JPH11226420A - Production of antibacterial film forming composition and antibacterial film - Google Patents
Production of antibacterial film forming composition and antibacterial filmInfo
- Publication number
- JPH11226420A JPH11226420A JP10056053A JP5605398A JPH11226420A JP H11226420 A JPH11226420 A JP H11226420A JP 10056053 A JP10056053 A JP 10056053A JP 5605398 A JP5605398 A JP 5605398A JP H11226420 A JPH11226420 A JP H11226420A
- Authority
- JP
- Japan
- Prior art keywords
- film
- titanium oxide
- antibacterial
- antibacterial film
- forming composition
- 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 35
- 239000000203 mixture Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 239000010931 gold Substances 0.000 claims abstract description 48
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 47
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052737 gold Inorganic materials 0.000 claims abstract description 38
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 42
- 239000010419 fine particle Substances 0.000 claims description 21
- 230000000845 anti-microbial effect Effects 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000004599 antimicrobial Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 9
- 239000011347 resin Substances 0.000 claims description 9
- 229920005989 resin Polymers 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims 1
- 230000000996 additive effect Effects 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 27
- 239000002904 solvent Substances 0.000 abstract description 7
- 239000010936 titanium Substances 0.000 abstract description 5
- 239000004408 titanium dioxide Substances 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 235000011837 pasties Nutrition 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 36
- 238000000034 method Methods 0.000 description 24
- 239000010408 film Substances 0.000 description 21
- 239000010409 thin film Substances 0.000 description 18
- 238000010304 firing Methods 0.000 description 7
- 239000005361 soda-lime glass Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- -1 titanium alkoxides Chemical class 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000007639 printing Methods 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 description 2
- 229940088601 alpha-terpineol Drugs 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229940100630 metacresol Drugs 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000000171 quenching effect Effects 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 1
- GEGLCBTXYBXOJA-UHFFFAOYSA-N 1-methoxyethanol Chemical compound COC(C)O GEGLCBTXYBXOJA-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012136 culture method Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- MGQFVQQCNPBJKC-UHFFFAOYSA-N dibutoxy(diethyl)silane Chemical compound CCCCO[Si](CC)(CC)OCCCC MGQFVQQCNPBJKC-UHFFFAOYSA-N 0.000 description 1
- GQNWJCQWBFHQAO-UHFFFAOYSA-N dibutoxy(dimethyl)silane Chemical compound CCCCO[Si](C)(C)OCCCC GQNWJCQWBFHQAO-UHFFFAOYSA-N 0.000 description 1
- ZMAPKOCENOWQRE-UHFFFAOYSA-N diethoxy(diethyl)silane Chemical compound CCO[Si](CC)(CC)OCC ZMAPKOCENOWQRE-UHFFFAOYSA-N 0.000 description 1
- VSYLGGHSEIWGJV-UHFFFAOYSA-N diethyl(dimethoxy)silane Chemical compound CC[Si](CC)(OC)OC VSYLGGHSEIWGJV-UHFFFAOYSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- ZIDTUTFKRRXWTK-UHFFFAOYSA-N dimethyl(dipropoxy)silane Chemical compound CCCO[Si](C)(C)OCCC ZIDTUTFKRRXWTK-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- KUCGHDUQOVVQED-UHFFFAOYSA-N ethyl(tripropoxy)silane Chemical compound CCCO[Si](CC)(OCCC)OCCC KUCGHDUQOVVQED-UHFFFAOYSA-N 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- RJMRIDVWCWSWFR-UHFFFAOYSA-N methyl(tripropoxy)silane Chemical compound CCCO[Si](C)(OCCC)OCCC RJMRIDVWCWSWFR-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- MCCIMQKMMBVWHO-UHFFFAOYSA-N octadecanoic acid;titanium Chemical compound [Ti].CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O MCCIMQKMMBVWHO-UHFFFAOYSA-N 0.000 description 1
- GYUPBLLGIHQRGT-UHFFFAOYSA-N pentane-2,4-dione;titanium Chemical compound [Ti].CC(=O)CC(C)=O GYUPBLLGIHQRGT-UHFFFAOYSA-N 0.000 description 1
- FABOKLHQXVRECE-UHFFFAOYSA-N phenyl(tripropoxy)silane Chemical compound CCCO[Si](OCCC)(OCCC)C1=CC=CC=C1 FABOKLHQXVRECE-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- GIHPVQDFBJMUAO-UHFFFAOYSA-N tributoxy(ethyl)silane Chemical compound CCCCO[Si](CC)(OCCCC)OCCCC GIHPVQDFBJMUAO-UHFFFAOYSA-N 0.000 description 1
- GYZQBXUDWTVJDF-UHFFFAOYSA-N tributoxy(methyl)silane Chemical compound CCCCO[Si](C)(OCCCC)OCCCC GYZQBXUDWTVJDF-UHFFFAOYSA-N 0.000 description 1
- INUOIYMEJLOQFN-UHFFFAOYSA-N tributoxy(phenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C1=CC=CC=C1 INUOIYMEJLOQFN-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Catalysts (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は抗菌膜形成組成物お
よび抗菌膜の製造方法に係り、詳しくは酸化チタンに金
微粒子を固定することにより抗菌性を向上させた抗菌膜
形成組成物および抗菌膜の製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antimicrobial film-forming composition and a method for producing the antimicrobial film, and more particularly to an antimicrobial film-forming composition and an antimicrobial film having improved antimicrobial properties by fixing fine gold particles to titanium oxide. And a method for producing the same.
