JP2012086104A - Photocatalyst composition - Google Patents
Photocatalyst composition Download PDFInfo
- Publication number
- JP2012086104A JP2012086104A JP2010232229A JP2010232229A JP2012086104A JP 2012086104 A JP2012086104 A JP 2012086104A JP 2010232229 A JP2010232229 A JP 2010232229A JP 2010232229 A JP2010232229 A JP 2010232229A JP 2012086104 A JP2012086104 A JP 2012086104A
- Authority
- JP
- Japan
- Prior art keywords
- photocatalyst
- group
- meth
- mass
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 92
- 239000000203 mixture Substances 0.000 title claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 120
- 239000000839 emulsion Substances 0.000 claims abstract description 70
- 229920000642 polymer Polymers 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 24
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 13
- 229920002554 vinyl polymer Polymers 0.000 claims description 69
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 68
- 239000000178 monomer Substances 0.000 claims description 64
- 150000003377 silicon compounds Chemical class 0.000 claims description 49
- 239000003995 emulsifying agent Substances 0.000 claims description 28
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000758 substrate Substances 0.000 claims description 14
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 12
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 12
- NYWITVDHYCKDAU-UHFFFAOYSA-N oxygen(2-) yttrium(3+) zirconium(4+) Chemical compound [O--].[O--].[Y+3].[Zr+4] NYWITVDHYCKDAU-UHFFFAOYSA-N 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 25
- 230000003373 anti-fouling effect Effects 0.000 abstract description 9
- -1 BiVO 4 Inorganic materials 0.000 description 67
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 43
- 125000004432 carbon atom Chemical group C* 0.000 description 30
- 238000006116 polymerization reaction Methods 0.000 description 25
- 239000007787 solid Substances 0.000 description 25
- 239000006185 dispersion Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 21
- 239000011248 coating agent Substances 0.000 description 20
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 14
- 239000007864 aqueous solution Substances 0.000 description 14
- 238000007720 emulsion polymerization reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 239000006087 Silane Coupling Agent Substances 0.000 description 11
- 150000003863 ammonium salts Chemical class 0.000 description 11
- 239000011521 glass Substances 0.000 description 11
- 239000007921 spray Substances 0.000 description 11
- 239000006096 absorbing agent Substances 0.000 description 10
- 239000007859 condensation product Substances 0.000 description 10
- 239000004611 light stabiliser Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 9
- 239000012964 benzotriazole Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- 159000000000 sodium salts Chemical class 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 8
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical group [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 7
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 7
- 239000002585 base Substances 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 150000002736 metal compounds Chemical class 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 125000000542 sulfonic acid group Chemical group 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 125000003142 tertiary amide group Chemical group 0.000 description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- 125000005011 alkyl ether group Chemical group 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 5
- 125000006353 oxyethylene group Chemical group 0.000 description 5
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 125000003156 secondary amide group Chemical group 0.000 description 5
- 239000000344 soap Substances 0.000 description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001033 ether group Chemical group 0.000 description 4
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002344 surface layer Substances 0.000 description 4
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical group CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000008119 colloidal silica Substances 0.000 description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000010526 radical polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 125000003396 thiol group Chemical group [H]S* 0.000 description 3
- ARVUDIQYNJVQIW-UHFFFAOYSA-N (4-dodecoxy-2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC(OCCCCCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 ARVUDIQYNJVQIW-UHFFFAOYSA-N 0.000 description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- MCDBEBOBROAQSH-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C=C MCDBEBOBROAQSH-UHFFFAOYSA-N 0.000 description 2
- UVRCNEIYXSRHNT-UHFFFAOYSA-N 3-ethylpent-2-enamide Chemical compound CCC(CC)=CC(N)=O UVRCNEIYXSRHNT-UHFFFAOYSA-N 0.000 description 2
- JMGZKPMMFXFSGK-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl prop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C=C JMGZKPMMFXFSGK-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- XDQWJFXZTAWJST-UHFFFAOYSA-N 3-triethoxysilylpropyl prop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C=C XDQWJFXZTAWJST-UHFFFAOYSA-N 0.000 description 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- YATIYDNBFHEOFA-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-ol Chemical compound CO[Si](OC)(OC)CCCO YATIYDNBFHEOFA-UHFFFAOYSA-N 0.000 description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 2
- HGEKXQRHZRDGKO-UHFFFAOYSA-N 3-tripropoxysilylpropyl prop-2-enoate Chemical compound CCCO[Si](OCCC)(OCCC)CCCOC(=O)C=C HGEKXQRHZRDGKO-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- XQAXGZLFSSPBMK-UHFFFAOYSA-M [7-(dimethylamino)phenothiazin-3-ylidene]-dimethylazanium;chloride;trihydrate Chemical compound O.O.O.[Cl-].C1=CC(=[N+](C)C)C=C2SC3=CC(N(C)C)=CC=C3N=C21 XQAXGZLFSSPBMK-UHFFFAOYSA-M 0.000 description 2
- RMKZLFMHXZAGTM-UHFFFAOYSA-N [dimethoxy(propyl)silyl]oxymethyl prop-2-enoate Chemical compound CCC[Si](OC)(OC)OCOC(=O)C=C RMKZLFMHXZAGTM-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
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- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
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- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
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- JFLKFZNIIQFQBS-FNCQTZNRSA-N trans,trans-1,4-Diphenyl-1,3-butadiene Chemical group C=1C=CC=CC=1\C=C\C=C\C1=CC=CC=C1 JFLKFZNIIQFQBS-FNCQTZNRSA-N 0.000 description 1
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- 238000006276 transfer reaction Methods 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
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- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
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- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- BJDLPDPRMYAOCM-UHFFFAOYSA-N triethoxy(propan-2-yl)silane Chemical compound CCO[Si](OCC)(OCC)C(C)C BJDLPDPRMYAOCM-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- UDUKMRHNZZLJRB-UHFFFAOYSA-N triethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OCC)(OCC)OCC)CCC2OC21 UDUKMRHNZZLJRB-UHFFFAOYSA-N 0.000 description 1
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- JLGNHOJUQFHYEZ-UHFFFAOYSA-N trimethoxy(3,3,3-trifluoropropyl)silane Chemical compound CO[Si](OC)(OC)CCC(F)(F)F JLGNHOJUQFHYEZ-UHFFFAOYSA-N 0.000 description 1
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 description 1
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- LGROXJWYRXANBB-UHFFFAOYSA-N trimethoxy(propan-2-yl)silane Chemical compound CO[Si](OC)(OC)C(C)C LGROXJWYRXANBB-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-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
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
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Landscapes
- Catalysts (AREA)
Abstract
Description
光触媒活性と耐候性を両立し、防汚性、透明性等に優れた光触媒体を与える光触媒組成物に関する。本発明の光触媒組成物は、特に建築外装、自動車、ディスプレイ、レンズのコーティングとして有用である。 The present invention relates to a photocatalyst composition that provides both a photocatalytic activity and weather resistance, and provides a photocatalyst having excellent antifouling properties and transparency. The photocatalyst composition of the present invention is particularly useful as a coating for architectural exteriors, automobiles, displays, and lenses.
