JP3261959B2 - Photocatalytic material - Google Patents
Photocatalytic materialInfo
- Publication number
- JP3261959B2 JP3261959B2 JP34658195A JP34658195A JP3261959B2 JP 3261959 B2 JP3261959 B2 JP 3261959B2 JP 34658195 A JP34658195 A JP 34658195A JP 34658195 A JP34658195 A JP 34658195A JP 3261959 B2 JP3261959 B2 JP 3261959B2
- Authority
- JP
- Japan
- Prior art keywords
- particles
- photocatalytic
- salt
- metal species
- silver
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 230000001699 photocatalysis Effects 0.000 title claims description 68
- 239000000463 material Substances 0.000 title claims description 41
- 239000002245 particle Substances 0.000 claims description 89
- 238000000034 method Methods 0.000 claims description 53
- 150000003839 salts Chemical class 0.000 claims description 51
- 239000011941 photocatalyst Substances 0.000 claims description 39
- 239000000758 substrate Substances 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 20
- 229910052802 copper Inorganic materials 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 17
- 229910052709 silver Inorganic materials 0.000 claims description 17
- 239000004332 silver Substances 0.000 claims description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940112669 cuprous oxide Drugs 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 description 97
- 239000002184 metal Substances 0.000 description 97
- 235000002639 sodium chloride Nutrition 0.000 description 53
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 26
- 239000002585 base Substances 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 239000000725 suspension Substances 0.000 description 19
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 16
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 15
- 241000251468 Actinopterygii Species 0.000 description 14
- 230000002829 reductive effect Effects 0.000 description 13
- 241000195493 Cryptophyta Species 0.000 description 12
- 230000000844 anti-bacterial effect Effects 0.000 description 12
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 11
- 229910052763 palladium Inorganic materials 0.000 description 11
- 239000004065 semiconductor Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- -1 gold (I) oxide Chemical compound 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 8
- 238000009395 breeding Methods 0.000 description 8
- 230000001488 breeding effect Effects 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000010828 elution Methods 0.000 description 8
- 230000003405 preventing effect Effects 0.000 description 8
- 239000007858 starting material Substances 0.000 description 8
- 239000010409 thin film Substances 0.000 description 8
- 150000004703 alkoxides Chemical class 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 7
- 238000010893 electron trap Methods 0.000 description 7
- 230000001678 irradiating effect Effects 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 7
- 238000005507 spraying Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 230000002411 adverse Effects 0.000 description 6
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003638 chemical reducing agent Substances 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 4
- 239000002781 deodorant agent Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 235000015170 shellfish Nutrition 0.000 description 4
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 4
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 229910021612 Silver iodide Inorganic materials 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 238000004332 deodorization Methods 0.000 description 3
- 230000001877 deodorizing effect Effects 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 229940045105 silver iodide Drugs 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- UACOWKKZSFRPRK-UHFFFAOYSA-L Br[Au]Br Chemical compound Br[Au]Br UACOWKKZSFRPRK-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- UCOBJOONLGFYMF-UHFFFAOYSA-L Cl[Au]Cl Chemical compound Cl[Au]Cl UCOBJOONLGFYMF-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 239000004277 Ferrous carbonate Substances 0.000 description 2
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- DGOHFTDNMSZWDQ-UHFFFAOYSA-N N#C[Au]C#N Chemical compound N#C[Au]C#N DGOHFTDNMSZWDQ-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 2
- 229940044175 cobalt sulfate Drugs 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 2
- IQYVXTLKMOTJKI-UHFFFAOYSA-L cobalt(ii) chlorate Chemical compound [Co+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IQYVXTLKMOTJKI-UHFFFAOYSA-L 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 2
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 2
- WIVXEZIMDUGYRW-UHFFFAOYSA-L copper(i) sulfate Chemical compound [Cu+].[Cu+].[O-]S([O-])(=O)=O WIVXEZIMDUGYRW-UHFFFAOYSA-L 0.000 description 2
- IJCCOEGCVILSMZ-UHFFFAOYSA-L copper;dichlorate Chemical compound [Cu+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O IJCCOEGCVILSMZ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229940076286 cupric acetate Drugs 0.000 description 2
- 229960003280 cupric chloride Drugs 0.000 description 2
- 229940045803 cuprous chloride Drugs 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005566 electron beam evaporation Methods 0.000 description 2
- 238000001017 electron-beam sputter deposition Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 229940032950 ferric sulfate Drugs 0.000 description 2
- 229940046149 ferrous bromide Drugs 0.000 description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 2
- 235000019268 ferrous carbonate Nutrition 0.000 description 2
- 229960004652 ferrous carbonate Drugs 0.000 description 2
- 229960002089 ferrous chloride Drugs 0.000 description 2
- 229940076136 ferrous iodide Drugs 0.000 description 2
- 229960001781 ferrous sulfate Drugs 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- GKYAEPNRZNDEMO-UHFFFAOYSA-L gold(1+);sulfate Chemical compound [Au+].[Au+].[O-]S([O-])(=O)=O GKYAEPNRZNDEMO-UHFFFAOYSA-L 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000003100 immobilizing effect Effects 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- JRSGPUNYCADJCW-UHFFFAOYSA-K iron(3+);trichlorate Chemical compound [Fe+3].[O-]Cl(=O)=O.[O-]Cl(=O)=O.[O-]Cl(=O)=O JRSGPUNYCADJCW-UHFFFAOYSA-K 0.000 description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 2
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229940078494 nickel acetate Drugs 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 2
- RZLUIDROFNIMHF-UHFFFAOYSA-L nickel(2+);dichlorate Chemical compound [Ni+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O RZLUIDROFNIMHF-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- PQTLYDQECILMMB-UHFFFAOYSA-L platinum(2+);sulfate Chemical compound [Pt+2].[O-]S([O-])(=O)=O PQTLYDQECILMMB-UHFFFAOYSA-L 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000000384 rearing effect Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000014102 seafood Nutrition 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 229940071536 silver acetate Drugs 0.000 description 2
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 2
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 2
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 description 2
- 229940098221 silver cyanide Drugs 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 2
- 229910000367 silver sulfate Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 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
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 229940102001 zinc bromide Drugs 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 2
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910005540 GaP Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- KZNMRPQBBZBTSW-UHFFFAOYSA-N [Au]=O Chemical compound [Au]=O KZNMRPQBBZBTSW-UHFFFAOYSA-N 0.000 description 1
- XEIPQVVAVOUIOP-UHFFFAOYSA-N [Au]=S Chemical compound [Au]=S XEIPQVVAVOUIOP-UHFFFAOYSA-N 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000001098 anti-algal effect Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- ASENRGFQFJSWMN-UHFFFAOYSA-N chloric acid zinc Chemical compound [Zn].Cl(=O)(=O)O ASENRGFQFJSWMN-UHFFFAOYSA-N 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- IDUKLYIMDYXQQA-UHFFFAOYSA-N cobalt cyanide Chemical compound [Co].N#[C-] IDUKLYIMDYXQQA-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 229910000152 cobalt phosphate Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- ZBDSFTZNNQNSQM-UHFFFAOYSA-H cobalt(2+);diphosphate Chemical compound [Co+2].[Co+2].[Co+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZBDSFTZNNQNSQM-UHFFFAOYSA-H 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- HZXMRANICFIONG-UHFFFAOYSA-N gallium phosphide Chemical compound [Ga]#P HZXMRANICFIONG-UHFFFAOYSA-N 0.000 description 1
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 description 1
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 1
- NQSHARDUOZPOKY-UHFFFAOYSA-M gold;gold(1+);sulfanide Chemical compound [SH-].[Au].[Au+] NQSHARDUOZPOKY-UHFFFAOYSA-M 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 1
- HEJPGFRXUXOTGM-UHFFFAOYSA-K iron(3+);triiodide Chemical compound [Fe+3].[I-].[I-].[I-] HEJPGFRXUXOTGM-UHFFFAOYSA-K 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000462 iron(III) oxide hydroxide Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- TVWWSIKTCILRBF-UHFFFAOYSA-N molybdenum trisulfide Chemical compound S=[Mo](=S)=S TVWWSIKTCILRBF-UHFFFAOYSA-N 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- NLEUXPOVZGDKJI-UHFFFAOYSA-N nickel(2+);dicyanide Chemical compound [Ni+2].N#[C-].N#[C-] NLEUXPOVZGDKJI-UHFFFAOYSA-N 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- JQPTYAILLJKUCY-UHFFFAOYSA-N palladium(ii) oxide Chemical compound [O-2].[Pd+2] JQPTYAILLJKUCY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- INXLGDBFWGBBOC-UHFFFAOYSA-N platinum(2+);dicyanide Chemical compound [Pt+2].N#[C-].N#[C-] INXLGDBFWGBBOC-UHFFFAOYSA-N 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process 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
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 229940019931 silver phosphate Drugs 0.000 description 1
- 229910000161 silver phosphate Inorganic materials 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- JOKPITBUODAHEN-UHFFFAOYSA-N sulfanylideneplatinum Chemical compound [Pt]=S JOKPITBUODAHEN-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
- GTQFPPIXGLYKCZ-UHFFFAOYSA-L zinc chlorate Chemical compound [Zn+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O GTQFPPIXGLYKCZ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Catalysts (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【発明の属する技術分野】本発明は、特に水環境で長期
に使用するのに好適な抗菌、脱臭、汚れ防止、防藻等の
効果を有する光触媒粒子活性を有する粒子、または光触
媒活性を有する粒子を含む部材に関する。さらには、そ
れらを利用した水の浄化方法、及び観賞魚または魚貝飼
育用水槽の防藻方法に関する。TECHNICAL FIELD The present invention relates to particles having photocatalytic particle activity or particles having photocatalytic activity suitable for long-term use especially in an aqueous environment, such as antibacterial, deodorizing, dirt-preventing and anti-algal effects. And a member including: Furthermore, the present invention relates to a method for purifying water using them and a method for preventing algae in an aquarium for breeding ornamental fish or fish and shellfish.
【０００２】[0002]
【従来の技術】近年、抗菌、脱臭に関する意識が高ま
り、種々の提案がなされている。その１つの方法に光触
媒を利用した方法がある。2. Description of the Related Art In recent years, awareness of antibacterial activity and deodorization has increased, and various proposals have been made. One of the methods is a method using a photocatalyst.
【０００３】例えば、水環境下においては、特公平５−
５０２９４号において、光半導体微粒子を基材表面に固
定化してなる光滅菌性充填材を有することを特徴とする
滅菌性リアクターが開示されており、それにより３時間
で９９％以上の滅菌に成功している。For example, in a water environment,
Japanese Patent No. 50294 discloses a sterilization reactor having a photosterilizing filler obtained by immobilizing optical semiconductor fine particles on the surface of a base material, thereby achieving a sterilization of 99% or more in 3 hours. ing.
