JP5145021B2 - Photocatalyst-containing coating composition - Google Patents
Photocatalyst-containing coating composition Download PDFInfo
- Publication number
- JP5145021B2 JP5145021B2 JP2007326453A JP2007326453A JP5145021B2 JP 5145021 B2 JP5145021 B2 JP 5145021B2 JP 2007326453 A JP2007326453 A JP 2007326453A JP 2007326453 A JP2007326453 A JP 2007326453A JP 5145021 B2 JP5145021 B2 JP 5145021B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- photocatalyst
- titanium
- metal
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011941 photocatalyst Substances 0.000 title claims description 100
- 239000008199 coating composition Substances 0.000 title claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000010936 titanium Substances 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052719 titanium Inorganic materials 0.000 claims description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 24
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 23
- 239000013522 chelant Substances 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 21
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 125000003700 epoxy group Chemical group 0.000 claims description 12
- 238000009833 condensation Methods 0.000 claims description 11
- 230000005494 condensation Effects 0.000 claims description 11
- 239000003446 ligand Substances 0.000 claims description 11
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 4
- -1 polypropylene Polymers 0.000 description 128
- 229910052751 metal Inorganic materials 0.000 description 54
- 239000002184 metal Substances 0.000 description 54
- 150000004703 alkoxides Chemical class 0.000 description 29
- 229910044991 metal oxide Inorganic materials 0.000 description 27
- 150000004706 metal oxides Chemical class 0.000 description 27
- 239000010410 layer Substances 0.000 description 24
- 229920005989 resin Polymers 0.000 description 20
- 239000011347 resin Substances 0.000 description 20
- 238000000034 method Methods 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 229910000000 metal hydroxide Inorganic materials 0.000 description 15
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000011521 glass Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 239000002245 particle Substances 0.000 description 13
- 230000001699 photocatalysis Effects 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 125000003545 alkoxy group Chemical group 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 239000011135 tin Substances 0.000 description 9
- 238000002834 transmittance Methods 0.000 description 9
- 239000012790 adhesive layer Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 230000003373 anti-fouling effect Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000004744 fabric Substances 0.000 description 8
- 239000000945 filler Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 8
- 238000006460 hydrolysis reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 8
- 150000004692 metal hydroxides Chemical class 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002023 wood Substances 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 125000004423 acyloxy group Chemical group 0.000 description 7
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 150000002739 metals Chemical class 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 7
- 239000000523 sample Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000001877 deodorizing effect Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000005871 repellent Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011133 lead Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 230000002940 repellent Effects 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 229910052725 zinc Inorganic materials 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 125000000623 heterocyclic group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 230000001771 impaired effect Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920001778 nylon Polymers 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002985 plastic film Substances 0.000 description 3
- 229920006255 plastic film Polymers 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 235000010215 titanium dioxide Nutrition 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- DRGAZIDRYFYHIJ-UHFFFAOYSA-N 2,2':6',2''-terpyridine Chemical class N1=CC=CC=C1C1=CC=CC(C=2N=CC=CC=2)=N1 DRGAZIDRYFYHIJ-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 125000005018 aryl alkenyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000004350 aryl cycloalkyl group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 description 2
- PIJPYDMVFNTHIP-UHFFFAOYSA-L lead sulfate Chemical compound [PbH4+2].[O-]S([O-])(=O)=O PIJPYDMVFNTHIP-UHFFFAOYSA-L 0.000 description 2
- 239000002649 leather substitute Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 2
- 125000004527 pyrimidin-4-yl group Chemical group N1=CN=C(C=C1)* 0.000 description 2
- 125000004528 pyrimidin-5-yl group Chemical group N1=CN=CC(=C1)* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- 229910052711 selenium Inorganic materials 0.000 description 2
- 239000011669 selenium Substances 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
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- 125000004159 quinolin-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C([H])C(*)=NC2=C1[H] 0.000 description 1
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- NVKTUNLPFJHLCG-UHFFFAOYSA-N strontium chromate Chemical compound [Sr+2].[O-][Cr]([O-])(=O)=O NVKTUNLPFJHLCG-UHFFFAOYSA-N 0.000 description 1
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- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- RSPCKAHMRANGJZ-UHFFFAOYSA-N thiohydroxylamine Chemical class SN RSPCKAHMRANGJZ-UHFFFAOYSA-N 0.000 description 1
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- 150000003609 titanium compounds Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- ISCVFOODKHAEBC-UHFFFAOYSA-N trichloro(oxiran-2-ylmethyl)silane Chemical compound Cl[Si](Cl)(Cl)CC1CO1 ISCVFOODKHAEBC-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- SEAZOECJMOZWTD-UHFFFAOYSA-N trimethoxy(oxiran-2-ylmethyl)silane Chemical compound CO[Si](OC)(OC)CC1CO1 SEAZOECJMOZWTD-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
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Landscapes
- Paints Or Removers (AREA)
Description
本発明は、光触媒含有コーティング用組成物、特に、密着性が良く、接着層を必要としない光触媒含有コーティング用組成物に関する。 The present invention relates to a photocatalyst-containing coating composition, and particularly to a photocatalyst-containing coating composition that has good adhesion and does not require an adhesive layer.
紫外線のエネルギーによって、水の分解、脱臭、殺菌、水の浄化、排水処理等の各種の化学反応を進行させる光触媒として、n型半導体の酸化チタンが知られている。光触媒を粉末状もしくは溶液に懸濁させた形で使用した方が一般的に触媒活性が高いと言われているものの、実用的には何らかの担体上に担持した形で使用せざるを得ない場合が多い。 An n-type semiconductor titanium oxide is known as a photocatalyst that causes various chemical reactions such as water decomposition, deodorization, sterilization, water purification, and wastewater treatment to proceed by ultraviolet energy. Although it is generally said that the photocatalyst is used in the form of powder or suspended in a solution, its catalytic activity is generally higher, but in practice it must be used in the form of being supported on some support. There are many.
光触媒を担持する担体材質は種々提案されており、例えば、(A)ニトロセルロース、ガラス、ポリ塩化ビニル、プラスチック、ナイロン、メタクリル樹脂、ポリプロピレン等光透過性物質、(B)ポリプロピレン繊維、セラミック、(C)ガラス、セラミック、ナイロン、アクリル、ポリエステル等がある。
しかし、これらの材質の中で有機物を主体とするものは、光触媒を担持するとその触媒作用により有機物が分解されたり劣化したりすることが報告されており、耐久性に問題があった。
Various support materials for supporting a photocatalyst have been proposed. For example, (A) nitrocellulose, glass, polyvinyl chloride, plastic, nylon, methacrylic resin, polypropylene and other light transmitting materials, (B) polypropylene fiber, ceramic, ( C) Glass, ceramic, nylon, acrylic, polyester, etc.
However, among these materials, those mainly composed of organic substances have been reported to be decomposed or deteriorated due to their catalytic action when carrying a photocatalyst, which has a problem in durability.
また、担体材料がガラスやセラミック等の無機物の場合であっても、光触媒を担持するために有機高分子樹脂を接着剤に用いると光触媒粒子表面が樹脂により被覆されるために触媒活性が低下するばかりか、この樹脂が光触媒作用により分解劣化を起こして光触媒が剥離するなど、耐久性にも問題が生じた。
そこで、担体材料が耐熱性の無機物の場合には、有機物が全く残存しないスパッタリング法、有機チタネートの塗布−焼成法やチタニアゾルの吹き付け−焼成法等の方法が採用されている。
Even if the carrier material is an inorganic substance such as glass or ceramic, if an organic polymer resin is used as an adhesive to support the photocatalyst, the surface of the photocatalyst particles is covered with the resin, so that the catalytic activity decreases. In addition, the resin suffered degradation due to photocatalytic action, and the photocatalyst peeled off.
Therefore, when the carrier material is a heat-resistant inorganic substance, a sputtering method in which no organic substance remains, an organic titanate coating-firing method, a titania sol spraying-firing method, or the like is employed.
しかし、これらの方法は、担体上での光触媒粒子の生成、結晶化及び担体との接着性を持たせるために、高温度での焼成が必要であり、大面積の担持ができにくいばかりか、製造コストが非常に高いと言う問題があった。 However, these methods require the generation of photocatalyst particles on the carrier, crystallization, and adhesion with the carrier, so that firing at a high temperature is necessary, and it is difficult to carry a large area. There was a problem that the manufacturing cost was very high.
一方、光触媒をガラス繊維紙に担持するために、接着剤として金属酸化物ゾルを用いる方法も提案された。
しかし、シリカゾル等の金属酸化物ゾルの接着力はファン・デア・ワールス力によるものである為に非常に弱く、接着性、耐久性が不十分であり、また、高温度での焼き付け処理が必要であったりして、熱分解を起こしやすい汎用樹脂を含む全ての担体に適用できるものではなかった。
On the other hand, a method of using a metal oxide sol as an adhesive for supporting the photocatalyst on glass fiber paper has also been proposed.
However, the adhesive strength of metal oxide sols such as silica sol is very weak because of the van der Waals force, the adhesiveness and durability are insufficient, and the baking process at high temperature is necessary. In other words, it has not been applicable to all carriers including general-purpose resins that easily undergo thermal decomposition.
また、光触媒粉末をシリカや粘土鉱物等の金属酸化物ゲルに担持した例においては、担体の吸着剤としての効果によりプロピオンアルデヒドガスの光触媒分解反応が促進されるとした報告がある。
しかしながら、こうした金属酸化物ゲルの中に均一に分散させた光触媒を高い触媒活性を維持したまま、接着性及び耐久性に優れた担持体を得たと言う報告は皆無であった。
Further, in an example in which the photocatalyst powder is supported on a metal oxide gel such as silica or clay mineral, there is a report that the photocatalytic decomposition reaction of propionaldehyde gas is promoted by the effect as an adsorbent of the carrier.
However, there has been no report that a photocatalyst dispersed uniformly in such a metal oxide gel has a carrier having excellent adhesion and durability while maintaining high catalytic activity.
さらに、光触媒をフッ素樹脂で固定化する方法も提案された。しかし、フッ素樹脂は高価であるばかりか、光触媒粒子を強固に接着するためには、触媒粒子表面の多くをフッ素樹脂で覆ってしまうことが必要で、結果、触媒活性は、粉末時に比べて低下してしまうと言う問題があった。光触媒をフッ素樹脂やポリオルガノシロキサン等の難分解性結着剤と混合して基体に担持しようと試みた例(特許文献1)があるが、接着性や長期耐久性等の実用上の課題の解決には不十分なものである。 Furthermore, a method for fixing the photocatalyst with a fluororesin has also been proposed. However, not only is fluororesin expensive, but in order to firmly adhere photocatalyst particles, it is necessary to cover most of the catalyst particle surface with fluororesin, and as a result, the catalytic activity is lower than when powdered. There was a problem to say. There is an example (Patent Document 1) in which a photocatalyst is mixed with a hard-to-decompose binder such as a fluororesin or polyorganosiloxane and is carried on a substrate (Patent Document 1). However, there are practical problems such as adhesion and long-term durability. Insufficient solution.
上述のように、光触媒を担体上に担持するために解決しなくてはならない課題として、1)光触媒と担体との接着性が良好であること、2)光触媒活性が担体上へ担持されることにより低下しないこと、3)担持した光触媒によって担体及び接着剤が劣化せず長期にわたって強度を維持し、耐久性と触媒活性を保っていること、の3点が挙げられる。更に高温多湿の環境で使用する場合には、例えば沸騰水中に浸漬した後の付着性が優れていることが要求される。
また、光触媒を担体へ担持するための光触媒コーティング剤に要求される特性として、最低でも1カ月望ましくは3カ月以上保存しても粘度増加や粒子沈降がない光触媒塗布液が必要である。また、実用製品へ光触媒をコートした時に光触媒作用を低下させることなく担持させることも必要である。
As described above, the problems that must be solved in order to support the photocatalyst on the carrier are as follows: 1) the adhesiveness between the photocatalyst and the carrier is good, and 2) the photocatalytic activity is supported on the carrier. 3) that the carrier and the adhesive are not deteriorated by the supported photocatalyst and that the strength is maintained over a long period of time, and durability and catalytic activity are maintained. Further, when used in a high temperature and high humidity environment, for example, it is required to have excellent adhesion after being immersed in boiling water.
In addition, as a characteristic required for a photocatalyst coating agent for supporting a photocatalyst on a carrier, a photocatalyst coating liquid that does not increase in viscosity and does not settle particles even when stored for at least 1 month, preferably 3 months or more is required. It is also necessary to carry a photocatalyst without lowering the photocatalytic action when the photocatalyst is coated on a practical product.
本発明者らは、上記課題を解決するため、光触媒層と担体との間に、シリコン含有量2〜60重量%のアクリル−シリコン樹脂、エポキシ−シリコン樹脂等のシリコン変性樹脂、コロイダルシリカを5〜40重量%含有する樹脂、又は一般式SiCln1(OH)n2R1n3(OR2)n4で表される化合物の重縮合反応生成物であるポリシロキサンを3〜60重量%含有する樹脂を含有する接着層を設けた(特許文献2)。
しかしながら、当該方法は、接着層を介して触媒層を設けることにより、担体との密着性は良好となるが、一方では、膨張収縮の違いから生じた応力により光触媒層にクラックが発生しやすく、透明性と言う点で十分ではなかった。
In order to solve the above-mentioned problems, the inventors of the present invention provide a silicon-modified resin such as an acrylic-silicon resin or an epoxy-silicon resin having a silicon content of 2 to 60% by weight and colloidal silica between the photocatalyst layer and the carrier. 3 to 60% by weight of a polysiloxane which is a polycondensation reaction product of a resin represented by ˜40% by weight or a compound represented by the general formula SiCln 1 (OH) n 2 R 1 n 3 (OR 2 ) n 4 The adhesive layer containing the resin to perform was provided (patent document 2).
