JP5512934B2 - Sol comprising amorphous Zr-O-based particles as a dispersoid, method for producing the same, photocatalyst coating liquid using the sol as a binder, and method for producing a photocatalytic functional product coated with the photocatalyst coating liquid - Google Patents
Sol comprising amorphous Zr-O-based particles as a dispersoid, method for producing the same, photocatalyst coating liquid using the sol as a binder, and method for producing a photocatalytic functional product coated with the photocatalyst coating liquid Download PDFInfo
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- JP5512934B2 JP5512934B2 JP2008123114A JP2008123114A JP5512934B2 JP 5512934 B2 JP5512934 B2 JP 5512934B2 JP 2008123114 A JP2008123114 A JP 2008123114A JP 2008123114 A JP2008123114 A JP 2008123114A JP 5512934 B2 JP5512934 B2 JP 5512934B2
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- based particles
- salt
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- 239000002245 particle Substances 0.000 title claims description 153
- 239000011941 photocatalyst Substances 0.000 title claims description 121
- 239000011248 coating agent Substances 0.000 title claims description 118
- 238000000576 coating method Methods 0.000 title claims description 117
- 229910007746 Zr—O Inorganic materials 0.000 title claims description 100
- 239000007788 liquid Substances 0.000 title claims description 58
- 238000004519 manufacturing process Methods 0.000 title claims description 38
- 230000001699 photocatalysis Effects 0.000 title claims description 19
- 239000011230 binding agent Substances 0.000 title description 40
- 150000007522 mineralic acids Chemical class 0.000 claims description 76
- 150000003839 salts Chemical class 0.000 claims description 75
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 60
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 46
- 239000006185 dispersion Substances 0.000 claims description 29
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 28
- 229910017604 nitric acid Inorganic materials 0.000 claims description 28
- 229910052726 zirconium Inorganic materials 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 24
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 23
- 235000019253 formic acid Nutrition 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000002612 dispersion medium Substances 0.000 claims description 15
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 68
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 65
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 34
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 28
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 28
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 23
- 229960004106 citric acid Drugs 0.000 description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 235000011054 acetic acid Nutrition 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 16
- 239000011521 glass Substances 0.000 description 16
- 239000012535 impurity Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 14
- 239000004310 lactic acid Substances 0.000 description 14
- 235000014655 lactic acid Nutrition 0.000 description 14
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 14
- 239000011975 tartaric acid Substances 0.000 description 14
- 235000002906 tartaric acid Nutrition 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000000108 ultra-filtration Methods 0.000 description 13
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- -1 inorganic acid salt Chemical class 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000001384 succinic acid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 235000011044 succinic acid Nutrition 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001879 gelation Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 3
- 239000005695 Ammonium acetate Substances 0.000 description 3
- 238000007696 Kjeldahl method Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 235000019257 ammonium acetate Nutrition 0.000 description 3
- 229940043376 ammonium acetate Drugs 0.000 description 3
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000000502 dialysis Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000008719 thickening Effects 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 150000003754 zirconium Chemical class 0.000 description 3
- 150000003755 zirconium compounds Chemical class 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 239000004280 Sodium formate Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 235000011056 potassium acetate Nutrition 0.000 description 2
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 2
- 235000019254 sodium formate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- AXIFGFAGYFPNFC-UHFFFAOYSA-I 2-hydroxy-2-oxoacetate;niobium(5+) Chemical compound [Nb+5].OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O AXIFGFAGYFPNFC-UHFFFAOYSA-I 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- WRAGBEWQGHCDDU-UHFFFAOYSA-M C([O-])([O-])=O.[NH4+].[Zr+] Chemical compound C([O-])([O-])=O.[NH4+].[Zr+] WRAGBEWQGHCDDU-UHFFFAOYSA-M 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000001687 destabilization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000012669 liquid formulation Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002822 niobium compounds Chemical class 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- LZRGWUCHXWALGY-UHFFFAOYSA-N niobium(5+);propan-2-olate Chemical compound [Nb+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LZRGWUCHXWALGY-UHFFFAOYSA-N 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- CENHPXAQKISCGD-UHFFFAOYSA-N trioxathietane 4,4-dioxide Chemical compound O=S1(=O)OOO1 CENHPXAQKISCGD-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing 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
- 239000008096 xylene Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 1
Images
Description
本発明は、非晶質のＺｒ−Ｏ系粒子を分散質とするゾル、その製造方法、このゾルをバインダーとする光触媒体コーティング液、およびその光触媒体コーティング液を塗布した光触媒機能製品の製造方法に関する。 The present invention relates to a sol having amorphous Zr-O-based particles as a dispersoid, a method for producing the sol, a photocatalyst coating liquid using the sol as a binder, and a method for producing a photocatalytic functional product coated with the photocatalyst coating liquid About.
光触媒体は、光を照射されることで活性を示す触媒であって、例えば特許文献１〔ＷＯ９８／１５６００パンフレット〕、特許文献２〔特開２００３−１０５２６２号公報〕、特許文献３〔特開平９−３２８３３６号公報〕、特許文献４〔特開２００４−５９６８６号公報〕、特許文献５〔ＷＯ０１／０２３４８３パンフレット〕、特許文献６〔特開平１１−２０９６９１号公報〕、特許文献７〔ＷＯ９９／０２８３９３パンフレット〕などに開示されるように、バインダー成分と共に基材に塗布して、塗膜として使用されている。 The photocatalyst is a catalyst that exhibits activity when irradiated with light. For example, Patent Document 1 [WO 98/15600 pamphlet], Patent Document 2 [JP 2003-105262 A], Patent Document 3 [JP 9 No. -328336], Patent Document 4 [Japanese Patent Laid-Open No. 2004-59686], Patent Document 5 [Patent WO 01/023483], Patent Document 6 [Japanese Patent Laid-Open No. 11-209691], Patent Document 7 [WO 99/028393 Pamphlet]. As disclosed in the above, it is applied to a substrate together with a binder component and used as a coating film.
しかし、従来の光触媒体コーティング液から形成される塗膜は、基材への密着強度が必ずしも十分ではなく、このため、コーティング液中の光触媒体に対するバインダー成分の使用量を多くする必要があった。バインダー成分の使用量が多いと、光触媒体が十分にその活性を発現しにくくなる。 However, the coating film formed from the conventional photocatalyst coating liquid does not necessarily have sufficient adhesion strength to the base material, and therefore it is necessary to increase the amount of binder component used for the photocatalyst in the coating liquid. . If the amount of the binder component used is large, the photocatalyst will not sufficiently exhibit its activity.
光触媒体に対するバインダー成分として、金属無機塩が使用されることがあるが、光触媒体コーティング液の処方によっては、この金属無機塩には不純物が含まれやすく、しかも、この不純物が光触媒能や光触媒体塗膜の特性を阻害することもある。また、金属無機酸塩の水溶液は含有イオン濃度が高いために光触媒体との均一な混合が困難になる場合がある。 A metal inorganic salt may be used as a binder component for the photocatalyst, but depending on the formulation of the photocatalyst coating liquid, the metal inorganic salt is likely to contain impurities, and this impurity is a photocatalyst or photocatalyst. It may impair the properties of the coating film. Further, since the aqueous solution of the metal inorganic acid salt has a high ion concentration, it may be difficult to uniformly mix with the photocatalyst.
一方、金属酸化物や金属水酸化物のゾルをバインダー成分として使用する場合、金属酸化物や金属水酸化物は金属無機塩類よりも不純物濃度が低い点で有利である。 On the other hand, when a metal oxide or metal hydroxide sol is used as a binder component, the metal oxide or metal hydroxide is advantageous in that it has a lower impurity concentration than the metal inorganic salts.
そこで本発明者は、バインダー成分として光触媒体コーティング液に添加することにより、少ない添加量で、十分な密着力を示す塗膜を形成し得るバインダー成分を開発するべく鋭意検討した結果、光触媒体コーティング液にとって悪影響を及ぼす可能性のある不純物が混入しにくい非晶質のＺｒ−Ｏ系粒子を分散質とするゾルが優れたバインダー特性を有することを見出し、本発明に至った。 Therefore, the present inventors have intensively studied to develop a binder component that can form a coating film exhibiting sufficient adhesion with a small addition amount by adding it as a binder component to the photocatalyst coating liquid. The present inventors have found that a sol having an amorphous Zr—O-based particle that is difficult to be mixed with impurities that may adversely affect the liquid has excellent binder properties, and has led to the present invention.
すなわち本発明は、下記の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル、その製造方法、このゾルをバインダーとする光触媒体コーティング液、およびその光触媒体コーティング液を塗布した光触媒機能製品の製造方法に関する。 That is, the present invention relates to a sol having the following amorphous Zr-O-based particles as a dispersoid, a method for producing the sol, a photocatalyst coating liquid using the sol as a binder, and a photocatalytic functional product to which the photocatalyst coating liquid is applied. It relates to the manufacturing method.
（１）粒子径Ｄ５０が１〜２０ｎｍであり非晶質であるＺｒ−Ｏ系粒子が分散媒中に分散されてなり、無機酸とカルボン酸またはその塩を含み、ゼータ電位が２０ｍＶ以上であることを特徴とする非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（２）１モルのＺｒに対して０．０５〜１モルのカルボン酸またはその塩を含むことを特徴とする上記（１）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（３）カルボン酸がギ酸または酢酸から選ばれる１種または２種であることを特徴とする上記（１）または上記（２）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（４）無機酸／カルボン酸またはその塩のモル比が０．１〜５であることを特徴とする上記（１）〜上記（３）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（５）無機酸が硝酸であることを特徴とする上記（１）〜上記（４）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
(1) A Zr—O-based particle having a particle diameter D50 of 1 to 20 nm and amorphous is dispersed in a dispersion medium, contains an inorganic acid and a carboxylic acid or a salt thereof, and has a zeta potential of 20 mV or more. A sol having amorphous Zr—O-based particles as a dispersoid.
(2) Amorphous Zr—O-based particles as described in (1) above, containing 0.05 to 1 mol of carboxylic acid or a salt thereof with respect to 1 mol of Zr are used as dispersoids. Sol.
(3) The amorphous Zr-O-based particles according to (1) or (2) above, wherein the carboxylic acid is one or two selected from formic acid or acetic acid is used as a dispersoid. Sol.
(4) Disperse the amorphous Zr—O-based particles according to (1) to (3) above, wherein the molar ratio of inorganic acid / carboxylic acid or salt thereof is 0.1 to 5 The quality sol.
(5) A sol having amorphous Zr—O-based particles as described in (1) to (4) above as a dispersoid, wherein the inorganic acid is nitric acid.
（６）粒子径Ｄ５０が１〜２０ｎｍであり非晶質であるＺｒ−Ｏ系粒子が分散媒中に分散されてなり、カルボン酸またはその塩を含み、ゼータ電位が−２０ｍＶ以下であることを特徴とする非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（７）１モルのＺｒに対して０．０５〜１モルのカルボン酸またはその塩を含むことを特徴とする上記（６）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（８）カルボン酸がクエン酸、酒石酸、グリコール酸および乳酸から選ばれる１種または２種以上であることを特徴とする上記（６）または上記（７）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（９）カルボン酸が、(1)クエン酸、酒石酸、グリコール酸および乳酸から選ばれる１種または２種以上と(2)ギ酸、酢酸および蓚酸から選ばれる１種または２種以上の組み合わせであることを特徴とする上記（７）〜上記（８）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（１０）（(1)クエン酸、酒石酸、グリコール酸および乳酸から選ばれる１種または２種以上）／（(2)ギ酸、酢酸および蓚酸から選ばれる１種または２種以上）のモル比が０．１〜３であることを特徴とする上記（９）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル。
（１１）分散媒中に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの無機酸または無機酸の中和により生成した無機酸塩を、カルボン酸またはその塩と置換することを特徴とする、非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法。
(6) The Zr—O-based particles having a particle diameter D50 of 1 to 20 nm and being amorphous are dispersed in a dispersion medium, containing a carboxylic acid or a salt thereof, and having a zeta potential of −20 mV or less. A sol having amorphous Zr-O-based particles as a dispersoid.
(7) Amorphous Zr—O-based particles as described in (6) above, containing 0.05 to 1 mol of carboxylic acid or a salt thereof with respect to 1 mol of Zr are used as dispersoids. Sol.
(8) The amorphous Zr-O as described in (6) or (7) above, wherein the carboxylic acid is one or more selected from citric acid, tartaric acid, glycolic acid and lactic acid Sol with dispersoids of system particles.
(9) The carboxylic acid is a combination of one or more selected from (1) citric acid, tartaric acid, glycolic acid and lactic acid and (2) one or more selected from formic acid, acetic acid and succinic acid A sol comprising the amorphous Zr—O-based particles as described in (7) to (8) above as a dispersoid.
(10) (1) One or more selected from (1) citric acid, tartaric acid, glycolic acid and lactic acid) / ((2) One or more selected from formic acid, acetic acid and succinic acid) A sol having an amorphous Zr—O-based particle as described in (9) above as a dispersoid.
(11) An inorganic acid of a sol containing an inorganic acid in a dispersion medium and having amorphous Zr-O-based particles as a dispersoid, or an inorganic acid salt generated by neutralization of an inorganic acid, a carboxylic acid or a salt thereof A method for producing a sol using amorphous Zr—O-based particles as a dispersoid, which comprises substitution.
（１２）分散媒中に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルが、水酸化ジルコニウム、無機酸および溶媒からなり、ＺｒＯ2換算のジルコニウム濃度をＸ重量％、１モルのＺｒに対する無機酸のグラム当量数Ｙとした場合、ＸおよびＹが以下の式（Ａ）
３≦Ｘ≦２０ （Ａ）
および式（Ｂ）
（２．０−０．０７Ｘ）≦Ｙ≦（３．０−０．０８Ｘ） （Ｂ）
を満足する反応分散液を調製し、ついで該反応液を８０℃以上で加熱して得られたゾルであることを特徴とする上記（１１）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法。
（１３）１モルのＺｒに対して０．０５〜１モルのカルボン酸またはその塩を含むように置換することを特徴とする上記（１１）または上記（１２）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法。
（１４）無機酸が硝酸であることを特徴とする上記（１１）〜上記（１３）に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法。
（１５）光触媒体、粒子径Ｄ５０が１〜２０ｎｍであり非晶質であるＺｒ−Ｏ系粒子カルボン酸とその塩、または、無機酸とカルボン酸またはその塩を含み、光触媒体１００重量部に対する前記Ｚｒ−Ｏ系粒子のＺｒＯ2換算の含有量が１５〜１２０重量部であることを特徴とする光触媒体コーティング液。
(12) A sol containing an inorganic acid in a dispersion medium and containing amorphous Zr—O-based particles as a dispersoid is composed of zirconium hydroxide, an inorganic acid and a solvent, and the zirconium concentration in terms of ZrO 2 is X wt%. When the gram equivalent number Y of inorganic acid with respect to 1 mol of Zr, X and Y are the following formulas (A)
3 ≦ X ≦ 20 (A)
And formula (B)
(2.0−0.07X) ≦ Y ≦ (3.0−0.08X) (B)
The amorphous Zr-O-based particles as described in (11) above, which is a sol obtained by preparing a reaction dispersion satisfying the following conditions, and then heating the reaction liquid at 80 ° C. or higher: A method for producing a sol as a dispersoid.