【０００４】また、特公平６−７９０５号には、高分子
物質や塵芥の混合物が、光触媒反応を起こす触媒である
半導体表面に付着し、これを覆ってしまうため、触媒ま
で紫外線が達せず、触媒がエネルギーを受けにくくな
り、光触媒反応が低下し、反応劣化を引き起こすのを防
止するために、半導体からなる光触媒層と、それに対向
して設けられた紫外線灯および発熱体と、送風機からな
り、光触媒層全体が順次加熱されるように、光触媒層あ
るいは発熱体、または光触媒層及び発熱体が移動する光
触媒による脱臭装置が開示されている。Further, Japanese Patent Publication No. 6-7905 discloses that a mixture of a polymer substance and dust adheres to and covers the surface of a semiconductor which is a catalyst that causes a photocatalytic reaction, so that ultraviolet light does not reach the catalyst. The catalyst is less likely to receive energy, the photocatalytic reaction is reduced, and in order to prevent deterioration of the reaction, a photocatalytic layer made of a semiconductor, an ultraviolet lamp and a heating element provided opposite thereto, and a blower, A deodorizing device using a photocatalyst or a heating element, or a photocatalyst in which the photocatalyst layer and the heating element move so that the entire photocatalyst layer is sequentially heated is disclosed.
【０００５】さらに、特開平７−２４４５１号には、水
棲生物の飼養域に配置した酸化チタン触媒体に紫外線を
含有した光を照射し、該飼養域の水を浄化する方法が開
示されている。Further, Japanese Patent Application Laid-Open No. Hei 7-24451 discloses a method for purifying water in a rearing area by irradiating a titanium oxide catalyst disposed in a rearing area of aquatic organisms with light containing ultraviolet rays. .
【０００６】また、白金、金、銀、パラジウム、銅等の
金属成分を添加すると、光触媒活性が向上することも広
く知られている。It is also widely known that the addition of a metal component such as platinum, gold, silver, palladium and copper improves the photocatalytic activity.
【０００７】[0007]
【発明が解決しようとする課題】特公平６−７９０５号
で指摘されている異物が、光触媒反応を起こす触媒であ
る半導体表面に付着しこれを覆ってしまう現象は、液体
中ではより速く進行する。その原因として、特にアルカ
リ金属、アルカリ土類金属等の無機イオン質が半導体粒
子活性点を覆うことが最近明らかになってきた。アルカ
リ金属、アルカリ土類金属等の無機イオン質が半導体粒
子活性点を覆うと、光触媒活性が著しく損なわれる。し
たがって、光触媒を水環境下で長期にわたり安定して用
いるには特公平５−５０２９４号、及び特開平７−２４
４５１号に開示されている要件のみでは不足である。The phenomenon in which foreign matter, which is pointed out in Japanese Patent Publication No. 6-7905, attaches to and covers the surface of a semiconductor, which is a catalyst that causes a photocatalytic reaction, proceeds faster in a liquid. . As a cause thereof, it has recently become clear that inorganic ionic substances such as alkali metals and alkaline earth metals cover the active sites of the semiconductor particles. When an inorganic ionic substance such as an alkali metal or an alkaline earth metal covers the active sites of the semiconductor particles, the photocatalytic activity is significantly impaired. Therefore, in order to use a photocatalyst stably in a water environment for a long period of time, Japanese Patent Publication No. 5-50294 and Japanese Patent Laid-Open No. 7-24
The requirements disclosed in No. 451 alone are insufficient.
【０００８】またその際、白金、金、銀、パラジウム、
銅等の光触媒活性を向上する成分を単に水溶性化合物の
塗布等の方法で添加すると、これら重金属が水環境下に
溶出し、生態系に悪影響を及ぼすおそれがある。At that time, platinum, gold, silver, palladium,
If a component that improves the photocatalytic activity, such as copper, is simply added by a method such as coating a water-soluble compound, these heavy metals may be eluted in an aqueous environment, which may adversely affect the ecosystem.
【０００９】そこで、本発明では上記事情に鑑み、特に
水環境下における光触媒反応の低下を、生態系に悪影響
を及ぼすことなく、有効に防止し、長期にわたる光触媒
活性を有する粒子、または光触媒材を提供することを目
的とした。[0009] Therefore, in the present invention in view of the above circumstances, in particular a reduction in photocatalytic reactions in an aqueous environment, without adversely affecting the ecosystem, effectively preventing the particles have a long-term photocatalytic activity or photocatalytic, The purpose was to provide materials .
【００１０】[0010]
【課題を解決するための手段】本発明では、上記課題を
解決すべく、光触媒機能粒子が基材表面に固定化されて
なる光触媒材において、前記光触媒機能粒子は、光触媒
活性を有する粒子に、銀又は銅が固定され、この銀又は
銅表面に難溶性または不溶性の塩を形成する処理が施さ
れており、かつ前記光触媒活性を有する粒子は、平均粒
径０．０５μｍ以下のゾルを基材表面に塗布して形成さ
れていることを特徴とする光触媒材を提供する。According to the present invention, in order to solve the above-mentioned problems, photocatalytic functional particles are immobilized on a substrate surface.
In the photocatalyst material comprising the photocatalyst functional particles, the particles having a photocatalytic activity, silver or copper is fixed, it is subjected process of forming a hardly soluble or insoluble salts to the silver or copper surface
And the particles having photocatalytic activity are average particles.
A sol with a diameter of 0.05 μm or less is
It is to provide a photocatalytic Baizai, characterized in that.
【００１１】このような構造にすることにより、光触媒
活性を有する粒子の活性なサイトが予め電子捕捉効果を
有する金属種で固定化されることになるので、高分子物
質や塵芥、アルカリ金属、アルカリ土類金属等の無機イ
オン質が半導体粒子活性点に付着しにくく、長期使用時
の光触媒反応の低下を有効に防止できる。かつ電子捕捉
効果を有する金属種には難溶性または不溶性処理が施さ
れているので、水環境下で使用する場合に、金属が水環
境下に溶出し、生態系に悪影響を及ぼすおそれを未然に
回避できる。With such a structure, the active sites of the particles having photocatalytic activity are fixed in advance by a metal species having an electron trapping effect. Inorganic ionic substances such as earth metals do not easily adhere to the active points of the semiconductor particles, and a decrease in the photocatalytic reaction during long-term use can be effectively prevented. The metal species that have an electron-capturing effect are treated with poor solubility or insolubility, so that when used in an aqueous environment, the metals may elute into the aqueous environment and adversely affect the ecosystem. Can be avoided.
【００１２】本発明の好ましい態様においては、難溶性
または不溶性処理は、金属種上に難溶性または不溶性の
塩を形成する処理で行う。かかる方法は具体的には、ま
ず水溶性の電子捕捉効果を有する金属種を含む物質を光
触媒粒子に適用し、その後で水溶性の電子捕捉効果を有
する金属種上に難溶性または不溶性の塩を形成する方法
なので、光触媒粒子に直接難溶性または不溶性の電子捕
捉効果を有する金属種を含む物質を適用する場合と比較
して、光触媒粒子に電子捕捉効果を有する金属種を均一
に適用できる利点を有する。In a preferred embodiment of the present invention, the hardly soluble or insoluble treatment is performed by forming a hardly soluble or insoluble salt on a metal species. Specifically, such a method first applies a substance containing a metal species having a water-soluble electron-capturing effect to the photocatalyst particles, and then forms a hardly soluble or insoluble salt on the metal species having a water-soluble electron-trapping effect. Since it is a method of forming, compared with the case where a substance containing a metal species having an electron capturing effect that is hardly soluble or insoluble directly on the photocatalyst particles is applied, the advantage that the metal species having an electron capturing effect can be uniformly applied to the photocatalytic particles is provided. Have.
【００１３】本発明の好ましい態様においては、難溶性
または不溶性処理は、固定された金属種のうちの水溶性
成分を予め抽出除去する処理で行ってもよい。かかる方
法は具体的には、まず水溶性の電子捕捉効果を有する金
属種を含む物質を光触媒粒子に適用し、次に金属種の一
部を還元、または難溶性または不溶性の塩に変化させ、
その後余剰の水溶性成分を予め抽出除去する方法である
が、ここで抽出除去工程の存在により、より確実に金属
種の溶出を防止できる。[0013] In a preferred embodiment of the present invention, the hardly soluble or insoluble treatment may be carried out by extracting and removing a water-soluble component of the fixed metal species in advance. Specifically, such a method firstly applies a substance containing a water-soluble metal species having an electron-trapping effect to the photocatalyst particles, and then reduces or partially converts the metal species to a hardly soluble or insoluble salt,
After that, excess water-soluble components are extracted and removed in advance. Here, the extraction and removal step can more reliably prevent the elution of metal species.
【００１４】本発明の好ましい態様においては、難溶性
または不溶性の塩は、光触媒活性を有する粒子に固定化
された金属種の塩であるようにする。このようにするこ
とにより、適用した金属種に難溶性の塩または不溶性の
塩を生成しうる溶液、気体等を直接反応させるのみで、
前記金属種上に難溶性の塩または不溶性の塩を形成しう
るので、工程上簡便である。In a preferred embodiment of the present invention, the hardly soluble or insoluble salt is a salt of a metal species immobilized on particles having photocatalytic activity. By doing so, a solution or gas that can produce a hardly soluble salt or an insoluble salt in the applied metal species is simply reacted directly,
Since a hardly soluble salt or an insoluble salt can be formed on the metal species, the process is simple.
【００１５】本発明の好ましい態様においては、難溶性
または不溶性の塩は、抗菌性を有する金属種の塩である
ようにする。このようにすることにより、光触媒による
抗菌作用の他に、適用した金属種による抗菌作用を加味
できるので、より抗菌性能が向上する。また光を照射し
ない場合でも抗菌性を発揮しうるようになる。In a preferred embodiment of the present invention, the hardly soluble or insoluble salt is a salt of a metal species having antibacterial properties. By doing so, since the antibacterial action of the applied metal species can be added in addition to the antibacterial action of the photocatalyst, the antibacterial performance is further improved. In addition, antimicrobial properties can be exhibited even when light is not irradiated.
【００１６】本発明の好ましい態様においては、難溶性
または不溶性の塩は、銀塩であるようにする。銀は他の
金属種と比較して抗菌作用が強いので、より抗菌性能が
向上する。In a preferred embodiment of the present invention, the hardly soluble or insoluble salt is a silver salt. Silver has a stronger antibacterial effect than other metal species, so that the antibacterial performance is further improved.
【００１７】本発明の好ましい態様においては、光触媒
活性を有する粒子、及び金属種は、基材表面に固定化さ
れているようにする。基材に固定された状態で使用する
方が、粒子の場合と比較して水を濁らせることなく、ま
た回収にも簡便である。In a preferred embodiment of the present invention, the particles having photocatalytic activity and the metal species are immobilized on the substrate surface. When used in a state of being fixed to the base material, water is not turbid as compared with the case of particles, and the collection is easier.
【００１８】本発明の好ましい態様においては、難溶性
または不溶性の塩が白色または無色の塩であるようにす
る。このようにすることにより、光触媒基材に施された
色、模様、透明性、光沢等の意匠的外観を維持できる。In a preferred embodiment of the present invention, the hardly soluble or insoluble salt is a white or colorless salt. By doing so, it is possible to maintain the design appearance such as the color, pattern, transparency, and gloss applied to the photocatalyst substrate.