However, in this method, by providing the catalyst layer via the adhesive layer, the adhesion to the carrier is improved, but on the other hand, the photocatalyst layer is likely to crack due to the stress caused by the difference in expansion and contraction, It was not enough in terms of transparency.
その他、ケイ素化合物使用した光触媒コーティング剤として、(a)(R1 )nSi(OR2 )4−n(式中、R1は、2個存在するときは同一または異なり、炭素数1〜10の1価の有機基を示し、R2は、同一または異なり、炭素数1〜5のアルキル基または炭素数1〜6のアシル基を示し、nは1〜2の整数である)で表されるオルガノシランおよび該オルガノシランの加水分解物から選ばれた少なくとも1種、(b)SiO結合を有し、重量平均分子量が300〜100,000の3官能および/または2官能のオルガノシロキサンオリゴマー、ならびに(c)光触媒、を含有するコーティング組成物もある(特許文献3)。
特許文献3の技術は、光触媒コーティング層単独で用いることを目的としたものではなく、必要に応じて、下塗り層あるいはプライマー層と併用するものであり、実施例はいずれも下塗り層を設けたものである。性能面では、透明性や耐煮沸性という点で十分ではなかった。
In addition, as a photocatalytic coating agent using a silicon compound, (a) (R 1 ) n Si (OR 2 ) 4-n (wherein R 1 is the same or different when two exist, and has 1 to 10 carbon atoms) R 2 is the same or different and represents an alkyl group having 1 to 5 carbon atoms or an acyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 2). (B) a trifunctional and / or bifunctional organosiloxane oligomer having an SiO bond and a weight average molecular weight of 300 to 100,000, There is also a coating composition containing (c) a photocatalyst (Patent Document 3).
The technique of Patent Document 3 is not intended to be used alone as a photocatalyst coating layer, but is used in combination with an undercoat layer or a primer layer as necessary, and all examples are provided with an undercoat layer. It is. In terms of performance, transparency and boiling resistance were not sufficient.
本発明は、1)担体との接着性が良好であること、2)光触媒活性が担体上へ担持されることにより低下しないこと、3)担持した光触媒によって担体が劣化せず長期にわたって強度を維持し、耐久性と触媒活性を保っていること、かつ、4)接着層を必要としないこと、及び5)透明性が低下しないことを満たす光触媒コーティング剤を提供することである。 In the present invention, 1) the adhesion to the carrier is good, 2) the photocatalytic activity is not lowered by being supported on the carrier, and 3) the carrier is not deteriorated by the supported photocatalyst and the strength is maintained for a long time. And providing a photocatalyst coating agent that satisfies durability and catalytic activity, 4) does not require an adhesive layer, and 5) does not lower transparency.
本発明者らは、上記課題を解決すべく鋭意研究を行った結果、シロキサンとしてエポキシ基を有するシロキサンをモノマーとして使用し、それを縮合させた物を金属酸化物ゾル等と混合することにより、上記課題を達成することができることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the inventors of the present invention use a siloxane having an epoxy group as a siloxane as a monomer, and mix the condensed product with a metal oxide sol or the like. The present inventors have found that the above problems can be achieved and have completed the present invention.
即ち、本発明は、
(1)(a)式(I)
RnSiX4−n・・・(I)
(式中、Rはエポキシ基を有する有機基を表し、Xは水酸基又は加水分解性基を表す。nは1又は2を表し、nが2のとき各Rは同一でも異なっていてもよく、(4−n)が2以上のとき各Xは同一でも異なっていてもよい。)で表される有機ケイ素化合物の縮合物、(b)光触媒、及び
(c)金属酸化物及び/又は金属水酸化物
を含有し、各成分の組成が、固形分として、固形分全体に対して、
(a)=5〜90質量%
(b)=5〜70重量%
(c)=5〜50重量%
であることを特徴とする光触媒含有コーティング組成物、
(2)光触媒がチタン酸化物であることを特徴とする(1)記載の光触媒含有コーティング用組成物、
(3)金属酸化物がアルミナであることを特徴とする(1)記載の光触媒コーティング用組成物、に関する。
That is, the present invention
(1) (a) Formula (I)
R n SiX 4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.), (B) a photocatalyst, and (c) a metal oxide and / or metal water. Containing oxides, the composition of each component as a solid content, the entire solid content,
(A) = 5-90 mass%
(B) = 5 to 70% by weight
(C) = 5-50% by weight
A photocatalyst-containing coating composition, characterized in that
(2) The photocatalyst-containing coating composition according to (1), wherein the photocatalyst is a titanium oxide,
(3) The composition for photocatalyst coating according to (1), wherein the metal oxide is alumina.
また、本発明は、
(4)(A)式(I)
RnSiX4−n・・・(I)
(式中、Rはエポキシ基を有する有機基を表し、Xは水酸基又は加水分解性基を表す。nは1又は2を表し、nが2のとき各Rは同一でも異なっていてもよく、(4−n)が2以上のとき各Xは同一でも異なっていてもよい。)で表される有機ケイ素化合物を、溶媒中、水及びシラノール縮合触媒の存在下に縮合させる工程、及び
(B)溶媒中、工程(A)で得られた有機ケイ素化合物の縮合物、光触媒、並びに金属酸化物及び/又は金属水酸化物を混合する工程
からなる上記(1)〜(3)のいずれかに記載の光触媒含有コーティング組成物の製造方法、
(5)有機ケイ素化合物が3−グリシドキシプロピルトリメトキシシランであり、シラノール縮合触媒がチタン酸化物であることを特徴とする(4)に記載の光触媒コーティング組成物の製造方法、及び
(6)上記(1)〜(3)のいずれかに記載の光触媒コーティング用組成物を担持した基体、に関する。
The present invention also provides:
(4) (A) Formula (I)
R n SiX 4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, A step of condensing the organosilicon compound represented by (4-n) of 2 or more in the presence of water and a silanol condensation catalyst in a solvent; and (B ) In any one of the above (1) to (3), which comprises the step of mixing the condensate of the organosilicon compound obtained in step (A), the photocatalyst, and the metal oxide and / or metal hydroxide in a solvent. A method for producing the photocatalyst-containing coating composition according to claim 1,
(5) The method for producing a photocatalytic coating composition according to (4), wherein the organosilicon compound is 3-glycidoxypropyltrimethoxysilane, and the silanol condensation catalyst is titanium oxide, and (6) The present invention relates to a substrate carrying the photocatalyst coating composition according to any one of (1) to (3) above.
本発明において、エポキシ基が存在する有機ケイ素化合物と金属酸化物及び/又は金属水酸化物ゾル、とりわけ、アルミナゾルを組み合わせて使用することにより、
(1)接着層が不要であること、(2)担体との密着性が良いこと、(3)膜を厚くすることができること、(4)親水性が良好であること、(5)透明性が低下しない等の効果を奏する光触媒コーティング組成物を得ることができる。
In the present invention, by using a combination of an organosilicon compound having an epoxy group and a metal oxide and / or metal hydroxide sol, especially an alumina sol,
(1) Adhesive layer is unnecessary, (2) Adhesion with the carrier is good, (3) The film can be thickened, (4) Good hydrophilicity, (5) Transparency Can be obtained.
(1)光触媒含有コーティング組成物
本発明の光触媒含有コーティング組成物は、通常、溶媒中に、
(a)式(I)
RnSiX4−n・・・(I)
(式中、Rはエポキシ基を有する有機基を表し、Xは水酸基又は加水分解性基を表す。nは1又は2を表し、nが2のとき各Rは同一でも異なっていてもよく、(4−n)が2以上のとき各Xは同一でも異なっていてもよい。)で表される有機ケイ素化合物の縮合物、(b)光触媒、及び
(c)金属酸化物及び/又は水酸化物
を含有する組成物であり、本発明の効果を阻害しない限り、その他の成分を含んでいても良い。
上記(a)〜(c)の各成分は、固形分として、固形分全体の質量に対して、以下の割合で配合される。
(a)=5〜90質量%、好ましくは10〜70質量%
(b)=5〜70質量%、好ましくは5〜50質量%
(c)=5〜50質量%、好ましくは5〜40質量%
(1) Photocatalyst-containing coating composition The photocatalyst-containing coating composition of the present invention is usually in a solvent,
(A) Formula (I)
R n SiX 4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.), (B) photocatalyst, and (c) metal oxide and / or hydroxylation It is a composition containing a product, and may contain other components as long as the effects of the present invention are not impaired.
Each of the components (a) to (c) is blended as a solid content in the following ratio with respect to the mass of the entire solid content.
(A) = 5-90 mass%, preferably 10-70 mass%
(B) = 5-70 mass%, preferably 5-50 mass%
(C) = 5-50% by mass, preferably 5-40% by mass
本発明において使用する溶媒は、組成物の調製法において記載されたものを使用する。 As the solvent used in the present invention, those described in the method for preparing the composition are used.
以下に、本発明の光触媒含有コーティング組成物の各成分について詳述する。
1)有機ケイ素化合物及びその縮合物
本発明の有機ケイ素化合物は、式(I)
RnSiX4−n・・・(I)で表される化合物である。
式(I)中、Rは、エポキシ基を有する有機基を示し、化合物中に1又は2個有する。
Below, each component of the photocatalyst containing coating composition of this invention is explained in full detail.
1) Organosilicon compound and condensate thereof The organosilicon compound of the present invention has the formula (I)
R n SiX 4-n is a compound represented by (I).
In formula (I), R shows the organic group which has an epoxy group, and has 1 or 2 in a compound.
本発明においてエポキシ基を有する有機ケイ素化合物が好適である理由は、エポキシ基が開環、反応することにより、基板との接着性の向上に寄与しているからと考えられる。 The reason why the organosilicon compound having an epoxy group is suitable in the present invention is considered to be that the epoxy group is ring-opened and reacted, thereby contributing to improvement in adhesion to the substrate.
ここで、「有機基」とは、少なくとも1個のエポキシ基(オキシラン環)を末端、側鎖、又は骨格内に有することができる有機基であれば制限されず、置換されていてもよい炭化水素基又は置換されていてもよい複素環基をいう。炭化水素基には、酸素、窒素又はケイ素を含有していてもよい。 Here, the “organic group” is not limited as long as it is an organic group that can have at least one epoxy group (oxirane ring) in the terminal, side chain, or skeleton, and may be substituted carbon. It refers to a hydrogen group or an optionally substituted heterocyclic group. The hydrocarbon group may contain oxygen, nitrogen or silicon.
「炭化水素基」としては、アルキル基、シクロアルキル基、アルケニル基、シクロアルケニル基、アリール基、アリールアルキル基、アリールアルケニル基、アリールシクロアルキル基等が挙げられる。
「アルキル基」は、炭素数1〜10の直鎖又は分岐状のアルキル基が好ましく、例えばメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、t−ブチル基、n−ペンチル基、イソペンチル基、ネオペンチル基、2−メチルブチル基、2,2−ジメチルプロピル基、n−ヘキシル基、イソヘキシル基n−ヘプチル基、n−オクチル基、ノニル基、イソノニル基、デシル基等が挙げられる。
「シクロアルキル基」は、炭素数3〜10のシクロアルキル基が好ましく、例えばシクロプロピル基、シクロブチル基、シクロペンチル基、シクロへキシル基、シクロヘプチル基、シクロオクチル基等が挙げられる。
Examples of the “hydrocarbon group” include an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group, an arylalkyl group, an arylalkenyl group, and an arylcycloalkyl group.
The “alkyl group” is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group. N-pentyl group, isopentyl group, neopentyl group, 2-methylbutyl group, 2,2-dimethylpropyl group, n-hexyl group, isohexyl group n-heptyl group, n-octyl group, nonyl group, isononyl group, decyl group Etc.
The “cycloalkyl group” is preferably a cycloalkyl group having 3 to 10 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
「アルケニル基」は、いずれか1カ所以上に炭素−炭素二重結合を有する炭化水素基である。炭素数2〜10の直鎖又は分岐鎖のアルケニル基が好ましく、例えば、エテニル基、プロパ−1−エン−1−イル基、プロパ−2−エン−1−イル基、プロパ−1−エン−2−イル基、ブタ−1−エン−1−イル基、ブタ−2−エン−1−イル基、ブタ−3−エン−1−イル基、ブタ−1−エン−2−イル基、ブタ−3−エン−2−イル基、ペンタ−1−エン−1−イル基、ペンタ−4−エン−1−イル基、ペンタ−1−エン−2−イル基、ペンタ−4−エン−2−イル基、3−メチル−ブタ−1−エン−1−イル基、ヘキサ−1−エン−1−イル基、ヘキサ−5−エン−1−イル基、ヘプタ−1−エン−1−イル基、ヘプタ−6−エン−1−イル基、オクタ−1−エン−1−イル基、オクタ−7−エン−1−イル基等が挙げられる。
「シクロアルケニル基」は、いずれか1カ所以上に炭素−炭素二重結合を有する環状の炭化水素基である。炭素数3〜10のシクロアルケニル基が好ましく、例えば、1−シクロペンテン−1−イル基、2−シクロペンテン−1−イル基、1−シクロヘキセン−1−イル基、2−シクロヘキセン−1−イル基、3−シクロヘキセン−1−イル基等が挙げられる。
An “alkenyl group” is a hydrocarbon group having a carbon-carbon double bond at any one or more positions. A straight chain or branched chain alkenyl group having 2 to 10 carbon atoms is preferable, for example, an ethenyl group, a prop-1-en-1-yl group, a prop-2-en-1-yl group, and a prop-1-ene- 2-yl group, but-1-en-1-yl group, but-2-en-1-yl group, but-3-en-1-yl group, but-1-en-2-yl group, butane -3-en-2-yl group, penta-1-en-1-yl group, penta-4-en-1-yl group, penta-1-en-2-yl group, penta-4-en-2 -Yl group, 3-methyl-but-1-en-1-yl group, hexa-1-en-1-yl group, hexa-5-en-1-yl group, hepta-1-en-1-yl Group, hepta-6-en-1-yl group, octa-1-en-1-yl group, octa-7-en-1-yl group and the like.