【０００２】[0002]
【従来の技術】従来から酸化チタンの光触媒作用を利用
して大気中の汚染物質などを分解除去しようする試みは
広く行われ、抗菌、脱臭機能を有する種々の窓ガラスに
使用されている。酸化チタンの光触媒機能を向上させる
方法としては、これまで酸化チタンゾル表面にＡｇ，Ｃ
ｕ，Ｐｔ，Ｎｉ，Ｆｅ，Ｃｏ等の金属粒子を固定し、こ
れを基材上に塗布、焼成することで酸化チタン薄膜の光
触媒作用を向上させる方法（特開平８−１３１８３４号
公報）、Ａｇをイオンあるいはメタルの状態で酸化チタ
ン粒子の表面近傍に含有させ、この酸化チタン粒子を焼
成して酸化チタン薄膜を作製し抗菌性能を改善する方法
（特開平９−２２７３１９号公報）、酸化チタン粒子の
内部あるいは表面に鉄化合物を存在させ、この酸化チタ
ン粒子を焼成して得られた酸化チタン薄膜の光触媒機能
を向上させる方法（特開平７−３０３８３５号公報）、
酸化チタンの内部あるいは表面にバナジウム化合物を含
有させたものを焼成して得られた酸化チタン薄膜の光触
媒機能を向上させる方法（特開平７−２７５７０４号公
報）等が提案されている。これらの方法はいずれも酸化
チタン粒子の生成物を材料として使用することが前提条
件となった方法であり、その生成過程あるいは生成後の
次工程で種々の金属あるいは金属化合物が導入され、酸
化チタンの光触媒機能を向上させている。2. Description of the Related Art Conventionally, attempts to decompose and remove pollutants and the like in the atmosphere by using the photocatalytic action of titanium oxide have been widely made and used for various window glasses having antibacterial and deodorizing functions. As a method for improving the photocatalytic function of titanium oxide, a method of improving the titanium oxide sol surface with Ag, C
a method of improving the photocatalytic action of a titanium oxide thin film by fixing metal particles such as u, Pt, Ni, Fe, Co, etc., applying the particles on a base material, and firing the same (Japanese Patent Application Laid-Open No. 8-131834); A titanium oxide particle in the form of ions or metal in the vicinity of the surface of the titanium oxide particle, and baking the titanium oxide particle to form a titanium oxide thin film to improve antibacterial performance (Japanese Patent Application Laid-Open No. 9-227319). A method of improving the photocatalytic function of a titanium oxide thin film obtained by calcining the titanium oxide particles in the presence or absence of an iron compound inside or on the surface (JP-A-7-303835);
A method has been proposed for improving the photocatalytic function of a titanium oxide thin film obtained by firing a titanium oxide containing a vanadium compound inside or on the surface (Japanese Patent Application Laid-Open No. 7-275704). All of these methods are premised on using the product of titanium oxide particles as a material, and various metals or metal compounds are introduced in the production process or in the next step after the production, and the titanium oxide Has improved the photocatalytic function.
【０００３】また、ソーダライムガラス基材上にこれら
酸化チタン薄膜を付着させる場合、酸化珪素薄膜をソー
ダライムガラスと酸化チタン薄膜との間にプレコート膜
として設け、酸化チタン薄膜をソーダライムガラスから
移行してくるアルカリイオンから保護したり、また酸化
チタン薄膜を厚くすることで移行してくるアルカリイオ
ンの悪影響を小さくしていた。When these titanium oxide thin films are deposited on a soda lime glass substrate, a silicon oxide thin film is provided as a precoat film between the soda lime glass and the titanium oxide thin film, and the titanium oxide thin film is transferred from the soda lime glass. The adverse effects of migrating alkali ions have been reduced by protecting them from alkali ions and by increasing the thickness of the titanium oxide thin film.
【０００４】[0004]
【発明が解決しようとする課題】しかし、従来の方法で
は予め表面処理した酸化チタン粒子を作製した後、これ
を用いて焼成して酸化チタン薄膜を作製する工程を有し
ているため、生産性を向上する課題があった。また、ソ
ーダライムガラス基材上に酸化珪素薄膜を設けること
は、製造上、１工程増えることになって所定範囲の積層
した膜厚を維持することが困難になり、製造コストも上
昇する等の悪影響があった。また、抗菌材の厚膜化は焼
成時の収縮によって基材との剥離や脱落の原因にもなっ
ており、数μｍ以上に厚膜化することは困難であった。However, the conventional method has a step of preparing titanium oxide particles which have been surface-treated in advance, and then firing the particles to form a titanium oxide thin film. There was a problem to improve. In addition, providing a silicon oxide thin film on a soda lime glass substrate increases the number of steps by one in manufacturing, making it difficult to maintain a laminated film thickness in a predetermined range, and increasing the manufacturing cost. There were adverse effects. In addition, the thickening of the antibacterial material also causes peeling or falling off of the base material due to shrinkage during firing, and it has been difficult to increase the thickness to several μm or more.
【０００５】本発明はこのような問題点を改善するもの
であり、酸化チタンに金微粒子を固定することにより厚
みを薄くしても十分に抗菌性を発揮することができる抗
菌膜形成組成物および抗菌膜の製造方法を提供する。The present invention has been made to solve such a problem, and an antimicrobial film-forming composition which can sufficiently exhibit antimicrobial properties even when the thickness is reduced by fixing fine gold particles to titanium oxide. Provided is a method for manufacturing an antibacterial film.