光触媒とは、光照射によって他の物質の反応(例えば酸化、還元反応)を進行させる物質のことをいう。言い換えれば、伝導帯と価電子帯との間のエネルギーギャップよりも大きなエネルギー(すなわち短い波長)を有する光(励起光)を照射した際に、価電子帯中の電子の励起(光励起)が生じて、伝導電子と正孔とを生成しうる物質である。このとき、伝導帯に生成した電子の還元力及び/又は価電子帯に生成した正孔の酸化力を利用して、種々の化学反応を行うことができる。 The photocatalyst refers to a substance that causes a reaction (for example, oxidation or reduction reaction) of another substance to proceed by light irradiation. In other words, when light (excitation light) having energy larger than the energy gap between the conduction band and the valence band (ie, short wavelength) is irradiated, excitation of electrons in the valence band (photoexcitation) occurs. Thus, it is a substance that can generate conduction electrons and holes. At this time, various chemical reactions can be performed using the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band.
また、光触媒活性とは、光照射によって酸化、還元反応を進行させる活性をいう。光触媒は、この光触媒活性を有することにより、有機物質の分解作用や表面の親水化作用を示すことが知られている。かかる作用に基づいて、光触媒は環境浄化や防汚、防曇等の分野に応用されている。例えば、特許文献1では、光触媒粒子を含有する表層部を備え、降雨により自己清浄化(セルフクリーニング)される表面を有する屋外表示板、及びその清浄化方法が提案されている。特許文献1によると、光触媒を含有する表面層を備えることにより、光触媒の光励起に応じて、表層部の表面は親水性を呈する。そのため、屋外表示板の表面が降雨にさらされた時に付着堆積物及び/又は汚染物が雨滴により洗い流されることが可能となる、とされている。 The photocatalytic activity refers to an activity that causes an oxidation or reduction reaction to proceed by light irradiation. It is known that a photocatalyst exhibits a photocatalytic activity and exhibits an organic substance decomposing action and a surface hydrophilizing action. Based on this action, the photocatalyst is applied to fields such as environmental purification, antifouling, and antifogging. For example, Patent Document 1 proposes an outdoor display panel that includes a surface layer portion containing photocatalyst particles and has a surface that is self-cleaned by rain (self-cleaning), and a cleaning method therefor. According to Patent Document 1, by providing a surface layer containing a photocatalyst, the surface of the surface layer portion exhibits hydrophilicity according to photoexcitation of the photocatalyst. Therefore, when the surface of the outdoor display panel is exposed to rain, the deposited deposits and / or contaminants can be washed away by raindrops.
ところで、光触媒を環境浄化や防汚、防曇等の分野へ応用させる場合、基体への光触媒の固定化技術が非常に重要な役割を担う。この固定化技術では、(ア)光触媒活性を損なわずに基体へ強固に固定化するとともに、(イ)光触媒作用で基体及びそのコーティングが劣化しない安定性を付与する必要がある。 By the way, when applying a photocatalyst to fields such as environmental purification, antifouling, and antifogging, the technology for immobilizing the photocatalyst on the substrate plays a very important role. In this immobilization technique, it is necessary to (a) firmly fix the photocatalytic activity to the substrate without impairing the photocatalytic activity, and (b) provide stability that does not deteriorate the substrate and its coating by the photocatalytic action.
このような必要性を満足する光触媒の固定化を意図して、基体とその上に設けられた光触媒を含有する表層部との間に保護層を介在させる方法が提案されている。例えば、特許文献2では、基材フィルムの一方の面に所定の厚みを有するケイ素酸化物又はアルミニウム酸化物からなる蒸着層を設け、その上に酸化チタンを主成分とする光触媒層を設けた多層光触媒フィルムが提案されている。あるいは、特許文献3では、光触媒を樹脂塗料中に混合し、この樹脂塗料を基材へコーティングする方法も提案されている。さらには、例えば特許文献4に開示されているように、光触媒粒子表面に光触媒では分解困難な無機物を担持する方法も提案されている。 In order to fix the photocatalyst satisfying such a need, a method has been proposed in which a protective layer is interposed between the substrate and the surface layer portion containing the photocatalyst provided thereon. For example, in Patent Document 2, a multilayer in which a vapor deposition layer made of silicon oxide or aluminum oxide having a predetermined thickness is provided on one surface of a base film and a photocatalytic layer mainly composed of titanium oxide is provided thereon. Photocatalytic films have been proposed. Alternatively, Patent Document 3 proposes a method in which a photocatalyst is mixed in a resin paint and the resin paint is coated on a substrate. Furthermore, as disclosed in Patent Document 4, for example, a method of supporting an inorganic substance that is difficult to decompose with a photocatalyst on the surface of the photocatalyst particle has been proposed.
WO2007/069596、特開2009−221362号公報において、さらに耐汚染性、耐候性に優れた光触媒が開示されている。 In WO2007 / 069596 and JP2009-221362A, a photocatalyst further excellent in contamination resistance and weather resistance is disclosed.
本発明の課題は、特に光触媒活性と耐候性を両立し、防汚性、透明性等に優れた光触媒体を与える組成物を提供することである。 An object of the present invention is to provide a composition that provides both a photocatalytic activity and weather resistance, and provides a photocatalyst having excellent antifouling properties, transparency, and the like.
本発明者らは上記課題を解決すべく鋭意検討した結果、本発明に到達した。
すなわち、本発明は以下の通りである。
As a result of intensive studies aimed at solving the above problems, the present inventors have reached the present invention.
That is, the present invention is as follows.
1.粒子径が1以上100nm以下の光触媒粒子(a1)と、粒子径が1以上100nm以下の酸化珪素(a2)と、屈折率が1.8以上2.5以下の金属酸化物(a3){ただし光触媒粒子(a1)を除く}と、重合体エマルジョン粒子(B)を水中に分散させて含む光触媒組成物。 1. Photocatalyst particles (a1) having a particle diameter of 1 to 100 nm, silicon oxide (a2) having a particle diameter of 1 to 100 nm, and metal oxide (a3) having a refractive index of 1.8 to 2.5 {however A photocatalyst composition comprising the polymer emulsion particles (B) dispersed in water, excluding the photocatalyst particles (a1)}.
2.屈折率が1.8以上2.5以下の金属酸化物(a3)として、酸化ジルコニウムを含んでいる発明1に記載の光触媒組成物。 2. The photocatalyst composition of invention 1 containing zirconium oxide as a metal oxide (a3) having a refractive index of 1.8 to 2.5.
3.前記酸化ジルコニウムが酸化ジルコニウム−酸化イットリウム混合物コロイドである、発明2に記載の組成物。 3. The composition according to invention 2, wherein the zirconium oxide is a zirconium oxide-yttrium oxide mixture colloid.
4.前記重合体エマルジョン粒子(B)が、水及び乳化剤の存在下に加水分解性珪素化合物(b1)及び、ビニル単量体(b2)を重合して得られたものであり、粒子径が10〜800nmである、発明1〜3に記載の組成物。 4). The polymer emulsion particles (B) are obtained by polymerizing a hydrolyzable silicon compound (b1) and a vinyl monomer (b2) in the presence of water and an emulsifier, and have a particle size of 10 to 10. The composition according to any one of Inventions 1 to 3, which is 800 nm.