(13) Amorphous Zr as described in (11) or (12) above, wherein 1 to 3 moles of Zr is substituted so as to contain 0.05 to 1 mole of carboxylic acid or a salt thereof. A method for producing a sol using -O-based particles as a dispersoid.
(14) The method for producing a sol using the amorphous Zr—O-based particles as described in (11) to (13) above, wherein the inorganic acid is nitric acid.
(15) A photocatalyst comprising a Zr—O-based particle carboxylic acid and a salt thereof, or an inorganic acid and a carboxylic acid or a salt thereof, having a particle diameter D50 of 1 to 20 nm and amorphous, with respect to 100 parts by weight of the photocatalyst The photocatalyst coating liquid, wherein the Zr—O-based particles have a ZrO 2 equivalent content of 15 to 120 parts by weight.
（１６）上記（１５）に記載の光触媒体コーティング液を基材上に塗布し、溶媒を揮発させることを特徴とする光触媒機能製品の製造方法。 (16) A method for producing a photocatalytic functional product, wherein the photocatalyst coating liquid according to (15) is applied onto a substrate and the solvent is volatilized.
本発明の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルによれば、バインダー成分として光触媒体コーティング液に添加することにより、光触媒体の機能を阻害することなく、少ない添加量で、十分な密着力を示す塗膜を形成することができる。 According to the sol having the amorphous Zr-O-based particles of the present invention as a dispersoid, by adding to the photocatalyst coating liquid as a binder component, the function of the photocatalyst is not impaired, with a small addition amount, A coating film exhibiting sufficient adhesion can be formed.
以下に本発明の非晶質のＺｒ−Ｏ系粒子を分散質とするゾル、その製造方法、そのゾルをバインダーとする光触媒体コーティング液、およびその光触媒体コーティング液を塗布した光触媒機能製品の製造方法について詳細を説明する。 Hereinafter, a sol having the amorphous Zr-O-based particles of the present invention as a dispersoid, a production method thereof, a photocatalyst coating liquid using the sol as a binder, and production of a photocatalytic functional product coated with the photocatalyst coating liquid Details of the method will be described.
（１）ゼータ電位が２０ｍＶ以上のゾル
本発明の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルは、粒子径Ｄ５０が１〜２０ｎｍである非晶質のＺｒ−Ｏ系粒子を分散質とし、無機酸とカルボン酸またはその塩を含み、ゼータ電位が２０ｍＶ以上であることを特徴とする。
(1) Sol with zeta potential of 20 mV or more The sol using the amorphous Zr—O-based particles of the present invention as a dispersoid disperses amorphous Zr—O-based particles having a particle diameter D50 of 1 to 20 nm. And includes an inorganic acid and a carboxylic acid or a salt thereof, and has a zeta potential of 20 mV or more.
本発明において、粒子径Ｄ５０とはレーザードップラー法によってゾルの粒子径測定を行ったときの体積換算累積頻度が５０％となる粒子径を意味する。 In the present invention, the particle diameter D50 means a particle diameter at which the volume conversion cumulative frequency becomes 50% when the particle diameter of the sol is measured by the laser Doppler method.
本発明のゾルは、非晶質のＺｒ−Ｏ系粒子を分散質とする。
分散質であるＺｒ−Ｏ系粒子の粒子径Ｄ５０は、１〜２０ｎｍ、好ましくは１〜１５ｎｍである。粒子径Ｄ５０が１ｎｍ未満では、ジルコニウム塩類の水溶液としての性質が強くなりそれとの区別が明確にならず好ましくない。又、２０ｎｍを超えると本発明のゾルの特徴である、光触媒体のバインダーとしての反応活性や溶液としての性質が低下するので好ましくない。
なお、該Ｚｒ−Ｏ系粒子は非晶質であるため、２００℃以下の温度で恒量となるまで乾燥し、Ｘ線回折測定を行ったとき２θ＝１０〜５０°で特定の結晶系に帰属されるパターンを示さない。なお、Ｚｒ−Ｏ系粒子には、少なくともＺｒとＯが含まれればよく、例えばジルコニウムの水酸化物、酸化物、水和物のいずれでもよく、これらの混合物でも良い。
The sol of the present invention uses amorphous Zr—O-based particles as a dispersoid.
The particle diameter D50 of the Zr—O-based particles as the dispersoid is 1 to 20 nm, preferably 1 to 15 nm. If the particle diameter D50 is less than 1 nm, the properties of the zirconium salt as an aqueous solution become strong and the distinction from that becomes unclear, which is not preferable. On the other hand, if it exceeds 20 nm, the reaction activity as a binder of the photocatalyst and the properties as a solution, which are characteristics of the sol of the present invention, are not preferable.
Since the Zr—O-based particles are amorphous, they are dried to a constant weight at a temperature of 200 ° C. or lower and assigned to a specific crystal system at 2θ = 10 to 50 ° when X-ray diffraction measurement is performed. Does not show the pattern to be played. The Zr—O-based particles only need to contain at least Zr and O. For example, any of zirconium hydroxide, oxide, and hydrate, or a mixture thereof may be used.
一方、本発明のゾルにおいて、ジルコニウム濃度はＺｒＯ2換算で３〜２０重量％、好ましくは、５〜１８重量％の範囲内であるとよい。３重量％未満の場合非効率であり、２０重量％を超える場合は増粘、ゲル化のおそれがあり好ましくない。 On the other hand, in the sol of the present invention, the zirconium concentration is 3 to 20% by weight in terms of ZrO 2 , preferably 5 to 18% by weight. If it is less than 3% by weight, it is inefficient, and if it exceeds 20% by weight, there is a risk of thickening and gelation, which is not preferable.
本発明のゾルは、カルボン酸またはその塩を必須成分として含有しており、通常ｐＨ７以下、好ましくはｐＨ５以下である。ｐＨが７を超えると分散質の凝集、沈殿やゲル化等を起こしゾルとして安定でなくなるため好ましくない。また、ゾルの安定性はゼータ電位とも相関があり、ゼータ電位が２０ｍＶ以上、好ましくは３０ｍＶ以上、特に好ましくは４０ｍＶ以上、であればゾルの安定性が確保される。本発明のゾルの分散媒は特に限定されるものでなく、例えば水、メタノール、エタノール、アセトン、エーテル等であってもよい。好ましくは、通常、水が用いられる。
The sol of the present invention contains carboxylic acid or a salt thereof as an essential component, and is usually pH 7 or lower, preferably
カルボン酸またはその塩の含有量は、１モルのＺｒに対して０．０５〜１モル、好ましくは０．１〜０．５モルである。 Content of carboxylic acid or its salt is 0.05-1 mol with respect to 1 mol of Zr, Preferably it is 0.1-0.5 mol.
０．０５モル未満では、ゾルに含有される無機酸をカルボン酸またはその塩で置換し、光触媒体コーティング液の特性を向上させるという本発明のゾルの特徴が十分に発揮されず、１モルを超える場合は、ゾルの主用途である光触媒体コーティング液における特性発現の妨げになる可能性があり好ましくない。 If the amount is less than 0.05 mol, the inorganic acid contained in the sol is replaced with a carboxylic acid or a salt thereof, and the characteristics of the sol of the present invention for improving the characteristics of the photocatalyst coating liquid are not fully exhibited, and 1 mol When exceeding, it may become the hindrance of the characteristic expression in the photocatalyst body coating liquid which is the main use of sol, and is unpreferable.
本発明のゾルは硝酸、塩酸等の無機酸を含有するが、製品への不純物の混入の少ない硝酸が好ましい。 The sol of the present invention contains an inorganic acid such as nitric acid and hydrochloric acid, but nitric acid is preferable because it contains less impurities in the product.
さらに、本発明のゾル中の無機酸／カルボン酸またはその塩のモル比は、０．１〜５、好ましくは０．３〜３である。 Furthermore, the molar ratio of the inorganic acid / carboxylic acid or salt thereof in the sol of the present invention is 0.1 to 5, preferably 0.3 to 3.
このモル比が０．１未満の場合、光触媒コーティング液として用いた際、得られる塗膜が充分な密着性を示さない。またこのモル比が５を超える場合、ゾル中の非晶質Ｚｒ−Ｏ系粒子の分散安定性が損なわれ、凝集粒子が生成して、光触媒コーティング液として用いた際、得られる塗膜の意匠性に不具合が生じることがある。 When this molar ratio is less than 0.1, the resulting coating film does not exhibit sufficient adhesion when used as a photocatalyst coating solution. When the molar ratio exceeds 5, the dispersion stability of the amorphous Zr-O-based particles in the sol is impaired, and aggregated particles are generated and used as a photocatalyst coating liquid. May cause problems.
ゾルが無機酸とカルボン酸またはその塩の両方を上記モル比で含有するとき、ゼータ電位の絶対値が極大をとるため、正のゼータ電位を持つ光触媒体との均一な混合がより容易となる。 When the sol contains both an inorganic acid and a carboxylic acid or a salt thereof in the above molar ratio, the absolute value of the zeta potential is maximized, so that uniform mixing with a photocatalyst having a positive zeta potential becomes easier. .
上記のゼータ電位の絶対値の極大については次のように解釈できる。ゾルに含有される非晶質のＺｒ−Ｏ系粒子に表面電位を与えるのはプロトンであり、硝酸や塩酸などの無機酸はプロトンの供給能に優れる。表面電位から電気二重層に分布するカウンターイオンの電位を幾分差し引いたものがゼータ電位として観測されるから、表面電位を低下させにくいカウンターイオンの導入や、電気二重層内のカウンターイオンの濃度を低下させることによって高いゼータ電位が得られると推測される。そして、おそらく、カルボン酸またはその塩には、表面電位を低下させにくいカウンターイオンを供給したり、電離していないカルボン酸またはその塩がＺｒ−Ｏ系粒子表面に吸着するなどしてカウンターイオンの濃度を低下させる効果があり、プロトンを放出して表面電位を与える無機酸と表面電位を低下させにくいカルボン酸またはその塩のゾル中の濃度バランスがゼータ電位の重要な要因であると考えられる。 The maximum value of the absolute value of the zeta potential can be interpreted as follows. Protons impart a surface potential to the amorphous Zr—O-based particles contained in the sol, and inorganic acids such as nitric acid and hydrochloric acid are excellent in proton supply ability. Since the zeta potential is obtained by subtracting the potential of the counter ions distributed in the electric double layer from the surface potential, introduction of counter ions that are difficult to reduce the surface potential and the concentration of counter ions in the electric double layer It is presumed that a high zeta potential can be obtained by lowering. Probably, the carboxylic acid or its salt is supplied with a counter ion that does not easily lower the surface potential, or the non-ionized carboxylic acid or its salt is adsorbed on the surface of the Zr—O-based particle. It is thought that the concentration balance in the sol of an inorganic acid that releases protons and gives surface potential by releasing protons and carboxylic acid or its salt that hardly lowers surface potential is an important factor of zeta potential.
Ｚｒ−Ｏ系粒子が分散した状態を安定して保つためには１モルのＺｒに対する無機酸とカルボン酸またはその塩の合計が０．０５モル、好ましくは０．１モル以上は必要であるが、それ以上の無機酸とカルボン酸またはその塩の合計の量はゾルに必要な特性、用途に応じて自由に選択できる。なお、１モルのＺｒに対する無機酸とカルボン酸またはその塩の合計が１モルを超えることは、添加量に見合うＺｒ−Ｏ系粒子の分散性の向上などが見られない為、経済的な点から好ましくない。 In order to stably maintain the dispersed state of the Zr—O-based particles, the total amount of inorganic acid and carboxylic acid or salt thereof per 1 mol of Zr is 0.05 mol, preferably 0.1 mol or more. Further, the total amount of the inorganic acid and carboxylic acid or salt thereof can be freely selected according to the characteristics and application required for the sol. In addition, since the improvement of the dispersibility of Zr-O type | system | group particle | grains suitable for the addition amount is not seen that the sum total of the inorganic acid and carboxylic acid with respect to 1 mol of Zr or its salt exceeds 1 mol, it is economical. Is not preferable.
本発明で用いるカルボン酸またはその塩としては、ギ酸、ギ酸塩、酢酸、酢酸塩、プロピオン酸及びプロピオン酸塩等があげられ、これらの１種または２種以上を用いることが出来る（すなわち、本発明において、「カルボン酸またはその塩」とは、「カルボン酸および／またはその塩」、すなわち、(1)カルボン酸単独、(2)カルボン酸塩単独および(3)カルボン酸とカルボン酸塩との混合物、の３通りを含むことを意味する）。 Examples of the carboxylic acid or a salt thereof used in the present invention include formic acid, formate, acetic acid, acetate, propionic acid and propionate, and one or more of these can be used (that is, the present invention) In the present invention, “carboxylic acid or salt thereof” means “carboxylic acid and / or salt thereof”, that is, (1) carboxylic acid alone, (2) carboxylate salt alone, and (3) carboxylic acid and carboxylate salt. A mixture of the following:
これらのなかでもギ酸、ギ酸塩、酢酸および酢酸塩を用いるのが好ましい。ギ酸塩としては、ギ酸アンモニウム、ギ酸ナトリウム、およびギ酸カリウムが、また酢酸塩としては、酢酸アンモニウム、酢酸ナトリウム、および酢酸カリウムがあげられる。 Of these, formic acid, formate, acetic acid and acetate are preferably used. Examples of the formate include ammonium formate, sodium formate, and potassium formate, and examples of the acetate include ammonium acetate, sodium acetate, and potassium acetate.
（２）ゼータ電位が−２０ｍＶ以下のゾル
本発明の第二のゾルは、粒子径Ｄ５０が１〜２０ｎｍである非晶質のＺｒ−Ｏ系粒子を分散質とし、カルボン酸またはその塩を含み、ゼータ電位が−２０ｍＶ以下であることを特徴とする。
(2) Sol with zeta potential of −20 mV or less The second sol of the present invention comprises amorphous Zr—O-based particles having a particle diameter D50 of 1 to 20 nm as a dispersoid, and contains a carboxylic acid or a salt thereof. The zeta potential is -20 mV or less.
非晶質のＺｒ−Ｏ系粒子および分散媒としては、上記（１）ゼータ電位が２０ｍＶ以上のゾルの場合と同じものを用いることが出来る。 As the amorphous Zr—O-based particles and the dispersion medium, the same (1) sol having a zeta potential of 20 mV or more can be used.