【０００６】[0006]
【課題を解決するための手段】即ち、本願の請求項１記
載の発明は、少なくとも（ａ）有機チタン化合物あるい
は／そして酸化チタンゾルと、（ｂ）有機珪素化合物あ
るいは／そしてシリカゾルと、（ｃ）金微粒子と、そし
て（ｄ）有機溶剤を含んだペースト状であり、上記
（ａ）、（ｂ）、（ｃ）の添加量比が金属原子数比（Ｔ
ｉ＋Ｓｉ）／Ａｕで１／１〜５０／１である抗菌膜形成
組成物にある。本発明の抗菌膜形成組成物では、金微粒
子を酸化チタンに固定することにより厚みを小さくして
も抗菌性を改善することができる。That is, the invention according to claim 1 of the present application comprises at least (a) an organotitanium compound or / and titanium oxide sol, (b) an organosilicon compound or / and silica sol, and (c) It is a paste containing gold fine particles and (d) an organic solvent, and the addition ratio of (a), (b), and (c) is the metal atom number ratio (T
(i + Si) / Au in an antibacterial film-forming composition of 1/1 to 50/1. In the antimicrobial film-forming composition of the present invention, the antimicrobial properties can be improved even if the thickness is reduced by fixing the fine gold particles to titanium oxide.
【０００７】本願の請求項２記載の発明は、高分子材料
を含む抗菌膜形成組成物にある。The invention according to claim 2 of the present application resides in an antimicrobial film-forming composition containing a polymer material.
【０００８】本願の請求項３記載の発明は、少なくとも
（ａ）有機チタン化合物あるいは／そして酸化チタンゾ
ルと、（ｂ）有機珪素化合物あるいは／そしてシリカゾ
ルと、（ｃ）金微粒子と、（ｄ）有機溶剤を含んだペー
スト状であり、上記（ａ）、（ｂ）、（ｃ）の添加量比
が金属原子数比（Ｔｉ＋Ｓｉ）／Ａｕで１／１〜５０／
１からなる抗菌膜形成組成物を基材に塗布した後、焼成
して膜厚０．０１〜５．０μｍの焼成膜にした抗菌膜の
製造方法にある。The invention according to claim 3 of the present application provides at least (a) an organotitanium compound or / and titanium oxide sol, (b) an organosilicon compound or / and silica sol, (c) gold fine particles, and (d) an organic fine particle. It is a paste containing a solvent, and the addition ratio of (a), (b), and (c) is 1/1 to 50 / (metal atomic ratio (Ti + Si) / Au).
A method for producing an antibacterial film having a thickness of 0.01 to 5.0 µm after applying the antibacterial film-forming composition comprising No. 1 to a substrate and firing the composition.
【０００９】本願の請求項４記載の発明は、高分子材料
を含む抗菌膜の製造方法にある。The invention according to claim 4 of the present application resides in a method for producing an antibacterial film containing a polymer material.
【００１０】[0010]
【発明の実施の形態】本発明で使用する（ａ）有機チタ
ン化合物あるいは／そして酸化チタンゾルは、チタンの
エトキシド、プロポキジド等のアルコキシド類、アセチ
ルアセトン塩、有機酸塩、各種錯塩等であり、具体的に
はテトラエトキシチタン、テトラメトキシチタン、テト
ラプロポキシチタン、テトラブトキシチタン、チタンア
セチルアセトン塩、ステアリン酸チタンが挙げられる。
また、酸化チタンゾルは平均粒子径０．００１〜０．５
μｍのアナターゼ型酸化チタンが水、有機溶剤等の溶媒
中に１〜５０重量％の濃度で分散したものである。BEST MODE FOR CARRYING OUT THE INVENTION The (a) organotitanium compound and / or titanium oxide sol used in the present invention includes titanium alkoxides such as ethoxide and propoxide, acetylacetone salts, organic acid salts and various complex salts. Examples thereof include tetraethoxytitanium, tetramethoxytitanium, tetrapropoxytitanium, tetrabutoxytitanium, titanium acetylacetone salt, and titanium stearate.
The titanium oxide sol has an average particle size of 0.001 to 0.5.
μm anatase type titanium oxide dispersed in a solvent such as water or an organic solvent at a concentration of 1 to 50% by weight.
【００１１】本発明で使用する（ｂ）有機珪素化合物あ
るいは／そしてシリカゾルのうち、有機珪素化合物はＳ
ｉ（シリカ）のメトキシ、エトキシド、プロポキジド等
のアルコキシド類、アセチルアセトン塩、ポリオルガノ
シロキサン等であり、具体的にはメチルトリメトキシシ
ラン、メチルトリエトキシシラン、メチルトリエトキシ
シラン、メチルトリブトキシシラン、メチルトリプロポ
キシシラン、エチルトリメトキシシラン、エチルトリエ
トキシシラン、エチルトリブトキシシラン、エチルトリ
プロポキシシラン、フェニルトリメトキシシラン、フェ
ニルトリエトキシシラン、フェニルトリブトキシシラ
ン、フェニルトリプロポキシシラン、ジメチルジメトキ
シシラン、ジメチルジエトキシシラン、ジメチルジブト
キシシラン、ジメチルジプロポキシシラン、ジエチルジ
メトキシシラン、ジエチルジエトキシシラン、ジエチル
ジブトキシシラン、ジエチルジプロポキシジラン、フェ
ニルメチルジメトキシシラン、シラン−アセチルアセト
ン塩、ポリジメチルシロキサンが挙げられる。Among the organosilicon compound and / or silica sol (b) used in the present invention, the organosilicon compound is S
alkoxides such as methoxy, ethoxide and propoxide of i (silica), acetylacetone salts, polyorganosiloxanes and the like, specifically, methyltrimethoxysilane, methyltriethoxysilane, methyltriethoxysilane, methyltributoxysilane, methyl Tripropoxy silane, ethyl trimethoxy silane, ethyl triethoxy silane, ethyl tributoxy silane, ethyl tripropoxy silane, phenyl trimethoxy silane, phenyl triethoxy silane, phenyl tributoxy silane, phenyl tripropoxy silane, dimethyl dimethoxy silane, dimethyl di Ethoxysilane, dimethyldibutoxysilane, dimethyldipropoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, diethyldibutoxysilane, Ethyl dipropoxy Jiran, phenylmethyl dimethoxysilane, silane - acetylacetone salts, polydimethylsiloxane.
