial product containing the same, and antibacterial method using the same - Google Patents
Antibacterial porous material and antibacterial product containing the same, and antibacterial method using the same Download PDFInfo
- Publication number
- JP2019136655A JP2019136655A JP2018022409A JP2018022409A JP2019136655A JP 2019136655 A JP2019136655 A JP 2019136655A JP 2018022409 A JP2018022409 A JP 2018022409A JP 2018022409 A JP2018022409 A JP 2018022409A JP 2019136655 A JP2019136655 A JP 2019136655A
- Authority
- JP
- Japan
- Prior art keywords
- antibacterial
- porous material
- processed product
- film
- material according
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 148
- 239000011148 porous material Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 30
- 239000002245 particle Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 239000003242 anti bacterial agent Substances 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 29
- 238000000576 coating method Methods 0.000 claims description 29
- 239000006185 dispersion Substances 0.000 claims description 16
- 241000894006 Bacteria Species 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 241000588724 Escherichia coli Species 0.000 claims description 10
- 241000191967 Staphylococcus aureus Species 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000000919 ceramic Substances 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 9
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 7
- 239000004745 nonwoven fabric Substances 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 241000588747 Klebsiella pneumoniae Species 0.000 claims description 3
- 241000589517 Pseudomonas aeruginosa Species 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000000123 paper Substances 0.000 description 25
- -1 silver ions Chemical class 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- 229920005989 resin Polymers 0.000 description 13
- 239000011347 resin Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 239000002994 raw material Substances 0.000 description 12
- 239000000835 fiber Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000011230 binding agent Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920000728 polyester Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 229920001225 polyester resin Polymers 0.000 description 3
- 239000004645 polyester resin Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000929 Ru alloy Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229920002978 Vinylon Polymers 0.000 description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 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
- 229920006231 aramid fiber Polymers 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 238000012643 polycondensation polymerization Methods 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 241000589291 Acinetobacter Species 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 1
- 229920008790 Amorphous Polyethylene terephthalate Polymers 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 241000193738 Bacillus anthracis Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 206010008631 Cholera Diseases 0.000 description 1
- 241000194033 Enterococcus Species 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000589248 Legionella Species 0.000 description 1
- 208000007764 Legionnaires' Disease Diseases 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229920002821 Modacrylic Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical group [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 241000607768 Shigella Species 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 206010043376 Tetanus Diseases 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- XKXHCNPAFAXVRZ-UHFFFAOYSA-N benzylazanium;chloride Chemical compound [Cl-].[NH3+]CC1=CC=CC=C1 XKXHCNPAFAXVRZ-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- QHIWVLPBUQWDMQ-UHFFFAOYSA-N butyl prop-2-enoate;methyl 2-methylprop-2-enoate;prop-2-enoic acid Chemical compound OC(=O)C=C.COC(=O)C(C)=C.CCCCOC(=O)C=C QHIWVLPBUQWDMQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 206010013023 diphtheria Diseases 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000007756 gravure coating Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007759 kiss coating Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229920000428 triblock copolymer Polymers 0.000 description 1
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 1
- 201000008827 tuberculosis Diseases 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Plant Pathology (AREA)
- Dentistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Inorganic Chemistry (AREA)
- Agronomy & Crop Science (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本開示は、多孔質シリカに白金族金属を担持した抗菌用多孔質材料と、該抗菌用多孔質材料を含む抗菌剤、抗菌膜、抗菌加工製品及び抗菌用分散液と、これらを用いた抗菌方法とに関し、さらには抗菌加工製品の製造方法に関する。 The present disclosure relates to an antibacterial porous material in which a platinum group metal is supported on porous silica, an antibacterial agent, an antibacterial film, an antibacterial processed product and an antibacterial dispersion containing the antibacterial porous material, and an antibacterial using these And, more particularly, to a method for producing antimicrobial processed products.
従来から、衛生上の観点や、食品や化粧品の保存性を高めるために各種抗菌剤が用いられており、例えば天然抗菌剤や合成抗菌剤が用いられている。一般に合成抗菌剤としては有機系抗菌剤および無機系抗菌剤が知られており、有機系抗菌剤としては、安息香酸エステル類やソルビン酸塩などが知られているが、効果の持続期間が１〜２ヶ月程度と短い場合がある。また、天然抗菌剤に関しては、供給が不安定であり、生成に多くのコストがかかることが指摘されている。 Conventionally, various antibacterial agents have been used in order to enhance the hygiene viewpoint and the preservability of foods and cosmetics. For example, natural antibacterial agents and synthetic antibacterial agents have been used. In general, organic antibacterial agents and inorganic antibacterial agents are known as synthetic antibacterial agents, and benzoic acid esters and sorbates are known as organic antibacterial agents, but the duration of the effect is 1 It may be as short as ~ 2 months. In addition, it has been pointed out that the supply of natural antibacterial agents is unstable and a lot of production costs.
一方、無機系抗菌剤としては、銀イオン、銅イオンなどを含む抗菌剤が知られている。しかし、銀イオンや銅イオンは、光、熱、共存物質などの影響を受けやすいという問題点がある。 On the other hand, antibacterial agents containing silver ions, copper ions and the like are known as inorganic antibacterial agents. However, silver ions and copper ions have a problem that they are easily affected by light, heat, coexisting substances, and the like.
また、光触媒作用を利用した抗菌剤も知られており、特許文献１には、酸化タングステンからなる抗菌剤が開示されている。この抗菌剤は、酸化タングステンの光触媒作用により、光照射下では高い抗菌性能を発揮する。しかしながら光触媒作用を利用した抗菌剤は暗所下では抗菌性能が十分でないことから、特許文献２には暗所や紫外線をカットした蛍光灯の光照射でも抗菌性能を発現する抗菌剤が開示されている。 Further, an antibacterial agent using a photocatalytic action is also known, and Patent Document 1 discloses an antibacterial agent made of tungsten oxide. This antibacterial agent exhibits high antibacterial performance under light irradiation due to the photocatalytic action of tungsten oxide. However, since antibacterial agents utilizing photocatalysis do not have sufficient antibacterial performance in the dark, Patent Document 2 discloses an antibacterial agent that exhibits antibacterial performance even in the dark or by irradiation with a fluorescent light cut from ultraviolet rays. Yes.
光触媒作用を利用した抗菌剤の場合、必ず何らかの光照射が必要なことから、光触媒作用を利用しない抗菌剤の開発が望まれていた。 In the case of an antibacterial agent utilizing a photocatalytic action, since some kind of light irradiation is necessary, the development of an antibacterial agent not utilizing the photocatalytic action has been desired.
そこで本開示は、光触媒作用を利用しない抗菌用多孔質材料を提供することを目的とする。さらに、抗菌用多孔質材料を含む抗菌剤、抗菌膜、抗菌加工製品及び抗菌用分散液を提供することを目的とする。さらに、これらを用いた抗菌方法及び抗菌加工製品の製造方法を提供することを目的とする。 Then, this indication aims at providing the porous material for antibacterial which does not utilize a photocatalytic action. Furthermore, it aims at providing the antibacterial agent containing the porous material for antibacterial, an antibacterial film, an antibacterial processed product, and the antibacterial dispersion liquid. Furthermore, it aims at providing the antimicrobial method using these, and the manufacturing method of an antimicrobial processed product.
本発明者らは、鋭意検討を行った結果、多孔質シリカに白金族金属を含有する粒子を担持した抗菌用多孔質材料が上記課題を解決できることを見出し、本発明を完成するに至った。具体的には、本発明に係る抗菌用多孔質材料は、多孔質シリカに白金族金属を含有する粒子を担持した抗菌用多孔質材料であって、該抗菌用多孔質材料の細孔径が１〜５０ｎｍであり、かつＢＥＴ比表面積が３００〜２０００ｍ２／ｇであることを特徴とする。 As a result of intensive studies, the present inventors have found that an antibacterial porous material in which particles containing a platinum group metal are supported on porous silica can solve the above problems, and have completed the present invention. Specifically, the antibacterial porous material according to the present invention is an antibacterial porous material in which particles containing a platinum group metal are supported on porous silica, and the pore diameter of the antibacterial porous material is 1 ˜50 nm, and BET specific surface area is 300 to 2000 m 2 / g.