なお、本発明の第二のゾルにおいて、ジルコニウム濃度はＺｒＯ2換算で３〜２０重量％、好ましくは、５〜１８重量％の範囲内であるとよい。３重量％未満の場合非効率であり、２０重量％を超える場合は増粘、ゲル化のおそれがあり好ましくない。 In the second sol of the present invention, the zirconium concentration is 3 to 20% by weight, preferably 5 to 18% by weight in terms of ZrO 2 . If it is less than 3% by weight, it is inefficient, and if it exceeds 20% by weight, there is a risk of thickening and gelation, which is not preferable.
本発明の第二のゾルは、カルボン酸またはその塩を必須成分として含有しており、ｐＨ３〜１２、好ましくは６〜１０である。ｐＨ３未満または、ｐＨ１２を超える場合、含有する酸または塩基などの不純物が過剰となり、光触媒体コーティング液にとって好ましくない場合がある。 The 2nd sol of this invention contains carboxylic acid or its salt as an essential component, and is pH 3-12, Preferably it is 6-10. If the pH is less than 3 or exceeds pH 12, impurities such as acid or base contained may be excessive, which may be undesirable for the photocatalyst coating liquid.
カルボン酸またはその塩／Ｚｒのモル比は、０．０５〜１、好ましくは０．１〜０．５である。カルボン酸またはその塩はＺｒ−Ｏ系粒子表面に吸着し、負の表面電位を与え、ゾルを安定化するものと考えられる。 The molar ratio of carboxylic acid or its salt / Zr is 0.05 to 1, preferably 0.1 to 0.5. It is considered that carboxylic acid or a salt thereof is adsorbed on the surface of Zr—O-based particles, gives a negative surface potential, and stabilizes the sol.
０．０５未満では、Ｚｒ−Ｏ系粒子に十分な表面電位を与えられずゾルの安定が確保できない。１を超える場合は、ゾルの主用途である光触媒体コーティング液における特性発現の妨げになる可能性があり好ましくない。 If it is less than 0.05, a sufficient surface potential cannot be applied to the Zr—O-based particles, and sol stability cannot be ensured. When it exceeds 1, it may be an obstacle to the expression of characteristics in the photocatalyst coating liquid which is the main application of the sol, which is not preferable.
上記の負の表面電位の指標としてゼータ電位を基準とすることができ、ゾルの安定性を確保するには該ゾルのゼータ電位が−２０ｍＶ以下、好ましくは−３０ｍＶ以下、特に好ましくは−４０ｍＶ以下である。これは上記のカルボン酸またはその塩／Ｚｒのモル比に依存したものとなる。該ゾルのゼータ電位が−２０ｍＶ以下の場合、ゼータ電位が負の光触媒体との均一な混合が容易となる特徴がある。 The zeta potential can be used as a reference for the negative surface potential, and the zeta potential of the sol is −20 mV or less, preferably −30 mV or less, particularly preferably −40 mV or less to ensure the stability of the sol. It is. This depends on the carboxylic acid or its salt / Zr molar ratio. When the zeta potential of the sol is −20 mV or less, there is a feature that uniform mixing with a photocatalyst having a negative zeta potential is facilitated.
カルボン酸としてはクエン酸、酒石酸、グリコール酸および乳酸が挙げられ、これらはゾルの表面電位への寄与が特に大きいため必須成分である。 Examples of the carboxylic acid include citric acid, tartaric acid, glycolic acid, and lactic acid, which are essential components because they contribute particularly greatly to the surface potential of the sol.
本発明のゾルは硝酸、塩酸等の無機酸を含有しても良いが、この場合、製品への不純物の混入の少ない硝酸が好ましい。これらの無機酸は、本発明のゾルの製造段階で、１モルのＺｒに対して０．１〜３モルの塩基が加えられ、その後、精製されるため、通常の場合、これらの無機酸は確認されない場合が多い。 The sol of the present invention may contain an inorganic acid such as nitric acid and hydrochloric acid. In this case, nitric acid with less impurities mixed into the product is preferable. Since these inorganic acids are refined after 0.1 to 3 mol of base is added to 1 mol of Zr in the production stage of the sol of the present invention, in general, these inorganic acids are It is often not confirmed.
カルボン酸は(1)クエン酸、酒石酸、グリコール酸および乳酸から選ばれる１種または２種以上またはそれらと(2)ギ酸、酢酸および蓚酸から選ばれる１種または２種以上との組み合わせとしてもよい。 The carboxylic acid may be (1) one or more selected from citric acid, tartaric acid, glycolic acid, and lactic acid, or (2) one or more selected from formic acid, acetic acid, and succinic acid. .
クエン酸、酒石酸、グリコール酸、乳酸またはそれらの塩は該ゾルの用途である光触媒体コーティング液の特性発現の妨げになる可能性が高いため、該ゾルにはクエン酸、酒石酸、グリコール酸、乳酸またはそれらの塩が必要最低限含有されていることが好ましい。一方、ギ酸、酢酸、蓚酸またはそれらの塩はゼータ電位への寄与は小さいが、光触媒体塗膜の特性を向上させる効果が期待でき、ゾルに含有させた場合、該ゾルの応用製品の特性発現の妨げになる傾向が強いクエン酸、酒石酸、グリコール酸、乳酸またはそれらの塩の含有量を減らしても、上記ゼータ電位を−２０ｍＶ以下に維持することを可能とする。 Since citric acid, tartaric acid, glycolic acid, lactic acid or salts thereof are likely to hinder the development of the characteristics of the photocatalyst coating liquid used for the sol, the sol contains citric acid, tartaric acid, glycolic acid, lactic acid. Or it is preferable that those salts are contained at the minimum. On the other hand, formic acid, acetic acid, succinic acid or their salts have little contribution to the zeta potential, but can be expected to improve the properties of the photocatalyst coating film. Even if the content of citric acid, tartaric acid, glycolic acid, lactic acid or their salts, which tend to be a hindrance, is reduced, the zeta potential can be maintained at -20 mV or less.
上記カルボン酸の種類や組み合わせは、該ゾルの用途である光触媒体コーティング液の必要特性に応じて選択すればよく、特に限定されるものではない。また、(1)クエン酸、酒石酸、グリコール酸および乳酸またはそれらの塩から選ばれる１種または２種以上と(2)ギ酸、酢酸、蓚酸またはそれらの塩から選ばれる１種または２種以上のモル比（(1)／(2)）は０．１〜３が好ましい。０．１未満では、ゾルが不安定となるため、また、３を超えると光触媒コーティング液の特性に悪影響を及ぼす可能性があるため好ましくない。 The kind and combination of the carboxylic acid may be selected according to the required characteristics of the photocatalyst coating liquid used for the sol, and is not particularly limited. In addition, (1) one or more selected from citric acid, tartaric acid, glycolic acid and lactic acid or salts thereof and (2) one or more selected from formic acid, acetic acid, succinic acid or salts thereof The molar ratio ((1) / (2)) is preferably 0.1 to 3. If it is less than 0.1, the sol becomes unstable, and if it exceeds 3, the characteristics of the photocatalyst coating solution may be adversely affected.
以下に、非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法、このゾルをバインダーとする光触媒体コーティング液、およびその光触媒体コーティング液を塗布した光触媒機能製品の製造方法、について、詳細に説明する。 Hereinafter, a method for producing a sol using amorphous Zr-O-based particles as a dispersoid, a photocatalyst coating liquid using the sol as a binder, and a method for producing a photocatalytic functional product coated with the photocatalyst coating liquid will be described. This will be described in detail.
まず、非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法について説明する。
本発明のゾルの原料として用いる、分散媒中に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法は特に限定されないが、以下の方法で製造することができる。
First, a method for producing a sol using amorphous Zr—O-based particles as a dispersoid will be described.
A method for producing a sol used as a raw material for the sol of the present invention, which contains an inorganic acid in a dispersion medium and amorphous Zr-O-based particles as a dispersoid is not particularly limited, but can be produced by the following method. it can.
分散媒中に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの原料として用いる水酸化ジルコニウムは特に限定されない。一例を示せば、ジルコニウム塩類の水溶液を水酸化アルカリやアンモニア水で中和することで得られる沈殿を水洗し不純物を取り除いて得た水酸化ジルコニウムを用いることができる。 Zirconium hydroxide used as a sol raw material containing an inorganic acid in a dispersion medium and using amorphous Zr—O-based particles as a dispersoid is not particularly limited. For example, zirconium hydroxide obtained by washing a precipitate obtained by neutralizing an aqueous solution of a zirconium salt with an alkali hydroxide or aqueous ammonia to remove impurities can be used.
ジルコニウム塩類としては、特に限定されず、塩基性硫酸塩、オキシ塩化塩、硝酸塩、酢酸塩、その他有機酸塩等が例示され、オキシ塩化塩が安価で純度が高いという点で好ましい。 Zirconium salts are not particularly limited, and examples thereof include basic sulfates, oxychlorides, nitrates, acetates, and other organic acid salts. Oxychlorides are preferable because they are inexpensive and have high purity.
水酸化ジルコニウム、無機酸及び溶媒、好ましくは、水からなる反応分散液の調製に際して、まず、反応容器に必要量の水を入れそれを適度に攪拌しながら、ついで所定量の水酸化ジルコニウム、水酸化ジルコニウム、無機酸及び水の投入順序は特に限定されないが、作業性を考慮すると上記が好ましい。 In preparing a reaction dispersion composed of zirconium hydroxide, an inorganic acid and a solvent, preferably water, first, a required amount of water is put into a reaction vessel, and then a predetermined amount of zirconium hydroxide, The order of adding zirconium oxide, inorganic acid and water is not particularly limited, but the above is preferable in view of workability.
該分散液を調製する際の該分散液のジルコニウム濃度はＺｒＯ2換算で３〜２０重量％、好ましくは、５〜１８重量％の範囲内であるとよい。３重量％未満の場合非効率であり、２０重量％を超える場合は増粘、ゲル化のおそれがあり好ましくない。 The zirconium concentration of the dispersion when preparing the dispersion is 3 to 20% by weight in terms of ZrO 2 , preferably 5 to 18% by weight. If it is less than 3% by weight, it is inefficient, and if it exceeds 20% by weight, there is a risk of thickening and gelation, which is not preferable.
このジルコニウム濃度が高いほど該分散液に添加される無機酸の量が少なくなるため経済的に有利であり、生成するゾルが含む無機酸が少なくなることから環境負荷、不純物の低減が期待できる。 A higher zirconium concentration is economically advantageous because the amount of inorganic acid added to the dispersion is reduced, and since the inorganic acid contained in the generated sol is reduced, reduction of environmental burden and impurities can be expected.
ここで、ゾルの生成と無機酸の関係について簡単に述べる。水酸化ジルコニウムが解膠され非晶質のＺｒ−Ｏ系のゾル粒子が生成すると同時に酸由来のプロトンがゾル粒子の界面に吸着することでゾル粒子は帯電しその界面には電気二重層が形成される。この電気二重層の反発力によってゾル粒子同士は凝集せずに分散状態を保つことができる。酸濃度が低すぎる場合、十分な電気二重層を得られないためゾルは生成しない。 Here, the relationship between the generation of sol and the inorganic acid will be briefly described. Zirconium hydroxide is peptized to form amorphous Zr-O sol particles, and at the same time, protons derived from acid are adsorbed on the interface of the sol particles, charging the sol particles and forming an electric double layer at the interface. Is done. Due to the repulsive force of the electric double layer, the sol particles can be kept in a dispersed state without being aggregated. When the acid concentration is too low, a sufficient electric double layer cannot be obtained, so that no sol is generated.
無機酸には上記のゾル粒子に電気二重層を与える役割以外に水酸化ジルコニウムからの結晶性ジルコニアの生成を促す作用がある。この結晶性ジルコニアの生成機構は定かでないが、水酸化ジルコニウムを水に分散したものを加熱保持するよりも、いくらかの無機酸の存在下に加熱保持するとき結晶性ジルコニアの生成速度は速くなる。そして、結晶性ジルコニアが生成する場合には同時にジルコニアゾルの粒子径Ｄ５０は大きくなる傾向にある。おそらく無機酸が水酸化ジルコニウムに作用する事で結晶性ジルコニアの前駆体が生成されると考えられる。 In addition to the role of providing an electric double layer to the sol particles, the inorganic acid has an action of promoting the generation of crystalline zirconia from zirconium hydroxide. The formation mechanism of this crystalline zirconia is not clear, but the formation rate of crystalline zirconia is faster when heated and held in the presence of some inorganic acid than when a dispersion of zirconium hydroxide in water is heated and held. And when crystalline zirconia produces | generates, the particle diameter D50 of a zirconia sol tends to become large simultaneously. Presumably, an inorganic acid acts on zirconium hydroxide to produce a crystalline zirconia precursor.
結晶性ジルコニアの生成速度は反応分散液中の無機酸濃度に依存し、その生成速度が最大となる無機酸濃度は、上記の電気二重層形成のためには十分な濃度であるが本発明の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルを得るために適当な無機酸濃度よりは低濃度である。厳密には適当な無機酸濃度は反応分散液のジルコニウム濃度によって変化し、ジルコニウム濃度が高いほどより高い無機酸濃度を必要とするが、１モルのＺｒに対し必要な無機酸のグラム当量数で換算した場合に反応分散液のジルコニウム濃度が高いほどそのグラム当量数は低下する。 The production rate of crystalline zirconia depends on the inorganic acid concentration in the reaction dispersion, and the inorganic acid concentration at which the production rate is maximized is sufficient for the above-mentioned electric double layer formation. In order to obtain a sol having amorphous Zr—O-based particles as a dispersoid, the concentration is lower than a suitable inorganic acid concentration. Strictly speaking, the appropriate inorganic acid concentration varies depending on the zirconium concentration of the reaction dispersion. The higher the zirconium concentration, the higher the inorganic acid concentration required, but the number of gram equivalents of inorganic acid required per mole of Zr. When converted, the gram equivalent number decreases as the zirconium concentration of the reaction dispersion increases.
本発明の反応活性があり、溶液に近い性質を持ち、粒子径Ｄ５０が小さく、かつ、非晶質のＺｒ−Ｏ系粒子を分散質とするゾルを製造するには、反応分散液を調製する際に、１モルのＺｒに対する無機酸のグラム当量数Ｙが、上記ジルコニウム濃度をＸ重量％としたとき、下記の式（１）かつ式（２）を満足する範囲内にすることが望ましい。
３≦Ｘ≦２０ （１）
（２．０−０．０７Ｘ）≦Ｙ≦（３．０−０．０８Ｘ） （２）
In order to produce a sol having the reaction activity of the present invention, having properties close to a solution, a small particle diameter D50, and amorphous Zr-O-based particles as a dispersoid, a reaction dispersion is prepared. At this time, it is desirable that the gram equivalent number Y of the inorganic acid with respect to 1 mol of Zr is within a range satisfying the following formulas (1) and (2) when the zirconium concentration is X wt%.