【００１２】本発明で使用する金微粒子は、粒径が１〜
１００ｎｍ、好ましくは１〜５０ｎｍの金微粒子を高分
子内に凝集させることなく分散させて得られたもの（複
合物）、あるいは粒径１〜１００ｎｍ、好ましくは１０
ｎｍ以下の金微粒子をα−テレピネオール、トルエン等
溶剤中に独立分散したものである。The fine gold particles used in the present invention have a particle size of 1 to 1.
One obtained by dispersing gold fine particles of 100 nm, preferably 1 to 50 nm without aggregating in a polymer (composite), or a particle diameter of 1 to 100 nm, preferably 10 to 100 nm
It is obtained by independently dispersing gold fine particles having a diameter of not more than nm in a solvent such as α-terpineol and toluene.
【００１３】上記高分子内に金微粒子を分散させた複合
物を得る場合においては、高分子層を熱力学的に非平衡
化した状態に成形する必要がある。具体的には、高分子
を真空中で加熱して融解し蒸発させて基板の上に高分子
層を固化する真空蒸着方法、あるいは高分子を融解温度
以上で融解し、この状態のまま直ちに液体窒素等に投入
して急冷し、基板の上に高分子層を付着させる融解急冷
固化方法などがある。In order to obtain a composite in which fine gold particles are dispersed in the above polymer, it is necessary to form the polymer layer in a thermodynamically non-equilibrium state. Specifically, a polymer is heated in a vacuum to melt and evaporate to solidify the polymer layer on the substrate, or a vacuum deposition method in which the polymer is melted above the melting temperature and the liquid There is a melting quenching and solidifying method in which the polymer layer is quenched by being introduced into nitrogen or the like, and a polymer layer is deposited on a substrate.
【００１４】そのうち真空蒸着方法の場合には、通常の
真空蒸着装置を使用して１０-4〜１０-6Ｔｏｒｒの真空
度、蒸着速度０．１〜１００μｍ／分、好ましくは０．
５〜５μｍ／分で、ガラス等の基板の上に高分子層を得
ることができる。融解急冷固化方法では、高分子を融解
し、該高分子固有の臨界冷却速度以上の速度で冷却して
高分子層を得る。このようにして得られた高分子層は熱
力学的に不安定な非平衡化した状態におかれ、時間の経
過につれて平衡状態へ移行する。In the case of a vacuum deposition method, a vacuum degree of 10 -4 to 10 -6 Torr and a deposition rate of 0.1 to 100 μm / min, preferably 0.1 to 10 -6 Torr, using an ordinary vacuum deposition apparatus.
At 5 to 5 μm / min, a polymer layer can be obtained on a substrate such as glass. In the melting quenching and solidification method, a polymer is melted and cooled at a rate higher than the critical cooling rate inherent to the polymer to obtain a polymer layer. The polymer layer thus obtained is placed in a non-equilibrium state, which is thermodynamically unstable, and transitions to an equilibrium state over time.
【００１５】ここで使用する高分子は、例えばナイロン
６、ナイロン６６、ナイロン１１、ナイロン１２、ナイ
ロン６９、ポリエチレンテレフタレート（ＰＥＴ）、ポ
リビニルアルコール、ポリフェニレンスルフィド（ＰＰ
Ｓ）、ポリスチレン（ＰＳ）、ポリカーボネート、ポリ
メチルメタクリレート等であって、分子凝集エネルギー
として２０００ｃａｌ／ｍｏｌ以上有するものが好まし
い。この高分子は、通常言われている結晶性高分子や非
晶性高分子も含む。尚、分子凝集エネルギーについて
は、日本化学会編 化学便覧応用編（１９７３年発行）
の第８９０頁に詳細に定義されている。The polymer used herein is, for example, nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, polyethylene terephthalate (PET), polyvinyl alcohol, polyphenylene sulfide (PP
S), polystyrene (PS), polycarbonate, polymethyl methacrylate, etc., having a molecular aggregation energy of 2000 cal / mol or more are preferable. The polymer includes a crystalline polymer and an amorphous polymer which are generally referred to. The molecular cohesion energy is described in Chemical Chemistry Handbook, edited by The Chemical Society of Japan (issued in 1973)
On page 890.