The “cycloalkenyl group” is a cyclic hydrocarbon group having a carbon-carbon double bond at any one or more positions. A cycloalkenyl group having 3 to 10 carbon atoms is preferable, for example, a 1-cyclopenten-1-yl group, a 2-cyclopenten-1-yl group, a 1-cyclohexen-1-yl group, a 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group etc. are mentioned.
「アリール基」は、炭素数6〜14のアリール基が好ましく、例えば、フェニル基、ナフチル基、アントラセン−1−イル基、フェナントレン−1−イル基等が挙げられる。
「アリールアルキル基」は、C6−14アリールC1−10アルキル基が好ましく、ベンジル基、フェネチル基、3−フェニル−n−プロピル基、4−フェニル−n−ブチル基、5−フェニル−n−ペンチル基、8−フェニル−n−オクチル基、ナフチルメチル基等が挙げられる。
「アリールアルケニル基」は、C6−14アリールC2−10アルケニル基が好ましく、例えば、スチリル基、3−フェニル−プロパ−1−エン−1−イル基、3−フェニル−プロパ−2−エン−1−イル基、4−フェニル−ブタ−1−エン−1−イル基、4−フェニル−ブタ−3−エン−1−イル基、5−フェニル−ペンタ−1−エン−1−イル基、5−フェニル−ペンタ−4−エン−1−イル基、8−フェニル−オクタ−1−エン−1−イル基、8−フェニル−オクタ−7−エン−1−イル基、ナフチルエテニル基等が挙げられる。
「アリールシクロアルキル基」は、C6−14アリールC3−10シクロアルキル基が好ましく、例えば、3−フェニルシクロプロピル基、3−フェニルシクロブチル基、4−フェニルシクロペンチル基、4−フェニルシクロヘキシル基、4−ナフチルシクロヘキシル基等が挙げられる。
The “aryl group” is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, an anthracen-1-yl group, and a phenanthren-1-yl group.
The “arylalkyl group” is preferably a C 6-14 aryl C 1-10 alkyl group, and is a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 4-phenyl-n-butyl group, a 5-phenyl-n. -Pentyl group, 8-phenyl-n-octyl group, naphthylmethyl group and the like.
The “arylalkenyl group” is preferably a C 6-14 arylC 2-10 alkenyl group, such as a styryl group, 3-phenyl-prop-1-en-1-yl group, 3-phenyl-prop-2-ene. -1-yl group, 4-phenyl-but-1-en-1-yl group, 4-phenyl-but-3-en-1-yl group, 5-phenyl-pent-1-en-1-yl group 5-phenyl-pent-4-en-1-yl group, 8-phenyl-oct-1-en-1-yl group, 8-phenyl-oct-7-en-1-yl group, naphthylethenyl group, etc. Can be mentioned.
The “arylcycloalkyl group” is preferably a C 6-14 arylC 3-10 cycloalkyl group, for example, a 3-phenylcyclopropyl group, a 3-phenylcyclobutyl group, a 4-phenylcyclopentyl group, a 4-phenylcyclohexyl group. , 4-naphthylcyclohexyl group and the like.
「複素環基」は、炭素原子以外に窒素原子、酸素原子及び硫黄原子から選ばれる1乃至3個の複素原子を含む5〜11員環の複素環基が好ましく、例えば、2−フリル基、3−フリル基、2−チエニル基、3−チエニル基、ピロ−ル−1−イル基、ピロ−ル−2−イル基、ピロ−ル−3−イル基、ピリジン−2−イル基、ピリジン−3−イル基、ピリジン−4−イル基、ピラジン−2−イル基、ピラジン−3−イル基、ピリミジン−2−イル基、ピリミジン−4−イル基、ピリミジン−5−イル基、ピリダジン−3−イル基、ピリダジン−4−イル基、1,3−ベンゾジオキソール−4−イル基、1,3−ベンゾジオキソール−5−イル基、1,4−ベンゾジオキサン−5−イル基、1,4−ベンゾジオキサン−6−イル基、3,4−ジヒドロ−2H−1,5−ベンゾジオキセピン−6−イル基、3,4−ジヒドロ−2H−1,5−ベンゾジオキセピン−7−イル基、2,3−ジヒドロベンゾフラン−4−イル基、2,3−ジヒドロベンゾフラン−5−イル基、2,3−ジヒドロベンゾフラン−6−イル基、2,3−ジヒドロベンゾフラン−7−イル基、ベンゾフラン−4−イル基、ベンゾフラン−5−イル基、ベンゾフラン−6−イル基、ベンゾフラン−7−イル基、ベンゾチオフェン−4−イル基、ベンゾチオフェン−5−イル基、ベンゾチオフェン−6−イル基、ベンゾチオフェン−7−イル基、キノキサリン−2−イル基、キノキサリン−5−イル基、キノキサリン−6−イル基、インドール−4−イル基、インドール−5−イル基、インドール−6−イル基、インドール−7−イル基、イソインドール−4−イル基、イソインドール−5−イル基、イソインドール−6−イル基、イソインドール−7−イル基、イソベンゾフラン−4−イル基、イソベンゾフラン−5−イル基、イソベンゾフラン−6−イル基、イソベンゾフラン−7−イル基、クロメン−5−イル基、クロメン−6−イル基、クロメン−7−イル基、クロメン−8−イル基、イミダゾール−1−イル基、イミダゾール−2−イル基、イミダゾール−4−イル基、イミダゾール−5−イル基、ピラゾール−1−イル基、ピラゾール−3−イル基、ピラゾール−4−イル基、チアゾール−2−イル基、チアゾール−4−イル基、チアゾール−5−イル基、オキサゾール−2−イル基、オキサゾール−4−イル基、オキサゾール−5−イル基、イソオキサゾール−3−イル基、イソオキサゾール−4−イル基、イソオキサゾール−5−イル基、ピリミジン−2−イル基、ピリミジン−4−イル基、ピリミジン−5−イル基、ピリジン−2−イル基、ピリジン−3−イル基、ピリジン−4−イル基、ピロリジン−2−イル基、ピロリジン−3−イル基、ベンゾイミダゾール−1−イル基、ベンゾイミダゾール−2−イル基、ベンゾチアゾール−2−イル基、ベンゾオキサゾール−2−イル基、キノリン−2−イル基、キノリン−3−イル基、キノリン−4−イル基、イソキノリン−1−イル基、イソキノリン−3−イル基、イソキノリン−4−イル基、1,3,4−チアジアゾール−2−イル基、モルホリン−4−イル基等が挙げられる。 The “heterocyclic group” is preferably a 5- to 11-membered heterocyclic group containing 1 to 3 heteroatoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in addition to a carbon atom, such as a 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, pyrrol-1-yl group, pyrrol-2-yl group, pyrrol-3-yl group, pyridin-2-yl group, pyridine -3-yl group, pyridin-4-yl group, pyrazin-2-yl group, pyrazin-3-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyridazine- 3-yl group, pyridazin-4-yl group, 1,3-benzodioxol-4-yl group, 1,3-benzodioxol-5-yl group, 1,4-benzodioxan-5-yl Group, 1,4-benzodioxan-6-yl group, 3,4-dihydride -2H-1,5-benzodioxepin-6-yl group, 3,4-dihydro-2H-1,5-benzodioxepin-7-yl group, 2,3-dihydrobenzofuran-4-yl group 2,3-dihydrobenzofuran-5-yl group, 2,3-dihydrobenzofuran-6-yl group, 2,3-dihydrobenzofuran-7-yl group, benzofuran-4-yl group, benzofuran-5-yl group Benzofuran-6-yl group, benzofuran-7-yl group, benzothiophen-4-yl group, benzothiophen-5-yl group, benzothiophen-6-yl group, benzothiophen-7-yl group, quinoxaline-2 -Yl group, quinoxalin-5-yl group, quinoxalin-6-yl group, indol-4-yl group, indol-5-yl group, indol-6-yl group, indole 7-yl group, isoindol-4-yl group, isoindol-5-yl group, isoindol-6-yl group, isoindol-7-yl group, isobenzofuran-4-yl group, isobenzofuran-5 Yl group, isobenzofuran-6-yl group, isobenzofuran-7-yl group, chromen-5-yl group, chromen-6-yl group, chromen-7-yl group, chromen-8-yl group, imidazole-1 -Yl group, imidazol-2-yl group, imidazol-4-yl group, imidazol-5-yl group, pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group, thiazol-2- Yl, thiazol-4-yl, thiazol-5-yl, oxazol-2-yl, oxazol-4-yl, oxazol-5-yl, isooxy Sazol-3-yl group, isoxazol-4-yl group, isoxazol-5-yl group, pyrimidin-2-yl group, pyrimidin-4-yl group, pyrimidin-5-yl group, pyridin-2-yl group , Pyridin-3-yl group, pyridin-4-yl group, pyrrolidin-2-yl group, pyrrolidin-3-yl group, benzimidazol-1-yl group, benzimidazol-2-yl group, benzothiazol-2- Yl group, benzoxazol-2-yl group, quinolin-2-yl group, quinolin-3-yl group, quinolin-4-yl group, isoquinolin-1-yl group, isoquinolin-3-yl group, isoquinolin-4- Yl group, 1,3,4-thiadiazol-2-yl group, morpholin-4-yl group and the like.
式(I)中、Xは、水酸基又は加水分解性基を示す。
加水分解性基とは、例えば、無触媒、過剰の水の共存下、25℃〜100℃で加熱することにより、加水分解されてシラノール基を生成することができる基や、シロキサン縮合物を形成することができる基を意味し、具体的には、アルコキシ基、アシルオキシ基、ハロゲン基、イソシアネート基等を挙げることができ、炭素数1〜6のアルコキシ基又は炭素数1〜8(カルボニル基の炭素を除く)のアシルオキシ基が好ましい。
In formula (I), X represents a hydroxyl group or a hydrolyzable group.
A hydrolyzable group is, for example, a group that can be hydrolyzed to form a silanol group or a siloxane condensate by heating at 25 ° C. to 100 ° C. in the presence of no catalyst and excess water. Specifically, an alkoxy group, an acyloxy group, a halogen group, an isocyanate group and the like can be mentioned, and an alkoxy group having 1 to 6 carbon atoms or 1 to 8 carbon atoms (of a carbonyl group). Acyloxy groups) are preferred.
炭素数1〜6のアルコキシ基としては、メチルオキシ基、エチルオキシ基、プロピルオキシ基、イソプロピルオキシ基、n−ブチルオキシ基、イソブチルオキシ基、t−ブチルオキシ基、ヘキシルオキシ基等が挙げられ、炭素数1〜8のアシルオキシ基としては、アセチルオキシ基、ベンゾイルオキシ基等が挙げられる。ハロゲンとしてはフッ素原子、塩素原子、臭素原子、ヨウ素原子等が挙げられる。イソシアネート基としては、例えば、アルキル基に結合したイソシアネート基、シクロアルキル基に結合したイソシアネート基、アリール基に結合したイソシアネート基、シクロアルキル基が置換したアルキル基に結合したイソシアネート基、アリール基が置換したアルキル基に結合したイソシアネート基等が挙げられる。 Examples of the alkoxy group having 1 to 6 carbon atoms include a methyloxy group, an ethyloxy group, a propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group, a t-butyloxy group, and a hexyloxy group. Examples of the acyloxy group of 1 to 8 include an acetyloxy group and a benzoyloxy group. Examples of the halogen include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the isocyanate group include an isocyanate group bonded to an alkyl group, an isocyanate group bonded to a cycloalkyl group, an isocyanate group bonded to an aryl group, an isocyanate group bonded to an alkyl group substituted with a cycloalkyl group, and an aryl group. And an isocyanate group bonded to the alkyl group.
式(I)で表される有機ケイ素化合物を例示すると以下のとおりである。
グリシジルトリメトキシシラン、
グリシジルトリクロロシラン、
グリシジルトリアセチルオキシシラン、
グリシジルトリベンゾイルオキシシラン、
3−グリシドキシメチルトリメトキシシラン、
3−グリシドキシメチルトリアセチルオキシシラン、
3−グリシドキシメチルトリベンジルオキシシラン
3−グリシドキシプロピルトリメトキシシラン、
3−グリシドキシプロピルトリエトキシシラン、
3−グリシドキシプロピルメチルジエトキシシラン、
3−グリシドキシプロピルメチルジメトキシシラン、
3−グリシドキシプロピルクロルジメトキシシラン、
2−(3,4−エポキシシクロヘキシル)エチルトリメトキシシラン等。
これ等の化合物は、1種単独で、あるいは2種以上を混合して用いることができる。
Examples of the organosilicon compound represented by the formula (I) are as follows.
Glycidyltrimethoxysilane,
Glycidyltrichlorosilane,
Glycidyl triacetyloxysilane,
Glycidyl tribenzoyloxysilane,
3-glycidoxymethyltrimethoxysilane,
3-glycidoxymethyl triacetyloxysilane,
3-glycidoxymethyltribenzyloxysilane 3-glycidoxypropyltrimethoxysilane,
3-glycidoxypropyltriethoxysilane,
3-glycidoxypropylmethyldiethoxysilane,
3-glycidoxypropylmethyldimethoxysilane,
3-glycidoxypropyl chlorodimethoxysilane,
2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like.
These compounds can be used individually by 1 type or in mixture of 2 or more types.
上記有機ケイ素化合物の縮合物は、ゾルとなりうる縮合度であれば特に制限はないが、平均粒径が50nm以下のサイズであることが好ましく、20nm以下のサイズであることがより好ましい。縮合物は、組成物の調製法の項において記載された方法により製造することができる。 The condensate of the organosilicon compound is not particularly limited as long as it is a condensation degree capable of forming a sol, but the average particle size is preferably 50 nm or less, and more preferably 20 nm or less. The condensate can be produced by the method described in the section on preparation of the composition.