5.光触媒粒子(a1)が酸化チタンである、発明1〜4に記載の組成物。 5. Compositions according to inventions 1 to 4, wherein the photocatalyst particles (a1) are titanium oxide.
6.発明1〜5のいずれか一項に記載の組成物を基材上に形成してなることを特徴とする光触媒体。 6). A photocatalyst comprising the composition according to any one of inventions 1 to 5 formed on a substrate.
7.発明6に記載の光触媒体を外装に用いたことを特徴とする建築物。 7). A building characterized in that the photocatalyst according to the invention 6 is used for an exterior.
8.発明6に記載の光触媒体を外装に用いたことを特徴とする住宅。 8). A house characterized in that the photocatalyst according to the invention 6 is used for an exterior.
光触媒活性と耐候性を両立し、防汚性、透明性等に優れた光触媒体を、特殊な装置を用いずに、簡単に、少ない環境負荷で、かつ簡便に形成することができる。 A photocatalyst having both photocatalytic activity and weather resistance, and excellent in antifouling properties, transparency and the like can be easily and easily formed with little environmental load without using a special apparatus.
以下、本発明を詳細に説明する。
本発明は粒子径が1以上100nm以下の光触媒粒子(a1)と、粒子径が1以上100nm以下の酸化珪素(a2)と、屈折率が1.8以上2.5以下の金属酸化物(a3){ただし光触媒粒子(a1)を除く}と、重合体エマルジョン粒子(B)を水中に分散させて含む光触媒組成物である。
Hereinafter, the present invention will be described in detail.
The present invention relates to photocatalyst particles (a1) having a particle size of 1 to 100 nm, silicon oxide (a2) having a particle size of 1 to 100 nm, and metal oxide (a3) having a refractive index of 1.8 to 2.5. ) {Excluding photocatalyst particles (a1)} and polymer emulsion particles (B) dispersed in water.
本発明に用いる光触媒粒子(a1)の例としては、例えば、TiO2、ZnO、SrTiO3、BaTiO3、BaTiO4、BaTi4O9、K2NbO3、Nb2O5、Fe2O3、Ta2O5、K3Ta3Si2O3、WO3、SnO2、Bi2O3、BiVO4、NiO、Cu2O、RuO2、CeO2等、さらにはTi、Nb、Ta、及びVから選ばれた少なくとも1種の元素を有する層状酸化物(例えば特開昭62−74452号公報、特開平2−172535号公報、特開平7−24329号公報、特開平8−89799号公報、特開平8−89800号公報、特開平8−89804号公報、特開平8−198061号公報、特開平9−248465号公報、特開平10−99694号公報、特開平10−244165号公報等参照)を挙げることができる。 Examples of the photocatalyst particles (a1) used in the present invention include, for example, TiO 2 , ZnO, SrTiO 3 , BaTiO 3 , BaTiO 4 , BaTi 4 O 9 , K 2 NbO 3 , Nb 2 O 5 , Fe 2 O 3 , Ta 2 O 5 , K 3 Ta 3 Si 2 O 3 , WO 3 , SnO 2 , Bi 2 O 3 , BiVO 4 , NiO, Cu 2 O, RuO 2 , CeO 2, etc., and also Ti, Nb, Ta, and Layered oxides having at least one element selected from V (for example, JP-A-62-274452, JP-A-2-172535, JP-A-7-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694 See JP-A-10-244165 Publication) can be exemplified.
これらの光触媒の中でTiO2(酸化チタン)は無害であり、化学的安定性にも優れるため好ましい。酸化チタンとしては、アナターゼ、ルチル、ブルッカイトのいずれも使用できる。その中でも、ルチル型酸化チタンを用いると、活性と耐候性の制御が可能となるため好ましい。 Among these photocatalysts, TiO 2 (titanium oxide) is preferable because it is harmless and has excellent chemical stability. Any of anatase, rutile, and brookite can be used as titanium oxide. Among them, it is preferable to use rutile type titanium oxide because the activity and weather resistance can be controlled.
本発明は酸化珪素(a2)の配合により、耐候性、親水性に優れた光触媒体を得ることが可能となる。特に、重合体エマルジョン粒子(B)と相互作用すると、耐候性、耐薬品性、光学特性、更には防汚性、防曇性、帯電防止性等にさらに優れた光触媒体を形成することが可能となる。 In the present invention, a photocatalyst excellent in weather resistance and hydrophilicity can be obtained by blending silicon oxide (a2). In particular, when interacting with the polymer emulsion particles (B), it is possible to form a photocatalyst that is further superior in weather resistance, chemical resistance, optical properties, antifouling properties, antifogging properties, antistatic properties, etc. It becomes.
ここで、上記酸化珪素(a2)と重合体エマルジョン粒子(B)との相互作用の例としては、例えば酸化珪素(a2)が有する水酸基と重合体エマルジョン粒子(B)を構成する加水分解性金属化合物(b1)の重合生成物との縮合(化学結合)や、重合体エマルジョン粒子(B)の一部を構成する2級及び/又は3級アミド基等との結合(水素結合)等を例示することができる。 Here, as an example of the interaction between the silicon oxide (a2) and the polymer emulsion particles (B), for example, the hydroxyl group of the silicon oxide (a2) and the hydrolyzable metal constituting the polymer emulsion particles (B) Examples include condensation (chemical bonding) of the compound (b1) with the polymerization product and bonding (hydrogen bonding) with secondary and / or tertiary amide groups constituting part of the polymer emulsion particles (B). can do.
酸化珪素(a2)の状態としては、特に制限はないが、水及び/又は親水性有機溶媒中に分散していると取り扱い容易で好ましい。ここで、酸化珪素(a2)は親水性有機溶媒としては、例えばエチレングリコール、ブチルセロソルブ、n−プロパノール、イソプロパノール、n−ブタノール、エタノール、メタノール等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、ジメチルアセトアミド、ジメチルホルムアミド等のアミド類、ジメチルスルホキシド、ニトロベンゼン等、さらにはこれらの2種以上の混合物が挙げられる。
酸化珪素(a2)の粒子径は透明性の面から50nm以下である事が好ましい。
Although there is no restriction | limiting in particular as a state of silicon oxide (a2), if it is disperse | distributing in water and / or a hydrophilic organic solvent, it is easy to handle and preferable. Here, silicon oxide (a2) is a hydrophilic organic solvent, for example, alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol, and ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone. , Ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more of these.
The particle diameter of silicon oxide (a2) is preferably 50 nm or less from the viewpoint of transparency.
屈折率が1.8以上2.5以下の金属酸化物を配合することで塗膜の屈折率を制御することが可能となる他、紫外線遮蔽効果により耐候性が向上する。このような金属酸化物の例としては、酸化ジルコニウム、酸化亜鉛、酸化クロム、酸化カドミウム、酸化鉄、酸化銅、酸化セリウム、酸化スズ等がある。 By blending a metal oxide having a refractive index of 1.8 or more and 2.5 or less, it becomes possible to control the refractive index of the coating film, and weather resistance is improved by an ultraviolet shielding effect. Examples of such metal oxides include zirconium oxide, zinc oxide, chromium oxide, cadmium oxide, iron oxide, copper oxide, cerium oxide, and tin oxide.