【００１６】続いて、前記熱力学的に非平衡化した高分
子層は、その表面に金の層を密着させる工程へと移され
る。この工程では真空蒸着装置によって金の層を高分子
層に蒸着させるか、もしくは金箔を直接高分子層に密着
させる等の方法で金の層を高分子層に積層させる。Subsequently, the thermodynamically non-equilibrated polymer layer is transferred to a step of adhering a gold layer to its surface. In this step, the gold layer is deposited on the polymer layer by a method such as depositing a gold layer on the polymer layer by a vacuum deposition apparatus, or by directly attaching a gold foil to the polymer layer.
【００１７】上記金の層と高分子層とが密着した物を、
高分子のガラス転移点以上、融点以下の温度で加熱して
高分子層を安定状態へ移行させる。その結果、金は１０
０ｎｍ以下で、１〜５０ｎｍの領域に粒子径分布の最大
をもつ金微粒子となって高分子層内へ拡散浸透し、この
状態は高分子層が完全に緩和するまで続き、高分子層に
付着している金の層はその厚さも減少して最終的に無く
なる。上記金微粒子は凝集することなく高分子層内に分
布している。この場合、金微粒子の含有量は０．０１〜
８０重量％であるが、この含有量は高分子層の作製条件
を変えたり、金の層の厚みを変えることによって調節が
できる。The product in which the gold layer and the polymer layer are in close contact with each other is
The polymer layer is heated to a temperature equal to or higher than the glass transition point of the polymer and equal to or lower than the melting point to shift the polymer layer to a stable state. As a result, gold is 10
At 0 nm or less, it becomes gold fine particles having a maximum particle size distribution in the range of 1 to 50 nm and diffuses and penetrates into the polymer layer. This state continues until the polymer layer is completely relaxed and adheres to the polymer layer. The layer of gold that has been deposited is also reduced in thickness and eventually disappears. The gold fine particles are distributed in the polymer layer without aggregation. In this case, the content of the fine gold particles is 0.01 to
The content is 80% by weight, but the content can be adjusted by changing the production conditions of the polymer layer or changing the thickness of the gold layer.
【００１８】尚、本発明では、上記複合物の製造方法
は、上記の方法だけでなく、例えば溶融気化法に属する
気相法、沈殿法に属する液相法、固相法、分散法で金微
粒子を作製し、この微粒子を溶液あるいは融液からなる
高分子と機械的に混合する方法、あるいは高分子と金と
を同時に蒸発させ、気相中で混合する方法等がある。In the present invention, the method for producing the above-mentioned composite is not limited to the above-mentioned method, but may be, for example, a gas phase method belonging to a melt vaporization method, a liquid phase method belonging to a precipitation method, a solid phase method, or a dispersion method. There is a method of preparing fine particles and mechanically mixing the fine particles with a polymer made of a solution or a melt, or a method of simultaneously evaporating the polymer and gold and mixing them in a gas phase.
【００１９】得られた金微粒子を分散させた高分子は、
メタクレゾール、ジメチルホルムアミド、シクロヘキサ
ン、ギ酸等の有機溶剤からなる溶媒に混合し溶解させ、
金微粒子を均一に分散させた微粒子分散ペーストにす
る。金微粒子は粒径が小さく高分子との相互作用が存在
するためにペースト中で高分子との分離、沈澱および超
微粒子同志の凝集が生じない。The polymer in which the obtained fine gold particles are dispersed is
Meta-cresol, dimethylformamide, cyclohexane, mixed and dissolved in a solvent consisting of organic solvents such as formic acid,
A fine particle dispersion paste in which gold fine particles are uniformly dispersed is obtained. Since the gold fine particles have a small particle size and interact with the polymer, separation and precipitation from the polymer and aggregation of the ultrafine particles do not occur in the paste in the paste.
【００２０】また、金微粒子を溶剤中に独立分散させた
ものは、例えば特開平３−３４２１１号公報に開示され
ているようなガス中蒸発法と呼ばれる方法によって製造
される。即ち、チャンバ内にヘリウム不活性ガスを導入
して金を蒸発させ、不活性ガスとの衝突により冷却され
凝縮して得られるが、この場合生成直後の粒子が孤立状
態にある段階でα−テレピネオール等の有機溶剤の蒸気
を導入して粒子表面の被覆を行っている。Further, the one in which gold fine particles are independently dispersed in a solvent is produced by a method called a gas evaporation method disclosed in, for example, JP-A-3-34211. That is, gold is evaporated by introducing a helium inert gas into the chamber, and is cooled and condensed by collision with the inert gas. In this case, α-terpineol is obtained at a stage where particles immediately after generation are in an isolated state. The surface of the particles is coated by introducing a vapor of an organic solvent such as
【００２１】上記（ａ）有機チタン化合物あるいは／そ
して酸化チタンゾルと（ｂ）有機珪素化合物あるいは／
そしてシリカゾルと（ｃ）金微粒子の添加量比は、金属
原子数比（Ｔｉ＋Ｓｉ）／Ａｕで１／１〜５０／１であ
り、（Ｔｉ＋Ｓｉ）の量が１未満の場合には抗菌性の効
果が軽減し、また５０を越えると抗菌膜中に金微粒子の
量が少なくなるため、抗菌性を向上させる効果はみられ
ない。Ａｕが少なくなると、通常の酸化チタンとかわら
なくなる。Ａｕを所定量添加すると、紫外線により励起
された酸化チタンの原子がＡｕへ移動し、正孔と負孔を
より分離しやすくなるのも、抗菌性向上の原因になって
いると考えられる。The above (a) an organotitanium compound or / and a titanium oxide sol and (b) an organosilicon compound or /
The addition ratio of the silica sol to the (c) gold fine particles is 1/1 to 50/1 in a metal atom ratio (Ti + Si) / Au. When the amount of (Ti + Si) is less than 1, the antibacterial effect is obtained. If the ratio exceeds 50, the amount of fine gold particles in the antibacterial film decreases, so that the effect of improving the antibacterial property is not observed. When the amount of Au decreases, it does not replace normal titanium oxide. It is also considered that the addition of a predetermined amount of Au causes the atoms of titanium oxide excited by ultraviolet rays to move to Au, thereby making it easier to separate holes and holes, which also contributes to the improvement of antibacterial properties.