2)光触媒
本発明に使用される光触媒は、粉末状、ゾル状、溶液状など、光触媒活性を示すものであればいずれの形態も使用可能であるが。ゾル状の光触媒を使用する場合、粒子径が20nm以下、好ましくは10nm以下のものを使用すると、透明性が向上し、直線透過率が高くなるため、透明性を要求されるガラス基板やプラスチック成形体に塗布する場合に特に好ましい。また下地の担体に色や模様が印刷されたものの場合にこうした透明な光触媒層を塗布すると下地の色や柄を損なうことがない。
2) Photocatalyst Any form of the photocatalyst used in the present invention can be used as long as it shows photocatalytic activity such as powder, sol, and solution. When using a sol-like photocatalyst, if the particle diameter is 20 nm or less, preferably 10 nm or less, the transparency is improved and the linear transmittance is increased. Particularly preferred when applied to the body. In addition, in the case where a color or pattern is printed on the base carrier, if the transparent photocatalyst layer is applied, the base color or pattern is not impaired.
光触媒としては、TiO2、ZnO、SrTiO3、CdS、GaP、InP、GaAs、BaTiO3、KNbO3、Fe2O3、Ta2O5、WO3、SnO2、Bi2O3、NiO、Cu2O、SiC、SiO2、MoS2、InPb、RuO2、CeO2など、及び、これらの光触媒に、Pt、Rh、RuO2、Nb、Cu、Sn、Ni、Feなどの金属及びそれらの金属の酸化物を添加したものが使用することができる。また、これらの光触媒に光触媒還元作用を利用してPt、Rh、RhO2、Nb、Cu、Sn、Ni、Feなどの金属を添加したものなども全て使用可能である。光触媒の含有量は、多量なほど触媒活性が高くなるが、接着性の点から好ましくは固形分全体の70重量%以下である。
なお、光触媒は、上記紫外線応答型のみならず可視光応答型の光触媒も使用することができ、例えば、金属イオンドープ型、酸素欠陥型、窒素(窒素化合物)ドープ型などのチタン酸化物などが挙げられる。
The photocatalyst, TiO 2, ZnO, SrTiO 3 , CdS, GaP, InP, GaAs, BaTiO 3, KNbO 3, Fe 2 O 3, Ta 2 O 5, WO 3, SnO 2, Bi 2 O 3, NiO, Cu 2 O, SiC, SiO 2 , MoS 2 , InPb, RuO 2 , CeO 2, etc., and these photocatalysts, metals such as Pt, Rh, RuO 2 , Nb, Cu, Sn, Ni, Fe and their metals What added the oxide of these can be used. In addition, these photocatalysts obtained by adding a metal such as Pt, Rh, RhO 2 , Nb, Cu, Sn, Ni, and Fe using a photocatalytic reduction action can be used. The higher the content of the photocatalyst, the higher the catalytic activity. However, from the viewpoint of adhesiveness, the content is preferably 70% by weight or less based on the total solid content.
As the photocatalyst, not only the ultraviolet responsive type but also a visible light responsive type photocatalyst can be used. For example, metal oxide doped type, oxygen defect type, nitrogen (nitrogen compound) type doped titanium oxide, etc. Can be mentioned.
3)金属酸化物又は水酸化物
本発明で用いられる金属酸化物又は水酸化物は、光触媒を固着し、基板と強固に接着させる効果を有しており、光触媒としての活性を有する金属酸化物は含まれない。この金属酸化物又は水酸化物を原料として使用するときはゾルの状態で使用することが好ましい。金属酸化物又は水酸化物ゾルは、基板に塗布後、ゲル化する。5重量%未満では、接着層との接着が不十分となり、50重量%を超えると、光触媒活性が不十分となる。
金属成分としては、珪素、アルミニウム、チタニウム、ジルコニウム、マグネシウム、ニオビウム、タンタラム、タングステン、錫等を好ましく例示することができる。特に、アルミニウムが好ましい。
また、金属成分として、珪素、アルミニウム、チタニウム、ジルコニウム、ニオビウムの中から選ばれた2種以上の金属を含有する酸化物もしくは水酸化物を使用することができる。
3) Metal oxide or hydroxide The metal oxide or hydroxide used in the present invention has an effect of fixing the photocatalyst and firmly adhering to the substrate, and has activity as a photocatalyst. Is not included. When this metal oxide or hydroxide is used as a raw material, it is preferably used in a sol state. The metal oxide or hydroxide sol gels after being applied to the substrate. If it is less than 5% by weight, the adhesion with the adhesive layer is insufficient, and if it exceeds 50% by weight, the photocatalytic activity becomes insufficient.
Preferred examples of the metal component include silicon, aluminum, titanium, zirconium, magnesium, niobium, tantalum, tungsten, and tin. In particular, aluminum is preferable.
In addition, an oxide or hydroxide containing two or more metals selected from silicon, aluminum, titanium, zirconium, and niobium can be used as the metal component.
原料として用いられる金属酸化物又は金属水酸化物ゾルは、市販のものでもよいが、例えば、特許3609262号公報に記載されているように、(1)含水金属酸化物を一塩基酸またはその塩で解膠処理したり、(2)四塩化金属化合物を低温の水に添加した後透析したり、(3)塩酸水溶液に金属アルコキシドを添加したりして得ることができる。 The metal oxide or metal hydroxide sol used as a raw material may be a commercially available one. For example, as described in Japanese Patent No. 3609262, (1) a hydrated metal oxide is converted to a monobasic acid or a salt thereof. Or by dialysis after adding a metal tetrachloride compound to low-temperature water, or (3) adding a metal alkoxide to an aqueous hydrochloric acid solution.
市販のものとしては、シリカゾルとしては、例えば、日産化学工業(株)製、メタノールシリカゾルおよびイソプロパノールシリカゾル;触媒化成工業(株)製、オスカルなどが挙げられる。また、アルミナゾルとしては、例えば、日産化学工業(株)製のアルミナゾル520、同100、同200;川研ファインケミカル(株)製のアルミナクリアーゾル、アルミナゾル10、同132などが挙げられる。
これらの金属酸化物又は金属水酸化物ゾルは、1種単独であるいは2種以上を併用することができるが、アルミナゾルが特に好ましい。
Examples of commercially available silica sols include, for example, Nissan Chemical Industries, Ltd., methanol silica sol and isopropanol silica sol; Catalyst Kasei Kogyo Co., Ltd., Oscar. Examples of the alumina sol include alumina sol 520, 100, and 200 manufactured by Nissan Chemical Industries, Ltd .; alumina clear sol, alumina sol 10, and 132 manufactured by Kawaken Fine Chemical Co., Ltd.
These metal oxide or metal hydroxide sols can be used alone or in combination of two or more, and alumina sol is particularly preferable.
4)その他の成分
本発明の組成物には、得られる塗膜の着色、厚膜化などのために、別途充填材を添加・分散させることもできる。このような充填材としては、例えば、非水溶性の有機顔料や無機顔料、顔料以外の、粒子状、繊維状もしくは鱗片状のセラミックス、金属あるいは合金、ならびにこれらの金属の酸化物、水酸化物、炭化物、窒化物、硫化物などを挙げることができる。
4) Other components In the composition of the present invention, a filler may be added and dispersed separately for coloring and thickening of the resulting coating film. Examples of such fillers include water-insoluble organic pigments and inorganic pigments, particulate, fibrous or scale-like ceramics, metals or alloys other than pigments, and oxides and hydroxides of these metals. , Carbides, nitrides, sulfides and the like.
上記充填材の具体例としては、鉄、銅、アルミニウム、ニッケル、銀、亜鉛、フェライト、カーボンブラック、ステンレス鋼、二酸化ケイ素、顔料用酸化チタン、酸化アルミニウム、酸化クロム、酸化マンガン、酸化鉄、酸化ジルコニウム、酸化コバルト、合成ムライト、水酸化アルミニウム、水酸化鉄、炭化ケイ素、窒化ケイ素、窒化ホウ素、クレー、ケイソウ土、消石灰、石膏、タルク、炭酸バリウム、炭酸カルシウム、炭酸マグネシウム、硫酸バリウム、ベントナイト、雲母、亜鉛緑、クロム緑、コバルト緑、ビリジアン、ギネー緑、コバルトクロム緑、シェーレ緑、緑土、マンガン緑、ピグメントグリーン、群青、紺青、ピグメントグリーン、岩群青、コバルト青、セルリアンブルー、ホウ酸銅、モリブデン青、硫化銅、コバルト紫、マルス紫、マンガン紫、ピグメントバイオレット、亜酸化鉛、鉛酸カルシウム、ジンクエロー、硫化鉛、クロム黄、黄土、カドミウム黄、ストロンチウム黄、チタン黄、リサージ、ピグメントエロー、亜酸化銅、カドミウム赤、セレン赤、クロムバーミリオン、ベンガラ、亜鉛白、アンチモン白、塩基性硫酸鉛、チタン白、リトポン、ケイ酸鉛、酸化ジルコン、タングステン白、鉛、亜鉛華、バンチソン白、フタル酸鉛、マンガン白、硫酸鉛、黒鉛、ボーン黒、ダイヤモンドブラック、サーマトミック黒、植物性黒、チタン酸カリウムウィスカー、二硫化モリブデンなどを挙げることができる。これらの充填材は、単独でまたは2種以上を混合して使用することができる。充填材の使用量は、組成物の全固形分100重量部に対して、通常、300重量部以下である。 Specific examples of the filler include iron, copper, aluminum, nickel, silver, zinc, ferrite, carbon black, stainless steel, silicon dioxide, titanium oxide for pigment, aluminum oxide, chromium oxide, manganese oxide, iron oxide, and oxidation. Zirconium, cobalt oxide, synthetic mullite, aluminum hydroxide, iron hydroxide, silicon carbide, silicon nitride, boron nitride, clay, diatomaceous earth, slaked lime, gypsum, talc, barium carbonate, calcium carbonate, magnesium carbonate, barium sulfate, bentonite, Mica, Zinc green, Chrome green, Cobalt green, Viridian, Guinea green, Cobalt chromium green, Shale green, Green earth, Manganese green, Pigment green, Ultramarine, Bitumen, Pigment green, Rock ultramarine, Cobalt blue, Cerulean blue, Boric acid Copper, molybdenum blue, copper sulfide, cobalt purple Mars Purple, Manganese Purple, Pigment Violet, Lead Oxide, Calcium Leadate, Zinc Yellow, Lead Sulfide, Chrome Yellow, Ocher, Cadmium Yellow, Strontium Yellow, Titanium Yellow, Resurge, Pigment Yellow, Cuprous Oxide, Cadmium Red, Selenium Red , Chrome vermilion, bengara, zinc white, antimony white, basic lead sulfate, titanium white, lithopone, lead silicate, zircon oxide, tungsten white, lead, zinc white, bunchison white, lead phthalate, manganese white, lead sulfate Graphite, bone black, diamond black, thermatomic black, vegetable black, potassium titanate whisker, molybdenum disulfide, and the like. These fillers can be used alone or in admixture of two or more. The amount of the filler used is usually 300 parts by weight or less with respect to 100 parts by weight of the total solid content of the composition.
さらに、本発明の組成物には、所望により、オルトギ酸メチル、オルト酢酸メチル、テトラエトキシシランなどの公知の脱水剤;ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレン脂肪酸エステル、ポリカルボン酸型高分子界面活性剤、ポリカルボン酸塩、ポリリン酸塩、ポリアクリル酸塩、ポリアミドエステル塩、ポリエチレングリコールなどの分散剤;メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロースなどのセルロース類や、ひまし油誘導体、フェロけい酸塩などの増粘剤;炭酸アンモニウム、炭酸水素アンモニウム、亜硝酸アンモニウム、水素化ホウ素ナトリウム、カルシウムアジドなどの無機発泡剤や、アゾビスイソブチロニトリルなどのアゾ化合物、ジフェニルスルホン−3,3′−ジスルホヒドラジンなどのヒドラジン化合物、セミカルバジド化合物、トリアゾール化合物、N−ニトロソ化合物などの有機発泡剤のほか、界面活性剤、シランカップリング剤、チタンカップリング剤、染料などの他の添加剤を配合することもできる。 Furthermore, the composition of the present invention may optionally contain a known dehydrating agent such as methyl orthoformate, methyl orthoacetate, tetraethoxysilane; polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, Dispersants such as polycarboxylic acid type polymer surfactant, polycarboxylate, polyphosphate, polyacrylate, polyamide ester salt, polyethylene glycol; methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, etc. Thickeners such as celluloses, castor oil derivatives, ferrosilicates; ammonium carbonate, ammonium bicarbonate, ammonium nitrite, sodium borohydride, calcium azide In addition to inorganic foaming agents, azo compounds such as azobisisobutyronitrile, hydrazine compounds such as diphenylsulfone-3,3'-disulfohydrazine, organic foaming agents such as semicarbazide compounds, triazole compounds, and N-nitroso compounds In addition, other additives such as a surfactant, a silane coupling agent, a titanium coupling agent, and a dye may be blended.