本発明に係る抗菌用多孔質材料では、前記白金族金属が、白金、ロジウム、ルテニウム、イリジウム及びパラジウムから選ばれる少なくとも一種である形態を包含する。 The antibacterial porous material according to the present invention includes a form in which the platinum group metal is at least one selected from platinum, rhodium, ruthenium, iridium and palladium.
本発明に係る抗菌剤は、本発明に係る抗菌用多孔質材料を含むことを特徴とする。 The antibacterial agent according to the present invention includes the antibacterial porous material according to the present invention.
本発明に係る抗菌膜は、本発明に係る抗菌用多孔質材料を含むことを特徴とする。 The antibacterial membrane according to the present invention includes the antibacterial porous material according to the present invention.
本発明に係る抗菌加工製品は、加工製品が本発明に係る抗菌用多孔質材料を含むことを特徴とする。 The antibacterial processed product according to the present invention is characterized in that the processed product includes the antibacterial porous material according to the present invention.
本発明に係る抗菌加工製品では、前記加工製品が、不織布、セラミックハニカム、または、ペーパーハニカムのいずれか一つであることが好ましい。 In the antibacterial processed product according to the present invention, the processed product is preferably any one of a nonwoven fabric, a ceramic honeycomb, and a paper honeycomb.
本発明に係る抗菌加工製品の製造方法は、本発明に係る抗菌用多孔質材料を分散した分散液を加工製品の表面に塗工して、抗菌膜を形成する工程を有することを特徴とする。 The method for producing an antibacterial processed product according to the present invention comprises a step of forming an antibacterial film by coating a dispersion of the antibacterial porous material according to the present invention on the surface of the processed product. .
本発明に係る抗菌加工製品の製造方法では、前記加工製品が不織布、セラミックハニカム、または、ペーパーハニカムのいずれか一つであることが好ましい。 In the method for manufacturing an antibacterial processed product according to the present invention, the processed product is preferably any one of a nonwoven fabric, a ceramic honeycomb, and a paper honeycomb.
本発明に係る抗菌方法は、本発明に係る抗菌剤を用いることを特徴とする。 The antibacterial method according to the present invention is characterized by using the antibacterial agent according to the present invention.
また、本発明に係る抗菌方法は、本発明に係る抗菌用多孔質材料を分散した分散液を加工製品に塗工して、抗菌膜を形成する工程を有することを特徴とする。 In addition, the antibacterial method according to the present invention is characterized by having a step of forming an antibacterial film by applying a dispersion liquid in which the antibacterial porous material according to the present invention is dispersed to a processed product.
本発明に係る抗菌方法では、黄色ブドウ球菌、大腸菌、肺炎桿菌、緑膿菌、黄色ブドウ球菌、および大腸菌から選ばれる少なくとも１種の菌に対して抗菌性を発揮させる形態を包含する。 The antibacterial method according to the present invention includes a form in which antibacterial activity is exerted against at least one bacterium selected from Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, Staphylococcus aureus, and Escherichia coli.
本発明に係る抗菌用分散液は、本発明に係る抗菌用多孔質材料を分散した分散液であることを特徴とする。 The antibacterial dispersion liquid according to the present invention is a dispersion liquid in which the antibacterial porous material according to the present invention is dispersed.
本開示によれば、光触媒作用を利用せずに高い抗菌性能を発揮する抗菌用多孔質材料を提供することができる。さらに本開示によれば、抗菌用多孔質材料を含む抗菌剤、抗菌膜、抗菌加工製品及び抗菌用分散液を提供することができる。さらに本開示によれば、これらを用いた抗菌方法及び抗菌加工製品の製造方法を提供することができる。 According to the present disclosure, it is possible to provide an antibacterial porous material that exhibits high antibacterial performance without using photocatalysis. Furthermore, according to the present disclosure, an antibacterial agent including an antibacterial porous material, an antibacterial film, an antibacterial processed product, and an antibacterial dispersion can be provided. Furthermore, according to the present disclosure, an antibacterial method using these and a method for manufacturing an antibacterial processed product can be provided.
以降、本発明について実施形態を示して詳細に説明するが本発明はこれらの記載に限定して解釈されない。本発明の効果を奏する限り、実施形態は種々の変形をしてもよい。 Hereinafter, the present invention will be described in detail with reference to embodiments, but the present invention is not construed as being limited to these descriptions. As long as the effect of the present invention is exhibited, the embodiment may be variously modified.
以下、本実施形態について、詳細に説明する。本実施形態の抗菌用多孔質材料は、多孔質シリカに白金族金属を含有する粒子を担持した抗菌用多孔質材料であって、抗菌用多孔質材料の細孔径（細孔直径）が１〜５０ｎｍであり、かつＢＥＴ比表面積が３００〜２０００ｍ２／ｇである。細孔径は１〜１０ｎｍが好ましく、ＢＥＴ比表面積は５００〜１５００ｍ２／ｇが好ましい。 Hereinafter, this embodiment will be described in detail. The antibacterial porous material of this embodiment is an antibacterial porous material in which particles containing a platinum group metal are supported on porous silica, and the antibacterial porous material has a pore diameter (pore diameter) of 1 to 1. 50 nm and BET specific surface area is 300-2000 m 2 / g. The pore diameter is preferably 1 to 10 nm, and the BET specific surface area is preferably 500 to 1500 m 2 / g.
また抗菌性能の観点から、白金族金属を含有する粒子を担持する前の多孔質シリカの全細孔容積は０．５〜０．８ｃｍ３／ｇ、より好ましくは０．５〜０．６ｃｍ３／ｇ、平均細孔径は２〜１０ｎｍが好ましく、３〜５ｎｍがより好ましい。用いる多孔質シリカは粉末状であってもペレット状であってもよい。 From the viewpoint of antibacterial performance, the total pore volume of the porous silica before supporting the particles containing the platinum group metal is 0.5 to 0.8 cm 3 / g, more preferably 0.5 to 0.6 cm 3. / G, the average pore diameter is preferably 2 to 10 nm, more preferably 3 to 5 nm. The porous silica used may be in the form of powder or pellets.
白金族金属を含む粒子を担持する前の多孔質シリカのＢＥＴ比表面積は８００ｍ２／ｇ以上、細孔径は３ｎｍ以上の多孔質シリカを使用することが好ましい。ＢＥＴ比表面積および細孔径の上限は特にないが、通常はＢＥＴ比表面積は１１００ｍ２／ｇ以下、細孔径は５０ｎｍ以下である。 It is preferable to use porous silica having a BET specific surface area of 800 m 2 / g or more and a pore diameter of 3 nm or more before supporting the particles containing a platinum group metal. There is no particular upper limit for the BET specific surface area and the pore diameter, but usually the BET specific surface area is 1100 m 2 / g or less and the pore diameter is 50 nm or less.