【００１９】本発明の好ましい態様においては、上記光
触媒機能粒子、または光触媒材を、水中に配置して水の
浄化方法を行うようにする。水の浄化を上記光触媒機能
粒子、または光触媒材で行えば、光触媒による水の抗
菌、防藻等を長期にわたり発揮することができる。ま
た、重金属の溶出がほとんど生じないので、生態系に悪
影響を及ぼすおそれもない。さらに無機抗菌剤のように
金属イオンの溶出で作用を生じさせるわけではないの
で、塩素イオン等の存在により効果が低下、短期化する
こともない。In a preferred embodiment of the present invention, the photocatalyst function particles or photocatalytic Baizai, and placed in the water to perform the method of purifying water. By performing the purification of water the photocatalyst functional particles or photocatalytic at Baizai, and can exhibit antibacterial of water by the photocatalyst, the algae and the like for a long time. In addition, since the elution of heavy metals hardly occurs, there is no possibility of adversely affecting the ecosystem. Further, since the action is not caused by the elution of metal ions unlike the inorganic antibacterial agent, the effect is not reduced or shortened due to the presence of chloride ions.
【００２０】本発明の好ましい態様においては、上記光
触媒機能粒子、または光触媒材を、水槽中に配置して観
賞魚または魚貝飼育用水槽の防藻方法を行うようにす
る。水槽中に配置して観賞魚または魚貝飼育用水槽の防
藻を、上記光触媒機能粒子、または光触媒材で行えば、
光触媒による水槽内の防藻等を長期にわたり発揮するこ
とができる。また、重金属の溶出がほとんど生じないの
で、生態系に悪影響を及ぼすおそれもない。さらに無機
抗菌剤のように金属イオンの溶出で作用を生じさせるわ
けではないので、塩素イオン等の存在により効果が低
下、短期化することもない。In a preferred embodiment of the present invention, the photocatalyst function particles or photocatalytic Baizai, and so arranged in the water tank perform algae methods ornamental fish or seafood breeding tanks. The algae of ornamental fish or seafood breeding tanks are placed in a water tank, by performing the above photocatalyst functional particles or photocatalytic Baizai,
Algae prevention and the like in the water tank by the photocatalyst can be exhibited for a long time. In addition, since the elution of heavy metals hardly occurs, there is no possibility of adversely affecting the ecosystem. Further, since the action is not caused by the elution of metal ions unlike the inorganic antibacterial agent, the effect is not reduced or shortened due to the presence of chloride ions.
【００２１】本発明の好ましい態様においては、光触媒
材を、水槽中に配置する観賞魚または魚貝飼育用水槽の
防藻方法において、前記基材は耐熱性基材にする。基材
を耐熱性にすることで、光触媒活性を有する粒子を加熱
工程のみで強固に固定できる。[0021] In a preferred embodiment of the present invention, photocatalytic
In the method for preventing algae in an aquarium for breeding ornamental fish or fish and shellfish in which a material is placed in an aquarium, the base material is a heat-resistant base material. By making the base material heat resistant, the particles having photocatalytic activity can be firmly fixed only by the heating step.
【００２２】本発明の好ましい態様においては、光触媒
材を、水槽中に配置する観賞魚または魚貝飼育用水槽の
防藻方法において、前記基材は透明基材にする。基材を
透明にすることで意匠性が良好になり、また観賞する際
に清涼感を発揮できるとともに、光の照射効率が向上す
る。[0022] In a preferred embodiment of the present invention, photocatalytic
In the method for preventing algae in an aquarium for breeding ornamental fish or fish and shellfish in which the material is placed in an aquarium, the base material is a transparent base material. By making the base material transparent, the design is improved, and a refreshing feeling can be exhibited when watching, and the light irradiation efficiency is improved.
【００２３】本発明の好ましい態様においては、上記観
賞魚または魚貝飼育用水槽の防藻方法において、基材は
球状であるようにする。基材が球状だと、水槽内に投入
しやすく、また形状もシンプルで意匠性がよい。また基
材上に形成する光触媒活性を有する粒子層に終端がない
ため剥離しにくい。さらに、球状基材は、例えば溶融し
たガラスをカットしながら傾斜のある加熱されたプレー
ト上に落下させ、該プレートに温度勾配を設けて転がる
うちに徐々に冷却されていく装置などで簡単に作製でき
るのでコスト上も安価にできる。In a preferred embodiment of the present invention, in the method for preventing algae in an aquarium for breeding ornamental fish or fish and shells, the base material is spherical. When the base material is spherical, it is easy to put into a water tank, and the shape is simple and the design is good. In addition, since there is no terminal in the photocatalytically active particle layer formed on the substrate, it is difficult to peel off. Furthermore, the spherical base material is easily produced, for example, by dropping a molten glass on a heated plate with an inclination while cutting the glass, providing a temperature gradient to the plate, and gradually cooling the plate while rolling. Because it can be done, the cost can be reduced.
【００２４】本発明の好ましい態様においては、上記観
賞魚または魚貝飼育用水槽の防藻方法において、基材は
楕円体状であるようにする。基材が楕円体状だと、水槽
内に投入しやすく、また形状もシンプルで意匠性がよ
い。また基材上に形成する光触媒活性を有する粒子層に
終端がないため剥離しにくい。さらに誤って床等に落し
たときにも転がりにくい。In a preferred embodiment of the present invention, in the method for preventing algae in an aquarium for breeding ornamental fish or fish and shells, the base material is formed in an ellipsoidal shape. When the base material is elliptical, it is easy to put into a water tank, and the shape is simple and the design is good. In addition, since there is no terminal in the photocatalytically active particle layer formed on the substrate, it is difficult to peel off. Furthermore, it is difficult to roll when accidentally dropped on a floor or the like.
【００２５】[0025]
【発明の実施の形態】以下に本発明の光触媒機能粒子に
ついて具体的に説明する。本発明の光触媒機能粒子は、
光触媒活性を有する粒子に、難溶性または不溶性処理さ
れた電子捕捉効果を有する金属種が固定されている。こ
こで光触媒活性を有する粒子とは、抗菌機能、防臭機
能、防藻機能等の光触媒機能を発揮するのに充分なバン
ド・ギャップを有する半導体粒子のことである。光触媒
粒子が抗菌機能を有する理由としては所定以上の電圧が
印加されることにより感電死するという説（特公平４−
２９３９３号）もあるが、一般には防臭機能と同様に、
光照射時に生じる活性酸素のためと考えられている。活
性酸素を生成するためには、半導体の伝導帯の位置がバ
ンドモデルで表すとき水素発生電位より上方にあり、か
つ価電子帯の上端が酸素発生電位より下方にあることを
要する。この条件を満たす半導体には、酸化チタン、チ
タン酸ストロンチウム、酸化亜鉛、炭化ケイ素、リン化
ガリウム、硫化カドミウム、セレン化カドミウム、三硫
化モリブデン等がある。また微粒化すると伝導帯の位置
は上方に移動するので、１〜１０ｎｍ程度の微粒子なら
ば、酸化スズ、三酸化タングステン、酸化第二鉄等も活
性酸素を生成しうる可能性がある。このうち化学的に安
定で、安価に活性の高い微粒子を得ることができること
から、アナターゼ型酸化チタンが特に好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The photocatalytic functional particles of the present invention will be specifically described below. The photocatalytic functional particles of the present invention,
A metal species having an electron trapping effect, which has been treated to be hardly soluble or insoluble, is fixed to particles having photocatalytic activity. Here, the particles having photocatalytic activity are semiconductor particles having a band gap sufficient to exhibit a photocatalytic function such as an antibacterial function, a deodorant function, and an algal function. The reason that the photocatalyst particles have an antibacterial function is that the photocatalyst particles are electrocuted when a voltage higher than a predetermined voltage is applied (Japanese Patent Publication No. Hei 4-
29393), but generally, like the deodorant function,
It is thought to be due to active oxygen generated during light irradiation. In order to generate active oxygen, the position of the conduction band of the semiconductor needs to be above the hydrogen generation potential when represented by a band model, and the upper end of the valence band needs to be below the oxygen generation potential. Semiconductors that satisfy this condition include titanium oxide, strontium titanate, zinc oxide, silicon carbide, gallium phosphide, cadmium sulfide, cadmium selenide, and molybdenum trisulfide. When the particles are atomized, the position of the conduction band moves upward. Therefore, with fine particles of about 1 to 10 nm, there is a possibility that tin oxide, tungsten trioxide, ferric oxide, and the like can also generate active oxygen. Of these, anatase-type titanium oxide is particularly preferable because fine particles that are chemically stable and have high activity can be obtained at low cost.
【００２６】電子捕捉効果を有する金属種とは、Ｐｔ、
Ｐｄ、Ａｕ、Ａｇ、Ｃｕ、Ｎｉ、Ｆｅ、Ｃｏ、Ｚｎ等の
イオン化傾向の小さく、自身が還元されやすい金属及び
そのイオンをいう。尚、これらの金属種は、複数併用し
て用いても構わない。電子捕捉効果を有する金属種を光
触媒活性を有する粒子に固定する方法は、電子捕捉効果
を有する金属種を含む金属塩の懸濁液または溶液を光触
媒活性を有する粒子に適用し、乾燥させることによる。The metal species having an electron trapping effect include Pt,
Pd, Au, Ag, Cu, Ni, Fe, Co, Zn, etc., which have a small ionization tendency and are easily reduced, and their metals. Note that these metal species may be used in combination of two or more. A method of fixing a metal species having an electron trapping effect to particles having a photocatalytic activity is to apply a suspension or solution of a metal salt containing a metal species having an electron trapping effect to the particles having a photocatalytic activity, and to dry the suspension. .
【００２７】金属種の難溶性または不溶性処理とは、光
触媒活性を有する粒子に固定された金属種の形態を水に
対する溶解度が小さい、若しくはない状態にすることで
ある。具体的には、難溶性または不溶性の塩へと化学反
応で変化させる方法と、光、電気、加熱、還元剤等を利
用して難溶性または不溶性の還元金属に変化させる方法
がある。The treatment of hardly dissolving or insoluble metal species means that the form of the metal species immobilized on the particles having photocatalytic activity has a low or no solubility in water. Specifically, there are a method of changing to a hardly soluble or insoluble salt by a chemical reaction, and a method of changing to a hardly soluble or insoluble reduced metal using light, electricity, heating, a reducing agent or the like.
【００２８】難溶性または不溶性の塩へと化学反応で変
化させる方法は、例えば、金属種と難溶性または不溶性
の塩を形成しうる陰イオンを含む溶液と、上記金属種が
固定された光触媒活性を有する粒子とを接触させる方法
や、金属種と難溶性または不溶性の塩を形成しうる気体
と、反応しうる温度で、上記金属種が固定された光触媒
活性を有する粒子とを接触させる方法がある。上記２つ
のいずれの方法においても難溶性または不溶性の塩は金
属種の外側に形成されることになるので、この場合は、
反応が１００％進行しなくても難溶性または不溶性処理
は完了する。The method of converting into a hardly soluble or insoluble salt by a chemical reaction includes, for example, a solution containing an anion capable of forming a hardly soluble or insoluble salt with a metal species, a photocatalytic activity in which the metal species is fixed, And a method of contacting a gas capable of forming a hardly soluble or insoluble salt with a metal species at a temperature capable of reacting with a metal species-fixed particle having photocatalytic activity. is there. In either of the above two methods, the sparingly soluble or insoluble salt will be formed outside the metal species.