3 ≦ X ≦ 20 (1)
(2.0−0.07X) ≦ Y ≦ (3.0−0.08X) (2)
この無機酸のグラム当量数Ｙがとる範囲は上記で述べたゾル粒子に電気二重層を与えるには十分で、かつ、結晶性ジルコニアが生成しない無機酸濃度となるような範囲である。このグラム当量数Ｙが上記範囲の下限未満の場合、生成するゾルの粒子径が大きくなり過ぎたり、結晶性ジルコニアが生成し目的とする本発明の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルが得られない。 The range that the gram equivalent number Y of the inorganic acid takes is a range that is sufficient to give the sol particles the electric double layer and has an inorganic acid concentration that does not produce crystalline zirconia. When the gram equivalent number Y is less than the lower limit of the above range, the particle size of the sol to be formed becomes too large, or crystalline zirconia is generated, and the desired amorphous Zr-O-based particles of the present invention are dispersed. A sol is not obtained.
図１にＸ、Ｙの値を変化させ、合成したゾルの結晶性についてＸ線回折測定によって調べた結果を示す。 FIG. 1 shows the result of examining the crystallinity of the synthesized sol by changing the values of X and Y by X-ray diffraction measurement.
ゾルの結晶性は、ゾルを２００℃以下の温度で恒量となるまで乾燥しＸ線回折測定によって得られる回折パターンにおいて２θ＝１０〜５０°で特定の結晶系に帰属されるパターンを示さないものを非晶質とし、それ以外を結晶質と分類した。 The crystallinity of the sol does not show a pattern attributed to a specific crystal system at 2θ = 10 to 50 ° in a diffraction pattern obtained by drying the sol to a constant weight at a temperature of 200 ° C. or lower and obtaining an X-ray diffraction measurement. Was classified as amorphous, and the others were classified as crystalline.
上記の式（１）を満足するＸ、Ｙの範囲において非晶質のゾルが得られ、それ以外では結晶性のゾルが得られた。そのうち非晶質のゾルは１〜２０ｎｍの粒子径Ｄ５０であった。
すなわち、上記の式（１）を満足するようにＸ、Ｙを制御することで本発明のゾルが得られることが判る。
なお、上限を超える場合は、ゾルの生成には過剰量となり不経済であるばかりでなく、環境負荷や生成するゾルの不純物を増加させるため好ましくない。
An amorphous sol was obtained in the range of X and Y satisfying the above formula (1), and a crystalline sol was obtained otherwise. Among them, the amorphous sol had a particle diameter D50 of 1 to 20 nm.
That is, it can be seen that the sol of the present invention can be obtained by controlling X and Y so as to satisfy the above formula (1).
If the upper limit is exceeded, the amount of sol produced is excessive, which is uneconomical and undesirably increases the environmental load and impurities of the produced sol.
上記無機酸は特に限定されるものではないが、不純物が少なく、ゾルの生成速度が速いという点で硝酸が好ましい。 Although the said inorganic acid is not specifically limited, Nitric acid is preferable at the point that there are few impurities and the production | generation speed | rate of sol is quick.
次に、調製された反応分散液を適度に攪拌しながら８０℃以上、好ましくは９０℃以上に加熱し、保持する。保持する温度はゾルの生成速度に影響し、８０℃未満では十分な生成速度を得られず非効率である。１００℃以上で保持する場合は溶媒の蒸発を避けるためオートクレーブ等の密閉容器を使用することが望ましい。保持時間は特に限定されず、反応分散液が完全に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルとなったことを反応分散液の粒子径分布測定及び恒量まで１００℃で乾燥後のＸ線回折測定などで確認すればそこで加熱を終了してよいが、通常１２〜９６時間である。 Next, the prepared reaction dispersion is heated to 80 ° C. or higher, preferably 90 ° C. or higher, with appropriate stirring, and held. The temperature to be maintained affects the sol production rate, and if it is less than 80 ° C., a sufficient production rate cannot be obtained, which is inefficient. When the temperature is kept at 100 ° C. or higher, it is desirable to use a closed container such as an autoclave in order to avoid evaporation of the solvent. The holding time is not particularly limited, and it is confirmed that the reaction dispersion is a sol containing an inorganic acid and containing amorphous Zr-O-based particles as a dispersoid until the particle size distribution measurement and constant weight of the reaction dispersion are reached. If confirmed by X-ray diffraction measurement after drying at 100 ° C., the heating may be terminated there, but it is usually 12 to 96 hours.
上記の様にして作製された、分散媒中に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルは、以下の「ゼータ電位が２０ｍＶ以上のゾルの製造方法」および「ゼータ電位が−２０ｍＶ以下のゾルの製造方法」において、その原料として用いられる。 The sol produced as described above and containing an inorganic acid in the dispersion medium and containing amorphous Zr—O-based particles as a dispersoid is represented by the following “method for producing a sol having a zeta potential of 20 mV or more” and It is used as a raw material in “a method for producing a sol having a zeta potential of −20 mV or less”.
（１）ゼータ電位が２０ｍＶ以上のゾルの製造方法
本発明の第一の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法は、分散媒中に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの無機酸を、カルボン酸またはその塩と置換することを特徴とする。
(1) Method for producing sol having zeta potential of 20 mV or more The method for producing sol using the first amorphous Zr-O-based particles of the present invention as a dispersoid comprises an inorganic acid in a dispersion medium and an amorphous material. It is characterized in that the inorganic acid of the sol having the quality Zr—O-based particles as a dispersoid is substituted with a carboxylic acid or a salt thereof.
無機酸をカルボン酸またはその塩に置換する方法については、特に限定されるものでないが、その一例として以下に記載する。 Although it does not specifically limit about the method of replacing an inorganic acid with carboxylic acid or its salt, It describes below as an example.
上記で得られたゾル中の無機酸を限外ろ過、透析、逆浸透等の方法で除去し、カルボン酸またはその塩を添加する。カルボン酸またはその塩の添加は、無機酸を所定の濃度まで除去した後に行ってもよいし、無機酸を除去しながら行ってもよい。この処理によって、無機酸の濃度を低減させ、カルボン酸またはその塩の濃度を高め、しかもゾルのジルコニウム濃度を濃縮することが可能であるため、ゾルの用途によって処理の回数、時間を任意に選択できる。用いるカルボン酸またはその塩としては、ギ酸、ギ酸塩、酢酸、酢酸塩、プロピオン酸及びプロピオン酸塩があげられ、これらのなかでもギ酸、ギ酸塩、酢酸および酢酸塩を用いるのが好ましい。ギ酸塩としては、ギ酸アンモニウム、ギ酸ナトリウム、およびギ酸カリウムが、また酢酸塩としては、酢酸アンモニウム、酢酸ナトリウム、および酢酸カリウムがあげられる。 The inorganic acid in the sol obtained above is removed by methods such as ultrafiltration, dialysis, and reverse osmosis, and carboxylic acid or a salt thereof is added. The addition of carboxylic acid or a salt thereof may be performed after removing the inorganic acid to a predetermined concentration, or may be performed while removing the inorganic acid. By this treatment, the concentration of inorganic acid can be reduced, the concentration of carboxylic acid or its salt can be increased, and the concentration of zirconium in the sol can be increased. it can. Examples of the carboxylic acid or salt thereof used include formic acid, formate, acetic acid, acetate, propionic acid and propionate. Among these, formic acid, formate, acetic acid and acetate are preferably used. Examples of the formate include ammonium formate, sodium formate, and potassium formate, and examples of the acetate include ammonium acetate, sodium acetate, and potassium acetate.
なお、カルボン酸またはその塩／Ｚｒのモル比が０．０５〜１、好ましくは０．１〜０．５となるように置換（添加）することが好ましい。０．０５未満では、Ｚｒ−Ｏ系粒子に十分な表面電位を与えられずゾルの安定が確保できない。１を超える場合は、ゾルの主用途である光触媒体コーティング液における特性発現の妨げになる可能性があり好ましくない。 In addition, it is preferable to perform substitution (addition) so that the molar ratio of carboxylic acid or a salt thereof / Zr is 0.05 to 1, preferably 0.1 to 0.5. If it is less than 0.05, a sufficient surface potential cannot be given to the Zr—O-based particles, and sol stability cannot be secured. When it exceeds 1, it may be an obstacle to the expression of characteristics in the photocatalyst coating liquid which is the main application of the sol, which is not preferable.
上記塩類を使用する場合は、ギ酸や酢酸を用いた場合よりもゾルのｐＨを上昇させることになるが、ゾルの分散を安定に保ったままｐＨ７超にすることはできない。即ち、上記の方法ではゼータ電位が正のゾルのみが製造できる。 When the above salts are used, the pH of the sol is raised more than when formic acid or acetic acid is used. However, the pH cannot exceed 7 while keeping the dispersion of the sol stable. That is, in the above method, only a sol having a positive zeta potential can be produced.
なお、本発明のゾルは、ｐＨ７以下、好ましくはｐＨ５以下である。ｐＨが７を超えると分散質の凝集、沈殿やゲル化等を起こしゾルとして安定でなくなるため好ましくない。 The sol of the present invention has a pH of 7 or less, preferably a pH of 5 or less. A pH exceeding 7 is not preferable because it causes dispersoid aggregation, precipitation, gelation, and the like, and becomes unstable as a sol.
なお、上記の様にカルボン酸またはその塩を添加しない場合は、限外ろ過、透析、逆浸透等を繰り返しても、カルボン酸またはその塩を添加した場合と同等以下に無機酸をゾル中から排除することは非常に困難である。つまり、カルボン酸またはその塩の添加によってゾルからの無機酸の除去効率を高めているのが本発明の特徴である。 In the case where carboxylic acid or a salt thereof is not added as described above, even if ultrafiltration, dialysis, reverse osmosis or the like is repeated, the inorganic acid is reduced from the sol to the same level or less as when carboxylic acid or a salt thereof is added. It is very difficult to eliminate. That is, it is a feature of the present invention that the removal efficiency of the inorganic acid from the sol is enhanced by the addition of carboxylic acid or a salt thereof.
得られるゾル中の無機酸／カルボン酸またはその塩のモル比は０．１〜５、好ましくは０．３〜３の範囲である。このモル比が０．１未満の場合、光触媒コーティング液として用いた際、得られる塗膜が充分な密着性を示さない。またこのモル比が５を超える場合、ゾル中の非晶質Ｚｒ−Ｏ系粒子の分散安定性が損なわれ、凝集粒子が生成して、光触媒コーティング液として用いた際、得られる塗膜の意匠性に不具合が生じることがある。 The molar ratio of inorganic acid / carboxylic acid or salt thereof in the obtained sol is 0.1 to 5, preferably 0.3 to 3. When this molar ratio is less than 0.1, the resulting coating film does not exhibit sufficient adhesion when used as a photocatalyst coating solution. When the molar ratio exceeds 5, the dispersion stability of the amorphous Zr-O-based particles in the sol is impaired, and aggregated particles are generated and used as a photocatalyst coating liquid. May cause problems.
なお、本発明のゾルは硝酸、塩酸等の無機酸を含有するが、製品への不純物の混入の少ない硝酸が好ましい。一方、本発明のゾルの粒子径およびＺｒＯ2換算のジルコニウム濃度は、原料として用いたゾルと同等のものが得られる。 The sol of the present invention contains an inorganic acid such as nitric acid and hydrochloric acid, but nitric acid is preferable because it contains less impurities in the product. On the other hand, the particle diameter of the sol of the present invention and the zirconium concentration in terms of ZrO 2 are equivalent to those of the sol used as a raw material.
以上に記載した製造方法により、本発明のゾルのゼータ電位は２０ｍＶ以上、好ましくは３０ｍＶ以上、特に好ましくは４０ｍＶ以上となる。 By the production method described above, the zeta potential of the sol of the present invention is 20 mV or more, preferably 30 mV or more, particularly preferably 40 mV or more.
（２）ゼータ電位が−２０ｍＶ以下のゾルの製造方法
本発明の第二の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法は、分散媒中に無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの無機酸を塩基で中和した後、中和により生成した無機酸塩をカルボン酸またはその塩と置換することを特徴とする。
(2) Method for Producing a Sol with a Zeta Potential of −20 mV or Less The second method for producing a sol using the amorphous Zr—O-based particles as a dispersoid according to the present invention contains an inorganic acid in a dispersion medium and is non- The inorganic acid of the sol having crystalline Zr—O-based particles as a dispersoid is neutralized with a base, and then the inorganic acid salt generated by the neutralization is replaced with a carboxylic acid or a salt thereof.
中和により生成した無機酸塩をカルボン酸またはその塩に置換する方法については、特に限定されるものでないが、その一例として以下に記載する。 The method for substituting the carboxylic acid or salt thereof with the inorganic acid salt produced by neutralization is not particularly limited, but an example thereof is described below.
まず、上記で得られた無機酸を含有し非晶質のＺｒ−Ｏ系粒子を分散質とするゾルへカルボン酸またはその塩を添加する。ここで添加するカルボン酸またはその塩としては、Ｚｒ−Ｏ系粒子の表面電位を負にする効果の高い、クエン酸、酒石酸、グリコール酸および乳酸またはそれらの塩が挙げられる。カルボン酸またはその塩／Ｚｒのモル比が０．０５〜１、好ましくは０．１〜０．５となるように置換（添加）することが好ましい。０．０５未満では、Ｚｒ−Ｏ系粒子に十分な表面電位を与えられずゾルの安定が確保できない。１を超える場合は、ゾルの主用途である光触媒体コーティング液における特性発現の妨げになる可能性があり好ましくない。 First, carboxylic acid or a salt thereof is added to a sol containing the inorganic acid obtained above and containing amorphous Zr—O-based particles as a dispersoid. Examples of the carboxylic acid or salt thereof added here include citric acid, tartaric acid, glycolic acid and lactic acid, or a salt thereof, which has a high effect of making the surface potential of Zr—O-based particles negative. It is preferable to perform substitution (addition) so that the molar ratio of carboxylic acid or a salt thereof / Zr is 0.05 to 1, preferably 0.1 to 0.5. If it is less than 0.05, a sufficient surface potential cannot be applied to the Zr—O-based particles, and sol stability cannot be ensured. When it exceeds 1, it may be an obstacle to the expression of characteristics in the photocatalyst coating liquid which is the main application of the sol, which is not preferable.
なお、本発明のゾルは硝酸、塩酸等の無機酸を含有する場合もあるが、製品への不純物の混入の少ない硝酸が好ましい。 The sol of the present invention may contain an inorganic acid such as nitric acid or hydrochloric acid, but nitric acid with little impurities mixed into the product is preferred.