そのなかでも酸化ジルコニウムが好ましい。酸化ジルコニウムの状態としては、特に制限はないが、水分散体が取り扱い上好ましい。中でも、pH8〜11の水分散体が配合安定性の面から好ましい。その粒子径は透明性の面から100nm以下であることが必要であり、好ましくは、50nm以下、より好ましくは30nm以下である
特に、酸化ジルコニウムを酸化イットリウムで安定化した、酸化ジルコニウム−酸化イットリウム混合物コロイドを用いた組成物から得られる、光触媒体は特に高い透明性をもち、下地の意匠性を阻害しないので好ましい。その混合比は、酸化ジルコニウムの質量/酸化イットリウムの質量=20/1〜1/1である事が好ましい。
Of these, zirconium oxide is preferable. The state of zirconium oxide is not particularly limited, but an aqueous dispersion is preferable for handling. Among these, an aqueous dispersion having a pH of 8 to 11 is preferable from the viewpoint of blending stability. The particle diameter is required to be 100 nm or less from the viewpoint of transparency, preferably 50 nm or less, more preferably 30 nm or less. Particularly, a zirconium oxide-yttrium oxide mixture in which zirconium oxide is stabilized with yttrium oxide. A photocatalyst obtained from a composition using a colloid is preferable because it has particularly high transparency and does not impair the design of the base. The mixing ratio is preferably such that the mass of zirconium oxide / the mass of yttrium oxide = 20/1 to 1/1.
酸化ジルコニウムとしては、日産化学工業(株)製のナノユースZR−30BS(商品名)、ZR−30BH(商品名)、ZR−30BF(商品名)、ZR−30AH(商品名)、ZR−30AL(商品名)、第一希土化学(株)製のZSL−10A(商品名)、ZSL−10T(商品名)、ZSL−20N(商品名)等を挙げることができる。 Zirconium oxide includes nano-use ZR-30BS (trade name), ZR-30BH (trade name), ZR-30BF (trade name), ZR-30AH (trade name), ZR-30AL (manufactured by Nissan Chemical Industries, Ltd.) Trade name), ZSL-10A (trade name), ZSL-10T (trade name), ZSL-20N (trade name), etc., manufactured by Daiichi Tochi Chemical Co., Ltd. can be mentioned.
光触媒粒子(a1)の配合量は、組成物の全質量{光触媒粒子(a1)、酸化珪素(a2)、金属酸化物(a3)、重合体エマルジョン粒子(B)の質量合計}に対して、1〜25質量%の範囲が活性と耐候性、透明性の面から好ましい。同様に、酸化珪素(a2)の配合量は組成物の全質量に対して10〜75質量%が親水性、耐候性の面から好ましく、金属酸化物(a3)は組成物の全質量に対して1〜25質量%が耐候性、透明性、屈折率の制御上好ましい。 The blending amount of the photocatalyst particles (a1) is based on the total mass of the composition {total mass of the photocatalyst particles (a1), silicon oxide (a2), metal oxide (a3), and polymer emulsion particles (B)}. The range of 1-25 mass% is preferable from the surface of activity, weather resistance, and transparency. Similarly, the blending amount of silicon oxide (a2) is preferably 10 to 75% by mass based on the total mass of the composition from the viewpoint of hydrophilicity and weather resistance, and the metal oxide (a3) is based on the total mass of the composition. 1 to 25% by mass is preferable for controlling weather resistance, transparency and refractive index.
本発明の光触媒組成物に用いる重合体エマルジョン粒子(B)としては、種々公知のものを用いることが可能である。
例えば、アクリルエマルジョン、スチレン−ブタジエンエマルジョン、PTFEエマルジョン、等を例示することが可能である。
As the polymer emulsion particles (B) used in the photocatalyst composition of the present invention, various known ones can be used.
For example, acrylic emulsion, styrene-butadiene emulsion, PTFE emulsion, etc. can be exemplified.
本実施形態において、重合体エマルジョン粒子(B)は、乳化重合等の方法で得られた重合体粒子を用いることができる。重合体エマルジョン粒子を構成するポリマーとしては、水性媒体中でのラジカル重合、アニオン重合、カチオン重合などによって得られる従来公知のポリ(メタ)アクリレート系、ポリビニルアセテート系、酢酸ビニル−アクリル系、エチレン酢酸ビニル系、シリコーン系、ポリブタジエン系、スチレンブタジエン系、NBR系、ポリ塩化ビニル系、塩素化ポリプロピレン系、ポリエチレン系、ポリスチレン系、塩化ビニリデン系、ポリスチレン−(メタ)アクリレート系、スチレン−無水マレイン酸系に代表される単重合体又は共重合体、シリコーン変性アクリル系、フッ素−アクリル系、アクリル−シリコン系、エポキシ−アクリル系に代表される変性共重合体が挙げられる。これらは水分散体の状態にあり、1種を単独で又は2種以上を組み合わせて用いられる。その好ましい例としては、アクリル樹脂エマルジョン、アクリル−シリコン樹脂エマルジョンなどがある。重合体エマルジョン粒子は、アクリル酸エステル、メタクリル酸エステル等の単量体の乳化重合等で得ることができる。 In this embodiment, polymer particles obtained by a method such as emulsion polymerization can be used as the polymer emulsion particles (B). Examples of the polymer constituting the polymer emulsion particles include conventionally known poly (meth) acrylate-based, polyvinyl acetate-based, vinyl acetate-acrylic-based, ethylene acetic acid obtained by radical polymerization, anionic polymerization, cationic polymerization, etc. in an aqueous medium. Vinyl, silicone, polybutadiene, styrene butadiene, NBR, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, vinylidene chloride, polystyrene- (meth) acrylate, styrene-maleic anhydride And a modified copolymer represented by a silicone-modified acrylic, a fluorine-acrylic, an acrylic-silicone, and an epoxy-acrylic. These are in the state of an aqueous dispersion, and are used alone or in combination of two or more. Preferred examples thereof include an acrylic resin emulsion and an acrylic-silicon resin emulsion. The polymer emulsion particles can be obtained by emulsion polymerization of monomers such as acrylic acid ester and methacrylic acid ester.
なかでも、水及び乳化剤の存在下に加水分解性珪素化合物(b1)及び、ビニル単量体(b2)を重合して得られる粒子径が10〜800nmである重合体エマルジョン粒子(B)を用いて得られる光触媒組成物からは、特に耐候性、透明性、柔軟性の高い光触媒体を得ることが可能であり、特に好ましい。 Among them, polymer emulsion particles (B) having a particle diameter of 10 to 800 nm obtained by polymerizing hydrolyzable silicon compound (b1) and vinyl monomer (b2) in the presence of water and an emulsifier are used. From the photocatalyst composition obtained in this way, a photocatalyst having particularly high weather resistance, transparency and flexibility can be obtained, which is particularly preferable.
本発明の重合体エマルジョン粒子(B)を製造するのに用いる上記加水分解性珪素化合物(b1)としては、下記式(1)で表される化合物やその縮合生成物、シランカップリング剤を例示することができる。 Examples of the hydrolyzable silicon compound (b1) used to produce the polymer emulsion particles (B) of the present invention include compounds represented by the following formula (1), condensation products thereof, and silane coupling agents. can do.