Even if the reaction does not proceed 100%, the hardly soluble or insoluble treatment is completed.
【００２９】加熱を利用して難溶性または不溶性の還元
金属に変化させる方法でも温度は表面から高くなるの
で、難溶性または不溶性の還元金属は金属種の外側に形
成されることになるので、従って、この場合は反応が１
００％進行しなくても難溶性または不溶性処理は完了す
る。なお、この方法の取り得る金属種はＰｔ、Ｐｄ、Ａ
ｕ、Ａｇ等であり、Ｃｕ、Ｎｉ、Ｆｅ、Ｃｏ、Ｚｎ等で
は加熱時に逆に酸化されるのでこの方法は適切ではな
い。In the method of changing to a hardly soluble or insoluble reduced metal by using heating, the temperature rises from the surface, so that the hardly soluble or insoluble reduced metal is formed outside the metal species. , In this case the reaction is 1
Even if it does not progress by 00%, the hardly soluble or insoluble treatment is completed. The metal species that can be used in this method are Pt, Pd, A
This method is not appropriate for Cu, Ni, Fe, Co, Zn, and the like because they are oxidized in reverse during heating.
【００３０】還元剤を利用して難溶性または不溶性の還
元金属に変化させる方法でも還元剤からの電子の流入は
金属種の外側で生じるので、難溶性または不溶性の還元
金属は金属種の外側に形成されることになる。従って、
この場合も反応が１００％進行しなくても難溶性または
不溶性処理は完了する。なお、ここで、還元剤にはアル
デヒド類、アルコール類、オレフィン類等が好適に利用
できる。Even in the method of converting into a hardly soluble or insoluble reduced metal by using a reducing agent, since the inflow of electrons from the reducing agent occurs outside the metal species, the hardly soluble or insoluble reduced metal becomes outside the metal species. Will be formed. Therefore,
Also in this case, even if the reaction does not proceed 100%, the hardly soluble or insoluble treatment is completed. Here, aldehydes, alcohols, olefins and the like can be suitably used as the reducing agent.
【００３１】光を利用して難溶性または不溶性の還元金
属に変化させる方法では、還元は光触媒の近くにある金
属種、すなわち内側の金属種から進行する。したがっ
て、この方法によれば、難溶性または不溶性処理を上記
工程のみで完了させるには、反応を１００％進行させる
必要がある。ただし、この場合にさらに残留した水溶性
の塩を抽出除去するようにすれば、完全に上記反応を完
了させることなく、難溶性または不溶性処理を完了させ
ることができる。この方法で工程時間は短縮化される。In the method of converting light into a hardly soluble or insoluble reduced metal using light, the reduction proceeds from a metal species near the photocatalyst, that is, a metal species inside. Therefore, according to this method, in order to complete the hardly soluble or insoluble treatment only by the above steps, the reaction needs to proceed 100%. However, in this case, if the remaining water-soluble salt is further extracted and removed, the hardly soluble or insoluble treatment can be completed without completely completing the above reaction. In this way, the processing time is reduced.
【００３２】さらに、光を利用して難溶性または不溶性
の還元金属に変化させる方法以外の方法においても、さ
らに残留した水溶性の塩を抽出除去するようにすれば、
難溶性または不溶性処理をより完全に行うことができ
る。Further, in a method other than the method of using light to change to a hardly soluble or insoluble reduced metal, if the remaining water-soluble salt is further extracted and removed,
The hardly soluble or insoluble treatment can be performed more completely.
【００３３】ここで難溶性の塩とは、水に対する溶解度
が小さな塩のことであり、具体的には、塩化銀、炭酸
銀、リン酸銀、ヨウ化銀、臭化銀、シュウ酸銀、酸化
銀、チオ硫酸銀、シアン化銀、ロダン化銀、塩化第一
銅、ヨウ化第一銅、臭化第一銅、ロダン化第一銅、硫化
第一銅、リン酸第二銅、シュウ酸第二銅、硫化第二銅、
炭酸第一鉄、シュウ酸第一鉄、硫化第一鉄、リン酸第二
鉄、炭酸コバルト、シュウ酸コバルト、シアン化コバル
ト、硫化コバルト、炭酸ニッケル、シュウ酸ニッケル、
シアン化ニッケル、硫化ニッケル、ヨウ化第一金、酸化
第一金、炭酸亜鉛、リン酸亜鉛、シュウ酸亜鉛、酸化亜
鉛、シアン化亜鉛、硫化亜鉛等のことである。Here, the sparingly soluble salt is a salt having low solubility in water, and specifically, silver chloride, silver carbonate, silver phosphate, silver iodide, silver bromide, silver oxalate, and the like. Silver oxide, silver thiosulfate, silver cyanide, silver rhodanide, cuprous chloride, cuprous iodide, cuprous bromide, cuprous rhodanide, cuprous sulfide, cupric phosphate, shu Cupric acid, cupric sulfide,
Ferrous carbonate, ferrous oxalate, ferrous sulfide, ferric phosphate, cobalt carbonate, cobalt oxalate, cobalt cyanide, cobalt sulfide, nickel carbonate, nickel oxalate,
Nickel cyanide, nickel sulfide, gold (I) iodide, gold (I) oxide, zinc carbonate, zinc phosphate, zinc oxalate, zinc oxide, zinc cyanide, zinc sulfide and the like.
【００３４】不溶性の塩とは、水に溶解しない塩のこと
であり、具体的には、硫化銀、酸化第一銅、シアン化第
一銅、酸化第二銅、リン酸第一鉄、酸化第一鉄、酸化第
二鉄、硫化第二鉄、リン酸コバルト、酸化コバルト、リ
ン酸ニッケル、酸化ニッケル、ヨウ化パラジウム、臭化
パラジウム、酸化パラジウム、塩化白金、ヨウ化白金、
臭化白金、酸化白金、シアン化白金、硫化白金、シアン
化第一金、硫化第一金、酸化第二金、硫化第二金等のこ
とである。The insoluble salt is a salt that does not dissolve in water, and specifically includes silver sulfide, cuprous oxide, cuprous cyanide, cupric oxide, ferrous phosphate, and oxide. Ferrous, ferric oxide, ferric sulfide, cobalt phosphate, cobalt oxide, nickel phosphate, nickel oxide, palladium iodide, palladium bromide, palladium oxide, platinum chloride, platinum iodide,
Platinum bromide, platinum oxide, platinum cyanide, platinum sulfide, gold (I) cyanide, gold (I) sulfide, gold (II) oxide, gold (II) sulfide and the like.
【００３５】水溶性の塩とは、水に対する溶解度の大き
な塩のことであり、具体的には、硝酸銀、塩素酸銀、酢
酸銀、硫酸銀、塩化第二銅、硫酸第一銅、硫酸第二銅、
臭化第二銅、酢酸第一銅、酢酸第二銅、塩素酸第二銅、
硝酸第二銅、ロダン化第二銅、塩化第一鉄、塩化第二
鉄、硫酸第一鉄、硫酸第二鉄、ヨウ化第一鉄、臭化第一
鉄、臭化第二鉄、シュウ酸第二鉄、酢酸第一鉄、酢酸第
二鉄、塩素酸第一鉄、塩素酸第二鉄、硝酸第一鉄、硝酸
第二鉄、チオ硫酸第一鉄、ロダン化第一鉄、ロダン化第
二鉄、塩化コバルト、硫酸コバルト、ヨウ化コバルト、
臭化コバルト、酢酸コバルト、塩素酸コバルト、硝酸コ
バルト、塩化ニッケル、硫酸ニッケル、ヨウ化ニッケ
ル、臭化ニッケル、酢酸ニッケル、塩素酸ニッケル、硝
酸ニッケル、ロダン化ニッケル、硫酸パラジウム、塩化
パラジウム、ロダン化パラジウム、塩化白金酸、硫酸白
金、塩化第二金、硫酸第二金、臭化第二金、シアン化第
二金、塩化亜鉛、硫酸亜鉛、ヨウ化亜鉛、臭化亜鉛、酢
酸亜鉛、塩素酸亜鉛、硝酸亜鉛、シアン化亜鉛等が挙げ
られる。The water-soluble salt is a salt having a high solubility in water, and specifically, silver nitrate, silver chlorate, silver acetate, silver sulfate, cupric chloride, cuprous sulfate, and copper sulfate. Copper,
Cupric bromide, cuprous acetate, cupric acetate, cupric chlorate,
Cupric nitrate, cupric rhodanide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, ferrous iodide, ferrous bromide, ferric bromide, shu Ferric acid, ferrous acetate, ferric acetate, ferrous chlorate, ferric chlorate, ferrous nitrate, ferric nitrate, ferrous thiosulfate, ferrous rhodanate, rodane Ferric iodide, cobalt chloride, cobalt sulfate, cobalt iodide,
Cobalt bromide, cobalt acetate, cobalt chlorate, cobalt nitrate, nickel chloride, nickel sulfate, nickel iodide, nickel bromide, nickel acetate, nickel chlorate, nickel nitrate, nickel rhodanate, palladium sulfate, palladium chloride, rhodane Palladium, chloroplatinic acid, platinum sulfate, gold (II) chloride, gold (II) sulfate, gold (II) bromide, gold (II) cyanide, zinc chloride, zinc sulfate, zinc iodide, zinc bromide, zinc acetate, chloric acid Zinc, zinc nitrate, zinc cyanide and the like can be mentioned.
【００３６】難溶性または不溶性の塩が無色または白色
であることが好ましい。基材に形成した色、模様等の色
彩による外観を損なうことがないからである。上記難溶
性の塩または不溶性の塩のうち、白色塩を形成する物質
としては、塩化銀、臭化銀、シュウ酸銀、チオ硫酸銀、
シアン化銀、ロダン化銀、ヨウ化銀、塩化第一銅、臭化
第一銅、ロダン化第一銅、シアン化第一銅、炭酸第一
鉄、炭酸亜鉛、酸化亜鉛、シュウ酸亜鉛、シアン化亜
鉛、リン酸亜鉛、硫化亜鉛等が挙げられる。Preferably, the hardly soluble or insoluble salt is colorless or white. This is because the appearance due to the color such as the color and pattern formed on the base material is not impaired. Among the hardly soluble salts or insoluble salts, substances that form white salts include silver chloride, silver bromide, silver oxalate, silver thiosulfate,
Silver cyanide, silver rhodanide, silver iodide, cuprous chloride, cuprous bromide, cuprous rhodanide, cuprous cyanide, ferrous carbonate, zinc carbonate, zinc oxide, zinc oxalate, Zinc cyanide, zinc phosphate, zinc sulfide and the like.
【００３７】本発明による光触媒機能粒子は、粒子状の
まま静水中等に懸濁させて用いてもよいし、基材表面に
固定して用いてもよい。The photocatalytic functional particles according to the present invention may be used in the form of particles suspended in still water or the like, or may be used fixed on the surface of a substrate.