また、組成物のコーティング性をより向上させるためにレベリング剤を配合することができる。このようなレベリング剤のうち、フッ素系のレベリング剤(商品名。以下同様)としては、例えば、ビーエムケミー(BM−CHEMIE)社のBM1000、BM1100;エフカケミカルズ社のエフカ772、エフカ777;共栄社化学(株)製のフローレンシリーズ;住友スリーエム(株)のFCシリーズ;東邦化学(株)のフルオナールTFシリーズなどを挙げることができ、シリコーン系のレベリング剤としては、例えば、ビックケミー社のBYKシリーズ;シュメグマン(Sshmegmann)社のSshmegoシリーズ;エフカケミカルズ社のエフカ30、エフカ31、エフカ34、エフカ35、エフカ36、エフカ39、エフカ83、エフカ86、エフカ88などを挙げることができ、エーテル系またはエステル系のレベリング剤としては、例えば、日信化学工業(株)のカーフィノール;花王(株)のエマルゲン、ホモゲノールなどを挙げることができる。 Moreover, a leveling agent can be mix | blended in order to improve the coating property of a composition more. Among such leveling agents, examples of fluorine-based leveling agents (trade names; the same applies hereinafter) include BM1000 and BM1100 of BM-CHEMIE; Fuka 772 and Fuka 777 of Fuka Chemicals; Examples include the Floren series manufactured by Kagaku Co., Ltd .; the FC series manufactured by Sumitomo 3M Co., Ltd .; the Fluoronal TF series manufactured by Toho Chemical Co., Ltd., etc. Examples of silicone leveling agents include BYK series manufactured by BYK Chemie Corporation; Sshmego series from Sshmegmann; Fuka 30, Fuka 31, Fuka 34, Efka 35, Efka 36, Efka 39, Efka 83, Efka 86, Efka 88, etc. from Efka Chemicals can be mentioned. Ester-based The coupling agent, for example, Kafinoru of Nissin Chemical Industry Co., Kao Corp. Emulgen, and the like Homogenol.
また、本発明に用いられる組成物、には、他の樹脂をブレンドしてもよい。他の樹脂としては、アクリル−ウレタン樹脂、エポキシ樹脂、ポリエステル、アクリル樹脂、フッ素樹脂、アクリル樹脂エマルジョン、エポキシ樹脂エマルジョン、ポリウレタンエマルジョン、ポリエステルエマルジョンなどが挙げられる。 Moreover, you may blend other resin with the composition used for this invention. Examples of other resins include acrylic-urethane resins, epoxy resins, polyesters, acrylic resins, fluororesins, acrylic resin emulsions, epoxy resin emulsions, polyurethane emulsions, and polyester emulsions.
(2)光触媒コーティング用組成物の調製法
本発明の組成物を調製するには、次の2つの工程を行う。即ち、
第1工程
式(I)
RnSiX4−n・・・(I)
(式中、Rはエポキシ基を有する有機基を表し、Xは水酸基又は加水分解性基を表す。nは1又は2を表し、nが2のとき各Rは同一でも異なっていてもよく、(4−n)が2以上のとき各Xは同一でも異なっていてもよい。)で表される有機ケイ素化合物を、溶媒中、水及びシラノール縮合触媒の存在下に縮合させる。
第2工程
溶媒中、工程(A)で得られた有機ケイ素化合物の縮合物、光触媒、並びに金属酸化物及び/又は水酸化物を混合して光触媒含有コーティング組成物を製造する。
(2) Preparation method of composition for photocatalyst coating In order to prepare the composition of this invention, the following two processes are performed. That is,
First Step Formula (I)
R n SiX 4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.) The organic silicon compound represented by (4) is condensed in a solvent in the presence of water and a silanol condensation catalyst.
Second Step A photocatalyst-containing coating composition is produced by mixing the condensate of the organosilicon compound obtained in step (A), a photocatalyst, and a metal oxide and / or hydroxide in a solvent.
第2工程においては、有機ケイ素化合物の縮合物の液に、光触媒と金属酸化物及び/又は水酸化物を添加してもよいし、光触媒と金属酸化物及び/又は水酸化物の混合液に、有機ケイ素化合物の縮合物の液を添加しても良い。ここで用いられる、溶媒は、第1工程で使用されるものと同様のものを使用できる。また、上記有機ケイ素化合物の縮合物、光触媒、金属酸化物及び金属水酸化物の形態は、特に制限はないが、ゾルの形態で使用するのが好ましい。 In the second step, the photocatalyst and the metal oxide and / or hydroxide may be added to the liquid of the condensate of the organosilicon compound, or the mixed liquid of the photocatalyst and the metal oxide and / or hydroxide. Alternatively, a liquid of a condensate of an organosilicon compound may be added. The solvent used here can be the same as that used in the first step. The form of the condensate, photocatalyst, metal oxide and metal hydroxide of the organosilicon compound is not particularly limited, but is preferably used in the form of a sol.
第1工程の方法は、以下のとおりである。
前記有機ケイ素化合物、水及びシラノール縮合触媒を溶媒中で混合する。シラノール縮合触媒の使用量は、触媒として使用する範囲であれば特に制限はないが、通常、有機ケイ素化合物1モルに対して0.001〜0.2モルである。
使用する水は、有機ケイ素化合物の加水分解を行うに足りる範囲であれば特に制限はないが、通常、有機ケイ素化合物1モルに対して1〜10モルである。
The method of the first step is as follows.
The organosilicon compound, water and silanol condensation catalyst are mixed in a solvent. Although there will be no restriction | limiting in particular if the usage-amount of a silanol condensation catalyst is a range used as a catalyst, Usually, it is 0.001-0.2 mol with respect to 1 mol of organosilicon compounds.
The water to be used is not particularly limited as long as it is sufficient to hydrolyze the organosilicon compound, but it is usually 1 to 10 moles per mole of the organosilicon compound.
反応温度は0〜100℃、反応時間は1時間〜10日である。
溶媒としては、水のほか、メタノール、エタノール、n−プロパノール、n−ブタノールなどのエタノール系溶媒を1種単独で、あるいは2種以上を組み合わせて用いることができる。また、上記溶媒に、酢酸メチル、酢酸エチル等のエステル系溶媒;アセトン、ジエチルケトン等のケトン系溶媒;ジエチルエーテル、テトラヒドロフラン等のエーテル系溶媒;等の溶媒を混合して用いてもよい。
The reaction temperature is 0 to 100 ° C., and the reaction time is 1 hour to 10 days.
As the solvent, water, ethanol solvents such as methanol, ethanol, n-propanol, and n-butanol can be used singly or in combination of two or more. In addition, a solvent such as an ester solvent such as methyl acetate or ethyl acetate; a ketone solvent such as acetone or diethyl ketone; an ether solvent such as diethyl ether or tetrahydrofuran;
本発明において使用されるシラノール縮合触媒としては、金属酸化物、金属水酸化物、金属アルコキシド類、金属アルコキシド類の部分加水分解生成物、酸触媒などからなる群から選ばれる少なくとも1種の化合物が挙げられるが、好ましくは、金属酸化物であり、特にチタン酸化物微粒子が好ましい。
以下に、各シラノール縮合触媒について詳述する。
The silanol condensation catalyst used in the present invention includes at least one compound selected from the group consisting of metal oxides, metal hydroxides, metal alkoxides, partial hydrolysis products of metal alkoxides, acid catalysts, and the like. Of these, metal oxides are preferable, and titanium oxide fine particles are particularly preferable.
Below, each silanol condensation catalyst is explained in full detail.
1)金属酸化物
金属酸化物としては、特に限定されないが、TiO2,ZrO2,Al2O3などが挙げられ、特にTiO2の微粒子が好ましい。
以下に、特に、TiO2のナノ粒子の調製法について記載するが、調製法はこれに限定されるものではない。他の金属酸化物についても同様にして調製することができる。
The 1) the metal oxide in the metal oxide is not particularly limited, is like TiO 2, ZrO 2, Al 2 O 3, in particular of the TiO 2 fine particles are preferable.
Hereinafter, particularly, but describes the preparation method of nanoparticles of TiO 2, preparation method is not limited thereto. Other metal oxides can be similarly prepared.
チタン原子に、加水分解性基とキレート配位子とが結合してなるチタンキレート化合物と、該チタンキレート化合物に対して大過剰の水とを混合して得られるチタン酸化物ナノ粒子であり、通常有機溶媒に分散した状態で用いられる。
チタンキレート化合物は、チタン原子に、加水分解性基及びキレート配位子が結合してなるチタン化合物であれば、特に制限されない。
中心金属原子であるチタン原子の原子価は、通常2〜4価、好ましくは4価である。
Titanium oxide nanoparticles obtained by mixing a titanium chelate compound in which a hydrolyzable group and a chelate ligand are bonded to a titanium atom, and a large excess of water with respect to the titanium chelate compound, Usually used in a state dispersed in an organic solvent.
The titanium chelate compound is not particularly limited as long as it is a titanium compound in which a hydrolyzable group and a chelate ligand are bonded to a titanium atom.
The valence of the titanium atom which is the central metal atom is usually 2 to 4, preferably 4.
加水分解性基としては、水と反応して分解する基であれば特に制限されない。具体的には、置換基を有していてもよいアルコキシル基、置換基を有していてもよいアシルオキシ基、ハロゲン原子、イソシアネート基、シアノ基、アミノ基、アミド基等が挙げられる。
置換基を有していてもよいアルコキシル基としては、メトキシ基、エトキシ基、n−プロポキシ基、イソプロポキシ基、n−ブトキシ基、sec−ブトキシ基、t−ブトキシ基、n−ペンチルオキシ基、n−へキシルオキシ基等が挙げられる。
置換基を有していてもよいアシルオキシ基としては、アセトキシ基、プロピオニルオキシ基、n−プロピルカルボニルオキシ基、イソプロピルカルボニルオキシ基、n−ブチルカルボニルオキシ基等が挙げられる。
前記アルコキシル基、アシルオキシ基の置換基としては、ハロゲン原子、カルボキシル基、アミド基、イミド基、エステル基、水酸基等が挙げられる。
前記ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
The hydrolyzable group is not particularly limited as long as it is a group that reacts with water and decomposes. Specific examples include an alkoxyl group which may have a substituent, an acyloxy group which may have a substituent, a halogen atom, an isocyanate group, a cyano group, an amino group, an amide group, and the like.
Examples of the alkoxyl group which may have a substituent include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, Examples include n-hexyloxy group.
Examples of the acyloxy group which may have a substituent include an acetoxy group, a propionyloxy group, an n-propylcarbonyloxy group, an isopropylcarbonyloxy group, and an n-butylcarbonyloxy group.
Examples of the substituent for the alkoxyl group and acyloxy group include a halogen atom, a carboxyl group, an amide group, an imide group, an ester group, and a hydroxyl group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
これらの中でも、置換基を有していてもよいアルコキシル基、置換基を有していてもよいアシルオキシ基、ハロゲン原子又はイソシアネート基が好ましく、置換基を有していてもよいアルコキシル基がより好ましく、炭素数1〜4のアルコキシル基が特に好ましい。
キレート配位子としては、金属と結合してキレートを形成し得る配位子であれば特に制限されず、中性配位子でも陰イオンでも構わない。少なくとも一箇所で金属原子に結合していればよく、単座配位子であっても、多座配位子であってもよい。また、例えば、2座配位子であっても2座で一つの金属原子に結合していなくてもよい。
キレート配位子の具体例としては、以下のものが挙げられる。ただし、キレート配位子となり得るキレート化合物として例示する。
Among these, an alkoxyl group which may have a substituent, an acyloxy group which may have a substituent, a halogen atom or an isocyanate group are preferable, and an alkoxyl group which may have a substituent is more preferable. Particularly preferred are alkoxy groups having 1 to 4 carbon atoms.
The chelate ligand is not particularly limited as long as it can bind to a metal to form a chelate, and may be a neutral ligand or an anion. What is necessary is just to couple | bond with the metal atom at at least one place, and it may be a monodentate ligand or a polydentate ligand. For example, even if it is a bidentate ligand, it does not need to be bound to one metal atom by bidentate.
Specific examples of the chelate ligand include the following. However, it illustrates as a chelate compound which can become a chelate ligand.
シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等の飽和脂肪族ジカルボン酸類;アセチルアセトン、ベンゾイルアセトン、ヘキサフルオロアセチルアセトン等のβ−ジケトン類;アセト酢酸メチル、アセト酢酸エチル等のβ−ケトエステル類;エチレングリコール等のグリコール類;オキシ酢酸等のグリコール酸類;エチレンジアミン四酢酸(EDTA)及びそのナトリウム塩、エチレンジアミン、1,3−プロパンジアミン、ジエチレントリアミン、ペンタメチルジエチレントリアミン、ヘキサメチルトリエチレンテトラミン、トリス[2−(ジメチルアミノ)エチル]アミン、トリ(ピリジニルメチル)アミン等の含窒素化合物;
フランカルボン酸、チオフェンカルボン酸、ニコチン酸、イソニコチン酸、フェナントロリン、ジフェナントロリン、置換フェナントロリン、2,2’:6’,2”−ターピリジン、ピリジンイミン、架橋脂肪族ジアミン、4−4’−ジ(5−ノニル)−2,2’−ビピリジン、O,S,Se,Teの配位したビピリジン、アルキルイミノピリジン、アルキルビピリジニルアミン、アルキル置換トリピリジン、ジ(アルキルアミノ)アルキルピリジン、エチレンジアミンジピリジン、その他の複素環化合物;
Saturated aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid; β-diketones such as acetylacetone, benzoylacetone and hexafluoroacetylacetone; Β-ketoesters such as methyl acetate and ethyl acetoacetate; glycols such as ethylene glycol; glycolic acids such as oxyacetic acid; ethylenediaminetetraacetic acid (EDTA) and its sodium salt, ethylenediamine, 1,3-propanediamine, diethylenetriamine, penta Nitrogen-containing compounds such as methyldiethylenetriamine, hexamethyltriethylenetetramine, tris [2- (dimethylamino) ethyl] amine, tri (pyridinylmethyl) amine;
Furancarboxylic acid, thiophenecarboxylic acid, nicotinic acid, isonicotinic acid, phenanthroline, diphenanthroline, substituted phenanthroline, 2,2 ': 6', 2 "-terpyridine, pyridineimine, bridged aliphatic diamine, 4-4'-di (5-nonyl) -2,2′-bipyridine, bipyridine coordinated with O, S, Se, Te, alkyliminopyridine, alkylbipyridinylamine, alkyl-substituted tripyridine, di (alkylamino) alkylpyridine, ethylenediaminedi Pyridine, other heterocyclic compounds;
2−メルカプトエタノール等のメルカプトアルコール類;エタンジチオール等のジチオール類;2−メルカプトエチルアミン等のメルカプトアミン類;2,4−ペンタンジチオン等のジチオケトン類;等の硫黄含有化合物等が挙げられる。
これらは1種単独で、あるいは2種以上を組み合わせて用いることができる。チタンキレート化合物の製造方法としては、特に制約はなく、例えば、後述するチタンアルコキシド化合物の有機溶媒溶液に、所定量のキレート化合物を添加する方法等が挙げられる。キレート化合物の添加量は、チタンアルコキシド化合物1モルに対して、通常1〜5倍モル、好ましくは1〜3倍モルである。
Sulfur-containing compounds such as mercapto alcohols such as 2-mercaptoethanol; dithiols such as ethanedithiol; mercaptoamines such as 2-mercaptoethylamine; dithioketones such as 2,4-pentanedithione;
These can be used alone or in combination of two or more. There is no restriction | limiting in particular as a manufacturing method of a titanium chelate compound, For example, the method etc. which add a predetermined amount chelate compound to the organic solvent solution of the titanium alkoxide compound mentioned later etc. are mentioned. The addition amount of the chelate compound is usually 1 to 5 times mol, preferably 1 to 3 times mol for 1 mol of the titanium alkoxide compound.