SiWxRy (1)
(式中、Wは炭素数1〜20のアルコキシ基、水酸基、炭素数1〜20のアセトキシ基、ハロゲン原子、水素原子、炭素数1〜20のオキシム基、エノキシ基、アミノキシ基、及びアミド基から選ばれた少なくとも1種の基を表す。Rは、直鎖状又は分岐状の炭素数が1〜30個のアルキル基、炭素数5〜20のシクロアルキル基、及び置換されていないか又は炭素数1〜20のアルキル基若しくは炭素数1〜20のアルコキシ基若しくはハロゲン原子で置換されている炭素数6〜20のアリール基から選ばれる少なくとも1種の炭化水素基を表す。xは1以上4以下の整数であり、yは0以上3以下の整数である。また、x+y=4である。)
SiWxRy (1)
Wherein W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide group. R represents at least one group selected from: R represents a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or substituted group; It represents at least one hydrocarbon group selected from an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, where x is 1 or more. (It is an integer of 4 or less, and y is an integer of 0 to 3. Further, x + y = 4.)
ここでシランカップリング剤とは、ビニル重合性基、エポキシ基、アミノ基、メタクリル基、メルカプト基、イソシアネート基等の有機物と反応性を有する官能基が分子内に存在する、加水分解性珪素化合物(b1)を表す。 Here, the silane coupling agent is a hydrolyzable silicon compound in which a functional group having reactivity with an organic substance such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an isocyanate group exists in the molecule. Represents (b1).
上記珪素アルコキシド及びシランカップリング剤の具体例としては、例えばテトラメトキシシラン、テトラエトキシシラン、テトラ−n−プロポキシシラン、テトライソプロポキシシラン、テトラ−n−ブトキシシラン等のテトラアルコキシシラン類;メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、n−プロピルトリメトキシシラン、n−プロピルトリエトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、n−ブチルトリメトキシシラン、n−ブチルトリエトキシシラン、n−ペンチルトリメトキシシラン、n−ヘキシルトリメトキシシラン、n−ヘプチルトリメトキシシラン、n−オクチルトリメトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン、シクロヘキシルトリメトキシシラン、シクロヘキシルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、3−クロロプロピルトリメトキシシラン、3−クロロプロピルトリエトキシシラン、3,3,3−トリフロロプロピルトリメトキシシラン、3,3,3−トリフロロプロピルトリエトキシシラン、3−アミノプロピルトリメトキシシラン、3−アミノプロピルトリエトキシシラン、2−ヒドロキシエチルトリメトキシシラン、2−ヒドロキシエチルトリエトキシシラン、2−ヒドロキシプロピルトリメトキシシラン、2−ヒドロキシプロピルトリエトキシシラン、3−ヒドロキシプロピルトリメトキシシラン、3−ヒドロキシプロピルトリエトキシシラン、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン、3−イソシアナートプロピルトリメトキシシラン、3−イソシアナートプロピルトリエトキシシラン、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、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、2−(3,4−エポキシシクロヘキシル)エチルトリエトキシシラン、3−(メタ)アクリルオキシプロピルトリメトキシシラン、3−(メタ)アタクリルオキシプロピルトリエトキシシラン、3−(メタ)アクリロイルオキシプロピルトリn−プロポキシシラン、3−(メタ)アクリロイルオキシプロピルトリイソプロポキシシラン、3−ウレイドプロピルトリメトキシシラン、3−ウレイドプロピルトリエトキシシラン等のトリアルコキシシラン類;ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン、ジ−n−プロピルジメトキシシラン、ジ−n−プロピルジエトキシシラン、ジイソプロピルジメトキシシラン、ジイソプロピルジエトキシシラン、ジ−n−ブチルジメトキシシラン、ジ−n−ブチルジエトキシシラン、ジ−n−ペンチルジメトキシシラン、ジ−n−ペンチルジエトキシシラン、ジ−n−ヘキシルジメトキシシラン、ジ−n−ヘキシルジエトキシシラン、ジ−n−ヘプチルジメトキシシラン、ジ−n−ヘプチルジエトキシシラン、ジ−n−オクチルジメトキシシラン、ジ−n−オクチルジエトキシシラン、ジ−n−シクロヘキシルジメトキシシラン、ジ−n−シクロヘキシルジエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシラン、3−(メタ)アクリロイルオキシプロピルメチルジメトキシシラン等のジアルコキシシラン類;トリメチルメトキシシラン、トリメチルエトキシシラン等のモノアルコキシシラン類等を挙げることができる。また、これらの珪素アルコキシドやシランカップリング剤は、単独で又は2種以上を混合して使用することができる。 Specific examples of the silicon alkoxide and silane coupling agent include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane; Methoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n -Butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane, n-octyltrimethoxysilane, vinyltrimethoxysilane Vinyltriethoxysilane, allyltrimethoxysilane, cyclohexyltrimethoxysilane, cyclohexyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-chloropropyltriethoxysilane, 3, 3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-hydroxyethyltrimethoxysilane, 2- Hydroxyethyltriethoxysilane, 2-hydroxypropyltrimethoxysilane, 2-hydroxypropyltriethoxysilane, 3-hydroxypropyltrimethoxysilane, 3-hydroxypropyltrimethoxysilane Toxisilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (Meth) acryloyloxypropyltriethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, 3-ureidopropylto Trialkoxysilanes such as limethoxysilane and 3-ureidopropyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyldi Ethoxysilane, diisopropyldimethoxysilane, diisopropyldiethoxysilane, di-n-butyldimethoxysilane, di-n-butyldiethoxysilane, di-n-pentyldimethoxysilane, di-n-pentyldiethoxysilane, di-n- Hexyldimethoxysilane, di-n-hexyldiethoxysilane, di-n-heptyldimethoxysilane, di-n-heptyldiethoxysilane, di-n-octyldimethoxysilane, di-n-octyldiethoxysilane, di-n - Dialkoxysilanes such as cyclohexyldimethoxysilane, di-n-cyclohexyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane; trimethylmethoxysilane, trimethylethoxysilane, etc. And monoalkoxysilanes. These silicon alkoxides and silane coupling agents can be used alone or in admixture of two or more.
上記珪素アルコキシドやシランカップリング剤が縮合生成物として使用されるとき、該縮合生成物のポリスチレン換算重量平均分子量は、好ましくは200〜5000、さらに好ましくは300〜1000である。 When the silicon alkoxide or silane coupling agent is used as a condensation product, the condensation product preferably has a polystyrene equivalent weight average molecular weight of 200 to 5,000, more preferably 300 to 1,000.
上記珪素アルコキシドの中では、フェニル基を有する珪素アルコキシド、例えばフェニルトリメトキシシラン、フェニルトリエトキシシラン、ジフェニルジメトキシシラン等が、水及び乳化剤の存在下における重合安定性に優れるため非常に好ましい。 Among the silicon alkoxides, silicon alkoxides having a phenyl group, for example, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, and the like are very preferable because of excellent polymerization stability in the presence of water and an emulsifier.