【００３８】粒子状のまま静水中等に懸濁させて用いる
場合の光触媒機能粒子は、例えば以下のようにして作製
する。その１つの方法は、光触媒粒子の懸濁液と金属塩
溶液（または懸濁液）を混合し、得られた混合液に紫外
線を含む光を照射して光触媒粒子に金属種を固定し、さ
らに上記金属種に難溶性または不溶性の塩を形成する陰
イオンを含む溶液を接触させることによる。他の方法と
しては、光触媒粒子の懸濁液と金属塩溶液（または懸濁
液）を混合し、得られた混合液に紫外線を含む光を照射
して光触媒粒子に金属種を固定し、さらに光触媒粒子に
付着した水溶性金属塩を水中で抽出させてもよい。また
他の方法としては、光触媒粒子の懸濁液と金属塩溶液
（または懸濁液）を混合し、得られた混合液に紫外線を
含む光を照射して光触媒粒子に金属種を固定し、さらに
光触媒粒子に付着した水溶性金属塩を還元処理させても
よい。また他の方法としては、光触媒粒子の懸濁液と金
属塩溶液（または懸濁液）を混合し、得られた混合液に
紫外線を含む光を照射して光触媒粒子に金属種を固定
し、さらに上記金属種の表面に加熱等の方法で難溶性ま
たは不溶性の保護酸化膜を形成してもよい。The photocatalytic functional particles used when suspended in still water or the like in the form of particles are produced, for example, as follows. One of the methods is to mix a suspension of photocatalyst particles with a metal salt solution (or suspension), irradiate the resulting mixture with light containing ultraviolet rays to fix metal species to the photocatalyst particles, By contacting a solution containing an anion that forms a hardly soluble or insoluble salt with the metal species. As another method, a suspension of the photocatalyst particles and a metal salt solution (or suspension) are mixed, and the resulting mixture is irradiated with light containing ultraviolet rays to fix the metal species to the photocatalyst particles. The water-soluble metal salt attached to the photocatalyst particles may be extracted in water. As another method, a suspension of the photocatalyst particles and a metal salt solution (or suspension) are mixed, and the resulting mixed solution is irradiated with light including ultraviolet rays to fix the metal species to the photocatalyst particles, Further, the water-soluble metal salt attached to the photocatalyst particles may be subjected to a reduction treatment. As another method, a suspension of the photocatalyst particles and a metal salt solution (or suspension) are mixed, and the resulting mixed solution is irradiated with light including ultraviolet rays to fix the metal species to the photocatalyst particles, Further, a hardly soluble or insoluble protective oxide film may be formed on the surface of the metal species by a method such as heating.
【００３９】ここで光触媒粒子またはゾルはなるべく懸
濁液中に単分散させるようにする。例えばアナターゼ型
酸化チタンの場合には等電点がｐＨ６．５なので酸性ま
たはアルカリ性で分散させる。この際、分散性を向上さ
せるために分散剤（解膠剤）や表面活性剤若しくは表面
処理剤を添加してもよい。また懸濁液に用いる溶液は基
本的に何でもよい。一般的には水やエタノールがよく使
用される。Here, the photocatalyst particles or sol are preferably monodispersed in a suspension. For example, in the case of anatase type titanium oxide, since the isoelectric point is pH 6.5, it is dispersed in an acidic or alkaline state. At this time, a dispersant (deflocculant), a surface active agent or a surface treating agent may be added to improve dispersibility. The solution used for the suspension may be basically any solution. Generally, water and ethanol are often used.
【００４０】光触媒粒子の懸濁液またはゾルと金属塩溶
液を混合する際には、両者のｐＨをほば等しくするほう
がよい。懸濁液中の光触媒粒子またはゾルの分散性を変
化させずにすむからである。こで金属塩溶液とは、Ｐ
ｔ、Ｐｄ、Ａｕ、Ａｇ、Ｃｕ、Ｎｉ、Ｆｅ、Ｃｏ、Ｚｎ
等の電子捕捉効果を有する金属元素を含む塩と溶媒とか
らなる溶液をいう。このような塩としては、硝酸銀、塩
素酸銀、酢酸銀、硫酸銀、塩化第二銅、硫酸第一銅、硫
酸第二銅、臭化第二銅、酢酸第一銅、酢酸第二銅、塩素
酸第二銅、硝酸第二銅、ロダン化第二銅、塩化第一鉄、
塩化第二鉄、硫酸第一鉄、硫酸第二鉄、ヨウ化第一鉄、
臭化第一鉄、臭化第二鉄、シュウ酸第二鉄、酢酸第一
鉄、酢酸第二鉄、塩素酸第一鉄、塩素酸第二鉄、硝酸第
一鉄、硝酸第二鉄、チオ硫酸第一鉄、ロダン化第一鉄、
ロダン化第二鉄、塩化コバルト、硫酸コバルト、ヨウ化
コバルト、臭化コバルト、酢酸コバルト、塩素酸コバル
ト、硝酸コバルト、塩化ニッケル、硫酸ニッケル、ヨウ
化ニッケル、臭化ニッケル、酢酸ニッケル、塩素酸ニッ
ケル、硝酸ニッケル、ロダン化ニッケル、硫酸パラジウ
ム、塩化パラジウム、ロダン化パラジウム、塩化白金
酸、硫酸白金、塩化第二金、硫酸第二金、臭化第二金、
シアン化第二金、塩化亜鉛、硫酸亜鉛、ヨウ化亜鉛、臭
化亜鉛、酢酸亜鉛、塩素酸亜鉛、硝酸亜鉛、シアン化亜
鉛等が挙げられる。また溶媒としては水、エタノール、
プロパノール等が使用できるが、なるべく光触媒粒子ま
たはゾルの懸濁液と同じ種類を用いることが望ましい。[0040] In mixing the suspension or sol and the metal salt solution of the photocatalyst particles child is better to equalize if ho the pH of both. This is because the dispersibility of the photocatalyst particles or the sol in the suspension does not need to be changed. Here, the metal salt solution is P
t, Pd, Au, Ag, Cu, Ni, Fe, Co, Zn
And the like, and a solution comprising a salt containing a metal element having an electron capturing effect and a solvent. Such salts include silver nitrate, silver chlorate, silver acetate, silver sulfate, cupric chloride, cuprous sulfate, cupric sulfate, cupric bromide, cuprous acetate, cupric acetate, Cupric chlorate, cupric nitrate, cupric rhodanate, ferrous chloride,
Ferric chloride, ferrous sulfate, ferric sulfate, ferrous iodide,
Ferrous bromide, ferric bromide, ferric oxalate, ferrous acetate, ferric acetate, ferrous chlorate, ferric chlorate, ferrous nitrate, ferric nitrate, Ferrous thiosulfate, ferrous rodane,
Ferric rhodanide, cobalt chloride, cobalt sulfate, cobalt iodide, cobalt bromide, cobalt acetate, cobalt chlorate, cobalt nitrate, nickel chloride, nickel sulfate, nickel iodide, nickel bromide, nickel acetate, nickel chlorate , Nickel nitrate, nickel rhodanate, palladium sulfate, palladium chloride, palladium rhodanide, chloroplatinic acid, platinum sulfate, gold (II) chloride, gold (II) sulfate, gold (II) bromide,
Gold (II) cyanide, zinc chloride, zinc sulfate, zinc iodide, zinc bromide, zinc acetate, zinc chlorate, zinc nitrate, zinc cyanide and the like. The solvent is water, ethanol,
Although propanol and the like can be used, it is desirable to use the same type as the suspension of the photocatalyst particles or the sol as much as possible.
【００４１】光触媒粒子の懸濁液またはゾルと金属塩溶
液とを撹絆しながら紫外線を含む光を照射する工程にお
いて、紫外線を含む光を照射する光源は、紫外線を照射
しうるものであればよく、例えば、紫外線ランプ、ＢＬ
Ｂランプ、キセノンランプ、水銀灯、蛍光灯などが挙げ
られる。紫外線を含む光の照射方法も基本的には問わな
いが、容器上方から照射するほうがよい。容器による紫
外線の吸収がないからである。In the step of irradiating light containing ultraviolet light while stirring the suspension or sol of the photocatalyst particles and the metal salt solution, the light source for irradiating light containing ultraviolet light may be any one capable of irradiating ultraviolet light. Well, for example, UV lamp, BL
B lamps, xenon lamps, mercury lamps, fluorescent lamps and the like can be mentioned. The method of irradiating light including ultraviolet rays is basically not limited, but it is better to irradiate from above the container. This is because ultraviolet rays are not absorbed by the container.
【００４２】難溶性または不溶性の塩を形成する陰イオ
ンを含む溶液は、金属種と前記溶液が接触することによ
り反応し、難溶性または不溶性の塩を金属種表面に形成
しうる溶液である。 例えば、金属種が銀（イオン）の
場合は、塩化ナトリウム、塩化カリウム、塩化アンモニ
ウム、塩化第二鉄等の可溶性塩化物や、可溶性臭化物、
可溶性ヨウ化物、可溶性シアン化物、可溶性ロダン化
物、可溶性リン酸塩、可溶性シュウ酸塩、可溶性チオ硫
酸塩、可溶性炭酸塩等を含む溶液をさす。また金属種が
銅（イオン）の場合は、可溶性リン酸塩、可溶性シュウ
酸塩等を含む溶液をさす。また金属種が鉄の場合は、可
溶性リン酸塩等を含む溶液をさす。また金属種がコバル
トまたはニッケル（イオン）の場合は、可溶性シュウ酸
塩、可溶性シアン化物、可溶性炭酸塩等を含む溶液をさ
す。また金属種が亜鉛（イオン）の場合は、可溶性リン
酸塩、可溶性シュウ酸塩、可溶性シアン化物、可溶性炭
酸塩等を含む溶液をさす。The solution containing an anion that forms a hardly soluble or insoluble salt is a solution that can react by contact of the metal species with the solution to form a hardly soluble or insoluble salt on the surface of the metal species. For example, when the metal species is silver (ion), soluble chlorides such as sodium chloride, potassium chloride, ammonium chloride, and ferric chloride;
A solution containing a soluble iodide, a soluble cyanide, a soluble rhodanide, a soluble phosphate, a soluble oxalate, a soluble thiosulfate, a soluble carbonate and the like. When the metal species is copper (ion), it refers to a solution containing a soluble phosphate, a soluble oxalate, and the like. When the metal species is iron, it refers to a solution containing a soluble phosphate or the like. When the metal species is cobalt or nickel (ion), it refers to a solution containing soluble oxalate, soluble cyanide, soluble carbonate and the like. When the metal species is zinc (ion), it refers to a solution containing a soluble phosphate, a soluble oxalate, a soluble cyanide, a soluble carbonate and the like.