白金族金属を含む粒子を担持する前の多孔質シリカの製造方法としては、特に限定されるものではないが、例えば特開２０１７−２３８８９号公報に記載にしたがって、製造することができる。具体的には、次のとおりである。まず、無機原料と有機原料を混合し、反応させることにより、有機物を鋳型としてそのまわりに無機物の骨格が形成された有機物と無機物の複合体を形成させる。次いで、得られた複合体から有機物を除去することにより、多孔質シリカが得られる。無機原料としては、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン等のアルコキシシラン、ケイ酸ソーダ、カネマイト（ｋａｎｅｍｉｔｅ、ＮａＨＳｉ２Ｏ５・３Ｈ２Ｏ）、シリカ、シリカ−金属複合酸化物等が挙げられる。これらの無機原料はシリケート骨格を形成する。これらは、単独で又は２種以上を混合して用いることができる。鋳型として使用される有機原料は、特に限定されるものではないが、例えば界面活性剤等が挙げられる。界面活性剤は陽イオン性、陰イオン性、非イオン性のうちのいずれであってもよく、具体的には、アルキルトリメチルアンモニウム（好ましくはアルキル基の炭素数が８〜１８のアルキルトリメチルアンモニウム）、アルキルアンモニウム、ジアルキルジメチルアンモニウム、ベンジルアンモニウムの塩化物、臭化物、ヨウ化物又は水酸化物の他、脂肪酸塩、アルキルスルホン酸塩、アルキルリン酸塩、ポリエチレンオキサイド系非イオン性界面活性剤、一級アルキルアミン、トリブロックコポリマー型のポリアルキレンオキサイド、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル等が挙げられる。これらは、単独で又は２種以上を混合して用いることができる。無機原料と有機原料を混合する場合、適当な溶媒を用いることができる。溶媒としては、特に限定されるものではないが、例えば水、有機溶媒、水と有機溶媒との混合物等が挙げられる。無機物と有機物の複合体の形成方法は特に限定されるものではないが、例えば、有機原料を溶媒に溶解後、無機原料を添加し、所定のｐＨに調製した後に、反応混合物を所定の温度に保持して縮重合反応を行う方法が挙げられる。縮重合反応の反応温度は使用する有機原料や無機原料の種類や濃度によって異なるが、通常０〜１００℃程度が好ましく、より好ましくは３５〜８０℃である。縮重合反応の反応時間は、通常１〜２４時間程度が好ましい。また、上記の縮重合反応は、静置状態、撹拌状態のいずれで行ってもよく、またそれらを組み合わせて行ってもよい。縮重合反応後に得られる複合体から有機原料を除去することによって、多孔質シリカが得られる。有機物と無機物の複合体からの有機物の除去は、４００〜８００℃で焼成する方法、水やアルコール等の溶媒で処理する方法等の方法により行うことができる。 Although it does not specifically limit as a manufacturing method of the porous silica before carrying | supporting the particle | grains containing a platinum group metal, For example, it can manufacture according to description in Unexamined-Japanese-Patent No. 2017-23889. Specifically, it is as follows. First, an inorganic raw material and an organic raw material are mixed and reacted to form an organic matter-inorganic matter composite in which an inorganic matter skeleton is formed around the organic matter as a template. Subsequently, porous silica is obtained by removing organic substances from the obtained composite. Examples of inorganic raw materials include alkoxysilanes such as tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane, sodium silicate, kanemite (Kanemite, NaHSi 2 O 5 .3H 2 O), silica, and silica-metal composite oxide. It is done. These inorganic raw materials form a silicate skeleton. These can be used alone or in admixture of two or more. Although the organic raw material used as a casting_mold | template is not specifically limited, For example, surfactant etc. are mentioned. The surfactant may be any of cationic, anionic, and nonionic, specifically, alkyltrimethylammonium (preferably alkyltrimethylammonium having an alkyl group having 8 to 18 carbon atoms). , Alkylammonium, dialkyldimethylammonium, benzylammonium chloride, bromide, iodide or hydroxide, fatty acid salt, alkylsulfonate, alkylphosphate, polyethylene oxide nonionic surfactant, primary alkyl Examples include amines, triblock copolymer type polyalkylene oxides, glycerin fatty acid esters, and polyglycerin fatty acid esters. These can be used alone or in admixture of two or more. When mixing an inorganic raw material and an organic raw material, a suitable solvent can be used. Although it does not specifically limit as a solvent, For example, water, an organic solvent, the mixture of water and an organic solvent, etc. are mentioned. The formation method of the complex of inorganic and organic is not particularly limited. For example, after dissolving the organic raw material in a solvent, adding the inorganic raw material and adjusting to a predetermined pH, the reaction mixture is brought to a predetermined temperature. A method of carrying out the condensation polymerization reaction while holding is mentioned. The reaction temperature of the polycondensation reaction varies depending on the type and concentration of the organic raw material and inorganic raw material to be used, but is usually preferably about 0 to 100 ° C, more preferably 35 to 80 ° C. The reaction time for the polycondensation reaction is usually preferably about 1 to 24 hours. In addition, the above condensation polymerization reaction may be performed either in a stationary state or in a stirring state, or may be performed in combination. By removing the organic raw material from the composite obtained after the polycondensation reaction, porous silica can be obtained. The removal of the organic substance from the complex of the organic substance and the inorganic substance can be performed by a method such as a method of baking at 400 to 800 ° C. or a method of treating with a solvent such as water or alcohol.
上記多孔質シリカに担持される白金族金属を含む粒子の粒子径は、上記多孔質シリカの細孔径の９５％以下であることが好ましく、２０〜５０％であることがより好ましい。９５％を超えると、細孔内で白金族金属を含む粒子が異形に成長してしまうおそれがあり、抗菌効果が低下する可能性がある。 The particle diameter of the particles containing a platinum group metal supported on the porous silica is preferably 95% or less of the pore diameter of the porous silica, and more preferably 20 to 50%. If it exceeds 95%, particles containing a platinum group metal may grow abnormally in the pores, and the antibacterial effect may be reduced.
多孔質シリカに担持させる白金族金属を含む粒子は、白金、ロジウム、ルテニウム、パラジウム、イリジウムの単体粒子、または、これらの合金粒子である。合金粒子としては、ルテニウム／パラジウム合金、白金／ルテニウム合金が好ましい。粒子の粒子径は、０．５ｎｍ〜１０ｎｍであることが好ましく、より好ましくは０．５ｎｍ〜４ｎｍである。 The particles containing a platinum group metal supported on porous silica are platinum, rhodium, ruthenium, palladium, iridium simple particles, or alloy particles thereof. As the alloy particles, ruthenium / palladium alloys and platinum / ruthenium alloys are preferable. The particle diameter of the particles is preferably 0.5 nm to 10 nm, more preferably 0.5 nm to 4 nm.
これら白金族金属を含む粒子は白金、ルテニウム、イリジウムの少なくとも一種を含む粒子が好ましく、白金、ルテニウムまたはイリジウムのいずれか一種の粒子がより好ましい。 The particles containing a platinum group metal are preferably particles containing at least one of platinum, ruthenium and iridium, and more preferably any one of platinum, ruthenium and iridium.
白金族金属を含む粒子は、白金族金属を含む粒子を担持する前の多孔質シリカの存在下で、白金族金属を含む溶液から核生成させて粒成長させることによって、多孔質シリカに担持させることが好ましい。こうすることによって多孔質シリカの細孔内に粒子径が揃った粒子を担持させることができる。 The particles containing the platinum group metal are supported on the porous silica by nucleating and growing the particles from the solution containing the platinum group metal in the presence of the porous silica before supporting the particles containing the platinum group metal. It is preferable. By doing so, particles having a uniform particle diameter can be carried in the pores of the porous silica.
白金族金属を含む溶液は、例えば、白金族金属の塩酸塩、硝酸塩、硫酸塩等の無機酸塩、白金族金属の有機錯体等の水溶液や有機溶媒との溶液である。取り扱いの観点から無機酸塩の水溶液が好ましく、溶解性の観点から酸溶液が好ましい。通常は、白金族金属の塩酸水が使用される。 The solution containing a platinum group metal is, for example, an inorganic acid salt such as a platinum group metal hydrochloride, nitrate or sulfate, an aqueous solution such as an organic complex of a platinum group metal, or a solution with an organic solvent. An aqueous solution of an inorganic acid salt is preferable from the viewpoint of handling, and an acid solution is preferable from the viewpoint of solubility. Usually, a hydrochloric acid solution of a platinum group metal is used.