【００２２】また、本発明で使用するバインダー樹脂
は、抗菌膜形成組成物の粘度を適度に維持して基材への
塗布時の取扱を良好に維持し、また基材上に塗布した抗
菌膜形成組成物膜の乾燥後の強度を保持する機能を有し
ている。このバインダー樹脂は焼成時において低温で分
解することが好ましいが、特に限定されるものではなく
有機溶剤に可溶なものであればよい。Further, the binder resin used in the present invention can maintain the viscosity of the composition for forming an antimicrobial film at an appropriate level, maintain good handling during application to a substrate, and can provide an antimicrobial film coated on a substrate. It has a function of maintaining the strength of the formed composition film after drying. This binder resin is preferably decomposed at a low temperature during firing, but is not particularly limited as long as it is soluble in an organic solvent.
【００２３】また、上記バインダー樹脂としては、例え
ばニトロセルロース、エチルセルロース、酢酸セルロー
ス、ブチルセルロース等のセルロース類が好ましい。こ
の添加量は印刷あるいは塗布条件によって決定され、制
限はない。尚、複合物を使用する場合には、高分子はこ
のバインダー樹脂と同じであってもよい。As the binder resin, for example, celluloses such as nitrocellulose, ethyl cellulose, cellulose acetate and butyl cellulose are preferable. This amount is determined by printing or coating conditions, and is not limited. When a composite is used, the polymer may be the same as the binder resin.
【００２４】本発明で使用する有機溶剤は、金あるいは
銀の微粒子を凝集させないものであり、例えばメタクレ
ゾール、カルビトール、ジメチルホルムアミド、ジメチ
ルイミダゾリジノン、ターピノール、ジアセトンアルコ
ール、エチレングリコールモノエチルエーテル、エチレ
ングリコールモノブチルエーテル等の高沸点溶剤であ
る。この有機溶剤はバインダー樹脂あるいはバインダー
樹脂や金あるいは銀の微粒子を分散させた高分子を溶解
するものあり、一種もしくは二種以上使用することがで
きる。The organic solvent used in the present invention does not agglomerate fine particles of gold or silver, and is, for example, metacresol, carbitol, dimethylformamide, dimethylimidazolidinone, terpinol, diacetone alcohol, ethylene glycol monoethyl ether. And high-boiling solvents such as ethylene glycol monobutyl ether. The organic solvent dissolves a binder resin or a polymer in which binder resin or fine particles of gold or silver are dispersed, and one or more kinds thereof can be used.
【００２５】上記抗菌膜形成組成物は、（ａ）有機チタ
ン化合物あるいは／そして酸化チタンゾルと、（ｂ）有
機珪素化合物あるいは／そしてシリカゾルと、（ｃ）金
微粒子とを、また必要に応じてバインダー樹脂とを
（ｄ）有機溶剤に溶かしたものを良く攪拌してペースト
状に得ることができる。The antimicrobial film-forming composition comprises (a) an organotitanium compound or / and a titanium oxide sol, (b) an organosilicon compound or / and a silica sol, (c) gold fine particles, and if necessary, a binder. A solution obtained by dissolving the resin in the organic solvent (d) can be sufficiently stirred to obtain a paste.
【００２６】このように作製されたペースト状の抗菌膜
形成組成物は、基材上にディップ法、スプレー法、ロー
ルコ−ト法、スピンコート法、スクリーン印刷、フレク
ソ印刷、グラビア印刷のような印刷法で適宜に使用され
る。塗膜の厚さは０．１〜３．０μｍである。上記スク
リーン印刷手順は、水平に置かれたスクリーン（例え
ば、ポリエステル平織物、２５５メッシュ）の下に、数
ミリメートルの間隔をもたせて印刷基板（ガラス）を設
置する。このスクリーンの上に抗菌膜形成剤をのせた
後、スキージーを用いてスクリーン全面にを広げる。こ
の時には、スクリーンと基材とは間隔を有している。続
いて、スクリーンが基材に接触する程度にスキージーで
スクリーンを押さえ付けて移動させる。これで一回の印
刷が終了し、以後これを繰り返す。The paste-form antimicrobial film-forming composition thus prepared is applied on a substrate by printing such as dipping, spraying, roll coating, spin coating, screen printing, flexo printing, and gravure printing. It is used as appropriate in the method. The thickness of the coating is from 0.1 to 3.0 μm. In the above screen printing procedure, a printing substrate (glass) is placed under a horizontally placed screen (for example, polyester plain fabric, 255 mesh) with a spacing of several millimeters. After the antibacterial film forming agent is placed on the screen, the entire surface of the screen is spread using a squeegee. At this time, the screen and the substrate have an interval. Subsequently, the screen is moved by pressing the screen with a squeegee so that the screen contacts the substrate. This completes one printing, and thereafter, this is repeated.