【００４３】基材表面に光触媒機能粒子を固定化して用
いる場合の、基材表面に光触媒機能粒子を固定化した防
臭、抗菌等の光触媒機能を有する多機能材の作製方法
は、例えば以下のようにして作製する。その１つの方法
は、基材表面に光触媒活性を有する層を形成する工程、
その上に上記金属種を含む溶液（または懸濁液）を適用
する工程、上記金属種と難溶性または不溶性の塩を形成
する陰イオンを含む溶液を金属種に接触させる工程を順
次行うことによる。他の方法としては、基材表面に光触
媒活性を有する層を形成する工程、その上に上記金属種
を含む溶液（または懸濁液）を適用する工程、上記金属
種を還元処理する工程を順次行うことにしてもよい。た
だし、この場合、還元処理を光還元により行う場合は、
さらに基材上に残留する水溶性の塩を抽出除去する工程
を行う。他の方法としては、光触媒活性を有する粒子に
金属種を固定する工程、上記金属種を固定した光触媒活
性を有する粒子を基材表面に適用する工程、上記金属種
がその表面に難溶性または不溶性の保護酸化膜を形成す
る温度で熱処理する工程を順次行うことにしてもよい。
他の方法としては、光触媒活性を有する粒子に金属種を
固定する工程、上記金属種を固定した光触媒活性を有す
る粒子を基材表面に適用し加熱固定する工程、上記金属
種と難溶性または不溶性の塩を形成する陰イオンを含む
溶液を金属種に接触させる工程を順次行うことにしても
よい。In the case where the photocatalytic function particles are immobilized on the substrate surface and used, a method for producing a multifunctional material having a photocatalytic function such as deodorization and antibacterial, in which the photocatalytic function particles are immobilized on the substrate surface, is as follows, for example. It is produced. One of the methods is a step of forming a layer having photocatalytic activity on a substrate surface,
A step of applying a solution (or suspension) containing the metal species thereon, and a step of contacting the metal species with a solution containing an anion that forms a hardly soluble or insoluble salt with the metal species. . As another method, a step of forming a layer having photocatalytic activity on the substrate surface, a step of applying a solution (or suspension) containing the metal species thereon, and a step of reducing the metal species are sequentially performed. You may decide to do it. However, in this case, if the reduction treatment is performed by photoreduction,
Further, a step of extracting and removing the water-soluble salt remaining on the substrate is performed. As another method, a step of fixing a metal species to particles having photocatalytic activity, a step of applying particles having photocatalytic activity in which the metal species is fixed to a surface of a substrate, and the metal species is hardly soluble or insoluble on the surface. May be sequentially performed at a temperature for forming the protective oxide film.
Other methods include a step of fixing a metal species to particles having photocatalytic activity, a step of applying particles having photocatalytic activity in which the metal species is fixed to the surface of a substrate and heating and fixing the same, and the metal species and the hardly soluble or insoluble The step of contacting a solution containing an anion that forms a salt with a metal species may be performed sequentially.
【００４４】ここで用いる基材の材質は、セラミック、
陶磁器材料、金属、ガラス、熱硬化性樹脂、熱可塑性樹
脂あるいはそれらの複合物等基本的に何でもよい。ただ
し、光触媒活性を有する粒子は上述のように酸化物半導
体であることから、基材表面に固定するには一般に３０
０℃以上の高温で熱処理する必要があるので、熱的安定
性に優れるセラミック、ガラスあるいは陶磁器材料であ
ることが好ましい。また基材をセラミック、陶磁器材料
若しくは金属にした場合には、軽量化の観点から多孔質
であることが好ましい。The material of the base material used here is ceramic,
Basically any material such as ceramic material, metal, glass, thermosetting resin, thermoplastic resin or a composite thereof can be used. However, since the particles having photocatalytic activity are oxide semiconductors as described above, generally 30 particles are required to be fixed on the surface of the base material.
Since it is necessary to perform heat treatment at a high temperature of 0 ° C. or more, it is preferable to use a ceramic, glass, or ceramic material having excellent thermal stability. When the substrate is made of ceramic, ceramic material or metal, it is preferably porous from the viewpoint of weight reduction.
【００４５】基材の形状も基本的にどのようなものでも
よく、例えぱ、タイル、壁材、床材等の板状物や棒状
物、球状物、円柱状物、円筒状物、角柱状物、中空の角
柱状物などの単純形状のものでも、衛生陶器、洗面台、
浴槽、流し台等およびその付属品などの複雑形状のもの
でも構わない。The shape of the substrate may be basically any shape, for example, a plate-like or rod-like material such as a tile, a wall material, a floor material, a spherical material, a cylindrical material, a cylindrical material, a prism-like material. Objects, simple shapes such as hollow prisms, sanitary ware, wash basins,
It may be of a complicated shape such as a bathtub, a sink, and its accessories.
【００４６】基材表面とは、最表面およびその近傍をい
う。したがって、基材表面に光触媒活性を有する粒子が
ある程度埋設、含浸されている場合、その埋設、含浸部
分までを含む。基材における光触媒活性を有する粒子を
固定する面は、基材表面の一部でもよいし、全面でもよ
い。The substrate surface refers to the outermost surface and its vicinity. Therefore, when particles having photocatalytic activity are buried or impregnated to some extent on the surface of the base material, this includes the buried and impregnated portions. The surface of the substrate on which the particles having photocatalytic activity are fixed may be a part of the surface of the substrate or the entire surface.
【００４７】ここで基材表面に光触媒活性を有する層を
形成する工程は、基本的に出発原料あるいはそれに適当
な処理を施したものを基材表面に塗布後、熱処理するこ
とにより行う。Here, the step of forming a layer having photocatalytic activity on the surface of the substrate is basically carried out by applying the starting material or a material obtained by subjecting it to an appropriate treatment on the surface of the substrate and then subjecting the material to a heat treatment.
【００４８】出発原料としては、光触媒活性を有する物
質のゾルや、光触媒活性を有する物質を構成する金属元
素を含むアルコキシド、有機金属塩、無機酸塩、ハロゲ
ン化物塩等を用いる。このような出発原料において、基
材が金属の場合は耐蝕性の観点から分散液はアルカリ性
または中性が好ましい。陶磁器、タイル、セラミック等
の場合は酸性、アルカリ性いずれの分散液を用いてもよ
い。このとき用いる酸としては、硝酸、硫酸、塩酸、酢
酸、リン酸、有機酸等が挙げられる。アルカリの場合は
アンモニア、アルカリ金属またはアルカリ土類金属を含
む水酸化物等が挙げられるが、熱処理後に金属汚染物が
生成しないことからアンモニアが特に好ましい。これら
の分散液に、さらに有機系、リン酸系の分散剤、表面活
性剤、表面処理剤等を添加してもよい。As a starting material, a sol of a substance having photocatalytic activity, an alkoxide containing a metal element constituting the substance having photocatalytic activity, an organic metal salt, an inorganic acid salt, a halide salt and the like are used. In such starting materials, when the base material is a metal, the dispersion is preferably alkaline or neutral from the viewpoint of corrosion resistance. In the case of ceramics, tiles, ceramics, etc., any of acidic and alkaline dispersions may be used. Examples of the acid used at this time include nitric acid, sulfuric acid, hydrochloric acid, acetic acid, phosphoric acid, and organic acids. In the case of an alkali, ammonia, a hydroxide containing an alkali metal or an alkaline earth metal and the like can be mentioned, but ammonia is particularly preferable because no metal contaminant is formed after the heat treatment. An organic or phosphoric acid-based dispersant, a surfactant, a surface treatment agent, or the like may be further added to these dispersions.
【００４９】また、出発原料としてゾルを用いる場合
は、光触媒活性を有する物質のゾルの平均粒径は０．０
５μｍ以下好ましくは０．０１μｍ以下がよい。粒径が
小さいほど光触媒活性が高いからである。ここで平均粒
径は、ゾルを粉末Ｘ線回折したときの結晶の最大ピーク
の積分幅からＳｃｈｅｒｒｅｒ式により求められる。出
発原料としてゾルを用いる場合、基材表面への塗布方法
としては、ゾルの懸濁液をスプレー・コーティング、ロ
ール・コーティング、ディップ・コーティング、スピン
・コーティング、ＣＶＤ、電子ビーム蒸着、スパッタな
どして塗布する方法があり、そのいずれでもよいし、そ
れ以外の方法でもよい。ただし、スプレー・コーティン
グ、ロール・コーティング、ディップ・コーティング
は、ＣＶＤ、電子ビーム蒸着、スパッタなどと比較して
特別の設備を要せず、安価に塗膜可能である利点があ
る。When a sol is used as a starting material, the average particle diameter of the sol of the substance having photocatalytic activity is 0.0
5 μm or less, preferably 0.01 μm or less. This is because the smaller the particle size, the higher the photocatalytic activity. Here, the average particle size is determined by the Scherrer equation from the integral width of the maximum peak of the crystal when the sol is subjected to powder X-ray diffraction. When a sol is used as a starting material, a method of applying the sol suspension to a substrate surface includes spray coating, roll coating, dip coating, spin coating, CVD, electron beam evaporation, and sputtering. There is a method of applying, and any of these methods may be used, and other methods may be used. However, spray coating, roll coating, and dip coating do not require special equipment as compared with CVD, electron beam evaporation, sputtering, and the like, and have the advantage that they can be coated at low cost.
【００５０】出発原料としてアルコキシドを用いる場合
は、アルコキシドに適当な希釈剤と必要ならば塩酸等の
加水分解抑制剤を添加した混合液を塗布する。ここで適
当な希釈剤とは、エタノール、プロパノール、メタノー
ル等のアルコール類が好ましいが、それに限定されるも
のではない。ただし水はできる限り含まないほうがよ
い。水が含まれるとチタンアルコキシド等の多くのアル
コキシドにおいて加水分解が爆発的に促進され、クラッ
クの一因をなすからである。アルコキシドの基材への塗
布方法は、例えば、乾燥空気をキャリヤーとしてフロー
・コーティング法により塗布する。When an alkoxide is used as a starting material, a mixture of the alkoxide and a suitable diluent and, if necessary, a hydrolysis inhibitor such as hydrochloric acid is applied. Here, suitable diluents are preferably alcohols such as ethanol, propanol and methanol, but are not limited thereto. However, it is better not to include water as much as possible. If water is contained, hydrolysis is explosively promoted in many alkoxides such as titanium alkoxides, which causes cracks. As a method of applying the alkoxide to the substrate, for example, the alkoxide is applied by a flow coating method using dry air as a carrier.
【００５１】出発原料としてアルコキシド、有機金属
塩、無機酸塩、ハロゲン化物塩等を用いた場合には、塗
布後の熱処理はこれら前駆体が酸化物に変化しかつ結晶
化すると同時に、このようにして得た光触媒活性を有す
る粒子が基材表面へ高い密着強度で固定化される温度で
行う。その温度は例えば、光触媒活性を有する粒子がア
ナターゼ型酸化チタンである場合には４００℃以上８０
０℃以下である。それに対し、出発原料としてゾルを用
いた場合には、既に酸化物結晶であるので、単に光触媒
活性を有する粒子が基材表面へ高い密着強度で固定化さ
れる温度で熱処理すればよい。When an alkoxide, an organic metal salt, an inorganic acid salt, a halide salt, or the like is used as a starting material, a heat treatment after coating simultaneously converts these precursors into oxides and crystallizes them. The process is performed at a temperature at which the particles having photocatalytic activity obtained as described above are fixed to the substrate surface with high adhesion strength. The temperature is, for example, 400 ° C. or higher and 80 ° C. when the particles having photocatalytic activity are anatase type titanium oxide.