白金族金属を含む粒子が担持された抗菌用多孔質材料は、抗菌性を発揮するため、抗菌剤として好適に使用される。抗菌とは、一般社団法人抗菌製品技術協議会のホームページ（ｈｔｔｐ：／／ｗｗｗ．ｋｏｈｋｉｎ．ｎｅｔ）の定義によれば、「製品の表面上における細菌の増殖を抑制すること」とあり、微生物や細菌を死滅させる滅菌や殺菌と区別されている。本実施形態における抗菌剤または抗菌作用とは、ある一定の空間内または製品表面上において細菌の増殖を抑制するまたは細菌数を減少させる効果を有するものであり、増殖の抑制は死滅によってもよい。 Since the antibacterial porous material on which particles containing a platinum group metal are supported exhibits antibacterial properties, it is preferably used as an antibacterial agent. According to the definition of the antibacterial product technology council website (http://www.kohkin.net), “antibacterial” means “suppressing the growth of bacteria on the surface of the product”. It is distinguished from sterilization and sterilization that kill bacteria. The antibacterial agent or antibacterial action in the present embodiment has an effect of suppressing the growth of bacteria or reducing the number of bacteria in a certain space or on the product surface, and the suppression of the growth may be due to death.
本実施形態の抗菌剤は上記抗菌用多孔質材料を含むものであり、該抗菌用多孔質材料をそのまま単独で抗菌剤として用いてもよいし、他の機能を有する剤との混合物、例えば他の抗菌剤、殺菌剤、芳香剤、乾燥剤等の剤との混合物とした抗菌剤でもよい。 The antibacterial agent of the present embodiment includes the above-mentioned antibacterial porous material, and the antibacterial porous material may be used alone as an antibacterial agent, or a mixture with an agent having other functions, for example, other The antibacterial agent made into a mixture with agents such as antibacterial agents, bactericides, fragrances, and desiccants.
また本実施形態に係る抗菌用多孔質材料を含む膜（以下抗菌膜と称する場合もある）としてもよい。抗菌膜は抗菌剤用多孔質シリカを樹脂と混合しフィルム状とすることにより作製することができる。または抗菌膜は抗菌用多孔質材料を含有する分散液を調製し、支持体に塗布後、塗膜を乾燥し、支持体を除去して膜状とすることにより作製することもできる。また他の樹脂と混合してフィルム状として他のフィルムと積層する、共押出等により他の樹脂との多層フィルムを形成する、などの方法で抗菌膜（抗菌層）を形成してもよい。樹脂としては、例えば、ナイロン、ポリエステル、ポリエチレン、ポリプロピレン、エチレン酢酸ビニル等、通常、フィルムに使用できる樹脂が例示できる。 Moreover, it is good also as a film | membrane (it may be hereafter called an antibacterial film | membrane) containing the porous material for antibacterial concerning this embodiment. The antibacterial membrane can be produced by mixing porous silica for an antibacterial agent with a resin to form a film. Alternatively, the antibacterial membrane can be prepared by preparing a dispersion containing an antibacterial porous material, applying the dispersion to a support, drying the coating, and removing the support to form a film. Moreover, you may form an antibacterial film (antibacterial layer) by methods, such as mixing with other resin, laminating | stacking with another film as a film form, or forming a multilayer film with other resin by coextrusion etc. Examples of the resin include resins that can be generally used for films, such as nylon, polyester, polyethylene, polypropylene, and ethylene vinyl acetate.
衛生上の観点から、つり革や手すりのような不特定多数の人が触れる製品、文房具や台所用品のような手で触れる製品、住環境における内装材、繊維製品等のあらゆる製品に抗菌性を付与するために、本実施形態に係る抗菌用多孔質材料を有する加工製品が抗菌加工製品として好ましい。このような抗菌加工製品は衛生上の観点から好ましい。 From a hygienic point of view, antibacterial properties are applied to all products such as straps and handrails that are touched by an unspecified number of people, products that are touched by hands such as stationery and kitchenware, interior materials in the living environment, and textile products. In order to give, the processed product which has the antibacterial porous material which concerns on this embodiment is preferable as an antibacterial processed product. Such an antibacterial processed product is preferable from the viewpoint of hygiene.
本実施形態に係る抗菌用多孔質材料は、加工製品の内表面または外表面であれば、どの部分に付与されていてもよく、特に、菌が接触しやすい面に付与されていることが好ましい。加工製品の材質は、特に限定されず、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙など、あらゆる材料からなる製品を対象にすることができる。さらに、プラスチックの基材としては、例えばポリ塩化ビニル系樹脂、ＡＢＳ系樹脂、ＡＥＳ系樹脂、ポリアクリル系樹脂、ポリウレタン系樹脂、ポリエチレンテレフタレート、非結晶性ポリエチレンテレフタレートコポリマー、完全非晶性ポリエステル系樹脂、ポリカーボネート、ポリエチレン、ポリプロピレンなどが挙げられる。本実施形態に係る抗菌加工製品としては、具体的には建築資材（天井材、タイル、ガラス、壁紙、壁材、床など）、自動車内装材（自動車インストルメントパネル、自動車用シート、自動車用天井材、自動車用ガラスなど）、家電製品（冷蔵庫、エアコンなど）、繊維製品（衣類、カーテンなど）、不特定多数の人が接触する物品（電車のつり革、デスクマット、テーブルクロス、エレベーターのボタン、階段や廊下の手摺など）などが挙げられる。 The porous material for antibacterial according to the present embodiment may be applied to any part as long as it is an inner surface or an outer surface of the processed product, and is particularly preferably applied to a surface that is easily contacted by bacteria. . The material of the processed product is not particularly limited, and for example, a product made of any material such as plastic, metal, ceramics, wood, concrete, and paper can be targeted. Furthermore, as a plastic substrate, for example, polyvinyl chloride resin, ABS resin, AES resin, polyacrylic resin, polyurethane resin, polyethylene terephthalate, amorphous polyethylene terephthalate copolymer, completely amorphous polyester resin , Polycarbonate, polyethylene, polypropylene and the like. Specifically, antibacterial processed products according to this embodiment include building materials (ceiling materials, tiles, glass, wallpaper, wall materials, floors, etc.), automotive interior materials (automotive instrument panels, automotive seats, automotive ceilings). Materials, automotive glass, etc.), household appliances (refrigerators, air conditioners, etc.), textile products (clothing, curtains, etc.), articles that can be contacted by an unspecified number of people (train straps, desk mats, table cloths, elevator buttons) Stairs, handrails in hallways, etc.).
また抗菌効果と取り扱いやすさの観点から、加工製品として後述するような、基材が抗菌用多孔質材料を有する抗菌加工製品が好ましい。 In addition, from the viewpoint of antibacterial effect and ease of handling, an antibacterial processed product in which the base material has a porous material for antibacterial purposes as described later as the processed product is preferable.
基材としては、その形状は例えばフィルム状、シート状、柱状、ハニカム状等の形状や不織布状、織布状、紙状、フェルト状が例示でき、塗布する表面は平滑であっても、凹凸であってもよい。その材質は金属、樹脂、木材、紙、繊維、天然皮革、合成皮革等が例示できる。 Examples of the substrate include a film shape, a sheet shape, a columnar shape, a honeycomb shape, a non-woven fabric shape, a woven fabric shape, a paper shape, and a felt shape. It may be. Examples of the material include metal, resin, wood, paper, fiber, natural leather, and synthetic leather.
基材としては抗菌効率の観点から、表面積が大きい基材が好ましく、取り扱いの観点からハニカム状の基材、不織布または紙が好ましい。ここでいうハニカム状とは、広義の意味であり、正六角形に限らず、立体図形を間断なく並べた三次元空間充填形状のものであって連通孔を有するものであり、孔の形状は円形や三角形、四角形、五角形、六角形等の多角形が例示できる。孔の形状は全て同じであっても、これら形状の２以上を有するものであっても良い。 As the substrate, a substrate having a large surface area is preferable from the viewpoint of antibacterial efficiency, and a honeycomb substrate, nonwoven fabric or paper is preferable from the viewpoint of handling. The honeycomb shape here has a broad meaning and is not limited to a regular hexagon, but a three-dimensional space-filled shape in which solid figures are arranged without interruption, and has communication holes, and the shape of the holes is circular. And polygons such as a triangle, a quadrangle, a pentagon, and a hexagon. The shapes of the holes may all be the same, or may have two or more of these shapes.