チタンキレート化合物の加水分解生成物であるチタン酸化物の分散液の製法は、詳しくは、WO2006−87986号パンフレットに記載されており、これに基づいて行うことができる。
分散液中のチタン酸化物の含有量は、分散液全体に対して酸化チタン換算濃度で0.1〜10重量%、好ましくは0.1〜5重量%である。
The method for producing a dispersion of titanium oxide which is a hydrolysis product of a titanium chelate compound is described in detail in WO 2006-87986 pamphlet, and can be performed based on this.
The content of titanium oxide in the dispersion is 0.1 to 10% by weight, preferably 0.1 to 5% by weight, in terms of titanium oxide, with respect to the entire dispersion.
分散液は、チタンキレート化合物の加水分解生成物であるチタン酸化物の微粒子が、水溶媒中又は有機溶媒中で凝集せずに安定に分散している性質を有するチタン酸化物粒子の分散液である。ここで、凝集せずに安定に分散している状態とは、有機溶媒中、チタンキレート化合物等の加水分解生成物の分散質が、凝結して不均質に分離していない状態を表し、好ましくは透明で均質な状態を表す。ここで透明とは、可視光における透過率が高い状態をいい、具体的には、分散質の濃度を酸化物換算で0.5重量%とし、石英セルの光路長を1cmとし、対照試料を有機溶媒とし、光の波長を550nmとする条件で測定した分光透過率で表して、好ましくは80〜100%の透過率を表す状態をいう。 The dispersion is a dispersion of titanium oxide particles having the property that fine particles of titanium oxide, which is a hydrolysis product of a titanium chelate compound, are stably dispersed without agglomerating in an aqueous solvent or an organic solvent. is there. Here, the state of being stably dispersed without agglomeration represents a state in which the dispersoid of a hydrolysis product such as a titanium chelate compound in an organic solvent is not coagulated and separated non-uniformly, preferably Represents a transparent and homogeneous state. Here, transparent means a state in which the transmittance in visible light is high. Specifically, the concentration of the dispersoid is 0.5% by weight in terms of oxide, the optical path length of the quartz cell is 1 cm, and the control sample is This is a state in which an organic solvent is used and the transmittance is preferably 80 to 100%, expressed by spectral transmittance measured under the condition that the wavelength of light is 550 nm.
分散液に含まれるチタン酸化物粒子の粒子径は特に限定されないが、通常1〜100nm、好ましくは1〜50nm、より好ましくは1〜20nmの範囲である。また、チタン酸化物粒子は単分散であるのが好ましい。 Although the particle diameter of the titanium oxide particle contained in a dispersion liquid is not specifically limited, Usually, 1-100 nm, Preferably it is 1-50 nm, More preferably, it is the range of 1-20 nm. The titanium oxide particles are preferably monodispersed.
2)金属水酸化物
金属水酸化物としては、特に限定されないが、Ti(OH)4,Zr(OH)4,Al(OH)3などが挙げられる。
2) Metal hydroxide Although it does not specifically limit as a metal hydroxide, Ti (OH) 4 , Zr (OH) 4 , Al (OH) 3 etc. are mentioned.
3)金属アルコキシド類
金属アルコキシド類としては、特に限定されないが、透明性に優れる有機薄膜を得ることができること等の理由から、チタン、ジルコニウム、アルミニウム、ケイ素、鉄、ゲルマニウム、インジウム、スズ、タンタル、亜鉛、タングステン及び鉛からなる群から選ばれる少なくとも1種の金属のアルコキシド類が好ましい。
金属アルコキシド類のアルコキシ基の炭素数は特に限定されないが、含有酸化物濃度、有機物の脱離容易性、入手容易性等から、炭素数1〜4のものがより好ましい。
3) Metal alkoxides The metal alkoxides are not particularly limited, but titanium, zirconium, aluminum, silicon, iron, germanium, indium, tin, tantalum, and the like can be obtained because an organic thin film having excellent transparency can be obtained. Preference is given to alkoxides of at least one metal selected from the group consisting of zinc, tungsten and lead.
The number of carbon atoms of the alkoxy group of the metal alkoxide is not particularly limited, but one having 1 to 4 carbon atoms is more preferable from the viewpoint of the concentration of the contained oxide, the ease of detachment of organic substances, the availability, and the like.
本発明に用いる金属アルコキシド類の具体例としては、Si(OCH3)4、Si(OC2H5)4、Si(OC3H7−i)4、Si(OC4H9−t)4等のケイ素アルコキシド;Ti(OCH3)4、Ti(OC2H5)4、Ti(OC3H7−i)4、Ti(OC4H9)4等のチタンアルコキシド;Ti[OSi(CH3)3]4、Ti[OSi(C2H5)3]4等のテトラキストリアルキルシロキシチタン;Zr(OCH3)4、Zr(OC2H5)4、Zr(OC3H7)4、Zr(OC4H9)4等のジルコニウムアルコキシド;Al(OCH3)4、Al(OC2H5)4、Al(OC3H7−i)4、Al(OC4H9)3等のアルミニウムアルコキシド;Ge(OC2H5)4等のゲルマニウムアルコキシド;In(OCH3)3、In(OC2H5)3、In(OC3H7−i)3、In(OC4H9)3等のインジウムアルコキシド;Sn(OCH3)4、Sn(OC2H5)4、Sn(OC3H7−i)4、Sn(OC4H9)4等のスズアルコキシド;Ta(OCH3)5、Ta(OC2H5)5、Ta(OC3H7−i)5、Ta(OC4H9)5等のタンタルアルコキシド;W(OCH3)6、W(OC2H5)6、W(OC3H7−i)6、W(OC4H9)6等のタングステンアルコキシド;Zn(OC2H5)2等の亜鉛アルコキシド;Pb(OC4H9)4等の鉛アルコキシド;等が挙げられる。これらの金属アルコキシド類は1種単独で、あるいは2種以上を組み合わせて用いることができる。 Specific examples of metal alkoxides used in the present invention include Si (OCH 3 ) 4 , Si (OC 2 H 5 ) 4 , Si (OC 3 H 7 -i) 4 , Si (OC 4 H 9 -t) 4. Silicon alkoxides such as Ti (OCH 3 ) 4 , Ti (OC 2 H 5 ) 4 , Ti (OC 3 H 7 -i) 4 , Ti (OC 4 H 9 ) 4 and other titanium alkoxides; Ti [OSi (CH 3 ) 3 ] 4 , tetrakistrialkylsiloxytitanium such as Ti [OSi (C 2 H 5 ) 3 ] 4 ; Zr (OCH 3 ) 4 , Zr (OC 2 H 5 ) 4 , Zr (OC 3 H 7 ) 4 Zr (OC 4 H 9 ) 4 and other zirconium alkoxides; Al (OCH 3 ) 4 , Al (OC 2 H 5 ) 4 , Al (OC 3 H 7 -i) 4 , Al (OC 4 H 9 ) 3 and the like Aluminum Al Coxide; Germanium alkoxide such as Ge (OC 2 H 5 ) 4 ; In (OCH 3 ) 3 , In (OC 2 H 5 ) 3 , In (OC 3 H 7 -i) 3 , In (OC 4 H 9 ) 3 Indium alkoxides such as Sn (OCH 3 ) 4 , Sn (OC 2 H 5 ) 4 , Sn (OC 3 H 7 -i) 4 , Sn (OC 4 H 9 ) 4 etc. Tin alkoxides; Ta (OCH 3 ) 5 , tantalum alkoxides such as Ta (OC 2 H 5 ) 5 , Ta (OC 3 H 7 -i) 5 , Ta (OC 4 H 9 ) 5 ; W (OCH 3 ) 6 , W (OC 2 H 5 ) 6 , W (OC 3 H 7 -i) 6 , tungsten alkoxides such as W (OC 4 H 9 ) 6 ; zinc alkoxides such as Zn (OC 2 H 5 ) 2 ; lead alkoxides such as Pb (OC 4 H 9 ) 4 ; Etc. It is. These metal alkoxides can be used alone or in combination of two or more.
また本発明においては、金属アルコキシド類として、2種以上の金属アルコキシド類の反応により得られる複合アルコキシド、1種もしくは2種以上の金属アルコキシド類と、1種もしくは2種以上の金属塩との反応により得られる複合アルコキシド、及びこれらの組み合わせを用いることもできる。
2種以上の金属アルコキシド類の反応により得られる複合アルコキシドとしては、アルカリ金属又はアルカリ土類金属のアルコキシドと、遷移金属のアルコキシドとの反応により得られる複合アルコキシドや、第3B族元素の組合せにより錯塩の形で得られる複合アルコキシド等を例示することができる。
In the present invention, as a metal alkoxide, a reaction of a composite alkoxide obtained by reaction of two or more metal alkoxides, one or more metal alkoxides, and one or two or more metal salts. It is also possible to use a composite alkoxide obtained by the above and a combination thereof.
The composite alkoxide obtained by the reaction of two or more kinds of metal alkoxides includes a complex alkoxide obtained by the reaction of an alkali metal or alkaline earth metal alkoxide and a transition metal alkoxide, or a complex salt by a combination of Group 3B elements. The compound alkoxide obtained by the form of this can be illustrated.
その具体例としては、BaTi(OR)6、SrTi(OR)6、BaZr(OR)6、SrZr(OR)6、LiNb(OR)6、LiTa(OR)6、及び、これらの組合せ、LiVO(OR)4、MgAl2(OR)8、(RO)3SiOAl(OR’)2、(RO)3SiOTi(OR’)3、(RO)3SiOZr(OR’)3、(RO)3SiOB(OR’)2、(RO)3SiONb(OR’)4、(RO)3SiOTa(OR’)4等のケイ素アルコキシドと、前記金属アルコキシド類との反応物及びその縮重合物等が挙げられる。ここで、R及びR’はアルキル基等を表す。 Specific examples, BaTi (OR) 6, SrTi (OR) 6, BaZr (OR) 6, SrZr (OR) 6, LiNb (OR) 6, LiTa (OR) 6 , and, combinations thereof, LiVO ( OR) 4 , MgAl 2 (OR) 8 , (RO) 3 SiOAl (OR ′) 2 , (RO) 3 SiOTi (OR ′) 3 , (RO) 3 SiOZr (OR ′) 3 , (RO) 3 SiOB ( OR ′) 2 , (RO) 3 SiONb (OR ′) 4 , (RO) 3 SiOTa (OR ′) 4, etc., and reaction products of the above metal alkoxides and polycondensates thereof. Here, R and R ′ represent an alkyl group or the like.
1種もしくは2種以上の金属アルコキシド類と1種もしくは2種以上の金属塩との反応により得られる複合アルコキシドとしては、金属塩と金属アルコキシド類との反応により得られる化合物を例示することができる。 Examples of the composite alkoxide obtained by reaction of one or more metal alkoxides with one or more metal salts include compounds obtained by reaction of metal salts with metal alkoxides. .
金属塩としては、塩化物、硝酸塩、硫酸塩、酢酸塩、ギ酸塩、シュウ酸塩等を、金属アルコキシド類としては、上述した金属アルコキシド類と同様のものをそれぞれ例示することができる。 Examples of the metal salt include chlorides, nitrates, sulfates, acetates, formates, oxalates, and the like, and examples of the metal alkoxides include those similar to the metal alkoxides described above.
4)金属アルコキシド類の部分加水分解生成物
金属アルコキシド類の部分加水分解生成物は、金属アルコキシド類を完全に加水分解する前に得られるものであって、オリゴマーの状態で存在する。
金属アルコキシド類の部分加水分解生成物の製造方法としては、有機溶媒中、上記例示した金属アルコキシド類に対し0.5〜2.0倍モル未満の水を用い、−100℃から有機溶媒還流温度範囲で加水分解する方法を好ましく例示することができる。具体的には、例えば、特開2007−125548号公報に記載されている方法により製造することができる。
4) Partial hydrolysis product of metal alkoxide The partial hydrolysis product of metal alkoxide is obtained before the metal alkoxide is completely hydrolyzed, and exists in an oligomer state.
As a method for producing a partial hydrolysis product of a metal alkoxide, 0.5 to 2.0 times less water than the above exemplified metal alkoxide is used in an organic solvent, and the organic solvent reflux temperature is from −100 ° C. A method of hydrolyzing within a range can be preferably exemplified. Specifically, for example, it can be produced by a method described in JP-A-2007-125548.