次に、上記ゾルへ塩基を添加する。塩基としては、水酸化アルカリ、アンモニア、アミン類が例示される。塩基はゾルの用途に応じて、適当なものを選択すればよいが、光触媒体コーティング液用途においては、アルカリ金属が光触媒活性を低下させる可能性があるため、アンモニアやアミン類の使用が好ましい。塩基は、Ｚｒ−Ｏ系粒子表面からプロトンを遊離させる、また、カルボン酸を電離させて、より多くのアニオンをＺｒ−Ｏ粒子表面に吸着させることによってＺｒ−Ｏ系粒子の表面電位を低下させる目的で添加される。塩基を添加する前にはＺｒ−Ｏ系粒子の表面電位は必ずしも負ではなく、Ｚｒ−Ｏ系粒子の表面電位が負になるような量の塩基を添加する必要がある。塩基の添加量については、使用されるカルボン酸またはその塩および無機酸の価数および量に依存するため一義的に決めることはできないが、概ね、１モルのＺｒに対して、モル比０．１〜３の塩基の添加が好ましい。 Next, a base is added to the sol. Examples of the base include alkali hydroxide, ammonia and amines. An appropriate base may be selected according to the use of the sol. However, in the photocatalyst coating liquid application, it is preferable to use ammonia or amines because alkali metal may reduce the photocatalytic activity. The base liberates protons from the surface of the Zr-O-based particles, and ionizes carboxylic acid to lower the surface potential of the Zr-O-based particles by adsorbing more anions on the Zr-O particle surface. Add for purpose. Before adding the base, the surface potential of the Zr—O-based particles is not necessarily negative, and it is necessary to add an amount of the base that makes the surface potential of the Zr—O-based particles negative. The amount of the base to be added cannot be uniquely determined because it depends on the valence and amount of the carboxylic acid or salt thereof and the inorganic acid to be used. Addition of 1-3 bases is preferred.
０．１未満では、Ｚｒ−Ｏ系粒子に十分な表面電位を与えることができず、結果としてゾルが不安定化するため、また、３を超えると逆に表面電位を与えるには過剰で、不純物が増加するため好ましくない。 If it is less than 0.1, a sufficient surface potential cannot be applied to the Zr—O-based particles, resulting in destabilization of the sol, and if it exceeds 3, it is excessive to provide a surface potential. Impurities increase, which is not preferable.
塩基を添加した後、ゾルのＺｒ−Ｏ系粒子のゼータ電位は負となり、無機酸から供給されたアニオンは溶媒バルクに遊離した状態となる。該ゾルを限外ろ過や透析等によって、精製することで該アニオンを効率的に除去できる。 After the base is added, the zeta potential of the Zr—O-based particles in the sol becomes negative, and the anion supplied from the inorganic acid is released into the solvent bulk. The anion can be efficiently removed by purifying the sol by ultrafiltration or dialysis.
本発明のゾルのｐＨは、３〜１２、好ましくは６〜１０である。ｐＨ３未満または、ｐＨ１２を超える場合、含有する酸または塩基などの不純物が過剰となり、光触媒体コーティング液にとって好ましくない場合がある。 The pH of the sol of the present invention is 3-12, preferably 6-10. If the pH is less than 3 or exceeds pH 12, impurities such as acid or base contained may be excessive, which may be undesirable for the photocatalyst coating liquid.
クエン酸、酒石酸、グリコール酸および乳酸またはそれらの塩および塩基を添加した後にギ酸、酢酸および蓚酸またはそれらの塩を添加（２回目の添加）しさらに精製することで、前段で添加した、クエン酸、酒石酸、グリコール酸および乳酸またはそれらの塩を効率的に除去できる。この２回目のカルボン酸またはその塩の添加は、添加時にゾルが塩基性であるため、該ゾルのｐＨ変動を抑制するためアンモニウム塩やアルカリ塩などの塩の形態で行うことが好ましい。 Citric acid, tartaric acid, glycolic acid and lactic acid or their salts and bases were added, then formic acid, acetic acid and succinic acid or their salts were added (second addition), and further purified, citric acid added in the previous stage , Tartaric acid, glycolic acid and lactic acid or their salts can be removed efficiently. This second addition of carboxylic acid or salt thereof is preferably carried out in the form of a salt such as an ammonium salt or an alkali salt in order to suppress pH fluctuation of the sol because the sol is basic at the time of addition.
２回目のカルボン酸またはその塩の添加後の精製によって、ゾルの用途の都合に応じて（(1)クエン酸、酒石酸、グリコール酸および乳酸から選ばれる１種または２種以上）／（(2)ギ酸、酢酸および蓚酸から選ばれる１種または２種以上）のカルボン酸（塩）の種類やモル比を任意に選択、調整できるが、そのモル比（(1)／(2)）は０．１〜３であることが望ましい。０．１未満では、ゾルが不安定となるため、また、３を超えると光触媒コーティング液の特性に悪影響を及ぼす可能性があるため好ましくない。 Depending on the convenience of use of the sol, (2) one or more selected from citric acid, tartaric acid, glycolic acid and lactic acid) / ((2 ) The type and molar ratio of the carboxylic acid (salt) selected from formic acid, acetic acid and oxalic acid can be selected and adjusted as desired, but the molar ratio ((1) / (2)) is 0. .1 to 3 is desirable. If it is less than 0.1, the sol becomes unstable, and if it exceeds 3, the characteristics of the photocatalyst coating solution may be adversely affected.
また、上記のカルボン酸（塩）の種類やモル比の調整によってゾルの多岐にわたる光触媒体コーティング液処方への順応性を高めることができる。 Also, adaptability to various photocatalyst coating liquid formulations of sol can be enhanced by adjusting the kind and molar ratio of the carboxylic acid (salt).
なお、本発明のゾルの粒子径およびＺｒＯ2換算のジルコニウム濃度は、原料として用いたゾルと同等のものが得られる。 The particle diameter of the sol of the present invention and the zirconium concentration in terms of ZrO 2 are equivalent to those of the sol used as a raw material.
以上に記載した製造方法により、本発明のゾルのゼータ電位は−２０ｍＶ以下、好ましくは−３０ｍＶ以下、特に好ましくは−４０ｍＶ以下となる。 By the production method described above, the zeta potential of the sol of the present invention is −20 mV or less, preferably −30 mV or less, particularly preferably −40 mV or less.
２回目のカルボン酸添加や精製の具体的な例としては、クエン酸、酒石酸、グリコール酸および乳酸またはそれらの塩と塩基を添加したゾル１００重量部に対して、１〜２重量％のカルボン酸塩水溶液１００重量部を添加し、分散質のＺｒ−Ｏ系粒子が透過しない膜によって限外ろ過し、１００重量部のゾルの分散媒を除去し、次に、上記のゾルへの１〜２重量％のカルボン酸塩水溶液１００重量部の添加、およびそれ以降の操作を４〜８回繰り返す方法等が挙げられる。 Specific examples of the second carboxylic acid addition and purification include 1-2% by weight of carboxylic acid with respect to 100 parts by weight of sol to which citric acid, tartaric acid, glycolic acid and lactic acid or salts and bases thereof are added. 100 parts by weight of an aqueous salt solution is added, ultrafiltered through a membrane that does not allow the dispersoid Zr—O-based particles to permeate, and 100 parts by weight of the sol dispersion medium is removed. Examples thereof include a method of adding 100 parts by weight of an aqueous solution of a weight percent carboxylate and repeating the subsequent operations 4 to 8 times.
以下、本発明の光触媒体コーティング液について詳細に説明する。
本発明の光触媒体コーティング液は、光触媒体、粒子径Ｄ５０が１〜２０ｎｍである非晶質のＺｒ−Ｏ系粒子とカルボン酸とその塩、または、無機酸とカルボン酸またはその塩を含み、光触媒体１００重量部に対する前記Ｚｒ−Ｏ系粒子のＺｒＯ2換算の含有量が１５〜１２０重量部であることを特徴とする。
本発明の光触媒体コーティング液に含まれる光触媒体とは、例えば紫外線や可視光線の照射により光触媒活性を発現する物質であり、具体的には、Ｘ線回折で求められる結晶構造を示し、金属元素と酸素、窒素、イオウ及び弗素との化合物の粉末が挙げられる。例えばＴｉ、Ｚｒ、Ｈｆ、Ｖ、Ｎｂ、Ｔａ、Ｃｒ、Ｍｏ、Ｗ、Ｍｎ、Ｔｃ、Ｒｅ、Ｆｅ、Ｃｏ、Ｎｉ、Ｒｕ、Ｒｈ、Ｐｄ、Ｏｓ、Ｉｒ、Ｐｔ、Ｃｕ、Ａｇ、Ａｕ、Ｚｎ、Ｃｄ、Ｇａ、Ｉｎ、Ｔｌ、Ｇｅ、Ｓｎ、Ｐｂ、Ｂｉ、Ｌａ、Ｃｅのような金属元素の１種または２種以上の酸化物、窒化物、硫化物、酸窒化物、酸硫化物、窒弗化物、酸弗化物、酸窒弗化物などが挙げられる。中でも、Ｔｉ、ＷまたはＮｂの酸化物が好ましく、とりわけアナターゼ型酸化チタン、ブルッカイト型酸化チタン、ルチル型酸化チタン〔ＴｉＯ2〕などが好ましい。
Hereinafter, the photocatalyst coating liquid of the present invention will be described in detail.
The photocatalyst coating liquid of the present invention contains a photocatalyst, amorphous Zr-O-based particles having a particle diameter D50 of 1 to 20 nm and a carboxylic acid and a salt thereof, or an inorganic acid and a carboxylic acid or a salt thereof, The content of the Zr—O-based particles in terms of ZrO 2 with respect to 100 parts by weight of the photocatalyst is 15 to 120 parts by weight.
The photocatalyst contained in the photocatalyst coating liquid of the present invention is a substance that exhibits photocatalytic activity, for example, by irradiation with ultraviolet rays or visible light, and specifically shows a crystal structure obtained by X-ray diffraction, and is a metal element. And a powder of a compound of oxygen, nitrogen, sulfur and fluorine. For example, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn One or more of metal elements such as Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce, nitride, sulfide, oxynitride, oxysulfide, Nitrogen fluoride, oxyfluoride, oxynitride fluoride and the like can be mentioned. Among these, oxides of Ti, W or Nb are preferable, and anatase type titanium oxide, brookite type titanium oxide, rutile type titanium oxide [TiO 2 ] and the like are particularly preferable.
本発明で用いる酸化チタンは、例えば非特許文献１〔「酸化チタン」（清野学著、技報堂出版）に記載されている硫酸法や塩素法により製造することができる。 Titanium oxide used in the present invention can be produced, for example, by the sulfuric acid method or the chlorine method described in Non-Patent Document 1 [“Titanium oxide” (Kyoto Seino, Gihodo Publishing).
また、本発明で用いる酸化チタンとしては、特開２００１−７２４１９号公報、特開２００１−１９０９５３号公報、特開２００１−３１６１１６号公報、特開２００１−３２２８１６号公報、特開２００２−２９７４９号公報、特開２００２−９７０１９号公報、ＷＯ０１／１０５５２パンフレット、特開２００１−２１２４５７公報、特開２００２−２３９３９５号公報）、ＷＯ０３／０８０２４４パンフレット、ＷＯ０２／０５３５０１パンフレット、特開２００７−６９０９３号公報、Chemistry Letters, Vol.32, No.2, P.196-197(2003)、Chemistry Letters, Vol.32, No.4, P.364-365(2003)、Chemistry Letters, Vol.32, No.8, P.772-773(2003)、Chem. Mater., 17, P.1548-1552(2005)等に記載の酸化チタンを用いてもよい。更に、特開２００１−２７８６２５号公報、特開２００１−２７８６２６号公報、特開２００１−２７８６２７号公報、特開２００１−３０２２４１号公報、特開２００１−３３５３２１号公報、特開２００１−３５４４２２号公報、特開２００２−２９７５０号公報、特開２００２−４７０１２号公報、特開２００２−６０２２１号公報、特開２００２−１９３６１８号公報、特開２００２−２４９３１９号公報などに記載の方法により得られる酸化チタンなども用いることができる。 Further, as titanium oxide used in the present invention, JP 2001-72419 A, JP 2001-190953 A, JP 2001-316116 A, JP 2001-322816 A, and JP 2002-29749 A. , JP 2002-97019, WO 01/10552, JP 2001-212457, 2002-239395), WO 03/080244, WO 02/053501, PA 2007-69093, Chemistry Letters , Vol.32, No.2, P.196-197 (2003), Chemistry Letters, Vol.32, No.4, P.364-365 (2003), Chemistry Letters, Vol.32, No.8, P .772-773 (2003), Chem. Mater., 17, P.1548-1552 (2005), etc. may be used. Furthermore, JP-A-2001-278625, JP-A-2001-278626, JP-A-2001-278627, JP-A-2001-302241, JP-A-2001-335321, JP-A-2001-354422, Titanium oxide obtained by the method described in JP 2002-29750 A, JP 2002-47012 A, JP 2002-60221 A, JP 2002-193618 A, JP 2002-249319 A, etc. Can also be used.
これらの酸化チタンは、それぞれ単独でまたは２種以上を組み合わせて用いられる。 These titanium oxides are used alone or in combination of two or more.
また、酸化チタンの分散液を用いると、酸化チタン粉末の分散処理工程を省け、バインダーと溶媒を添加・混合するだけで光触媒体コーティング液を得ることができる為、好適に用いられる。このような酸化チタン分散液としては、ＰＣ−２０１（酸化チタンゾル、チタン工業製）や、ＴＳ−Ｓ４１１０、４４２０、及び４４４０（酸化チタンゾル、住友化学製）が市販されている。 In addition, when a titanium oxide dispersion is used, a photocatalyst coating liquid can be obtained simply by adding and mixing a binder and a solvent without the step of dispersing the titanium oxide powder. As such a titanium oxide dispersion, PC-201 (titanium oxide sol, manufactured by Titanium Industry) and TS-S4110, 4420, and 4440 (titanium oxide sol, manufactured by Sumitomo Chemical) are commercially available.
光触媒体として使用しうる酸化タングステン〔ＷＯ3〕は、例えばメタタングステン酸アンモニウム、パラタングステン酸アンモニウム、およびタングステン酸（Ｈ2ＷＯ4）のようなタングステン化合物を焼成する方法で製造することができる。焼成は、タングステン化合物を酸化タングステンにすることができる条件で行えばよく、例えば、３５０℃〜７００℃の空気中で行うことができる。 Tungsten oxide [WO 3 ] that can be used as a photocatalyst can be produced by a method of firing a tungsten compound such as ammonium metatungstate, ammonium paratungstate, and tungstic acid (H 2 WO 4 ). Firing may be performed under conditions that allow the tungsten compound to be tungsten oxide, and can be performed in air at 350 ° C. to 700 ° C., for example.