ハニカム状の基材としてはセラミックハニカムやペーパーハニカムが例示できる。セラミックハニカムの成分は、コージェライト、炭化珪素、窒化珪素、アルミナ、ムライト、アルミニウムチタネート、チタニア及びジルコニアからなる群から選ばれる成分からなるものが好ましい。 Examples of the honeycomb substrate include a ceramic honeycomb and a paper honeycomb. The ceramic honeycomb component is preferably composed of a component selected from the group consisting of cordierite, silicon carbide, silicon nitride, alumina, mullite, aluminum titanate, titania and zirconia.
ペーパーハニカムは、クラフト紙、Ｋライナー紙、強化中芯原紙、耐水中芯原紙、水酸化アルミ紙等からなる群から選ばれる紙からなるものが好ましい。またこれら紙の中でも絶縁性を有する紙が好ましく、不燃性または難燃性を有するものが好ましい。 The paper honeycomb is preferably made of paper selected from the group consisting of kraft paper, K liner paper, reinforced core base paper, water-resistant core base paper, aluminum hydroxide paper and the like. Among these papers, paper having insulating properties is preferable, and paper having incombustibility or flame retardancy is preferable.
セラミックハニカムは上記成分を押出し成型により所定の形状に成型することで製造することができる。またペーパーハニカムは上記の紙を平板状、波形状、円柱状、蜂巣状等に連続成型積層することで製造することが出来る。これらを用途・環境に合わせて適宜選択し使用する。耐熱性の観点からセラミックハニカムが好ましく、軽量性の観点からペーパーハニカムが好ましい。 The ceramic honeycomb can be manufactured by molding the above components into a predetermined shape by extrusion molding. The paper honeycomb can be manufactured by continuously molding and laminating the above paper into a flat plate shape, a wave shape, a cylindrical shape, a honeycomb shape, or the like. These are appropriately selected and used according to the application and environment. A ceramic honeycomb is preferable from the viewpoint of heat resistance, and a paper honeycomb is preferable from the viewpoint of lightness.
不織布は、アラミド繊維、ガラス繊維、セルロース繊維、ナイロン繊維、ビニロン繊維、ポリエステル繊維、ポリエチレン繊維、ポリプロピレン繊維、ポリオレフィン繊維、レーヨン繊維、低密度ポリエチレン樹脂、エチレン酢酸ビニル樹脂、共重合ポリアミド樹脂、共重合ポリエステル樹脂、ポリフェニレンスルフィド樹脂等の繊維からなるものであり、耐熱性の観点からアラミド繊維、ガラス繊維、セルロース繊維、ナイロン繊維、ビニロン繊維、ポリエステル繊維が好ましく、難燃性や外気からの洗浄処理性に富んでいるという観点から、ポリエステル／モダアクリル樹脂の繊維がさらに好ましい。 Non-woven fabric is aramid fiber, glass fiber, cellulose fiber, nylon fiber, vinylon fiber, polyester fiber, polyethylene fiber, polypropylene fiber, polyolefin fiber, rayon fiber, low density polyethylene resin, ethylene vinyl acetate resin, copolymerized polyamide resin, copolymer It consists of fibers such as polyester resin and polyphenylene sulfide resin, and from the viewpoint of heat resistance, aramid fiber, glass fiber, cellulose fiber, nylon fiber, vinylon fiber, and polyester fiber are preferable. Flame retardancy and cleanability from the outside air From the viewpoint of richness, polyester / modacrylic resin fibers are more preferable.
紙は、和紙、洋紙、紙と板紙（ボール紙）、包装用紙（包装紙や封筒）等の紙が例示でき、防水や耐水性に富んでいるという観点から包装材料が、また、油や脂質への耐性や難燃性に富んでいるという観点から食品包装用材料がさらに好ましい。 Examples of paper include Japanese paper, paper, paper and paperboard (cardboard), and wrapping paper (wrapping paper and envelopes). From the viewpoint of water and water resistance, the packaging material, oil and lipid Food packaging materials are more preferable from the viewpoint of high resistance to fire and flame retardancy.
抗菌性を付与した抗菌加工製品とする場合、抗菌用多孔質材料は菌と接触する部分に存在すれば特に制限はないが、通常は基材等の加工製品の表面に付与される。 In the case of an antibacterial processed product imparted with antibacterial properties, the antibacterial porous material is not particularly limited as long as it is present in a portion in contact with bacteria, but is usually applied to the surface of a processed product such as a substrate.
抗菌用多孔質材料を有する加工製品を製造する方法としては、加工製品と抗菌用多孔質材料を熱融着する方法、加工製品に抗菌膜を形成する方法、加工製品の材料と抗菌用多孔質材料を予め混合したのち、目的とする加工製品の形状に成型する方法、等が挙げられる。これらの方法の中でも、加工製品に抗菌膜を形成する方法が加工製品の所望の部分に抗菌性能を付与することができることから好ましい。抗菌膜を形成する場所は菌と接触する箇所であれば特に制限はないが、抗菌膜は通常は加工製品の表面に設けられ、表面の一部分に形成されても全面に形成されてもよい。 As a method of manufacturing a processed product having an antibacterial porous material, a method of heat-sealing the processed product and the antibacterial porous material, a method of forming an antibacterial film on the processed product, a material of the processed product and an antibacterial porous material Examples include a method in which the materials are mixed in advance and then molded into the shape of the intended processed product. Among these methods, a method of forming an antibacterial film on a processed product is preferable because antibacterial performance can be imparted to a desired portion of the processed product. The place where the antibacterial film is formed is not particularly limited as long as it is a place where the antibacterial film is in contact with the bacteria.
抗菌膜を加工製品に形成する方法としては、上記抗菌用多孔質材料を水、またはエタノール等の有機溶媒に分散させ、必要に応じてバインダーや沈降防止剤を添加して分散液を調製し、この分散液を塗布液として、基材等の加工製品に塗布する方法が例示できる。 As a method of forming an antibacterial film on a processed product, the antibacterial porous material is dispersed in water or an organic solvent such as ethanol, and if necessary, a binder or an antisettling agent is added to prepare a dispersion. A method of applying this dispersion liquid as a coating liquid to a processed product such as a substrate can be exemplified.
バインダーとして、例えば、アルミナ、ジルコニア、シリカ等の無機バインダー、ポリエチレン系樹脂、ポリプロピレン系樹脂、メタクリル酸メチル等のアクリル系樹脂、ＡＢＳ樹脂、ＰＥＴ等のポリエステル系樹脂、フェノール樹脂、エポキシ樹脂、ウレタン樹脂、酢酸ビニル系樹脂、ポリビニルアルコール、カルボキシメチルセルロース等のセルロース、アラビヤゴム、ウレタン、フェノール、ジエン等の有機バインダーが例示できる。また塗布液にはさらに、シリカ、フェームドシリカ等の沈降防止剤を含んでいてもよい。 Examples of binders include inorganic binders such as alumina, zirconia, and silica, polyethylene resins, polypropylene resins, acrylic resins such as methyl methacrylate, ABS resins, polyester resins such as PET, phenol resins, epoxy resins, and urethane resins. Examples thereof include organic binders such as cellulose acetates such as vinyl acetate resins, polyvinyl alcohol and carboxymethyl cellulose, arabic rubber, urethane, phenol and diene. Further, the coating solution may further contain an anti-settling agent such as silica or famed silica.
塗布液を加工製品の表面に塗布したとき、塗膜に無機バインダーを含有させていると、塗布液を塗布した後の加工製品を昇温・減圧乾燥することによって、乾燥が促進される。さらに、塗膜に無機バインダーを含有させていると、塗膜と加工製品との密着性が向上する。 When the coating solution is applied to the surface of the processed product, if the coating film contains an inorganic binder, drying is promoted by heating and drying the processed product after applying the coating solution under reduced pressure. Furthermore, when the coating film contains an inorganic binder, the adhesion between the coating film and the processed product is improved.
塗膜に有機バインダーを含有させると、塗膜と水の相溶性が低減し、乾燥後の塗膜の撥水性が向上し、抗菌用多孔質材料の細孔内に水分が混入することを防止できる。さらに塗膜に有機バインダーを含有させると、塗膜と加工製品との密着性が向上する。 When an organic binder is included in the coating film, the compatibility between the coating film and water is reduced, the water repellency of the coating film after drying is improved, and moisture is prevented from entering the pores of the antibacterial porous material. it can. Further, when the coating film contains an organic binder, the adhesion between the coating film and the processed product is improved.