5)酸触媒
酸触媒としては、塩酸、硝酸、ホウ酸、ホウフッ化水素酸等の鉱酸、酢酸、ギ酸、シュウ酸、炭酸、トリフルオロ酢酸、p−トルエンスルホン酸、メタンスルホン酸等の有機酸等を例示することができる。さらには、光照射によって酸を発生する光酸発生剤、具体的には、ジフェニルヨードニウムヘキサフルオロホスフェート、トリフェニルホスホニウムヘキサフルオロホスフェート等を例示することができる。
5) Acid catalyst Acid catalysts include mineral acids such as hydrochloric acid, nitric acid, boric acid, borohydrofluoric acid, organic acids such as acetic acid, formic acid, oxalic acid, carbonic acid, trifluoroacetic acid, p-toluenesulfonic acid, and methanesulfonic acid. An acid etc. can be illustrated. Furthermore, photoacid generators that generate an acid upon irradiation with light, specifically, diphenyliodonium hexafluorophosphate, triphenylphosphonium hexafluorophosphate, and the like can be exemplified.
6)その他のシラノール縮合触媒
その他のシラノール縮合触媒としては、カルボン酸金属塩、カルボン酸エステル金属塩、カルボン酸金属塩ポリマー、カルボン酸金属塩キレート、チタン酸エステル及びチタン酸エステルキレート等を例示することができる。
6) Other silanol condensation catalysts Examples of other silanol condensation catalysts include carboxylic acid metal salts, carboxylic acid ester metal salts, carboxylic acid metal salt polymers, carboxylic acid metal salt chelates, titanate esters, and titanate ester chelates. be able to.
(3)光触媒コーティング用組成物の担体へのコーティング法
本発明の光触媒コーティング用組成物を担体に担持する方法としては、樹脂溶液を印刷法、シート成形法、スプレー吹き付け法、ディップコーティング法、スピンコーティング法等でコートし、乾燥する方法が使用できる。乾燥する温度は、溶媒や樹脂の種類により適宜選択して行う。
(3) Coating method of photocatalyst coating composition on carrier As a method of supporting the photocatalyst coating composition of the present invention on a carrier, a resin solution is printed, sheet molding, spray spraying, dip coating, spin coating A method of coating by a coating method or the like and drying can be used. The drying temperature is appropriately selected depending on the type of solvent and resin.
(4)用途
本発明の光触媒含有組成物をコーティングした構造体は、建築用塗料、壁紙、窓ガラス、ブラインド、カーテン、カーペット、照明器具、照明灯、ブラックライト、船底・漁網防汚塗料、水処理用充填剤、農ビフィルム、防草シート、包装資材等に使用できる。また、特に高温高湿の環境下でも使用可能な光触媒担持体とすることも可能である。
担体として使用できるガラスの形状としては、板状、管状、球状、繊維状等どのような複雑な形状でもよい。また、大きさは10μm以上であれば強固に担持する事ができる。また、施工済の窓ガラス、ショーケース、めがね等用途によっては、加工済のガラスに処理することにより、光触媒担持ガラスとすることもできる。
(4) Applications Structures coated with the photocatalyst-containing composition of the present invention are architectural paints, wallpaper, window glass, blinds, curtains, carpets, lighting fixtures, lighting lamps, black lights, ship bottoms / fishing net antifouling paints, water It can be used for processing fillers, agricultural films, herbicidal sheets, packaging materials, and the like. In addition, a photocatalyst carrier that can be used even in a high-temperature and high-humidity environment is also possible.
The shape of the glass that can be used as the carrier may be any complicated shape such as a plate shape, a tubular shape, a spherical shape, or a fibrous shape. If the size is 10 μm or more, it can be firmly supported. Moreover, depending on uses, such as a constructed window glass, a showcase, and glasses, it can also be set as photocatalyst carrying glass by processing into processed glass.
本発明による光触媒層を担持したガラスは、窓ガラス、計器用カバーガラス、照明器具、照明灯、ブラックライト、水処理用充填剤ををはじめ、カメラ、眼鏡レンズ等、抗菌、脱臭、防汚等の効果を必要とするあらゆる使用場面に使用できる。
本発明による光触媒層を担持したプラスチック成形体は、壁紙、内装用ボード、家具、電気機器、車輛用部品をはじめ、カメラ、メガネのレンズ等、抗菌、脱臭、防汚等の効果を必要とする多くの使用場面に使用できる。
プラスチック成形体の形状としては、フィルム状、板状、管状、球状、繊維状等どのような複雑な形状でもよい。また、大きさは10μm以上であれば強固に担持する事ができる。また、施工済の建築資材、家庭電化製品、めがね等用途によっては、加工済のプラスチック成形体に処理することにより、本発明の光触媒担持プラスチック成形体とすることもできるため、その応用範囲は極めて広いと言える。
Glass carrying a photocatalyst layer according to the present invention includes window glass, instrument cover glass, lighting fixtures, illumination lamps, black light, water treatment fillers, cameras, spectacle lenses, etc., antibacterial, deodorant, antifouling, etc. It can be used for any use scene that requires the effect of.
The plastic molded article carrying the photocatalyst layer according to the present invention requires antibacterial, deodorizing, antifouling, etc., including wallpaper, interior boards, furniture, electrical equipment, vehicle parts, cameras, glasses lenses, etc. Can be used for many use situations.
The shape of the plastic molded body may be any complicated shape such as a film shape, a plate shape, a tubular shape, a spherical shape, or a fibrous shape. If the size is 10 μm or more, it can be firmly supported. In addition, depending on applications such as construction materials, home appliances, and glasses that have already been constructed, the processed plastic molded product can be processed into the photocatalyst-supported plastic molded product of the present invention. It can be said that it is wide.
担体として使用できる布帛としては、毛、絹、綿、麻などの天然繊維、レーヨン、アセテートなどの再生繊維、ナイロン、アクリル、ポリアミド、ポリエステル、ポリアクリロニトリル、ポリ塩化ビニルなどの合成繊維、アラミドなどの耐熱性繊維の単独あるいは混紡繊維からなる織布、編布、不織布などがある。また、シリコン系撥水剤、パーフルオロアルキルアクリレートなどのフッ素撥水剤、ジルコニウム塩系撥水剤、エチレン尿素系撥水剤などの撥水剤で処理された布帛、必要に応じて耐久性を向上させるためにエチレンイミン系、エポキシ系、メラミン系等の架橋剤を併用している撥水加工された布帛、ポリアミドとポリエステルのフィブリル化型複合繊維等からなる擬革、織布、不織布、編布等の基材にポリウレタン接着剤を介してポリウレタン樹脂層が形成されてなる合成皮革等を用いることもできる。また、傘、テント、バッグ等、加工済の布帛に処理することにより、本発明の光触媒担持布帛とすることもできる。
本発明による光触媒層を担持した布帛は、抗菌、脱臭、防汚等の効果を必要とする多くの使用場面、たとえばカーテン、壁紙等のインテリア製品、テント、傘、テーブルクロス等の日用品、食品包装材等としてまた育苗シート等農業分野にも使用できる。
Fabrics that can be used as carriers include natural fibers such as hair, silk, cotton, and linen, regenerated fibers such as rayon and acetate, synthetic fibers such as nylon, acrylic, polyamide, polyester, polyacrylonitrile, and polyvinyl chloride, and aramid. Examples include woven fabrics, knitted fabrics, and non-woven fabrics composed of heat-resistant fibers alone or blended fibers. Also, fabrics treated with water repellents such as silicon water repellents, fluorine water repellents such as perfluoroalkyl acrylate, zirconium salt water repellents, ethylene urea water repellents, and durability as required. Water-repellent processed fabrics that use ethyleneimine-based, epoxy-based, and melamine-based crosslinkers together to improve, artificial leather made of fibrillated composite fibers of polyamide and polyester, woven fabrics, non-woven fabrics, knitted fabrics, etc. Synthetic leather or the like in which a polyurethane resin layer is formed on a base material such as cloth via a polyurethane adhesive can also be used. Moreover, it can also be set as the photocatalyst carrying | support cloth of this invention by processing to processed cloths, such as an umbrella, a tent, a bag.
The fabric carrying the photocatalyst layer according to the present invention has many uses such as antibacterial, deodorizing, and antifouling effects, such as interior products such as curtains and wallpaper, daily necessaries such as tents, umbrellas, and tablecloths, and food packaging. It can also be used in the agricultural field such as nursery sheets as a material.
本発明による光触媒層を担持した金属としては、アルミニウム、鉄、銅等の単体金属の他、ステンレス、しんちゅう、黄銅、アルミ合金、チタン合金等の各種合金などが挙げられる。また、使用する金属の形状、材質によっては、通常の塗料で塗装した金属シートや板、着色したカラー鋼板やカラーアルミサッシ等の上に本発明に係わる光触媒層を設けて光触媒担持体とすることができる。この場合、光触媒層の光透過率が高く透明であれば下地の塗料の色合いを損なうことがないので好ましい。
金属の形状としては、板状、管状、球状、繊維状、シート状等どのような複雑な形状でもよい。また、大きさは10ミクロン以上であれば強固に担持する事ができる。また、施工済の窓枠、家具、ショーケース、めがねフレーム等用途によっては、加工済の金属に処理することにより、本発明の光触媒担持金属とすることもできる。
本発明による光触媒層を担持した金属は、窓枠、家具、装飾品、内装パネル、外装パネル、水処理用充填剤をはじめ、ストレーナー、フィルター等、抗菌、脱臭、防汚等の効果を必要とする多くの使用場面に使用できる。
Examples of the metal carrying the photocatalyst layer according to the present invention include various metals such as stainless steel, brass, brass, aluminum alloy and titanium alloy in addition to simple metals such as aluminum, iron and copper. Depending on the shape and material of the metal used, a photocatalyst layer according to the present invention may be provided on a metal sheet or plate coated with a normal paint, a colored color steel plate, a color aluminum sash, or the like to form a photocatalyst carrier. Can do. In this case, it is preferable that the light transmittance of the photocatalyst layer is high and transparent, since the hue of the underlying paint is not impaired.
The metal shape may be any complicated shape such as a plate shape, a tubular shape, a spherical shape, a fiber shape, and a sheet shape. If the size is 10 microns or more, it can be firmly supported. Moreover, depending on uses, such as a constructed window frame, furniture, a showcase, and a spectacle frame, it can also be set as the photocatalyst carrying metal of this invention by processing to a processed metal.
The metal carrying the photocatalyst layer according to the present invention requires window frames, furniture, decorations, interior panels, exterior panels, fillers for water treatment, strainers, filters, etc., such as antibacterial, deodorizing, and antifouling effects. Can be used for many usage scenes.
本発明による光触媒層を設けた木材および木質材料の形状としては、板状、球状、シート状等どのような複雑な形状でも可能である。また、大きさは10μm以上であれば強固に担持する事ができ、施工済の壁、天井板、柱のほか、家具、木工細工等の加工済の木材および木質材料に処理することにより、本発明の光触媒担持木材および木質材料とすることもできる。
本発明による光触媒層を担持した木材および木質材料は、建築用材、家具、木工品、インテリア材および内装材等、抗菌、脱臭、防汚等の効果を必要とする多くの使用場面に使用できる。
本発明による光触媒担持構造体を設けたプラスチックフィルムは、その防汚、抗菌、脱臭機能を活かして、光触媒を担持していない面に接着剤を塗布したフィルムとすることで、自動車や各種輸送機器の窓ガラス、建築物の窓ガラス、冷凍・冷蔵ショーケースや温室などの内側に貼り付けることが可能になり、内部空間の微量有害物質の分解と、ガラス表面の汚染防止と破損時の飛散防止に有効な透視性の高いフィルムとすることが可能である。また、薄いプラスチックフィルムに本発明にかかわる光触媒担持構造体を成膜したものは食品包装用のラップフィルムとしても使用可能である。このプラスチックフィルムに使用できる樹脂としては、ポリエチレンテレフタレート樹脂、ポリカーボネート樹脂、ポリアクリル酸エステル樹脂、ポリメチルメタクリレート樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリスチレン樹脂、ポリ塩化ビニル樹脂、ポリフッ化ビニリデン樹脂、フッ化エチレン−プロピレン共重合樹脂、フッ化エチレン−エチレン共重合樹脂等のフィルム状に成形加工した時に550nmの波長の光の直線透過率が50%以上である透明性の高い合成樹脂フィルムまたはシートがいずれも使用できる。また、壁紙や化粧シートなどの裏面に粘着層と剥離フィルムを設け表面に模様を印刷した不透明な素材の表面にも、本発明にかかる光触媒担持構造体は透明であるため下地の壁紙や化粧シートに印刷された柄や模様を損なうことがないので好ましく採用できる。
The shape of the wood and wood material provided with the photocatalyst layer according to the present invention can be any complicated shape such as a plate shape, a spherical shape, and a sheet shape. In addition, if the size is 10μm or more, it can be firmly supported. In addition to the finished walls, ceiling boards, pillars, processed wood and wood materials such as furniture and woodwork, The photocatalyst-supporting wood and wood material of the invention can also be used.
The wood and wood material carrying the photocatalyst layer according to the present invention can be used in many usage scenes that require antibacterial, deodorizing, antifouling and other effects such as building materials, furniture, woodwork, interior materials and interior materials.
The plastic film provided with the photocatalyst carrying structure according to the present invention makes use of its antifouling, antibacterial, and deodorizing functions to form a film in which an adhesive is applied to the surface not carrying the photocatalyst, so that automobiles and various transport equipment Can be affixed to the inside of glass windows, building glass windows, frozen and refrigerated showcases and greenhouses, etc. to decompose trace amounts of harmful substances in the interior space, prevent contamination of the glass surface, and prevent scattering It is possible to make a film having high transparency that is effective for the above. Moreover, what formed into a film the photocatalyst support structure which concerns on this invention in the thin plastic film can be used also as a wrap film for food packaging. Resins that can be used for this plastic film include polyethylene terephthalate resin, polycarbonate resin, polyacrylate resin, polymethyl methacrylate resin, polyethylene resin, polypropylene resin, polyamide resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, polyfluoride resin. A highly transparent synthetic resin having a linear transmittance of light having a wavelength of 550 nm of 50% or more when molded into a film such as vinylidene resin, fluorinated ethylene-propylene copolymer resin, or fluorinated ethylene-ethylene copolymer resin. Either film or sheet can be used. In addition, since the photocatalyst-supporting structure according to the present invention is transparent on the surface of an opaque material in which an adhesive layer and a release film are provided on the back surface of a wallpaper or a decorative sheet and a pattern is printed on the surface, the underlying wallpaper or decorative sheet Since it does not impair the pattern or pattern printed on the film, it can be preferably used.