光触媒体として用い得る酸化ニオブ〔Ｎｂ2Ｏ5〕は、例えばシュウ酸水素ニオブのようなニオブ化合物を焼成する方法で製造することができる。またニオブペンタエトキシド、ニオブペンタイソプロポキシドのようなニオブアルコキシドをアルコールに溶解し、この溶液に無機酸とアルコールとからなる酸性溶液を混合し、濃縮して粘稠溶液を得、これを焼成する方法で得ることもできる。 Niobium oxide [Nb 2 O 5 ] that can be used as a photocatalyst can be produced by a method of firing a niobium compound such as niobium hydrogen oxalate, for example. Niobium alkoxides such as niobium pentaethoxide and niobium pentaisopropoxide are dissolved in alcohol, and an acidic solution composed of an inorganic acid and alcohol is mixed with this solution and concentrated to obtain a viscous solution, which is fired. It can also be obtained by
これら酸化チタン、酸化タングステンおよび酸化ニオブ以外の酸化物を光触媒体として用いる場合、この酸化物は、例えばセラミックスを構成する金属の塩化物、硫酸塩、オキシ硫酸塩もしくはオキシ塩化物とアンモニアを反応させ、この生成物を空気中で焼成する方法、または光触媒体を構成する金属のアンモニウム塩を空気中で焼成する方法などで調製することができる。 When these oxides other than titanium oxide, tungsten oxide, and niobium oxide are used as the photocatalyst, the oxide reacts with, for example, a metal chloride, sulfate, oxysulfate, or oxychloride that constitutes ceramics and ammonia. In addition, the product can be prepared by a method of calcining in air or a method of calcining an ammonium salt of a metal constituting the photocatalyst in the air.
光触媒体は、光触媒コーティング液を基準にして通常０．１重量％以上、好ましくは１重量％以上であり、通常３０重量％以下、好ましくは１５重量部以下である。光触媒体の濃度が０．１重量％未満の場合、得られる塗膜中の光触媒体の量が少なくなり、十分な光触媒活性が得られない。また３０重量％を越える場合、得られる塗膜の透明性が低下する等の不具合が生じる。 The photocatalyst body is usually 0.1% by weight or more, preferably 1% by weight or more, and usually 30% by weight or less, preferably 15 parts by weight or less, based on the photocatalyst coating solution. When the concentration of the photocatalyst is less than 0.1% by weight, the amount of the photocatalyst in the obtained coating film is small, and sufficient photocatalytic activity cannot be obtained. On the other hand, if it exceeds 30% by weight, problems such as a decrease in transparency of the resulting coating film occur.
コーティング液において光触媒体 光触媒体は通常、分散粒子径２００ｎｍ以下の２次粒子を形成して安定に分散している。この２次粒子径が小さいほど、分散液の安定性が向上して光触媒粒子の沈降を抑制することができるので好ましく、例えば１５０ｎｍ以下、さらには１００ｎｍ以下が好ましい。 Photocatalyst in the coating liquid The photocatalyst usually forms secondary particles having a dispersed particle diameter of 200 nm or less and is stably dispersed. The smaller the secondary particle diameter, the better the stability of the dispersion and the suppression of the settling of the photocatalyst particles, which is preferable, for example, 150 nm or less, more preferably 100 nm or less.
本発明の光触媒体コーティング液における、光触媒体１００重量部に対する非晶質Ｚｒ−Ｏ粒子の重量比は、酸化物（ＺｒＯ2）換算で１５重量部〜１２０重量部、好ましくは２０重量部〜７０重量部である。１５重量部未満では、密着性のよい強固な塗膜が得られなくなる場合があり、また１２０重量部を超えて含有させると、光触媒体がバインダー成分中に埋没してしまい、十分な光触媒活性の塗膜が得にくくなる。 In the photocatalyst coating liquid of the present invention, the weight ratio of the amorphous Zr-O particles to 100 parts by weight of the photocatalyst is 15 to 120 parts by weight, preferably 20 to 70 parts by weight in terms of oxide (ZrO 2 ). Parts by weight. If the amount is less than 15 parts by weight, a strong coating film having good adhesion may not be obtained. If the amount exceeds 120 parts by weight, the photocatalyst is buried in the binder component, and sufficient photocatalytic activity is obtained. It becomes difficult to obtain a coating film.
本発明の光触媒体コーティング液は溶媒を含み、溶媒としてはカルボン酸（塩）を溶解し、光触媒体及び非晶質Ｚｒ−Ｏ系粒子を安定に分散させるものであれば特に制限は無いが、水、メタノール、エタノール、イソポロパノール、ブタノール、アセトン、メチルエチルケトン、ジエチルエーテル、トルエン、キシレン等が用いられ、これらの中でも特に水、メタノール、エタノール、及びイソプロパノ-ルを用いるのが好ましい。 The photocatalyst coating liquid of the present invention contains a solvent, and the solvent is not particularly limited as long as it dissolves a carboxylic acid (salt) and stably disperses the photocatalyst and amorphous Zr-O-based particles. Water, methanol, ethanol, isopropanol, butanol, acetone, methyl ethyl ketone, diethyl ether, toluene, xylene and the like are used, and among these, water, methanol, ethanol, and isopropanol are particularly preferable.
本発明のコーティング液は、コーティング液から揮発成分を揮発させて得られる固形分の含有量が通常０．５重量％〜３０重量％、好ましくは１重量％〜２０重量％、より好ましくは２重量％〜１０重量％程度となるように水や溶媒で希釈されて用いられる。固形分含有量が０．５重量％未満のでは、十分な厚さの塗膜を形成しにくくなり、また固形分含有量が３０重量％を超えると、得られる塗膜の透明性が損なわれ易くなる。 In the coating liquid of the present invention, the solid content obtained by volatilizing volatile components from the coating liquid is usually 0.5 wt% to 30 wt%, preferably 1 wt% to 20 wt%, more preferably 2 wt%. It is diluted with water or a solvent so as to be about 10% to 10% by weight. If the solid content is less than 0.5% by weight, it will be difficult to form a sufficiently thick coating, and if the solid content exceeds 30% by weight, the transparency of the resulting coating will be impaired. It becomes easy.
本発明の光触媒体コーティング剤は、例えば光触媒体を単独で溶媒に分散させた光触媒体分散液と、カルボン酸（塩）を含む非晶質Ｚｒ−Ｏ系粒子のゾルを混合する方法で製造することができる。 The photocatalyst coating agent of the present invention is produced by, for example, a method of mixing a photocatalyst dispersion liquid obtained by dispersing a photocatalyst alone in a solvent and a sol of amorphous Zr-O-based particles containing a carboxylic acid (salt). be able to.
本発明のコーティング液は、必要に応じて、金属や金属（水）酸化物として光触媒体表面に担持されることにより、電子吸引性を発現する金属化合物を含むことができる。この金属化合物が酸化チタン表面に担持されることにより、光励起により光触媒体中に生じた電子と正孔の電荷分離が促進されて、高い光触媒活性を発現することができる。このような金属化合物として、Ｃｕ、Ｐｔ、Ａｇ、Ｆｅ、Ｎｂ、Ｗ、Ｐｄ、Ｒｕ、Ｒｈ、Ｃｏ等のコロイド粒子、硝酸塩、塩化物、硫酸塩、蓚酸塩等があげられる。 The coating liquid of this invention can contain the metal compound which expresses electron withdrawing property by being carry | supported on the photocatalyst body surface as a metal or a metal (water) oxide as needed. By carrying this metal compound on the surface of titanium oxide, charge separation of electrons and holes generated in the photocatalyst by photoexcitation is promoted, and high photocatalytic activity can be expressed. Examples of such metal compounds include colloidal particles such as Cu, Pt, Ag, Fe, Nb, W, Pd, Ru, Rh, and Co, nitrates, chlorides, sulfates, and oxalates.
本発明のコーティング液には、光触媒以外の無機化合物を添加することができる。無機化合物としては、例えば、シリカゾル、コロイダルシリカなどのようなケイ素(水)酸化物、非晶質アルミナ、アルミナゾルのようなアルミニウム(水)酸化物、ゼオライト、カオリナイトのようなアルミノ珪酸塩、酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウムおよび水酸化バリウムのようなアルカリ土類金属(水)酸化物、リン酸カルシウム、モレキュラーシーブまたは活性炭等があげられ、これらは１種または２種以上組み合わせて用いることができる。 An inorganic compound other than the photocatalyst can be added to the coating liquid of the present invention. Examples of inorganic compounds include silicon (water) oxides such as silica sol and colloidal silica, amorphous alumina, aluminum (water) oxides such as alumina sol, zeolites, aluminosilicates such as kaolinite, and oxidation. Magnesium, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide, alkaline earth metal (water) oxide, calcium phosphate, molecular sieve or activated carbon, etc. These can be used alone or in combination of two or more.
以下、本発明の光触媒機能製品の製造方法について説明する。
本発明の光触媒機能製品の製造方法は、上記のようにして作製された光触媒体コーティング液を基材上に塗布し、溶媒を揮発させることを特徴とする。
Hereafter, the manufacturing method of the photocatalyst functional product of this invention is demonstrated.
The method for producing a photocatalytic functional product of the present invention is characterized in that the photocatalyst coating liquid prepared as described above is applied onto a substrate and the solvent is volatilized.
具体的には、本発明のコーティング液の被膜形成方法としては、床、壁、天井、タイル、硝子、プラスチック、金属、陶磁器およびコンクリートのような基材に、例えばスピンコート、ディップコート、ドクターブレード、スプレーまたはハケ塗りなどにより行い、その後、室温〜２００℃の温度範囲で溶媒を乾燥蒸発させる。その後可視光線を多く含む蛍光灯、ハロゲンランプ、キセノンランプ、発光ダイオード、太陽光線等を照射すればよい。 Specifically, as a method for forming a coating film of the coating liquid of the present invention, a substrate such as a floor, a wall, a ceiling, a tile, glass, plastic, metal, ceramics and concrete, for example, spin coating, dip coating, doctor blade , Spraying or brushing, and then the solvent is dried and evaporated in the temperature range of room temperature to 200 ° C. Thereafter, a fluorescent lamp, a halogen lamp, a xenon lamp, a light emitting diode, sunlight, or the like containing a lot of visible light may be irradiated.
以下、本発明を実施例により詳細に説明するが、本発明は本実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to a present Example.
１．粒子径Ｄ５０（非晶質Ｚｒ−Ｏ系粒子のゾル）
粒度分布測定装置（商品名「ＵＰＡ１５０」、日機装製）を用いて、ゾルの体積換算粒度分布において累積頻度が５０％となる粒子径を測定した。
1. Particle size D50 (Amorphous Zr-O particle sol)
Using a particle size distribution measuring apparatus (trade name “UPA150”, manufactured by Nikkiso Co., Ltd.), the particle diameter at which the cumulative frequency is 50% in the volume conversion particle size distribution of the sol was measured.
２．ゼータ電位（非晶質Ｚｒ−Ｏ系粒子のゾル）
ゼータ電位測定装置（商品名「ＥＬＳ−Ｚ２」、大塚電子製）を用いてゾルのゼータ電位を測定した。
2. Zeta potential (amorphous Zr-O particle sol)
The zeta potential of the sol was measured using a zeta potential measuring device (trade name “ELS-Z2”, manufactured by Otsuka Electronics Co., Ltd.).
３．分散粒子径（光触媒分散液）
サブミクロン粒度分布測定装置（商品名「Ｎ４Ｐｌｕｓ」、コールター製）を用いて、試料の粒度分布を測定し、この装置に付属のソフトで、自動的に単分散モード解析して得られた結果を平均分散粒子径とした。
3. Dispersed particle size (photocatalyst dispersion)
Using a sub-micron particle size distribution analyzer (trade name “N4Plus”, manufactured by Coulter), measure the particle size distribution of the sample, and use the software included with this device to automatically analyze the monodisperse mode. The average dispersed particle size was used.
４．結晶構造
Ｘ線回折装置（商品名「ＲＩＮＴ２０００／ＰＣ」、リガク製）を用いて、酸化チタン分散液を真空乾燥して得られた酸化チタン粉末のＸ線回折スペクトルを測定し、そのスペクトルから主成分の結晶構造を求めた。
4). Using a crystal structure X-ray diffractometer (trade name “RINT2000 / PC”, manufactured by Rigaku), the X-ray diffraction spectrum of the titanium oxide powder obtained by vacuum drying the titanium oxide dispersion was measured. The crystal structure of the component was determined.
５．硬度試験
塗膜の硬度は、鉛筆硬度試験法（ＪＩＳ５６００-５-４）により測定した。
5. Hardness test The hardness of the coating film was measured by a pencil hardness test method (JIS 5600-5-4).
６．耐擦れ性試験
基板との耐擦れ性は、１２枚に重ねたチーズクロス（サマーズ社製）を消しゴム摩擦試験機（三光製作所製）に固定し、試料が塗布されたガラス基板を１０往復して擦った後、塗膜の状態を目視により下記３段階で評価した。
Ａ：塗膜に傷がない
Ｂ：塗膜に傷がついている部分が見られる。
Ｃ：塗膜に剥離が見られる。
6). The rubbing resistance with the rubbing resistance test substrate was fixed to an eraser rubbing tester (manufactured by Sanko Seisakusho) with 12 pieces of cheesecloth (manufactured by Summers), and the glass substrate on which the sample was applied was reciprocated 10 times. After rubbing, the state of the coating film was visually evaluated in the following three stages.
A: There is no scratch on the coating film B: A portion where the coating film is scratched is seen.
C: Peeling is observed in the coating film.
７．透明性評価
塗膜の透明性は、ヘイズ・透過・反射率計（商品名「ＨＲ−１００」、村上色彩技術研究所製）を用いて測定し、下記３段階で評価した。
Ａ：ヘイズ率１．０％未満
Ｂ：ヘイズ率１．０％以上５．０％未満
Ｃ：ヘイズ率５．０％以上
7). Transparency Evaluation The transparency of the coating film was measured using a haze / transmittance / reflectometer (trade name “HR-100”, manufactured by Murakami Color Research Laboratory) and evaluated in the following three stages.
A: Haze ratio less than 1.0% B: Haze ratio 1.0% or more and less than 5.0% C: Haze ratio 5.0% or more
８．付着性評価
付着性試験はＪＩＳ Ｋ５６００に準拠した碁盤目テープ法で行った．切り傷間隔 １ｍｍ、升目数２５で行った。
8). Adhesion evaluation The adhesion test was performed by a cross-cut tape method in accordance with JIS K5600. The cut interval was 1 mm and the number of cells was 25.
９．光触媒活性評価用塗布膜の作製
外径７０ｍｍ、内径６６ｍｍ、高さ１４ｍｍ、容量約４８ｍＬのガラス製シャーレ容器内に、固形分で１ｇ／ｍ２となるように光触媒コーティング液を滴下し、シャーレ全体に均一となるように展開した。これを１１０℃の乾燥機で１時間乾燥させ、光触媒塗布膜を作製した。その後ブラックライト（紫外線強度２ｍＷ/ｃｍ２，トプコン製紫外線強度計ＵＶＲ−２及び受光部ＵＤ−３６で測定）を１６時間照射して、光触媒塗膜を初期化した。
9. Preparation of Coating Film for Photocatalytic Activity Evaluation A photocatalyst coating solution is dropped into a glass petri dish having an outer diameter of 70 mm, an inner diameter of 66 mm, a height of 14 mm, and a capacity of about 48 mL so that the solid content is 1 g / m 2. Deployed to be uniform. This was dried with a dryer at 110 ° C. for 1 hour to produce a photocatalyst coating film. Thereafter, black light (UV intensity 2 mW / cm2, measured with a UV intensity meter UVR-2 manufactured by Topcon and a light receiving part UD-36) was irradiated for 16 hours to initialize the photocatalyst coating film.