沈降防止剤は、抗菌用多孔質材料を湿式分散するときに、添加され、水またはエタノール等の溶媒に分散させた分散液としたとき、及び、分散液を濃縮乾燥して粉末としたのち、水、溶媒等で乾燥粉末を再度分散させて塗膜用の塗布液としたとき、分散した粉末の沈降を抑制する。沈降防止剤は乾燥した塗膜となったときに塗膜中に存在する。塗布液の分散性が良好であると、均一な塗膜を形成することができ、この結果、抗菌膜における抗菌効果を向上させることができる。 The anti-settling agent is added when the antibacterial porous material is wet-dispersed, and when the dispersion is dispersed in a solvent such as water or ethanol, and after the dispersion is concentrated and dried to a powder, When the dry powder is dispersed again with water, a solvent or the like to form a coating solution for a coating film, sedimentation of the dispersed powder is suppressed. The anti-settling agent is present in the coating when it becomes a dry coating. When the dispersibility of the coating liquid is good, a uniform coating film can be formed, and as a result, the antibacterial effect in the antibacterial film can be improved.
上記塗布液において、分散媒の含有量は、抗菌剤１００質量部に対して、通常３００〜２００００質量部、好ましくは５００〜１００００質量部である。分散媒がこのような範囲で含有される場合、抗菌剤が沈降しにくく、また容積効率の点でも好ましい。 In the said coating liquid, content of a dispersion medium is 300-20000 mass parts normally with respect to 100 mass parts of antibacterial agents, Preferably it is 500-10000 mass parts. When the dispersion medium is contained in such a range, the antibacterial agent is unlikely to settle, and is preferable from the viewpoint of volume efficiency.
塗布液の塗布の方法も特に制限はなく、ブレードコーティング、グラビアコーティング、リバースコーティング、刷毛ロールコーティング、スプレーコーティング、キスコーティング、ダイコーティング、ディッピング、バーコーティング、アプリケーターなどの公知の方法で塗布し、分散媒を揮発させればよい。抗菌膜の膜厚は、０．１〜５００μｍであることが好ましく、０．１〜１００μｍであることがより好ましい。 The method of applying the coating liquid is also not particularly limited, and is applied and dispersed by a known method such as blade coating, gravure coating, reverse coating, brush roll coating, spray coating, kiss coating, die coating, dipping, bar coating, applicator, etc. What is necessary is just to volatilize a medium. The film thickness of the antibacterial film is preferably 0.1 to 500 μm, and more preferably 0.1 to 100 μm.
塗布液において、使用する有機溶媒等の量は、抗菌用多孔質材料１００質量部に対して、通常３００〜２００００質量部、好ましくは５００〜１００００質量部である。有機溶媒等がこのような範囲で含有される場合、抗菌用多孔質材料が沈降しにくく、また容積効率の点でも好ましい。 In the coating solution, the amount of the organic solvent and the like to be used is usually 300 to 20000 parts by mass, preferably 500 to 10,000 parts by mass with respect to 100 parts by mass of the antibacterial porous material. When the organic solvent or the like is contained in such a range, the antibacterial porous material is less likely to settle, and is preferable from the viewpoint of volume efficiency.
加工製品と抗菌膜との密着性を向上させる目的で、必要に応じて、抗菌膜と加工製品との間に下地層を形成してもよい。下地層は、変性シリコーンや変成シリコーンポリマーを含む下地層形成用コート液を加工製品表面に塗布することによって形成される。下地層の膜厚は、特に制限されるものではなく、その用途などに応じて、適宜設定すればよい。通常、２０ｎｍ〜３ｍｍ程度の範囲である。加工製品に付与する抗菌膜の膜厚は上述と同じである。 For the purpose of improving the adhesion between the processed product and the antibacterial film, a base layer may be formed between the antibacterial film and the processed product, if necessary. The underlayer is formed by applying an underlayer-forming coating solution containing a modified silicone or a modified silicone polymer to the surface of the processed product. The film thickness of the underlayer is not particularly limited, and may be set as appropriate according to the application. Usually, it is in the range of about 20 nm to 3 mm. The film thickness of the antibacterial film applied to the processed product is the same as described above.
上記抗菌剤を一定の空間内に設置する、または抗菌用多孔質材料を有する加工製品を用いる等の方法によって高い抗菌効果を長期に亘って発現することができる。抗菌効果の観点から、上記のような抗菌膜を加工製品に形成した抗菌加工製品を用いる抗菌方法が好ましい。対象となる菌は、黄色ブドウ球菌、大腸菌、肺炎桿菌、緑膿菌、炭疽菌、結核菌、コレラ菌、ジフテリア菌、破傷風菌、ペスト菌、赤痢菌、ボツリヌス菌、アシネトバクター、緑膿菌、ＮＤＭ−１産生多剤耐性菌、黄色ブドウ球菌、大腸菌、腸球菌、レジオネラ菌などの病原菌が例示でき、これらの菌の増殖を抑制できる。 A high antibacterial effect can be exhibited over a long period of time by a method such as installing the antibacterial agent in a certain space or using a processed product having a porous material for antibacterial purposes. From the viewpoint of the antibacterial effect, an antibacterial method using an antibacterial processed product in which the above-described antibacterial film is formed on the processed product is preferable. The target bacteria are Staphylococcus aureus, Escherichia coli, Klebsiella pneumoniae, Pseudomonas aeruginosa, anthrax, tuberculosis, cholera, diphtheria, tetanus, plague, shigella, botulinum, acinetobacter, aeruginosa, NDM -1 production multidrug resistant bacteria, Staphylococcus aureus, Escherichia coli, Enterococcus, Legionella, and other pathogenic bacteria can be exemplified, and the growth of these bacteria can be suppressed.
以下、実施例および比較例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例および比較例における各物性の測定および抗菌性活性の評価については、以下の方法で行った。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated concretely, this invention is not limited to these Examples. In addition, about the measurement of each physical property in an Example and a comparative example, and evaluation of antibacterial activity, it performed with the following method.
（実施例１）
（白金が担持された抗菌用多孔質材料の合成）
多孔質シリカとして、メソポーラスシリカ（太陽化学株式会社製 商品名ＴＭＰＳ−４アール 商標登録名ＴＭＰＳ）１ｇを５０ｍＬの水に懸濁させ、白金粒子の担持量が１質量％になるように塩化白金酸水溶液を滴下し、その溶液を室温にて一晩放置した。その後、懸濁液を、エバポレータを用いてオイル温度約７０℃にて加熱し、かつ減圧（３ｋＰａ）下において、溶媒を揮発させることで懸濁液を濃縮した後、終夜で乾燥した。得られた粉末を６０℃で１６〜１８時間、真空乾燥させた。その後、窒素ガス３００ｍｌ／ｍｉｎ及び水素ガスを３００ｍＬ／ｍｉｎで流通させながら、１００℃から２００℃の温度となるように水素−窒素の混合ガス雰囲気下で粉末を２時間加熱した。その後、水素で置換した水素雰囲気下において粉末を１００℃から２００℃で還元処理した。これにより、多孔質シリカに白金粒子を担持した抗菌用多孔質材料１（白金担持率１ｗｔ％）を得た。
Example 1
(Synthesis of antimicrobial porous material carrying platinum)
As porous silica, 1 g of mesoporous silica (trade name TMPS-4 are registered trademark TMPS, manufactured by Taiyo Kagaku Co., Ltd.) is suspended in 50 mL of water, and chloroplatinic acid so that the supported amount of platinum particles is 1% by mass. The aqueous solution was added dropwise and the solution was left overnight at room temperature. Thereafter, the suspension was heated at an oil temperature of about 70 ° C. using an evaporator, and the suspension was concentrated by volatilizing the solvent under reduced pressure (3 kPa), followed by drying overnight. The obtained powder was vacuum-dried at 60 ° C. for 16 to 18 hours. Thereafter, the powder was heated for 2 hours in a hydrogen-nitrogen mixed gas atmosphere at a temperature of 100 ° C. to 200 ° C. while flowing nitrogen gas at 300 ml / min and hydrogen gas at 300 mL / min. Thereafter, the powder was reduced at 100 to 200 ° C. in a hydrogen atmosphere substituted with hydrogen. As a result, an antibacterial porous material 1 (platinum support rate 1 wt%) in which platinum particles were supported on porous silica was obtained.