本発明に用いることができる加水分解性珪素化合物(b1)の中で、3−(メタ)アクリルオキシプロピルトリメトキシシラン、3−(メタ)アタクリルオキシプロピルトリエトキシシラン、3−(メタ)アクリロイルオキシプロピルメチルジメトキシシラン、3−(メタ)アクリロイルオキシプロピルトリn−プロポキシシラン、3−(メタ)アクリロイルオキシプロピルトリイソプロポキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、アリルトリメトキシシラン、2−トリメトキシシリルエチルビニルエーテル等のビニル重合性基を有するシランカップリング剤や、3−メルカプトプロピルトリメトキシシラン、3−メルカプトプロピルトリエトキシシラン等のチオール基を有するシランカップリング剤は、ビニル単量体(b2)との共重合又は連鎖移動反応により化学結合を生成することが可能である。このため、ビニル重合性基やチオール基を有するシランカップリング剤を、単独で又は上述した珪素アルコキシド、シランカップリング剤、及びそれらの縮合生成物と混合若しくは複合化させて用いた場合、本発明の重合体エマルジョン粒子(B)を構成する加水分解性珪素化合物(b1)の重合生成物とビニル単量体(b2)の重合生成物は、化学結合により複合化できる。この様な重合体エマルジョン粒子(B)を含有する光触媒組成物は、耐候性、耐薬品性、光学特性、強度等に優れた光触媒体を形成することができるため、非常に好ましい。 Among the hydrolyzable silicon compounds (b1) that can be used in the present invention, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyl Oxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2- Silane coupling agents having a vinyl polymerizable group such as trimethoxysilylethyl vinyl ether, and silane coupling agents having a thiol group such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane are vinyl. By copolymerization or chain transfer reaction with dimer (b2) it is possible to produce a chemical bond. For this reason, when a silane coupling agent having a vinyl polymerizable group or a thiol group is used alone or mixed with or complexed with the above-described silicon alkoxide, silane coupling agent, and their condensation products, the present invention. The polymer product of the hydrolyzable silicon compound (b1) and the polymer product of the vinyl monomer (b2) constituting the polymer emulsion particles (B) can be combined by chemical bonding. A photocatalyst composition containing such polymer emulsion particles (B) is very preferable because it can form a photocatalyst excellent in weather resistance, chemical resistance, optical properties, strength, and the like.
ビニル単量体(b2)としては、アクリル酸エステル、メタクリル酸エステル、芳香族ビニル化合物、シアン化ビニル類の他、カルボキシル基含有ビニル単量体、水酸基含有ビニル系単量体、エポキシ基含有ビニル単量体、カルボニル基含有ビニル単量体、アニオン型ビニル単量体のような官能基を含有する単量体等を挙げることができる。 Examples of the vinyl monomer (b2) include acrylic acid ester, methacrylic acid ester, aromatic vinyl compound, vinyl cyanide, carboxyl group-containing vinyl monomer, hydroxyl group-containing vinyl monomer, and epoxy group-containing vinyl. And monomers containing functional groups such as monomers, carbonyl group-containing vinyl monomers, and anionic vinyl monomers.
上記(メタ)アクリル酸エステルの例としては、アルキル部の炭素数が1〜50の(メタ)アクリル酸アルキルエステル、エチレンオキシド基の数が1〜100個の(ポリ)オキシエチレンジ(メタ)アクリレート等が挙げられる。(メタ)アクリル酸エステルの具体例としては、(メタ)アクリル酸メチル、(メタ)アクリル酸エチル、(メタ)アクリル酸n−ブチル、(メタ)アクリル酸2−エチルヘキシル、(メタ)アクリル酸メチルシクロヘキシル、(メタ)アクリル酸シクロヘキシル、(メタ)アクリル酸ラウリル、(メタ)アクリル酸ドデシル等が挙げられる。(ポリ)オキシエチレンジ(メタ)アクリレートの具体例としては、ジ(メタ)アクリル酸エチレングリコール、ジ(メタ)アクリル酸ジエチレングリコール、メトキシ(メタ)アクリル酸ジエチレングリコール、ジ(メタ)アクリル酸テトラエチレングリコール等が挙げられる。 Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester having 1 to 50 carbon atoms in the alkyl portion, and (poly) oxyethylene di (meth) acrylate having 1 to 100 ethylene oxide groups. Etc. Specific examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and methyl (meth) acrylate. Examples include cyclohexyl, cyclohexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and the like. Specific examples of (poly) oxyethylene di (meth) acrylate include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, diethylene glycol methoxy (meth) acrylate, tetraethylene glycol di (meth) acrylate Etc.
なお、本明細書中で、(メタ)アクリルとはメタアクリル又はアクリルを簡便に表記したものである。 In the present specification, (meth) acrylic is a simple description of methacrylic or acrylic.
上記カルボキシル基含有ビニル単量体としては、例えばアクリル酸、メタクリル酸、クロトン酸、イタコン酸、マレイン酸、フマール酸、無水マレイン酸、又はイタコン酸、マレイン酸、フマール酸などの2塩基酸のハーフエステル等である。カルボン酸基含有のビニル単量体を用いることによって、重合体エマルジョン粒子(B)にカルボキシル基を導入することができ、エマルジョンとしての安定性を向上させ、外部からの分散破壊作用に抵抗力を持たせることが可能となる。この際、導入したカルボキシル基は、一部又は全部を、アンモニアやトリエチルアミン、ジメチルエタノールアミン等のアミン類やNaOH、KOH等の塩基で中和することもできる。 Examples of the carboxyl group-containing vinyl monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, or half of a dibasic acid such as itaconic acid, maleic acid, and fumaric acid. Esters and the like. By using a carboxylic acid group-containing vinyl monomer, a carboxyl group can be introduced into the polymer emulsion particles (B), improving the stability as an emulsion, and having a resistance to dispersion and destruction from the outside. It is possible to have it. At this time, part or all of the introduced carboxyl group can be neutralized with an amine such as ammonia, triethylamine or dimethylethanolamine, or a base such as NaOH or KOH.
カルボキシル基含有ビニル単量体の使用量は、1種又は2種以上の混合物として、全ビニル単量体中において0〜50質量%であることが耐水性の面から好ましい。 It is preferable from the surface of water resistance that the usage-amount of a carboxyl group-containing vinyl monomer is 0-50 mass% in all the vinyl monomers as 1 type, or 2 or more types of mixtures.