【００２７】その後、基材を１００〜２００°Ｃの大気
中に１０分間放置して有機溶剤を除去して乾燥、あるい
は密閉容器中で脱気しながら乾燥した後、５００〜８０
０°Ｃで数分間熱処理して焼成する。焼成して得られた
抗菌膜の膜厚は、０．０１〜５．０μｍ、好ましくは
０．０５〜１．０μｍであり、０．０１μｍ未満になる
と基材から移動するアルカリイオンの影響で光触媒活性
が低下し、また抗菌性も低下する傾向がある。また、
５．０μｍを越えると、焼成時の酸化チタン薄膜自体の
収縮により、薄膜内部や薄膜と基材界面に欠陥が生じ、
また薄膜の耐久性が低下する傾向がある。Thereafter, the substrate is left in the air at 100 to 200 ° C. for 10 minutes to remove the organic solvent and dry it.
Bake by heat treatment at 0 ° C for several minutes. The thickness of the antibacterial film obtained by baking is 0.01 to 5.0 μm, preferably 0.05 to 1.0 μm. When the thickness is less than 0.01 μm, the photocatalyst is affected by alkali ions moving from the substrate. The activity tends to decrease, and the antibacterial property also tends to decrease. Also,
If the thickness exceeds 5.0 μm, defects occur inside the thin film or at the interface between the thin film and the base material due to shrinkage of the titanium oxide thin film itself during firing,
Also, the durability of the thin film tends to decrease.
【００２８】本発明の抗菌膜形成組成物を塗布する基材
としては、ナトリウムのようなアルカリ網目修飾イオン
を含むソーダライムガラスや並板ガラスなどのガラス、
金属、セラミックス、セメントコンクリート、ストレー
ト、石膏ボードなどであり、特に形状を問わない。The base material on which the antimicrobial film-forming composition of the present invention is applied may be a glass such as soda lime glass or side-by-side glass containing an alkali network modifying ion such as sodium.
Metals, ceramics, cement concrete, straight, plasterboard, etc., are not particularly limited in shape.
【００２９】[0029]
【実施例】次に、本発明を具体的な実施例により更に詳
細に説明する。 実施例１〜２、比較例１〜２ 表１に示す配合を、プロペラ攪拌装置を用いて５０°Ｃ
に温度調節された湯浴で暖めながら１時間混合して ６
０分間攪拌混合して抗菌膜形成剤を得た。この抗菌膜形
成組成物を前述のスクリーン印刷によって厚み３ｍｍ、
縦横５０ｍｍのソーダライムガラス上に塗布し、１５０
°Ｃに設定された乾燥機中で５分間乾燥し、７００°Ｃ
に設定された炉中で５分間焼成した後、空冷して酸化チ
タン薄膜を被覆したガラスを得た。Next, the present invention will be described in more detail with reference to specific examples. Examples 1 and 2 and Comparative Examples 1 and 2 The compositions shown in Table 1 were mixed at 50 ° C. using a propeller stirrer.
Mix for 1 hour while warming in a temperature-controlled water bath.
The mixture was stirred and mixed for 0 minute to obtain an antibacterial film-forming agent. This antibacterial film-forming composition is 3 mm thick by the screen printing described above,
Apply on soda lime glass of 50mm length and width, 150
Dry for 5 minutes in a drier set at 700C
After baking for 5 minutes in a furnace set to, the mixture was air-cooled to obtain a glass coated with a titanium oxide thin film.
【００３０】得られた酸化チタン薄膜被覆ガラスの酸化
チタンの膜厚を触針式膜厚計により測定した。また、酸
化チタン薄膜の抗菌性を測定した。この方法は試験用菌
株として大腸菌（Ｅｓｃｈｅｒｉｃｈｉａ ｃｏｌｉ
ＩＦＯ ３９７２）を用い、ＡＳＴＭ・Ｇｅ２１−７０
に準拠して、試験片を寒天培地に乗せ、上記菌株を培養
した菌液を０．５ｍｌ滴下した。これを蛍光灯照射下お
よび非照射下で３５°Ｃで保存した。尚、蛍光灯照射の
条件は、４０００〜５０００ルクスである。２４時間後
に、試料から生残菌を洗い出し、この洗い出し液の生残
菌を寒天平板培養法により測定した。得られた結果を表
１に示す。The titanium oxide film thickness of the obtained titanium oxide thin film-coated glass was measured by a stylus type film thickness meter. Further, the antibacterial property of the titanium oxide thin film was measured. This method uses Escherichia coli as a test strain.
ASTM Ge21-70 using IFO 3972).
The test piece was placed on an agar medium and 0.5 ml of a bacterial solution obtained by culturing the above strain was added dropwise according to the method described in 1. above. This was stored at 35 ° C. with and without irradiation with a fluorescent lamp. In addition, the condition of the fluorescent lamp irradiation is 4000 to 5000 lux. Twenty-four hours later, the surviving bacteria were washed out of the sample, and the surviving bacteria of the washed solution were measured by an agar plate culture method. Table 1 shows the obtained results.
【００３１】[0031]
【表１】 [Table 1]
【００３２】この結果、比較例１は膜厚が薄すぎるた
め、ソーダライムガラスの影響を受け抗菌性を発揮して
いないが、比較例２は膜厚が十分厚いために抗菌性が発
揮している。一方、実施低１は比較例１の酸化チタンに
金微粒子を固定したため、膜厚が薄いにもかかわらず抗
菌性を発揮していることが判る。また、実施例２では膜
厚をさらに薄くしているが、金微粒子の効果で抗菌性を
有していることが判る。As a result, Comparative Example 1 did not exhibit antibacterial properties due to the influence of soda lime glass because the film thickness was too small, whereas Comparative Example 2 exhibited antibacterial properties because it was sufficiently thick. I have. On the other hand, in Example 1, since the fine gold particles were fixed to the titanium oxide of Comparative Example 1, it can be seen that antibacterial properties were exhibited even though the film thickness was thin. Further, in Example 2, although the film thickness was further reduced, it can be seen that it has antibacterial properties due to the effect of the gold fine particles.