１０．光触媒活性：アセトアルデヒド分解能
１Ｌガスバッグに測定サンプルを入れて密閉し、ガスバッグ内を真空にした後、酸素と窒素との体積比が１：４である混合ガスを６００ｍｌ封入した。さらに１％アセトアルデヒドを含む窒素ガス３ ｍｌ封入し暗所で１時間安定化させた後、試料表面の照度が１０００ルクス（ミノルタ製照度計Ｔ−１０で測定）になるようにシャーレを設置し、アセトアルデヒドの分解反応を行った。試料表面付近の紫外光の強度は６．５μＷ／ｃｍ２（トプコン製紫外線強度計ＵＶＲ−２及び受光部ＵＤ−３６で測定）であった。光源には、市販の白色蛍光灯を用いた。蛍光灯照射後よりガスバッグ内のガスを１．５時間毎にサンプリングして、アセトアルデヒドの残存濃度をガスクロマトグラフ（商品名「ＧＣ−１４Ａ」、島津製作所製）にて測定した。
照射時間に対するアセトアルデヒドの濃度減少を対数軸にプロットし、得られた直線の傾きから一次反応速度定数を算出し、これをアセトアルデヒド分解能とした。一次反応速度定数が大きいほど、アセトアルデヒドの分解能は大きい。
10. Photocatalytic activity: Acetaldehyde-decomposable 1 L gas sample was sealed with a measurement sample, the gas bag was evacuated, and 600 ml of a mixed gas having a volume ratio of oxygen to nitrogen of 1: 4 was sealed. Furthermore, after 3 ml of nitrogen gas containing 1% acetaldehyde was sealed and stabilized in the dark for 1 hour, a petri dish was installed so that the illuminance of the sample surface was 1000 lux (measured with Minolta illuminometer T-10). Acetaldehyde was decomposed. The intensity of the ultraviolet light in the vicinity of the sample surface was 6.5 μW / cm 2 (measured with a UV intensity meter UVR-2 and a light receiving part UD-36 manufactured by Topcon). A commercially available white fluorescent lamp was used as the light source. The gas in the gas bag was sampled every 1.5 hours after the fluorescent lamp irradiation, and the residual concentration of acetaldehyde was measured with a gas chromatograph (trade name “GC-14A”, manufactured by Shimadzu Corporation).
The concentration reduction of acetaldehyde with respect to the irradiation time was plotted on the logarithmic axis, and the first-order rate constant was calculated from the slope of the obtained straight line, which was defined as acetaldehyde resolution. The higher the first order rate constant, the greater the resolution of acetaldehyde.
実施例１
〔光触媒分散液〕
光触媒体分散液には、酸化チタン光触媒ゾル（ＰＣ−２０１、チタン工業製）を用いた。分散粒径は５５ｎｍで、ＴｉＯ2濃度は２０重量％、結晶型はアナターゼであった。
Example 1
[Photocatalyst dispersion]
Titanium oxide photocatalyst sol (PC-201, manufactured by Titanium Industry) was used for the photocatalyst dispersion. The dispersed particle size was 55 nm, the TiO 2 concentration was 20% by weight, and the crystal type was anatase.
〔ギ酸を含む非晶質Ｚｒ−Ｏ系粒子を分散質とするゾル〕
水酸化ジルコニウム（ＺｒＯ2換算で３０重量％含有）３００ｇを純水１０７０ｇに分散し、適度に攪拌しながらそこへ６７．５重量％硝酸１２６ｇを添加し反応分散液を調製した。このとき反応分散液のジルコニウム濃度はＺｒＯ2換算で６重量％であり、１モルのＺｒに対する硝酸（ＨＮＯ3）のグラム当量数は１．８５であった。
[Sol with amorphous Zr-O-based particles containing formic acid as dispersoid]
300 g of zirconium hydroxide (containing 30% by weight in terms of ZrO 2 ) was dispersed in 1070 g of pure water, and 126 g of 67.5% by weight nitric acid was added thereto with proper stirring to prepare a reaction dispersion. At this time, the zirconium concentration of the reaction dispersion was 6% by weight in terms of ZrO 2 , and the number of gram equivalents of nitric acid (HNO 3 ) with respect to 1 mol of Zr was 1.85.
次に、該分散液を９５℃まで加熱し、２４時間保持した後静置し自然冷却し非晶質のゾルを得た。該ゾルはジルコニウム濃度がＺｒＯ2換算で６重量％であり、ｐＨは０．７であった。 Next, the dispersion was heated to 95 ° C., held for 24 hours, allowed to stand, and then naturally cooled to obtain an amorphous sol. The sol had a zirconium concentration of 6% by weight in terms of ZrO 2 and a pH of 0.7.
さらに、該ゾルの限外ろ過処理によって該ゾル中の硝酸を除去し、ジルコニウム濃度を濃縮することで、ジルコニウム濃度がＺｒＯ2換算で１０重量％であり、ｐＨが３．２、ケルダール法によって測定された１モルのＺｒに対する硝酸（ＨＮＯ3）のグラム当量数が０．４である以外は上記と同様のゾルを得た。 Furthermore, by removing nitric acid in the sol by ultrafiltration treatment of the sol and concentrating the zirconium concentration, the zirconium concentration is 10% by weight in terms of ZrO 2 , pH is 3.2, measured by Kjeldahl method A sol similar to the above was obtained except that the number of gram equivalents of nitric acid (HNO 3 ) with respect to 1 mol of Zr was 0.4.
得られた非晶質のゾル１０００ｇに対して、１０００ｇの１重量％ギ酸水溶液を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を５回繰り返した後、純水１０００ｇを添加し、限外ろ過処理によって溶媒を取り除く操作を行い、ジルコニウム濃度がＺｒＯ２換算で１０重量％であり、ｐＨが３．２のゾル、すなわちギ酸を含む非晶質Ｚｒ−Ｏ系粒のゾルを得た。 After 1000 g of 1 wt% formic acid aqueous solution was added to 1000 g of the obtained amorphous sol and 1000 g of solvent was removed by ultrafiltration treatment, 1000 g of pure water was added. The solvent was removed by an external filtration treatment to obtain a sol having a zirconium concentration of 10% by weight in terms of ZrO2 and a pH of 3.2, that is, an amorphous Zr-O-based particle sol containing formic acid.
酸塩基滴定で求めた、該ゾル中のＺｒに対する酸のモル比は、０．４であった。また、ケルダール法によって測定された硝酸／Ｚｒのモル比は０．２であった。上記Ｚｒに対する酸のモル比および硝酸／Ｚｒのモル比から計算されたギ酸／Ｚｒのモル比は０．２であり、硝酸／ギ酸のモル比は１であった。 The molar ratio of acid to Zr in the sol determined by acid-base titration was 0.4. The molar ratio of nitric acid / Zr measured by the Kjeldahl method was 0.2. The molar ratio of formic acid / Zr calculated from the molar ratio of acid to Zr and the molar ratio of nitric acid / Zr was 0.2, and the molar ratio of nitric acid / formic acid was 1.
上記のゾルの粒度分布測定より、ゾルの粒子径Ｄ５０は１５ｎｍであった。また、このゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは特定の結晶系に帰属されなかった。また、このゾルのゼータ電位は４２ｍＶであった。 From the measurement of the particle size distribution of the sol, the particle size D50 of the sol was 15 nm. Moreover, the X-ray diffraction pattern of this sol dried at 100 ° C. to a constant weight was not assigned to a specific crystal system. The sol had a zeta potential of 42 mV.
〔光触媒体コーティング液〕
上記の酸化チタン分散液５．０ｇに純水１７．６ｇ、およびギ酸を含む非晶質Ｚｒ−Ｏ系粒子のゾル（ＺｒＯ2換算濃度１０．４重量％）２．４ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、非晶質Ｚｒ−Ｏ系粒子のＺｒＯ2換算の重量は０．２５ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して２５重量部で混合したことになる。
[Photocatalyst coating liquid]
A photocatalyst is prepared by adding 17.6 g of pure water and 2.4 g of a sol of amorphous Zr—O-based particles containing formic acid (concentration of ZrO 2 of 10.4% by weight) to 5.0 g of the above titanium oxide dispersion. A coating solution was prepared. The amount of titanium oxide in the titanium oxide dispersion was 1.0 g, and the weight of amorphous Zr—O-based particles in terms of ZrO 2 was 0.25 g. From this, the upper component in the binder was mixed in an amount of 25 parts by weight with respect to 100 parts by weight of titanium oxide in terms of oxide.
〔バインダー含有光触媒体塗膜の形成〕
上記で得た光触媒体コーティング液を、縦８０ｍｍ、横８０ｍｍ、厚さ３ｍｍの十分に脱脂した硝子板に塗布した後、スピンコーター（商品名「１Ｈ−Ｄ７」、ミカサ製）を用いて、４５０ｒｐｍで１８０秒間回転させて、過剰のコーティング液を取り除き、室温で乾燥させた後、この硝子板を １１０℃で1時間乾燥して、硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。
[Formation of binder-containing photocatalyst coating film]
The photocatalyst coating liquid obtained above was applied to a fully degreased glass plate having a length of 80 mm, a width of 80 mm, and a thickness of 3 mm, and then 450 rpm using a spin coater (trade name “1H-D7”, manufactured by Mikasa). The glass plate was dried at room temperature and then dried at 110 ° C. for 1 hour to form a binder-containing photocatalyst film on the entire surface of the glass plate. The physical properties of the coating film are shown in Table 1.
実施例２
実施例１と同様の酸化チタン分散液５．０ｇに純水１５．９ ｇ、およびギ酸を含む非晶質Ｚｒ−Ｏ系粒子のゾル（ＺｒＯ2換算濃度１０．４重量％）４．１ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、非晶質Ｚｒ−Ｏ系粒子のＺｒＯ2換算の重量は０．４３ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して４３重量部で混合したことになる。
Example 2
In addition to 5.0 g of the same titanium oxide dispersion as in Example 1, 15.9 g of pure water and 4.1 g of a sol of amorphous Zr—O-based particles containing formic acid (ZrO 2 equivalent concentration 10.4 wt%) were added. This was added to prepare a photocatalyst coating liquid. The amount of titanium oxide in the titanium oxide dispersion was 1.0 g, and the weight of amorphous Zr—O-based particles in terms of ZrO 2 was 0.43 g. From this, the upper component in the binder was mixed in 43 parts by weight with respect to 100 parts by weight of titanium oxide in terms of oxide.
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
実施例３
実施例１と同様の酸化チタン分散液５．０ｇに純水１０．４ ｇ、およびギ酸を含む非晶質Ｚｒ−Ｏ系粒子のゾル（ＺｒＯ2換算濃度１０．４重量％）９．６ ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、非晶質Ｚｒ−Ｏ系粒子のＺｒＯ2換算の重量は１．０ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して１００重量部で混合したことになる。
Example 3
A sol of amorphous Zr—O-based particles containing 10.4 g of pure water and 5.0 g of pure water in the same titanium oxide dispersion as in Example 1 (ZrO 2 equivalent concentration 10.4 wt%) 9.6 g Was added to prepare a photocatalyst coating liquid. The amount of titanium oxide in the titanium oxide dispersion was 1.0 g, and the weight of amorphous Zr—O-based particles in terms of ZrO 2 was 1.0 g. From this, the upper component in the binder is 100 parts by weight with respect to 100 parts by weight of titanium oxide in terms of oxide.
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
実施例４
実施例１で得られた非晶質のゾル１０００ｇに対して、１．５重量％酢酸水溶液１０００ｇを添加した以外は上記実施例１と同様にしてジルコニウム濃度がＺｒＯ2換算で９重量％、ｐＨ３．６のゾルを得た。
Example 4
The zirconium concentration was 9 wt% in terms of ZrO 2 ,
酸塩基滴定で求めた、該ゾル中のＺｒに対する酸のモル比は、０．５であった。また、ケルダール法によって測定された硝酸／Ｚｒのモル比は０．３であった。上記Ｚｒに対する酸のモル比および硝酸／Ｚｒのモル比から計算された酢酸／Ｚｒのモル比は０．２であり、硝酸／酢酸のモル比は１．５であった。 The molar ratio of acid to Zr in the sol determined by acid-base titration was 0.5. The molar ratio of nitric acid / Zr measured by the Kjeldahl method was 0.3. The molar ratio of acetic acid / Zr calculated from the molar ratio of acid to Zr and the molar ratio of nitric acid / Zr was 0.2, and the molar ratio of nitric acid / acetic acid was 1.5.
該ゾルの粒子径分布は、実施例1とほぼ同じで、粒子径Ｄ５０は１２ｎｍであり、また、該ゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは、実施例1とほぼ同様であり、特定の結晶系に帰属されなかった。また、該ゾルのゼータ電位は４５ｍＶであった。 The particle size distribution of the sol is almost the same as in Example 1, the particle size D50 is 12 nm, and the X-ray diffraction pattern of the sol dried to a constant weight at 100 ° C. is almost the same as in Example 1. Yes, it was not assigned to a specific crystal system. The sol had a zeta potential of 45 mV.
実施例５
実施例１で得られた非晶質のゾル１０００ｇに対して、６４ｇの無水クエン酸を添加し、次に、１２０ｇの２５重量％アンモニア水を添加し、ジルコニウム濃度がＺｒＯ2換算で６重量％、ｐＨ９．５のゾルを得た。
Example 5
To 1000 g of the amorphous sol obtained in Example 1, 64 g of anhydrous citric acid was added, and then 120 g of 25 wt% aqueous ammonia was added. The zirconium concentration was 6 wt% in terms of ZrO 2. A sol having a pH of 9.5 was obtained.
該ゾル中のクエン酸／Ｚｒのモル比は０．４、硝酸／Ｚｒのモル比は０．４、および硝酸／クエン酸のモル比は１であった。 The molar ratio of citric acid / Zr in the sol was 0.4, the molar ratio of nitric acid / Zr was 0.4, and the molar ratio of nitric acid / citric acid was 1.
該ゾルの粒子系分布は、実施例1とほぼ同じで、粒子径Ｄ５０は１２ｎｍであり、また、該ゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは、実施例1とほぼ同様であり、特定の結晶系に帰属されなかった。また、該ゾルのゼータ電位は−４５ｍＶであった。 The particle system distribution of the sol is almost the same as in Example 1, the particle diameter D50 is 12 nm, and the X-ray diffraction pattern of the sol dried to a constant weight at 100 ° C. is almost the same as in Example 1. Yes, it was not assigned to a specific crystal system. Further, the zeta potential of the sol was −45 mV.