（実施例２）
（ルテニウムが担持された抗菌用多孔質材料の合成）
実施例１において、塩化白金酸の代わりに塩化ルテニウムを用いた以外は同様にして抗菌用多孔質材料２を得た。
(Example 2)
(Synthesis of antibacterial porous material carrying ruthenium)
In Example 1, an antibacterial porous material 2 was obtained in the same manner except that ruthenium chloride was used instead of chloroplatinic acid.
（実施例３）
（イリジウムが担持された抗菌用多孔質材料の合成）
実施例１において、塩化白金酸の代わりに塩化イリジウムを用いた以外は同様にして抗菌用多孔質材料３を得た。
(Example 3)
(Synthesis of antibacterial porous material carrying iridium)
In Example 1, the antibacterial porous material 3 was obtained in the same manner except that iridium chloride was used instead of chloroplatinic acid.
実施例１〜３の抗菌用多孔質材料は、いずれも、ＢＥＴ比表面積８０７ｍ２／ｇ、細孔径３〜４ｎｍ、平均細孔径３．７ｎｍ、全細孔容積０．７ｃｍ３／gであった。 The antibacterial porous materials of Examples 1 to 3 all had a BET specific surface area of 807 m 2 / g, a pore diameter of 3 to 4 nm, an average pore diameter of 3.7 nm, and a total pore volume of 0.7 cm 3 / g. .
実施例１〜３の抗菌用多孔質材料について、大腸菌および黄色ブドウ球菌に対する抗菌性活性の測定を行った。結果を表１に示した。 The antibacterial activity of Escherichia coli and Staphylococcus aureus was measured for the antibacterial porous materials of Examples 1 to 3. The results are shown in Table 1.
（比較例１）
金属を担持しない多孔質シリカとして、メソポーラスシリカ（太陽化学株式会社製 商品名ＴＭＰＳ−４アール 商標登録名ＴＭＰＳ）単体での抗菌性活性の測定を行った。使用したメソポーラスシリカのＢＥＴ比表面積８５０ｍ２／ｇ、細孔径３〜４ｎｍ、平均細孔径３．８ｎｍ、全細孔容積０．８５ｃｍ３／gであった。結果を表１に示した。
(Comparative Example 1)
As the porous silica not supporting a metal, the antibacterial activity of mesoporous silica (trade name TMPS-4R trademark registered name TMPS manufactured by Taiyo Kagaku Co., Ltd.) alone was measured. The mesoporous silica used had a BET specific surface area of 850 m 2 / g, a pore diameter of 3 to 4 nm, an average pore diameter of 3.8 nm, and a total pore volume of 0.85 cm 3 / g. The results are shown in Table 1.
（ＢＥＴ比表面積）
比表面積（ＳＢＥＴ）は窒素吸脱着測定より得られた吸着等温線を用いてＢＥＴ法により測定した。
（平均細孔径）
αＳプロット法により測定した。
（全細孔容積）
ＢＪＨ法により測定した。
(BET specific surface area)
The specific surface area (S BET ) was measured by the BET method using an adsorption isotherm obtained by nitrogen adsorption / desorption measurement.
(Average pore diameter)
It was measured by the αS plot method.
(Total pore volume)
It measured by BJH method.
なお、ＢＥＴ比表面積、平均細孔径及び全細孔容積は、比表面積／細孔分布測定装置（マイクロトラック・ベル株式会社製ＢＥＬＳＯＲＰ−ｍｉｎｉ ＩＩ）を用いて測定した。 The BET specific surface area, average pore diameter, and total pore volume were measured using a specific surface area / pore distribution measuring device (BELSORP-mini II manufactured by Microtrack Bell Co., Ltd.).
（抗菌性活性の測定）
普通寒天培地（栄研化学株式会社製）、３５±１℃、１８〜２４時間で前培養を行った。菌液は精製水で調製し、Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ ＮＢＲＣ ３９２７（大腸菌）の菌数は１０５〜１０６／ｍｌで播種した。Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ｓｕｂｓｐ． Ａｕｒｅｕｓ ＮＢＲＣ １２７３２（黄色ブドウ球菌）は同様に、生理食塩水で菌液を調製し、１０５〜１０６／ｍｌで播種した。試験菌液１０ｍｌに、試料１ｇを添加して２４時間室温で保存した。生菌数測定はＳＣＤＬＰ寒天培地（日本製薬株式会社製）を用い、混釈平板培養法にて３５±１℃、二日間培養して測定した。
抗菌活性値は（数１）の式で求めた。
（数１） 抗菌活性値＝ｌｏｇ（Ｎ0／Ｎ）
Ｎ0：試料を添加しない場合の生菌数
Ｎ：試料１ｇを添加し、２４時間室温で保存後の生菌数
なお、試料とは、実施例１、２または３で得られた試料（抗菌用多孔質材料）、或いは比較例１で得られた試料（多孔質シリカ単体）である。
(Measurement of antibacterial activity)
Pre-culture was performed in a normal agar medium (manufactured by Eiken Chemical Co., Ltd.) at 35 ± 1 ° C. for 18-24 hours. The bacterial solution was prepared with purified water, and Escherichia coli NBRC 3927 (Escherichia coli) was inoculated at 10 5 to 10 6 / ml. Staphylococcus aureus subsp. Similarly, Aureus NBRC 12732 (Staphylococcus aureus) was prepared with a physiological saline solution and seeded at 10 5 to 10 6 / ml. 1 g of the sample was added to 10 ml of the test bacterial solution and stored at room temperature for 24 hours. The viable cell count was measured by culturing at 35 ± 1 ° C. for 2 days by a pour plate culture method using an SCDLP agar medium (manufactured by Nippon Pharmaceutical Co., Ltd.).
The antibacterial activity value was determined by the formula (Equation 1).
(Equation 1) Antibacterial activity value = log (N 0 / N)
N 0 : Number of viable bacteria when no sample is added N: Number of viable bacteria after adding 1 g of sample and storing at room temperature for 24 hours Note that the sample is the sample (antibacterial) obtained in Example 1, 2 or 3 Porous material), or the sample (porous silica alone) obtained in Comparative Example 1.
上記表１から明らかなように、実施例１〜３の抗菌用多孔質材料は大腸菌および黄色ブドウ球菌に対して高い抗菌性能を発揮することがわかった。 As is apparent from Table 1 above, it was found that the antibacterial porous materials of Examples 1 to 3 exhibited high antibacterial performance against Escherichia coli and Staphylococcus aureus.