【００３３】[0033]
【発明の効果】以上のように本願の請求項１〜２記載の
発明は、少なくとも（ａ）有機チタン化合物あるいは／
そして酸化チタンゾルと、（ｂ）有機珪素化合物あるい
は／そしてシリカゾルと、（ｃ）金微粒子と、そして
（ｄ）有機溶剤を含んだペースト状であり、上記
（ａ）、（ｂ）、（ｃ）の添加量比が金属原子数比（Ｔ
ｉ＋Ｓｉ）／Ａｕで１／１〜５０／１である抗菌膜形成
組成物、またこの抵菌膜形成組成物を基材に塗布した
後、焼成して膜厚０．０５〜１．０μｍの焼成膜にした
抗菌膜の製造方法にあり、金微粒子を酸化チタンに固定
することにより厚みを小さくした抗菌膜形成組成物およ
びや抗菌膜を得ることができる。As described above, the inventions according to claims 1 and 2 of the present invention provide at least (a) an organotitanium compound and / or
It is a paste containing titanium oxide sol, (b) an organosilicon compound or / and silica sol, (c) gold fine particles, and (d) an organic solvent, and the above (a), (b), (c) Is the ratio of the number of metal atoms (T
An antimicrobial film-forming composition having a ratio of (i + Si) / Au of 1/1 to 50/1, and the antibacterial film-forming composition applied to a substrate, and then baked to a thickness of 0.05 to 1.0 μm. In the method for producing an antibacterial film formed into a film, an antibacterial film-forming composition and a slightly antibacterial film having a reduced thickness can be obtained by fixing fine gold particles to titanium oxide.
Claims (4)
いは／そして酸化チタンゾルと、（ｂ）有機珪素化合物
あるいは／そしてシリカゾルと、（ｃ）金微粒子と、そ
して（ｄ）有機溶剤を含んだペースト状であり、上記
（ａ）、（ｂ）、（ｃ）の添加量比が金属原子数比（Ｔ
ｉ＋Ｓｉ）／Ａｕで１／１〜５０／１であることを特徴
とする抗菌膜形成組成物。1. A paste containing at least (a) an organotitanium compound or / and a titanium oxide sol, (b) an organosilicon compound or / and a silica sol, (c) gold fine particles, and (d) an organic solvent. The addition ratio of the above (a), (b) and (c) is the same as the ratio of the number of metal atoms (T
An antimicrobial film-forming composition, wherein (i + Si) / Au is 1/1 to 50/1.
菌膜形成組成物。2. The antibacterial film-forming composition according to claim 1, further comprising a binder resin.
いは／そして酸化チタンゾルと、（ｂ）有機珪素化合物
あるいは／そしてシリカゾルと、（ｃ）金微粒子と、
（ｄ）有機溶剤を含んだペースト状であり、上記
（ａ）、（ｂ）、（ｃ）の添加量比が金属原子数比（Ｔ
ｉ＋Ｓｉ）／Ａｕで１／１〜５０／１からなる抗菌膜形
成組成物を基材に塗布した後、焼成して膜厚０．０１〜
５．０μｍの焼成膜にすることを特徴とする抗菌膜の製
造方法。3. At least (a) an organotitanium compound or / and a titanium oxide sol, (b) an organosilicon compound or / and a silica sol, and (c) gold fine particles.
(D) It is a paste containing an organic solvent, and the additive amount ratio of the above (a), (b) and (c) is the metal atom number ratio (T
An antimicrobial film-forming composition consisting of 1/1 to 50/1 (i + Si) / Au is applied to a substrate, and then baked to a film thickness of 0.01 to
A method for producing an antibacterial film, characterized in that a fired film having a thickness of 5.0 μm is formed.
菌膜の製造方法。4. The method for producing an antibacterial film according to claim 3, further comprising a binder resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056053A JPH11226420A (en) | 1998-02-19 | 1998-02-19 | Production of antibacterial film forming composition and antibacterial film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10056053A JPH11226420A (en) | 1998-02-19 | 1998-02-19 | Production of antibacterial film forming composition and antibacterial film |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11226420A true JPH11226420A (en) | 1999-08-24 |
Family
ID=13016352
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10056053A Pending JPH11226420A (en) | 1998-02-19 | 1998-02-19 | Production of antibacterial film forming composition and antibacterial film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11226420A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8372416B2 (en) | 2007-10-03 | 2013-02-12 | 3M Innovative Properties Company | Process for limiting the growth of microorganisms |
| JP2016093768A (en) * | 2014-11-12 | 2016-05-26 | 日本電信電話株式会社 | Method for producing photocatalyst thin film |
-
1998
- 1998-02-19 JP JP10056053A patent/JPH11226420A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8372416B2 (en) | 2007-10-03 | 2013-02-12 | 3M Innovative Properties Company | Process for limiting the growth of microorganisms |
| JP2016093768A (en) * | 2014-11-12 | 2016-05-26 | 日本電信電話株式会社 | Method for producing photocatalyst thin film |
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