実施例６
実施例５で得られたゾルに１０００ｇの純水を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を５回繰り返した後、１０００ｇの１.５重量％ギ酸アンモニウム水溶液を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を５回繰り返し、次に、１０００ｇの純水を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を２回繰り返してジルコニウム濃度がＺｒＯ2換算で７重量％、ｐＨ７．７のゾルを得た。
Example 6
The operation of adding 1000 g of pure water to the sol obtained in Example 5 and removing 1000 g of the solvent by ultrafiltration was repeated 5 times, and then 1000 g of a 1.5 wt% ammonium formate aqueous solution was added. The operation of removing 1000 g of the solvent by the external filtration treatment was repeated 5 times, and then the operation of adding 1000 g of pure water and removing the 1000 g of the solvent by the ultrafiltration treatment was repeated twice to obtain a zirconium concentration of 7 in terms of ZrO 2. A sol having a weight% of pH 7.7 was obtained.
該ゾル中のギ酸／Ｚｒモル比は０．２、クエン酸／Ｚｒモル比は０．１５およびクエン酸／酢酸のモル比は０．７５であった。 The formic acid / Zr molar ratio in the sol was 0.2, the citric acid / Zr molar ratio was 0.15, and the citric acid / acetic acid molar ratio was 0.75.
該ゾルの粒子系分布は、実施例1とほぼ同じで、粒子径Ｄ５０は１２ｎｍであり、また、該ゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは、実施例1とほぼ同様であり、特定の結晶系に帰属されなかった。また、該ゾルのゼータ電位は−４３ｍＶであった。 The particle system distribution of the sol is almost the same as in Example 1, the particle diameter D50 is 12 nm, and the X-ray diffraction pattern of the sol dried to a constant weight at 100 ° C. is almost the same as in Example 1. Yes, it was not assigned to a specific crystal system. Further, the zeta potential of the sol was −43 mV.
実施例７
実施例５で得られたゾルに１０００ｇの純水を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を５回繰り返した後、１０００ｇの２重量％酢酸アンモニウム水溶液を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を５回繰り返し、次に、１０００ｇの純水を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除きジルコニウム濃度がＺｒＯ2換算で６．５重量％、ｐＨ６．５のゾルを得た。
Example 7
The operation of adding 1000 g of pure water to the sol obtained in Example 5 and removing 1000 g of solvent by ultrafiltration was repeated 5 times, and then 1000 g of 2 wt% aqueous ammonium acetate solution was added, followed by ultrafiltration. The operation of removing 1000 g of the solvent by the treatment was repeated 5 times, then 1000 g of pure water was added, 1000 g of the solvent was removed by the ultrafiltration treatment, and the zirconium concentration was 6.5 wt% in terms of ZrO 2 , pH 6.5. The sol was obtained.
該ゾル中の酢酸／Ｚｒのモル比は０．３、クエン酸／Ｚｒのモル比は０．１およびクエン酸／酢酸のモル比は０．２５であった。 The acetic acid / Zr molar ratio in the sol was 0.3, the citric acid / Zr molar ratio was 0.1, and the citric acid / acetic acid molar ratio was 0.25.
該ゾルの粒子系分布は、実施例1とほぼ同じで、粒子径Ｄ５０は１２ｎｍであり、また、該ゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは、実施例1とほぼ同様であり、特定の結晶系に帰属されなかった。また、該ゾルのゼータ電位は−４８ｍＶであった。 The particle system distribution of the sol is almost the same as in Example 1, the particle diameter D50 is 12 nm, and the X-ray diffraction pattern of the sol dried to a constant weight at 100 ° C. is almost the same as in Example 1. Yes, it was not assigned to a specific crystal system. The sol had a zeta potential of −48 mV.
実施例８
実施例５で得られたゾルに１０００ｇの純水を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を５回繰り返した後、１０００ｇの１重量％蓚酸アンモニウム水溶液を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を５回繰り返し、次に、１０００ｇの純水を添加し、限外ろ過処理によって１０００ｇの溶媒を取り除く操作を２回繰り返してジルコニウム濃度がＺｒＯ2換算で６重量％、ｐＨ７．９のゾルを得た。
Example 8
The operation of adding 1000 g of pure water to the sol obtained in Example 5 and removing 1000 g of the solvent by ultrafiltration was repeated 5 times, and then 1000 g of 1 wt% ammonium oxalate aqueous solution was added, followed by ultrafiltration. The operation of removing 1000 g of the solvent by the treatment was repeated 5 times, and then the operation of adding 1000 g of pure water and removing the 1000 g of the solvent by the ultrafiltration treatment was repeated twice to obtain a zirconium concentration of 6% by weight in terms of ZrO 2. A sol having a pH of 7.9 was obtained.
該ゾル中の蓚酸／Ｚｒモル比が０．２、クエン酸／Ｚｒモル比が０．２およびクエン酸／蓚酸のモル比は１であった。 The oxalic acid / Zr molar ratio in the sol was 0.2, the citric acid / Zr molar ratio was 0.2, and the citric acid / succinic acid molar ratio was 1.
該ゾルの粒子系分布は、実施例1とほぼ同じで、粒子径Ｄ５０は１２ｎｍであり、また、該ゾルを１００℃で恒量まで乾燥したもののＸ線回折パターンは、実施例1とほぼ同様であり、特定の結晶系に帰属されなかった。また、該ゾルのゼータ電位は−４５ｍＶであった。 The particle system distribution of the sol is almost the same as in Example 1, the particle diameter D50 is 12 nm, and the X-ray diffraction pattern of the sol dried to a constant weight at 100 ° C. is almost the same as in Example 1. Yes, it was not assigned to a specific crystal system. Further, the zeta potential of the sol was −45 mV.
比較例１
実施例１で用いた酸化チタン分散液５ｇに純水１８．８ｇ、および炭酸ジルコニウムアンモニウム水溶液（ＺｒＯ2換算濃度２０重量％）１．３ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、ジルコニウム化合物のＺｒＯ2換算の重量は０．２５ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して２５重量部で混合したことになる。
Comparative Example 1
A photocatalyst coating liquid was prepared by adding 18.8 g of pure water and 1.3 g of zirconium ammonium carbonate aqueous solution (
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
比較例２
実施例１で用いた酸化チタン分散液５ｇに純水１８．３ｇ、および酢酸ジルコニウム水溶液（ＺｒＯ2換算濃度１５重量％）１．７ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、ジルコニウム化合物のＺｒＯ2換算の重量は０．２５ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して２５重量部で混合したことになる。
Comparative Example 2
A photocatalyst coating liquid was prepared by adding 18.3 g of pure water and 1.7 g of a zirconium acetate aqueous solution (ZrO 2 equivalent concentration: 15 wt%) to 5 g of the titanium oxide dispersion used in Example 1. The amount of titanium oxide in the titanium oxide dispersion was 1.0 g, and the weight of the zirconium compound in terms of ZrO 2 was 0.25 g. From this, the upper component in the binder was mixed in an amount of 25 parts by weight with respect to 100 parts by weight of titanium oxide in terms of oxide.
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
比較例３
実施例１で用いた酸化チタン分散液５ｇに純水１４ｇ、およびプロピオン酸ジルコニウム・エタノール溶液（ＺｒＯ2換算濃度２０重量％）１．３ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、ジルコニウム化合物のＺｒＯ2換算の重量は０．２５ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して２５重量部で混合したことになる。
Comparative Example 3
A photocatalyst coating liquid was prepared by adding 14 g of pure water and 1.3 g of zirconium propionate / ethanol solution (ZrO 2
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
比較例４
実施例１と同様の酸化チタン分散液５．０ｇに純水１５．６ｇ、およびカルボン酸またはその塩を含まず、硝酸を含む非晶質Ｚｒ−Ｏ系粒子の分散液（ＺｒＯ2換算濃度１０重量％，商品名ＺＳＬ−１０Ｔ，第一稀元素化学工業（株）製）４．３ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、非晶質Ｚｒ−Ｏ系粒子のＺｒＯ2換算の重量は０．４３ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して４３重量部で混合したことになる。
Comparative Example 4
A dispersion of amorphous Zr—O-based particles containing 15.6 g of pure water and carboxylic acid or a salt thereof and containing nitric acid (ZrO 2 equivalent concentration 10) A photocatalyst coating liquid was prepared by adding 4.3 g by weight%, trade name ZSL-10T, manufactured by Daiichi Rare Element Chemical Co., Ltd. The amount of titanium oxide in the titanium oxide dispersion was 1.0 g, and the weight of amorphous Zr—O-based particles in terms of ZrO 2 was 0.43 g. From this, the upper component in the binder was mixed in 43 parts by weight with respect to 100 parts by weight of titanium oxide in terms of oxide.
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
比較例５
実施例１と同様の酸化チタン分散液５．０ｇに純水１０．０ ｇ、およびカルボン酸またはその塩を含まず、硝酸を含む非晶質Ｚｒ−Ｏ系粒子の分散液（ＺｒＯ2換算濃度１０重量％，商品名ＺＳＬ−１０Ｔ，第一稀元素化学工業（株）製）１０．０ｇを添加して光触媒体コーティング液を調製した。酸化チタン分散液の酸化チタン量は１．０ｇで、非晶質Ｚｒ−Ｏ系粒子のＺｒＯ2換算の重量は１．０ｇであった。ここからバインダー中の上の成分は酸化物換算で、酸化チタン１００重量部に対して１００重量部で混合したことになる。
Comparative Example 5
A dispersion of amorphous Zr—O-based particles containing no nitric acid and 10.0 g of pure water and 5.0 g of pure water in the same titanium oxide dispersion as in Example 1 (concentrated in terms of ZrO 2) A photocatalyst coating liquid was prepared by adding 10.0 g of 10 wt%, trade name ZSL-10T, manufactured by Daiichi Rare Element Chemical Co., Ltd.). The amount of titanium oxide in the titanium oxide dispersion was 1.0 g, and the weight of amorphous Zr—O-based particles in terms of ZrO 2 was 1.0 g. From this, the upper component in the binder is 100 parts by weight with respect to 100 parts by weight of titanium oxide in terms of oxide.
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
比較例６
実施例１の酸化チタン分散液５．０ｇに純水２０．０ ｇを添加し、バインダーを含まない酸化チタン分散液を調製した。この液を用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。
Comparative Example 6
20.0 g of pure water was added to 5.0 g of the titanium oxide dispersion of Example 1 to prepare a titanium oxide dispersion containing no binder. Using this solution, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
この光触媒体コーティグを用いて、実施例１と同様にして硝子板の片面全体にバインダー含有光触媒体塗膜を形成した。塗膜の物性を表１に示した。 Using this photocatalyst coating, a binder-containing photocatalyst coating film was formed on the entire surface of the glass plate in the same manner as in Example 1. The physical properties of the coating film are shown in Table 1.
次に、表１の塗膜物性総合判定で○若しくは△であった、実施例１〜３、比較例２、比較例５の光触媒コーティング液の光触媒性能を評価した。また比較例６の酸化チタン分散液の光触媒性能も評価した。結果を表２に示した。 Next, the photocatalytic performance of the photocatalyst coating liquids of Examples 1 to 3, Comparative Example 2, and Comparative Example 5, which were evaluated as “◯” or “Δ” in the comprehensive physical property determination of Table 1, was evaluated. The photocatalytic performance of the titanium oxide dispersion of Comparative Example 6 was also evaluated. The results are shown in Table 2.
表１と２を比較すると、本発明のギ酸で安定化した非晶質Ｚｒ−Ｏ系粒子分散液をバインダーとする光触媒コーティング液（実施例１〜３）は、良好な塗膜物性を示し、しかもバインダーを含んでいるにも関わらず、バインダーを含まない酸化チタン分散液（比較例６）よりも高い光触媒活性を示した。 Comparing Tables 1 and 2, the photocatalyst coating liquids (Examples 1 to 3) using the amorphous Zr-O-based particle dispersion stabilized with formic acid according to the present invention as binders exhibit good coating properties, And although it contained the binder, the photocatalytic activity higher than the titanium oxide dispersion (Comparative Example 6) which does not contain a binder was shown.
本発明の光触媒コーティング液によれば、硝子、プラスチック、金属、陶磁器、コンクリートのような基材に、透明性と密着性に優れ、高い光触媒活性を示す膜を形成することができる。 According to the photocatalyst coating liquid of the present invention, a film having excellent transparency and adhesion and high photocatalytic activity can be formed on a substrate such as glass, plastic, metal, ceramics, and concrete.
Claims (10)
３≦Ｘ≦２０ （Ａ）
および式（Ｂ）
（２．０−０．０７Ｘ）≦Ｙ≦（３．０−０．０８Ｘ） （Ｂ）
を満足する反応分散液を調製し、ついで該反応液を８０℃以上で加熱して得られたゾルであることを特徴とする請求項５に記載の非晶質のＺｒ−Ｏ系粒子を分散質とするゾルの製造方法 A sol containing an inorganic acid in a dispersion medium and containing amorphous Zr—O-based particles as a dispersoid is composed of zirconium hydroxide, an inorganic acid and a solvent, and the zirconium concentration in terms of ZrO 2 is X wt%, 1 mol. When Y is the gram equivalent number Y of the inorganic acid relative to Zr, X and Y are represented by the following formula (A):
3 ≦ X ≦ 20 (A)
And formula (B)
(2.0−0.07X) ≦ Y ≦ (3.0−0.08X) (B)
The dispersion of amorphous Zr-O particles according to claim 5 is a sol obtained by preparing a reaction dispersion satisfying the following conditions, and then heating the reaction liquid at 80 ° C or higher. Sol production method
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| EP3266838A4 (en) * | 2015-02-26 | 2018-01-10 | LG Hausys, Ltd. | Composition for coating visible light active photocatalyst and filter for air purification |
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| JP5313051B2 (en) * | 2008-06-09 | 2013-10-09 | 住友化学株式会社 | Zirconium oxalate sol |
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| JPS632809A (en) * | 1986-06-19 | 1988-01-07 | Nippon Shokubai Kagaku Kogyo Co Ltd | Production of high-purity zirconia sol |
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| JP2560490B2 (en) * | 1988-09-30 | 1996-12-04 | 日産化学工業株式会社 | Method for producing zirconia sol |
| JPH06166519A (en) * | 1992-11-27 | 1994-06-14 | Mitsubishi Materials Corp | Production of zirconia sol |
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| JP2003093890A (en) * | 2001-09-25 | 2003-04-02 | Mitsubishi Heavy Ind Ltd | Method for preparing photocatalyst |
| JP2003212546A (en) * | 2002-01-28 | 2003-07-30 | Hosokawa Micron Corp | Zirconia fine powder and manufacturing method therefor |
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| EP1794087A1 (en) * | 2004-09-01 | 2007-06-13 | Advanced Nanotechnology Limited | A zirconia ceramic |
| JP4963820B2 (en) * | 2005-09-02 | 2012-06-27 | 第一稀元素化学工業株式会社 | Method for producing sol using Zr-O-based particles as dispersoid |
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| EP3266838A4 (en) * | 2015-02-26 | 2018-01-10 | LG Hausys, Ltd. | Composition for coating visible light active photocatalyst and filter for air purification |
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