また、上記水酸基含有ビニル単量体としては、例えば2−ヒドロキシエチル(メタ)アクリレート、2−ヒドロキシプロピリ(メタ)アクリレート、3−ヒドロキシプロピリ(メタ)アクリレート、2−ヒドロキシブチル(メタ)アクリレート、3−ヒドロキシブチル(メタ)アクリレート、4−ヒドロキシブチル(メタ)アクリレート等の(メタ)アクリル酸のヒドロキシアルキルエステルや、ジ−2−ヒドロキシエチルフマレート、モノ−2−ヒドロキシエチルモノブチルフマレート、アリルアルコールやエチレンオキシド基の数が1〜100個の(ポリ)オキシエチレンモノ(メタ)アクリレート、プロピレンオキシド基の数が1〜100個の(ポリ)オキシプロピレンモノ(メタ)アクリレート、さらには、「プラクセルFM、FAモノマー」(ダイセル化学(株)製の、カプロラクトン付加モノマーの商品名)や、その他のα,β−エチレン性不飽和カルボン酸のヒドロキシアルキルエステル類などを挙げることができる。上記(ポリ)オキシエチレン(メタ)アクリレートの具体例としては、(メタ)アクリル酸エチレングリコール、メトキシ(メタ)アクリル酸エチレングリコール、(メタ)アクリル酸ジエチレングリコール、メトキシ(メタ)アクリル酸ジエチレングリコール、(メタ)アクリル酸テトラエチレングリコール、メトキシ(メタ)アクリル酸テトラエチレングリコール等が挙げられる。また、(ポリ)オキシプロピレン(メタ)アクリレートの具体例としては、(メタ)アクリル酸プロピレングリコール、メトキシ(メタ)アクリル酸プロピレングリコール、(メタ)アクリル酸ジプロピレングリコール、メトキシ(メタ)アクリル酸ジプロピレングリコール、(メタ)アクリル酸テトラプロピレングリコール、メトキシ(メタ)アクリル酸テトラプロピレングリコール等が挙げられる。 Examples of the hydroxyl group-containing vinyl monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate. Hydroxyalkyl esters of (meth) acrylic acid such as 3-hydroxybutyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate, di-2-hydroxyethyl fumarate, mono-2-hydroxyethyl monobutyl fumarate , (Poly) oxyethylene mono (meth) acrylate having 1 to 100 allyl alcohol or ethylene oxide groups, (poly) oxypropylene mono (meth) acrylate having 1 to 100 propylene oxide groups, "Placcel FM, FA Nomar "(manufactured by Daicel Chemical Industries, Ltd., trade name of caprolactone addition monomer) and other alpha, and the like hydroxyalkyl esters of β- ethylenically unsaturated carboxylic acid. Specific examples of the (poly) oxyethylene (meth) acrylate include ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, diethylene glycol methoxy (meth) acrylate, (meth ) Tetraethylene glycol acrylate, tetraethylene glycol methoxy (meth) acrylate, and the like. Specific examples of (poly) oxypropylene (meth) acrylate include propylene glycol (meth) acrylate, propylene glycol methoxy (meth) acrylate, dipropylene glycol (meth) acrylate, dimethoxy meth (meth) acrylate. Examples include propylene glycol, tetrapropylene glycol (meth) acrylate, and tetrapropylene glycol methoxy (meth) acrylate.
上述した水酸基含有ビニル単量体の使用量は、1種又は2種以上の混合物として、全ビニル単量体中において、好ましくは0〜80質量%、より好ましくは0.1〜50質量%である。 The amount of the hydroxyl group-containing vinyl monomer mentioned above is preferably 0 to 80% by mass, more preferably 0.1 to 50% by mass in the total vinyl monomer as one or a mixture of two or more. is there.
また、上記グリシジル基含有ビニル単量体としては、例えばグリシジル(メタ)アクリレート、アリルグリシジルエーテル、アリルジメチルグリシジルエーテル等を挙げることができる。 Examples of the glycidyl group-containing vinyl monomer include glycidyl (meth) acrylate, allyl glycidyl ether, and allyl dimethyl glycidyl ether.
グリシジル基含有ビニル単量体や、カルボニル基含有ビニル単量体を使用すると、重合体エマルジョン粒子(B)が反応性を有し、ヒドラジン誘導体やカルボン酸誘導体、イソシアネート誘導体等により架橋させて耐溶剤性等の優れた光触媒体の形成が可能となる。グリシジル基含有ビニル単量体や、カルボニル基含有ビニル単量体の使用量は、全ビニル単量体中において好ましくは0〜50質量%である。 When a glycidyl group-containing vinyl monomer or a carbonyl group-containing vinyl monomer is used, the polymer emulsion particles (B) are reactive and crosslinked with hydrazine derivatives, carboxylic acid derivatives, isocyanate derivatives, etc. It is possible to form a photocatalyst having excellent properties. The amount of the glycidyl group-containing vinyl monomer or the carbonyl group-containing vinyl monomer used is preferably 0 to 50% by mass in the total vinyl monomers.
ビニル単量体(b2)として、2級及び/又は3級アミド基を有するビニル単量体(b3)を少なくとも1種用いることが好ましい。 It is preferable to use at least one vinyl monomer (b3) having a secondary and / or tertiary amide group as the vinyl monomer (b2).
2級及び/又は3級アミド基を有するビニル単量体(b3)の例としては、N−アルキル又はN−アルキレン置換(メタ)アクリルアミドを例示することができ、具体的には、例えばN−メチルアクリルアミド、N−メチルメタアクリルアミド、N−エチルアクリルアミド、N,N−ジメチルアクリルアミド、N,N−ジメチルメタアクリルアミド、N,N−ジエチルアクリルアミド、N−エチルメタアクリルアミド、N−メチル−N−エチルアクリルアミド、N−メチル−N−エチルメタアクリルアミド、N−イソプロピルアクリルアミド、N−n−プロピルアクリルアミド、N−イソプロピルメタアクリルアミド、N−n−プロピルメタアクリルアミド、N−メチル−N−n−プロピルアクリルアミド、N−メチル−N−イソプロピルアクリルアミド、N−アクリロイルピロリジン、N−メタクリロイルピロリジン、N−アクリロイルピペリジン、N−メタクリロイルピペリジン、N−アクリロイルヘキサヒドロアゼピン、N−アクリロイルモルホリン、N−メタクリロイルモルホリン、N−ビニルピロリドン、N−ビニルカプロラクタム、N,N’−メチレンビスアクリルアミド、N,N’−メチレンビスメタクリルアミド、N−ビニルアセトアミド、ダイアセトンアクリルアミド、ダイアセトンメタアクリルアミド、N−メチロールアクリルアミド、N−メチロールメタアクリルアミド等を挙げることができる。 As an example of the vinyl monomer (b3) having a secondary and / or tertiary amide group, N-alkyl or N-alkylene-substituted (meth) acrylamide can be exemplified. Methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide, N-methyl-N-ethylacrylamide N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl-Nn-propylacrylamide, N- Methyl-N-isopropyla Rilamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine, N-acryloylhexahydroazepine, N-acryloylmorpholine, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam, N , N′-methylenebisacrylamide, N, N′-methylenebismethacrylamide, N-vinylacetamide, diacetone acrylamide, diacetone methacrylamide, N-methylol acrylamide, N-methylol methacrylamide and the like.
上記2級及び/又は3級アミド基を有するビニル単量体(b3)の中で、3級アミド基を有するビニル単量体を用いることが好ましい。特にN,N−ジエチルアクリルアミドは、水及び乳化剤の存在下における重合安定性に非常に優れるとともに、上述した加水分解性珪素化合物(b1)の重合生成物の水酸基や金属酸化物(A)の水酸基と強固な水素結合を形成することが可能であるため、非常に好ましい。 Among the vinyl monomers (b3) having a secondary and / or tertiary amide group, it is preferable to use a vinyl monomer having a tertiary amide group. In particular, N, N-diethylacrylamide is very excellent in polymerization stability in the presence of water and an emulsifier, and also the hydroxyl group of the polymerization product of the hydrolyzable silicon compound (b1) and the hydroxyl group of the metal oxide (A). It is very preferable because a strong hydrogen bond can be formed.