これらの合成樹脂フィルムまたはシートはその表面に表面処理を行って光触媒担持構造体の接着性をより向上させることが可能で、光触媒層を塗布する面をコロナ放電処理やUV−オゾン処理などによって表面を物理的に極微量酸化させたり、シリコン系などの表面処理剤を薄く塗布して光触媒層との馴染みを良くしたものも好ましく使用できる。更に、実施例にも示したようにこれらの基材の表面もしくは裏面に、熱線反射・遮蔽機能や紫外線反射・遮蔽機能を持たせるための薄膜を成膜することが可能で、防汚・抗菌・消臭機能を併せ持った熱線反射フィルムや紫外線カットフィルムとすることが可能になる上に、本発明による光触媒担持構造体は極めて高い耐久性と光触媒活性を兼ね備えたものであるため、極めて付加価値の高い製品とすることができる。 These synthetic resin films or sheets can be surface-treated to improve the adhesion of the photocatalyst-supporting structure, and the surface on which the photocatalyst layer is applied can be surfaced by corona discharge treatment or UV-ozone treatment. It is also possible to preferably use a material that is physically oxidized in a very small amount or is thinly coated with a surface treatment agent such as silicon to improve the familiarity with the photocatalyst layer. Furthermore, as shown in the examples, it is possible to form a thin film for providing heat ray reflection / shielding function or ultraviolet light reflection / shielding function on the front or back surface of these base materials, and to provide antifouling / antibacterial properties. -In addition to being able to be a heat ray reflective film or UV cut film having a deodorizing function, the photocatalyst-supporting structure according to the present invention has extremely high durability and photocatalytic activity, so it has extremely high added value. High product.
次に、実施例により本発明をさらに詳細に説明するが、本発明は、実施例に限定されるものでない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to an Example.
[実施例1〜3]
<光触媒層形成用塗布液の調製>
ジイソプロポキシビスアセチルアセトナートチタン(日本曹達株式会社製、T−50、酸化チタン換算固形分量:16.5重量%)303.03gをエタノール溶媒584.21gに溶解した後、攪拌しながらイオン交換水112.76g(10倍モル/酸化チタンのモル)をゆっくり滴下し加水分解させた。1日後に溶液をろ過し、黄色透明な酸化チタン換算濃度5重量%の酸化チタンナノ分散液[A−1]を得た。酸化チタンの平均粒径は4.1nmで単分散性であった。有機ケイ素化合物は、3−グリシドキシプロピルトリメトキシシラン[B−1](信越化学工業株式会社製、KBM−403)を使用した。元素比(Ti/Si=1/9)となるように上記[A−1]427.25gと[B−1]572.75gを混合し12時間攪拌した液[C−1]を作製した。更にアルミニウム化合物としてアルミゾル10A(川研ファインケミカル製10%ベーマイトアルミナコロイド水溶液)[D−1]、光触媒として硝酸酸性酸化チタニアゾル分散液(結晶粒子径8nm)[E−1]を使用し、[C−1]液、[D−1]液、[E−1]液をそれぞれ混合調製することで光触媒層形成用塗布液[F−1]を得た。
<光触媒層形成用塗布液の組成>
<Preparation of photocatalyst layer forming coating solution>
Dissolve 303.03 g of diisopropoxybisacetylacetonate titanium (manufactured by Nippon Soda Co., Ltd., T-50, solid content in terms of titanium oxide: 16.5% by weight) in 584.21 g of ethanol solvent, and then ion-exchange with stirring. 112.76 g of water (10-fold mol / mol of titanium oxide) was slowly added dropwise to cause hydrolysis. One day later, the solution was filtered to obtain a yellow transparent titanium oxide nanodispersion [A-1] having a titanium oxide equivalent concentration of 5% by weight. The average particle size of titanium oxide was 4.1 nm and was monodispersed. As the organosilicon compound, 3-glycidoxypropyltrimethoxysilane [B-1] (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403) was used. [C-1] was prepared by mixing 427.25 g of the above [A-1] and 572.75 g of [B-1] so that the element ratio (Ti / Si = 1/9) was obtained, and stirring for 12 hours. Furthermore, aluminum sol 10A (10% boehmite alumina colloid aqueous solution manufactured by Kawaken Fine Chemical Co., Ltd.) [D-1] is used as the aluminum compound, and nitric acid acidic titania sol dispersion (crystal particle diameter 8 nm) [E-1] is used as the photocatalyst. 1] Liquid, [D-1] liquid, and [E-1] liquid were mixed and prepared to obtain a photocatalyst layer-forming coating liquid [F-1].
<Composition of coating solution for forming photocatalyst layer>
<光触媒層の作製>
上記で得られた塗膜形成用溶液[F−1]を担体[TA−1]にバーコーターを用いて製膜し、温風循環型乾燥器にて100℃で30分間乾燥し、膜厚1μm〜10μmの光触媒層を得た。
担体[TA−1]はソーダライムガラス板。
<Preparation of photocatalyst layer>
The film-forming solution [F-1] obtained above was formed into a film on the carrier [TA-1] using a bar coater, and dried at 100 ° C. for 30 minutes in a hot-air circulating drier. A photocatalyst layer of 1 μm to 10 μm was obtained.
Carrier [TA-1] is a soda lime glass plate.
<光触媒担持構造体の性能試験>
(1)光触媒活性の評価試験
上記で得た光触媒担持構造体を、大きさ70mm×70mmに切り出し、容量4リットルのパイレックス(登録商標)製ガラス容器中に設置した。この容器中に空気とアルデヒドの混合ガスをアルデヒド濃度が200ppmとなるように加えた。次いで、該試料に紫外線強度2mW/cm2のブラックライト(FL15BLB、東芝ライテック(株)製)の光を24時間照射後、容器内部のアルデヒドガス濃度をガスクロマトグラフィーにより測定し、その減少量により光触媒活性評価をした。評価結果を下記第3表に示す。
<Performance test of photocatalyst carrying structure>
(1) Photocatalytic activity evaluation test The photocatalyst-supporting structure obtained above was cut into a size of 70 mm x 70 mm and placed in a 4 liter Pyrex (registered trademark) glass container. A mixed gas of air and aldehyde was added to the container so that the aldehyde concentration was 200 ppm. Next, the sample was irradiated with light from a black light (FL15BLB, manufactured by Toshiba Lighting & Technology Co., Ltd.) with an ultraviolet intensity of 2 mW / cm 2 for 24 hours, and the aldehyde gas concentration inside the container was measured by gas chromatography. Photocatalytic activity was evaluated. The evaluation results are shown in Table 3 below.
評価基準は下記のとおりである。
24時間照射後のアルデヒドガス濃度の減少量による性能評価
200ppm以上 A
100〜200ppm B
100ppm以下 C
The evaluation criteria are as follows.
Performance evaluation by reduction of aldehyde gas concentration after irradiation for 24 hours 200 ppm or more A
100-200ppm B
100ppm or less C
(2)ヘイズ率の測定
接着層及び光触媒層を担持する前の担体をリファレンスとして、各試料の波長550nmの全光線透過率、及びヘイズ率を自記分光光度計(日立製作所(株)製U−4000型)で測定した。なお、ヘイズ率(%)とは「(全光線透過率−直線透過率)×100/全光線透過率」の数式より算出される。
評価結果を下記第3表に示す。[TA−1]に形成した実施例1〜3、比較例1〜3の光触媒担持体構造体は全てヘイズ率が1%以下で優れた透明性を示した。
(2) Measurement of haze ratio Using the carrier before supporting the adhesive layer and the photocatalyst layer as a reference, the total light transmittance at a wavelength of 550 nm and the haze ratio of each sample were recorded by a self-recording spectrophotometer (U-manufactured by Hitachi, Ltd.). 4000 type). The haze ratio (%) is calculated from the formula “(total light transmittance−linear transmittance) × 100 / total light transmittance”.
The evaluation results are shown in Table 3 below. The photocatalyst carrier structures of Examples 1 to 3 and Comparative Examples 1 to 3 formed on [TA-1] all exhibited excellent transparency with a haze ratio of 1% or less.
(3)テープ剥離試験
各試料表面に、切り傷によって2mmの間隔で25個のマス目を形成し、JIS K5400に規定する碁盤目テープ法試験により付着性の評価を行った。剥離しなかったものを○、剥離したものを×として評価した。評価結果を下記第3表に示す。
(3) Tape peeling test On the surface of each sample, 25 squares were formed at intervals of 2 mm by cuts, and adhesion was evaluated by a cross-cut tape method test specified in JIS K5400. Evaluations were made as ○ for those that did not peel, and × for those that did not peel. The evaluation results are shown in Table 3 below.
(4)指摩擦試験
試料表面を指で摩擦し、剥離しなかったものを○、剥離したものを×として評価した。評価結果を下記第2表に示す。
(4) Finger Friction Test A sample surface was rubbed with a finger, and the sample that was not peeled off was evaluated as ◯, and the sample that was peeled off was evaluated as ×. The evaluation results are shown in Table 2 below.
(5)鉛筆硬度試験
JIS K5600−5−4に従い行った。評価結果を下記第3表に示す。
(5) Pencil hardness test It was performed according to JIS K5600-5-4. The evaluation results are shown in Table 3 below.
(6)煮沸試験
沸騰させたイオン交換水及び水道水に光触媒担持構造体を15分間浸漬させた後にテープ剥離試験を行い剥離しなかったものを○、剥離したものを×として評価した。評価結果を下記第3表に示す。
(6) Boiling test A tape peeling test was conducted after immersing the photocatalyst-supporting structure in boiling ion-exchanged water and tap water for 15 minutes. The evaluation results are shown in Table 3 below.
(7)接触角試験
試料に紫外線強度2mW/cm2のブラックライト(FL15BLB、東芝ライテック(株)製)の光を48時間照射後、協和界面化学社製固液界面解析システムDropMaster700で水滴量0.4μLの接触角を測定した。評価結果を下記第3表に示す。
(7) Contact angle test After the sample was irradiated with light of black light (FL15BLB, manufactured by Toshiba Lighting & Technology Co., Ltd.) with an ultraviolet intensity of 2 mW / cm 2 for 48 hours, the amount of water drops was 0 using a solid-liquid interface analysis system DropMaster700 manufactured by Kyowa Interface Chemical Co., Ltd. A contact angle of 4 μL was measured. The evaluation results are shown in Table 3 below.
Claims (5)
RnSiX4−n・・・(I)
(式中、Rはエポキシ基を有する有機基を表し、Xは水酸基又は加水分解性基を表す。nは1又は2を表し、nが2のとき各Rは同一でも異なっていてもよく、(4−n)が2以上のとき各Xは同一でも異なっていてもよい。)で表される有機ケイ素化合物の縮合物、(b)光触媒、及び
(c)チタン原子に、加水分解性基とキレート配位子とが結合してなるチタンキレート化合物と、該チタンキレート化合物に対して大過剰の水とを混合して得られるチタン酸化物ナノ粒子、並びにアルミナ
を含有し、上記各成分の組成が、固形分として、固形分全体に対して、(a)=5〜90質量%、(b)=5〜70重量%、(c)=5〜50重量%であることを特徴とする光触媒含有コーティング用組成物。 (A) Formula (I)
R n SiX 4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is greater than or equal to 2, each X may be the same or different.) A condensate of an organosilicon compound represented by (b) a photocatalyst, and (c) a titanium atom with a hydrolyzable group Containing titanium oxide nanoparticles obtained by mixing a titanium chelate compound in which a chelate ligand is bound with a large excess of water with respect to the titanium chelate compound, and alumina , The composition of each of the above components is (a) = 5 to 90% by mass, (b) = 5 to 70% by weight, and (c) = 5 to 50% by weight with respect to the entire solid content. A composition for coating containing a photocatalyst.
RnSiX4−n・・・(I)
(式中、Rはエポキシ基を有する有機基を表し、Xは水酸基又は加水分解性基を表す。nは1又は2を表し、nが2のとき各Rは同一でも異なっていてもよく、(4−n)が2以上のとき各Xは同一でも異なっていてもよい。)で表される有機ケイ素化合物を、溶媒中、水及びチタン原子に、加水分解性基とキレート配位子とが結合してなるチタンキレート化合物と、該チタンキレート化合物に対して大過剰の水とを混合して得られるチタン酸化物ナノ粒子の存在下に縮合させる工程、及び
(B)溶媒中、工程(A)で得られた有機ケイ素化合物の縮合物、光触媒、並びにアルミナを混合する工程
からなる請求項1に記載の光触媒含有コーティング用組成物の製造方法。 (A) Formula (I)
R n SiX 4-n (I)
(In the formula, R represents an organic group having an epoxy group, X represents a hydroxyl group or a hydrolyzable group. N represents 1 or 2, and when n is 2, each R may be the same or different, (When n is 2 or more, each X may be the same or different.) In a solvent, water and a titanium atom, a hydrolyzable group, a chelate ligand, A step of condensing in the presence of titanium oxide nanoparticles obtained by mixing a titanium chelate compound formed by bonding a large excess of water with respect to the titanium chelate compound , and (B) a step in a solvent ( The method for producing a photocatalyst-containing coating composition according to claim 1, comprising a step of mixing the condensate of the organosilicon compound obtained in A), a photocatalyst, and alumina .
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