Claims (12)
An antibacterial dispersion, wherein the antibacterial porous material according to claim 1 is dispersed.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018022409A JP2019136655A (en) | 2018-02-09 | 2018-02-09 | Antibacterial porous material and antibacterial product containing the same, and antibacterial method using the same |
| PCT/JP2019/004242 WO2019156118A1 (en) | 2018-02-09 | 2019-02-06 | Antibacterial porous material, antibacterial product containing this, and antibacterial method using this |
| CN201980011678.0A CN111683532A (en) | 2018-02-09 | 2019-02-06 | Antibacterial porous material, antibacterial processed product containing same, and antibacterial method using same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018022409A JP2019136655A (en) | 2018-02-09 | 2018-02-09 | Antibacterial porous material and antibacterial product containing the same, and antibacterial method using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2019136655A true JP2019136655A (en) | 2019-08-22 |
Family
ID=67549729
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018022409A Pending JP2019136655A (en) | 2018-02-09 | 2018-02-09 | Antibacterial porous material and antibacterial product containing the same, and antibacterial method using the same |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP2019136655A (en) |
| CN (1) | CN111683532A (en) |
| WO (1) | WO2019156118A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019137637A (en) * | 2018-02-09 | 2019-08-22 | 株式会社フルヤ金属 | Antifungal porous material and antifungal product containing the same, and antifungal method using the same |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112870221B (en) * | 2021-01-05 | 2023-03-28 | 中山大学附属第五医院 | Chitosan nano rhodium material and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124425A (en) * | 1995-11-06 | 1997-05-13 | Sekisui Chem Co Ltd | Antimicrobial agent |
| JP2008544953A (en) * | 2005-05-10 | 2008-12-11 | チバ ホールディング インコーポレーテッド | Antibacterial porous silicon oxide particles |
| WO2011045627A1 (en) * | 2009-10-12 | 2011-04-21 | Arce Macias, Carlos, Francisco | Viricide agents having nanostructured biocatalysts materials of titanium dioxide (tio2) and silicium dioxide (si02) with platinum and iridium modified and dispersed on the surface |
| JP2019085336A (en) * | 2017-11-01 | 2019-06-06 | 株式会社ファンケル | Antibacterial agent |
Family Cites Families (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000128706A (en) * | 1998-10-26 | 2000-05-09 | Toyota Central Res & Dev Lab Inc | Cloth holding photocatalyst |
| JP2000154340A (en) * | 1998-11-20 | 2000-06-06 | Kenji Nakamura | Antibacterial inorganic porous composition and use thereof |
| DE19935230C2 (en) * | 1999-07-28 | 2003-06-26 | Kallies Feinchemie Ag | Biofilm inhibitor |
| EP1287886A1 (en) * | 2001-08-09 | 2003-03-05 | OMG AG & Co. KG | Catalyst for cleaning of exhaust gases of a combustion engine |
| KR100621452B1 (en) * | 2002-06-05 | 2006-09-13 | 도시오 고무로 | Antithrombogenic platiniferous ceramic composition and article containing the same |
| DE10353756A1 (en) * | 2003-11-17 | 2005-06-30 | Bio-Gate Bioinnovative Materials Gmbh | layer material |
| JP2009061372A (en) * | 2007-09-05 | 2009-03-26 | Taiyo Kagaku Co Ltd | Catalyst for selective oxidation of carbon monoxide and method of removing carbon monoxide in hydrogen by using it |
| KR101135571B1 (en) * | 2009-12-01 | 2012-04-17 | (주)에이씨티 | manufacturing method for silica powder coated by antiseptic, and composition for external skin comprising the silica powder |
| CN101744002B (en) * | 2009-12-29 | 2012-11-21 | 浙江理工大学 | Silicon-zinc mesoporous material silver-carrying antibacterial agent and preparation method thereof |
| CN101731275A (en) * | 2009-12-29 | 2010-06-16 | 浙江理工大学 | Silicon-zinc nano mesoporous inorganic antibacterial and preparation method thereof |
| JP2011225521A (en) * | 2010-03-30 | 2011-11-10 | Sony Corp | Fungicide, photo catalytic composite material, adsorbent, and depurative |
| CN103798289A (en) * | 2014-02-14 | 2014-05-21 | 浙江理工大学 | Preparation method of silver-loaded mesoporous silicon dioxide antibacterial agent |
| JP6617384B2 (en) * | 2015-07-15 | 2019-12-11 | 太陽化学株式会社 | Ethylene decomposing agent |
| CN105536825B (en) * | 2016-01-09 | 2018-11-23 | 深圳市康风环境科技发展有限公司 | Air sterilizing catalyst for clarifying and preparation method thereof |
| CN106975496B (en) * | 2017-04-11 | 2019-09-27 | 苏州格绿新材料科技有限公司 | Antibacterial catalysis reduction porous material and its preparation and the application on production reductive water |
-
2018
- 2018-02-09 JP JP2018022409A patent/JP2019136655A/en active Pending
-
2019
- 2019-02-06 CN CN201980011678.0A patent/CN111683532A/en active Pending
- 2019-02-06 WO PCT/JP2019/004242 patent/WO2019156118A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09124425A (en) * | 1995-11-06 | 1997-05-13 | Sekisui Chem Co Ltd | Antimicrobial agent |
| JP2008544953A (en) * | 2005-05-10 | 2008-12-11 | チバ ホールディング インコーポレーテッド | Antibacterial porous silicon oxide particles |
| WO2011045627A1 (en) * | 2009-10-12 | 2011-04-21 | Arce Macias, Carlos, Francisco | Viricide agents having nanostructured biocatalysts materials of titanium dioxide (tio2) and silicium dioxide (si02) with platinum and iridium modified and dispersed on the surface |
| JP2019085336A (en) * | 2017-11-01 | 2019-06-06 | 株式会社ファンケル | Antibacterial agent |
Non-Patent Citations (1)
| Title |
|---|
| LEE, D. W. ET AL.: "Synthesis of Pt-containing mesoporous silica using Pt precursor as a pore-forming agent", JOURNAL OF NON-CRYSTALLINE SOLIDS, vol. Vol.353, Issues 16-17, JPN6009034768, 1 June 2007 (2007-06-01), pages 1501 - 1507, ISSN: 0004678946 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019137637A (en) * | 2018-02-09 | 2019-08-22 | 株式会社フルヤ金属 | Antifungal porous material and antifungal product containing the same, and antifungal method using the same |
| JP7219539B2 (en) | 2018-02-09 | 2023-02-08 | 株式会社Furuya Eco-Front Technology | Antifungal porous material, antifungal processed product containing the same, and antifungal method using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111683532A (en) | 2020-09-18 |
| WO2019156118A1 (en) | 2019-08-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US10556230B2 (en) | Photocatalyst coating | |
| JP6911030B2 (en) | Antimicrobial, antiviral, and / or algae-proof materials composed of inorganic / organic hybrid compounds and methods for producing them. | |
| JP2006200834A (en) | Moisture absorbing and releasing filter, and humidifier | |
| WO2006046443A1 (en) | Fiber fabric having voc removing function | |
| WO2019156118A1 (en) | Antibacterial porous material, antibacterial product containing this, and antibacterial method using this | |
| JP5616542B2 (en) | Adsorbed, decomposed, blocked and deodorized composition for harmful substances and method for producing the same | |
| TWI783050B (en) | Decomposition materials and methods of decomposing them | |
| JP7219539B2 (en) | Antifungal porous material, antifungal processed product containing the same, and antifungal method using the same | |
| KR20170058121A (en) | High functional anti-biotic deodorization filter comprising silver nano-silica complex | |
| JP2016525960A (en) | Moisture absorbing / releasing wallpaper and method for producing the same | |
| JPH11342310A (en) | Functional electret filter and its production and air purifier | |
| JP4873923B2 (en) | Deodorizing and / or sanitizing sheet | |
| JP7412692B2 (en) | Antibacterial porous membrane and antibacterial coating material using it | |
| RU2008141552A (en) | FILTER MEDIUM FOR CLEANING LIQUID AND GAS, METHOD FOR ITS PRODUCTION AND METHOD FOR FILTERING | |
| CN105034466A (en) | Car cabin decorating plate with air purification function | |
| CN110093814B (en) | Preparation method of multi-effect indoor air quality assurance paper and obtained product | |
| TWM549778U (en) | Graphene filter structure | |
| KR101292531B1 (en) | Functional wall paper of and method of manufacturing the same | |
| JP2004188165A (en) | Functional member | |
| JP7345995B2 (en) | Titanium oxide composition, dispersion, and member having a titanium oxide composition in its surface layer | |
| WO2019058803A1 (en) | Sheet | |
| JP4614327B2 (en) | Method for producing porous fired product | |
| JP2005200784A (en) | Wallpaper for removing indoor air contaminant | |
| JP2012143720A (en) | Adsorption sheet and structure | |
| JP2004082691A (en) | Humidity conditioning member and room |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A711 Effective date: 20201225 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20210115 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20201225 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220111 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220308 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20220524 |