0 ° C. or less. On the other hand, when the sol is used as a starting material, since it is already an oxide crystal, the heat treatment may be performed simply at a temperature at which the particles having photocatalytic activity are fixed to the surface of the base material with high adhesion strength.
【００５２】その上に金属種を適用する工程は、Ｐｔ、
Ｐｄ、Ａｕ、Ａｇ、Ｃｕ、Ｎｉ、Ｆｅ、Ｃｏ、 Ｚｎ等
の電子捕捉効果を有する金属元素を含む塩と溶媒とから
なる溶液を塗布した後、紫外線を含む光を照射すること
により行う。ここで溶液の塗布方法は、基本的にどのよ
うな方法でもよいが、スプレー・コティング法またはデ
ィップ・コーティング法が筒便である。その両者を比較
すると、使用する溶液の量が少なくてすむこと、均一に
塗布できること、膜厚を制御しやすいこと、裏面に付け
たくないときにそれが可能であることなどの理由によ
り、スプレー・コーティング法がより好ましい。The step of applying a metal species thereon includes Pt,
This is performed by applying a solution containing a salt containing a metal element having an electron capturing effect such as Pd, Au, Ag, Cu, Ni, Fe, Co, and Zn and a solvent, and then irradiating light containing ultraviolet rays. Here, the method of applying the solution may be basically any method, but the spray coating method or the dip coating method is convenient. A comparison of the two shows that spray-coating can be used because of the small amount of solution used, uniform application, easy control of film thickness, and the ability to do so when it is not desired to attach to the back surface. A coating method is more preferred.
【００５３】スプレー・コーティング法により溶液を塗
布する場合は、紫外線を含む光を照射する前に塗布物を
乾燥させたほうがよい。塗布量に対する金属の固定化率
が向上するので、コスト上有利だからである。スプレー
・コーティング法により溶液を塗布する場合の溶媒も基
本的に限定されるものでなく、水、エタノール、プロパ
ノール、メタノール等種々の溶媒を利用できる。このう
ち分散性が同一ならばエタノールを使用することが最も
好ましい。エタノールは水系よりも乾燥速度が速いの
で、乾燥工程にかかる時間を短縮でき、生産性が向上す
るからである。また表面張力が低いので光触媒活性を有
する粒子層への濡れもよい。さらにメタノール等の他の
揮発性溶媒と異なり無害である。また分散性等の理由に
より水を使用しなければならない場合は、エタノール等
の犠牲酸化剤を少量添加すると光還元反応がより迅速に
進行するので好ましい。When the solution is applied by a spray coating method, it is preferable that the applied material be dried before irradiation with light including ultraviolet rays. This is because the rate of immobilizing the metal with respect to the applied amount is improved, which is advantageous in cost. The solvent used for applying the solution by the spray coating method is also not fundamentally limited, and various solvents such as water, ethanol, propanol and methanol can be used. Among them, it is most preferable to use ethanol if the dispersibility is the same. This is because ethanol has a higher drying speed than an aqueous system, so that the time required for the drying step can be shortened and the productivity is improved. In addition, since the surface tension is low, wetting of the particle layer having photocatalytic activity is also good. Furthermore, it is harmless unlike other volatile solvents such as methanol. When water must be used for reasons such as dispersibility, it is preferable to add a small amount of a sacrificial oxidizing agent such as ethanol since the photoreduction reaction proceeds more quickly.
【００５４】なお、基材と光触媒活性を有する粒子層と
の間に樹脂、釉薬、無機ガラス質、半田等のバインダー
からなる層を介してもよい。Incidentally, a layer made of a binder such as resin, glaze, inorganic glass, solder, etc. may be interposed between the substrate and the particle layer having photocatalytic activity.
【００５５】[0055]
実施例１ ５ｃｍ角のタイル基材表面に、平均粒径０．０１μｍの
酸化チタンゾルを塗布後、９００℃で熱処理し、ルチル
型酸化チタン薄膜を形成した。この段階で止めた試料を
比較試料１とする。その後、硝酸銀水溶液をスプレー・
コーティング法にて塗布し、２０ＷのＢＬＢランプを光
源として１０分光照射し、銀をルチル型酸化チタン薄膜
上に固定した。このときの銀の担持量は約２μｇ／ｃｍ
２であり、茶黒色に呈色した。その後、０．１ｍｏｌ／
ｌヨウ化カリウム水溶液を比較試料２上に０．１ｍｌ／
ｃｍ２の割合で塗布し反応させた。その結果、試料表面
は黄白色へと変化し白色化された。ヨウ化銀層が形成さ
れたためと考えられる。この試料を実施試料１とする。Example 1 A titanium oxide sol having an average particle size of 0.01 μm was applied to a 5 cm square tile base material surface, and then heat-treated at 900 ° C. to form a rutile-type titanium oxide thin film. The sample stopped at this stage is referred to as Comparative Sample 1. After that, spray the aqueous silver nitrate solution
The coating was applied by a coating method, and 10 spectral irradiations were performed using a 20 W BLB lamp as a light source to fix silver on the rutile-type titanium oxide thin film. The amount of silver carried at this time was about 2 μg / cm
2 , which turned brown and black. Then, 0.1mol /
l Potassium iodide aqueous solution was placed on comparative sample 2 at 0.1 ml /
It was applied and reacted at a rate of cm 2 . As a result, the sample surface turned yellow-white and became white. It is considered that the silver iodide layer was formed. This sample is referred to as a working sample 1.
【００５６】これら試料について、耐摩耗性および光活
性とその経時的変化を評価した。耐摩耗性試験について
は、プラスチック消しゴムを用いた摺動摩耗を行い、外
観の変化を比較し評価した。その結果、実施試料１、比
較試料１のいずれの試料も４０回以上摺動させても外観
上の変化を生じず、良好な結果を示した。光活性につい
ては△ｐＨ試験で評価した。△ｐＨ試験とは、試料表面
にヨウ化カリウム水溶液を滴下し、次いで滴下したヨウ
化カリウム水溶液に３０分間紫外線を照射し、照射前の
ヨウ化カリウム水溶液のｐＨと照射後のヨウ化カリウム
水溶液のｐＨとの差により光活性を評価する方法であ
る。すなわちこの方法によれば試料表面の光活性が高け
れば下記に示すような酸化還元反応がより進行するので
照射後のｐＨは照射前のｐＨより高くなっていく。 酸化反応：２Ｉ−＋２ｈ＋→Ｉ２ 還元反応：Ｏ２＋２Ｈ２Ｏ＋４ｅ−→４ＯＨ− また△ｐＨ試験の△ｐＨ値と実際の防臭等の効果の強さ
との対応性を評価するため防臭特性も調べた。防臭特性
はＲ３０（Ｌ）で評価した。Ｒ３０（Ｌ）とは光照射後
の除去率のことで、具体的には１１Ｌのガラス容器内に
試料を入れ、薄膜を形成した面を光源（ＢＬＢ蛍光灯４
Ｗ）から８ｃｍの距離に配置し、メチルメルカプタンガ
スを初期濃度３ｐｐｍとなるように容器内に注入し、３
０分間光照射したときの濃度変化を測定することで得ら
れる。結果を図１に示す。図１より△ｐＨがほば０なら
ば、Ｒ３０（Ｌ）も０％であり、△ｐＨが１程度ならば
Ｒ３０（Ｌ）は１００％に近い値が得られることが判明
した。したがってこの間の両者の関係が直線的ならぱ△
ｐＨが０．８以上あれば、少なくとも防臭効果に充分な
光活性が得られたことになる。With respect to these samples, abrasion resistance, photoactivity and changes with time were evaluated. For the abrasion resistance test, sliding abrasion using a plastic eraser was performed, and changes in appearance were compared and evaluated. As a result, even when each of the sample of the working sample 1 and the sample of the comparative sample 1 was slid 40 times or more, no change in the appearance was observed, and good results were shown. Photoactivity was evaluated by a ΔpH test. △ The pH test is to drop a potassium iodide aqueous solution on the sample surface, and then irradiate the dropped potassium iodide aqueous solution with ultraviolet rays for 30 minutes, and to adjust the pH of the potassium iodide aqueous solution before irradiation and the potassium iodide aqueous solution after irradiation. This is a method for evaluating photoactivity based on a difference from pH. That is, according to this method, if the photoactivity of the sample surface is high, the oxidation-reduction reaction as described below proceeds more, so that the pH after irradiation becomes higher than the pH before irradiation. Oxidation reaction: 2I − + 2h + → I 2 Reduction reaction: O 2 + 2H 2 O + 4e − → 4OH − Also, deodorant properties are evaluated in order to evaluate the correspondence between the ΔpH value of the ΔpH test and the strength of the actual effect such as deodorization. Examined. The deodorant properties were evaluated using R30 (L). R30 (L) is a removal rate after light irradiation. Specifically, a sample is placed in an 11 L glass container, and the surface on which the thin film is formed is exposed to a light source (BLB fluorescent lamp 4).
W) and placed at a distance of 8 cm, and methyl mercaptan gas was injected into the container so as to have an initial concentration of 3 ppm.
It can be obtained by measuring the change in density when light is irradiated for 0 minutes. The results are shown in FIG. It was found from FIG. 1 that if ΔpH is almost 0, R30 (L) is also 0%, and if ΔpH is about 1, R30 (L) is close to 100%. Therefore, if the relationship between the two is linear,
When the pH is 0.8 or more, it means that at least sufficient photoactivity for the deodorizing effect has been obtained.
【００５７】光活性の経時的変化は以下のような方法で
評価した。まず試料を公衆浴場の浴槽水を循環させるよ
うにした装置の循環路に配置し、所定期間連続で水を循
環させた。その後、試料を取り出し、オートクレーブ中
１２１℃で２０分洗浄し、８０体積％エタノールに２時
間浸漬し、５０℃で乾燥させて試料表面を洗浄した。洗
浄後、△ｐＨ試験を行い、循環装置配置前後の△ｐＨ値
を比較して光活性の経時的変化を評価した。結果を図２
に示す。図２より実施試料１では循環装置中に１か月放
置した試料でも△ｐＨの変化がほとんどなく、良好な光
活性を示すことが判明した。The change with time of the photoactivity was evaluated by the following method. First, the sample was placed in a circulation path of a device for circulating bath water in a public bath, and water was continuously circulated for a predetermined period. Thereafter, the sample was taken out, washed in an autoclave at 121 ° C. for 20 minutes, immersed in 80% by volume ethanol for 2 hours, and dried at 50 ° C. to wash the sample surface. After washing, a △ pH test was performed, and △ pH values before and after the arrangement of the circulating device were compared to evaluate changes over time in photoactivity. Figure 2 shows the results.
Shown in From FIG. 2, it was found that, in Example 1, even the sample left in the circulation device for one month showed almost no change in ΔpH and exhibited good photoactivity.
【００５８】実施例２ ５ｃｍ角のタイル基材表面に、平均粒径０．０１μｍの
酸化チタンゾルを塗布し、８３０℃で熱処理してアナタ
ーゼ型酸化チタン薄膜形成した。この段階で止めた試料
を比較試料２とする。その後、酢酸銅水溶液をスプレー
・コーティング法にて塗布し、２０ＷのＢＬＢランプで
１０分光照射して銅を固定した。その後、４００℃で熱
処理して銅粒子の表面に酸化第一銅による層を形成し、
実施試料２を得た。これら実施試料２および比較試料２
について光活性の経時的変化を評価した。結果を図３に
示す。図３より実施試料２では循環装置中に１か月放置
した試料でも△ｐＨの変化がほとんどなく、良好な光活
性を示すことが判明した。Example 2 A titanium oxide sol having an average particle size of 0.01 μm was applied to a 5 cm square tile base material surface and heat-treated at 830 ° C. to form an anatase type titanium oxide thin film. The sample stopped at this stage is referred to as Comparative Sample 2. Thereafter, an aqueous solution of copper acetate was applied by a spray coating method, and the copper was fixed by irradiating 10 spectra with a 20 W BLB lamp. Then, heat treatment at 400 ° C. to form a layer of cuprous oxide on the surface of the copper particles,
Working sample 2 was obtained. These working sample 2 and comparative sample 2
Were evaluated for changes over time in photoactivity. The results are shown in FIG. From FIG. 3, it was found that, in Example Sample 2, even when the sample was left in the circulation device for one month, there was almost no change in ΔpH, indicating good photoactivity.
【００５９】実施例３ ２ｍｍφのガラスビーズ基材上に、平均粒径０．０１μ
ｍの酸化チタンゾルを塗布し、８００℃で熱処理してア
ナターゼ型酸化チタン薄膜を形成した。ここで、酸化チ
タン塗布量は基材１００ｇに対し、１．２ｇとした。こ
の段階で止めた試料を比較試料３とする。その後、試料
を酢酸銅水溶液中に浸漬し、２０ＷのＢＬＢランプで５
分光照射して銅を固定した。この段階で止めた試料を比
較試料４とする。その後、余剰に付着した酢酸銅を１％
塩酸水溶液中に抽出させ、実施試料３を得た。得られた
試料を図４に示すように循環水槽内に設置し、８か月後
の濁度、ＣＯＤ値、大腸菌数、藻の発生量、銅イオンの
溶出濃度を調べた。結果を表１に示す。表１より８か月
後の濁度、ＣＯＤ値、大腸菌数、藻の発生量は、ブラン
クと比較していずれの試料も優れており、特に実施試料
３、比較試料４で優れた効果を示した。さらに実施試料
３では、比較試料４と比較して銅イオンの溶出が認めら
れず、金属の溶出が抑えられていることが判明した。Example 3 An average particle size of 0.01 μm was placed on a 2 mmφ glass bead base material.
applying a titanium oxide sol of m, and forms the form of anatase type titanium oxide thin film was heat-treated at 800 ° C.. Here, the amount of titanium oxide applied was 1.2 g with respect to 100 g of the base material. The sample stopped at this stage is referred to as Comparative Sample 3. Thereafter, the sample was immersed in an aqueous solution of copper acetate, and the sample was irradiated with a 20 W BLB lamp for 5 minutes.
The copper was fixed by spectral irradiation. The sample stopped at this stage is referred to as Comparative Sample 4. After that, 1% of excess copper acetate
Extraction into an aqueous hydrochloric acid solution provided a working sample 3. The obtained sample was placed in a circulating water tank as shown in FIG. 4, and the turbidity, COD value, E. coli count, algae generation amount, and copper ion elution concentration after 8 months were examined. Table 1 shows the results. From Table 1, the turbidity, COD value, number of E. coli, and the amount of algae generated after 8 months are all excellent compared to the blank, and the effect is particularly excellent in Working Sample 3 and Comparative Sample 4. Was. Further, in Example Sample 3, elution of copper ions was not observed as compared with Comparative Sample 4, and it was found that elution of metal was suppressed.
【００６０】[0060]
【表１】 [Table 1]
【００６１】[0061]
【発明の効果】光触媒活性を有する粒子に、難溶性また
は不溶性処理された銀又は銅が固定化されているように
することにより、長期にわたり光触媒活性を有し、かつ
生態系に悪影響を及ぼさない光触媒機能粒子またはそれ
を含む部材を提供することができる。さらに上記光触媒
機能粒子またはそれを含む部材は、上記性質に基づき、
水の浄化や、観賞魚用水槽、または魚貝飼育用水槽の防
藻に好適に利用できる。According to the present invention, silver or copper which has been treated with hardly soluble or insoluble is immobilized on particles having photocatalytic activity, so that they have photocatalytic activity for a long time and do not adversely affect ecosystems. Photocatalytic functional particles or members containing the same can be provided. Further, the photocatalytic functional particles or members containing the same are based on the above properties,
It can be suitably used for purifying water and for preventing algae in an aquarium for ornamental fish or an aquarium for breeding fish and shellfish.
【図１】表面にルチル型酸化チタン薄膜を形成したタイ
ルと、その上に金属種を担持させて更に難溶性の塩を形
成させたものの光活性を示すグラフ。FIG. 1 is a graph showing the photoactivity of a tile having a rutile-type titanium oxide thin film formed on the surface thereof and a metal species supported thereon to form a hardly soluble salt.
【図２】表面にルチル型酸化チタン薄膜を形成したタイ
ルと、その上に金属種を担持させて更に難溶性の塩を形
成させたものの光活性の経時変化を示すグラフ。FIG. 2 is a graph showing a change over time in photoactivity of a tile having a rutile-type titanium oxide thin film formed on a surface thereof and a metal species supported thereon to form a more sparingly soluble salt.
【図３】表面にアナターゼ型酸化チタン薄膜を形成した
タイルと、その上に金属種を担持させて更に熱処理した
ものに対する光活性の経時変化を示すグラフ。FIG. 3 is a graph showing a temporal change in photoactivity of a tile having an anatase-type titanium oxide thin film formed on a surface thereof and a tile having a metal species supported thereon and further subjected to a heat treatment.
【図４】本発明の実施例における循環水槽装置。FIG. 4 is a circulating water tank device according to an embodiment of the present invention.
１…ポンプ、２…実施例３の試料、３…水 1 pump, 2 samples of Example 3, 3 water
───────────────────────────────────────────────────── フロントページの続き (72)発明者 佐伯 義光 福岡県北九州市小倉北区中島２丁目１番 １号 東陶機器株式会社内 (56)参考文献 特開 平２−268103（ＪＰ，Ａ) 特開 平３−193191（ＪＰ，Ａ) 特開 平４−83587（ＪＰ，Ａ) 特開 昭63−20090（ＪＰ，Ａ) 特開 昭61−83106（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 C02F 1/50 A01N 59/16 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoshimitsu Saeki 2-1-1 Nakajima, Kokurakita-ku, Kitakyushu-shi, Fukuoka Prefecture Totoki Co., Ltd. (56) References JP-A-2-268103 (JP, A) JP-A-3-193191 (JP, A) JP-A-4-83587 (JP, A) JP-A-63-20090 (JP, A) JP-A-61-83106 (JP, A) (58) (Int.Cl. 7 , DB name) B01J 21/00-38/74 C02F 1/50 A01N 59/16
Claims (3)
てなる光触媒材において、前記光触媒機能粒子は、光触
媒活性を有する粒子に、銀又は銅が固定され、この銀又
は銅表面に難溶性または不溶性の塩を形成する処理が施
されており、かつ前記光触媒活性を有する粒子は、平均
粒径０．０５μｍ以下のゾルを基材表面に塗布して形成
されていることを特徴とする光触媒材。 1. A photocatalytic functional particle is immobilized on a substrate surface.
In the photocatalyst material comprising Te, the photocatalyst functional particles, the particles having a photocatalytic <br/> medium activity, silver or copper is fixed, the process facilities to form a hardly soluble or insoluble salts to the silver or copper surface
And the particles having photocatalytic activity are average
Formed by applying a sol with a particle size of 0.05 μm or less to the substrate surface
Photocatalytic Baizai characterized in that it is.
活性を有する粒子に固定化された銀又は銅の塩であるこ
とを特徴とする請求項１に記載の光触媒材。 Wherein the salt of the poorly soluble or insoluble, photocatalytic Baizai according to claim 1, characterized in that the particles having a photocatalytic activity are immobilized silver or copper salt.
不溶性の塩は、酸化第一銅であることを特徴とする請求
項２に記載の光触媒材。 3. A salt of a poorly soluble or insoluble is formed on the copper, the light according to claim 2, characterized in that the cuprous oxide catalyst Baizai.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34658195A JP3261959B2 (en) | 1994-12-01 | 1995-12-01 | Photocatalytic material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33230594 | 1994-12-01 | ||
| JP6-332305 | 1994-12-01 | ||
| JP34658195A JP3261959B2 (en) | 1994-12-01 | 1995-12-01 | Photocatalytic material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08229408A JPH08229408A (en) | 1996-09-10 |
| JP3261959B2 true JP3261959B2 (en) | 2002-03-04 |
Family
ID=26574150
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34658195A Expired - Lifetime JP3261959B2 (en) | 1994-12-01 | 1995-12-01 | Photocatalytic material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3261959B2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4979151B2 (en) * | 1998-02-19 | 2012-07-18 | アスカテック株式会社 | Antibacterial / deodorizing material and method for producing the same |
| JP2005288429A (en) * | 2004-03-11 | 2005-10-20 | Japan Vilene Co Ltd | Ozone decomposing material, method for manufacturing the same, ozone decomposing method and method for regenerating the same |
| JP2005270835A (en) * | 2004-03-25 | 2005-10-06 | Hitachi Chem Co Ltd | Fine particle structural body, its precursor composition, its production method, and its application |
| JP4772818B2 (en) | 2007-03-30 | 2011-09-14 | 国立大学法人北海道大学 | Tungsten oxide photocatalyst |
| JP4730400B2 (en) * | 2007-10-09 | 2011-07-20 | 住友化学株式会社 | Photocatalyst dispersion |
| JP5113723B2 (en) * | 2008-11-04 | 2013-01-09 | 住友化学株式会社 | Photocatalyst dispersion |
| JP2011050802A (en) * | 2009-01-27 | 2011-03-17 | Sumitomo Chemical Co Ltd | Method for producing dispersion liquid of noble metal-deposited photocatalyst particle |
| JP2011020009A (en) * | 2009-07-13 | 2011-02-03 | Hokkaido Univ | Photocatalyst body for decomposing volatile aromatic compound, and functional product of photocatalyst |
| JP5570006B2 (en) | 2009-12-24 | 2014-08-13 | 国立大学法人 東京大学 | Virus inactivating agent |
| JP2011190192A (en) * | 2010-03-12 | 2011-09-29 | Univ Of Tokyo | Microorganism-inactivating agent |
| JP5904524B2 (en) * | 2010-12-22 | 2016-04-13 | 国立大学法人 東京大学 | Virus inactivating agent |
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1995
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|---|---|
| JPH08229408A (en) | 1996-09-10 |
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