上記2級及び/又は3級アミド基を有するビニル単量体(b3)の使用量は、得られる重合体エマルジョン粒子(B)に対する質量比[(b3)/(B)]として0.1以上0.5以下であることが好ましく、また金属酸化物(A)との質量比(b3)/(A)が0.1以上1.0以下であることが好ましい。 The amount of the vinyl monomer (b3) having the secondary and / or tertiary amide group is 0.1 or more in terms of mass ratio [(b3) / (B)] to the resulting polymer emulsion particles (B). The mass ratio (b3) / (A) to the metal oxide (A) is preferably 0.1 or more and 1.0 or less.
上記以外のビニル単量体(b2)の具体例としては、例えば(メタ)アクリルアミド、エチレン、プロピレン、イソブチレン等のオレフィン類、ブタジエン等のジエン類、塩化ビニル、塩化ビニリデンフッ化ビニル、テトラフルオロエチレン、クロロトリフルオロエチレン等のハロオレフィン類、酢酸ビニル、プロピオン酸ビニル、n−酪酸ビニル、安息香酸ビニル、p−t−ブチル安息香酸ビニル、ピバリン酸ビニル、2−エチルヘキサン酸ビニル、バーサチック酸ビニル、ラウリン酸ビニル等のカルボン酸ビニルエステル類、酢酸イソプロペニル、プロピオン酸イソプロペニル等のカルボン酸イソプロペニルエステル類、エチルビニルエーテル、イソブチルビニルエーテル、シクロヘキシルビニルエーテル等のビニルエーテル類、スチレン、ビニルトルエン等の芳香族ビニル化合物、酢酸アリル、安息香酸アリル等のアリルエステル類、アリルエチルエーテル、アリルフェニルエーテル等のアリルエーテル類、さらに4−(メタ)アクリロイルオキシ−2,2,6,6,−テトラメチルピペリジン、4−(メタ)アクリロイルオキシ−1,2,2,6,6,−ペンタメチルピペリジン、パーフルオロメチル(メタ)アクリレート、パーフルオロプロピル(メタ)アクリレート、パーフルオロプロピロメチル(メタ)アクリレート、ビニルピロリドン、トリメチロールプロパントリ(メタ)アクリレート、(メタ)アクリル酸アリル等やそれらの併用が挙げられる。 Specific examples of the vinyl monomer (b2) other than the above include, for example, (meth) acrylamide, olefins such as ethylene, propylene, and isobutylene, dienes such as butadiene, vinyl chloride, vinylidene chloride, tetrafluoroethylene, and the like. , Haloolefins such as chlorotrifluoroethylene, vinyl acetate, vinyl propionate, vinyl n-butyrate, vinyl benzoate, vinyl pt-butylbenzoate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl versatic acid Carboxylic acid vinyl esters such as vinyl laurate, isopropenyl acetate, isopropenyl carboxylic acid such as isopropenyl propionate, vinyl ethers such as ethyl vinyl ether, isobutyl vinyl ether and cyclohexyl vinyl ether, styrene , Aromatic vinyl compounds such as vinyl toluene, allyl esters such as allyl acetate and allyl benzoate, allyl ethers such as allyl ethyl ether and allyl phenyl ether, and 4- (meth) acryloyloxy-2,2,6, 6, -tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6, -pentamethylpiperidine, perfluoromethyl (meth) acrylate, perfluoropropyl (meth) acrylate, perfluoropropylo Examples thereof include methyl (meth) acrylate, vinyl pyrrolidone, trimethylolpropane tri (meth) acrylate, allyl (meth) acrylate and the like and combinations thereof.
本発明においては、ビニル単量体(b2)の重合生成物の分子量を制御する目的で、連鎖移動剤を使用してもよい。 In the present invention, a chain transfer agent may be used for the purpose of controlling the molecular weight of the polymerization product of the vinyl monomer (b2).
かかる連鎖移動剤の一例としては、n−オクチルメルカプタン、n−ドデシルメルカプタン、t−ドデシルメルカプタンのようなアルキルメルカプタン類;ベンジルメルカプタン、ドデシルベンジルメルカプタンのような芳香族メルカプタン類;チオリンゴ酸のようなチオカルボン酸又はそれらの塩若しくはそれらのアルキルエステル類、又はポリチオール類、ジイソプロピルキサントゲンジスルフィド、ジ(メチレントリメチロールプロパン)キサントゲンジスルフィド及びチオグリコール、さらにはα−メチルスチレンのダイマー等のアリル化合物等を挙げることができる。 Examples of such chain transfer agents include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; thiocarboxylic acids such as thiomalic acid. Examples include acids or salts thereof or alkyl esters thereof, or polythiols, diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide and thioglycol, and allyl compounds such as dimer of α-methylstyrene. it can.
これら連鎖移動剤の使用量は、全ビニル単量体に対して好ましくは0.001〜30質量%、さらに好ましくは0.05〜10質量%の範囲で用いることができる。 The amount of these chain transfer agents used is preferably 0.001 to 30% by mass, more preferably 0.05 to 10% by mass, based on the total vinyl monomer.
加水分解性珪素化合物(b1)に対するビニル単量体(b2)の質量比(b2)/(b1)は、5/95〜95/5、好ましくは10/90〜90/10である。 The mass ratio (b2) / (b1) of the vinyl monomer (b2) to the hydrolyzable silicon compound (b1) is 5/95 to 95/5, preferably 10/90 to 90/10.
本発明において、加水分解性珪素化合物(b1)としてビニル重合性基を有するシランカップリング剤を用いることが耐候性の面から特に好ましく、その配合量は重合体エマルジョン粒子(B)100質量部に対して0.01以上20質量部以下であることが重合安定性の面から好ましい。さらに好ましくは、0.1以上10質量部以下である。 In the present invention, it is particularly preferable from the viewpoint of weather resistance to use a silane coupling agent having a vinyl polymerizable group as the hydrolyzable silicon compound (b1), and the blending amount thereof is 100 parts by mass of the polymer emulsion particles (B). On the other hand, it is preferably from 0.01 to 20 parts by mass from the viewpoint of polymerization stability. More preferably, it is 0.1 to 10 parts by mass.
また、ビニル重合性基を有するシランカップリング剤の配合量は、ビニル単量体(b2)100質量部に対して0.1以上100質量部以下であることが重合安定性の面から好ましい。 Moreover, it is preferable from the surface of superposition | polymerization stability that the compounding quantity of the silane coupling agent which has a vinyl polymerizable group is 0.1-100 mass parts with respect to 100 mass parts of vinyl monomers (b2).
本発明においては、上述した加水分解性珪素化合物(b1)に環状シロキサンオリゴマーを併用して用いることが可能である。環状シロキサンオリゴマーの併用により、本発明の光触媒組成物からは、柔軟性等に優れた光触媒体を形成することができる。 In the present invention, it is possible to use a cyclic siloxane oligomer in combination with the hydrolyzable silicon compound (b1) described above. By using the cyclic siloxane oligomer in combination, a photocatalyst excellent in flexibility and the like can be formed from the photocatalyst composition of the present invention.
上記環状シロキサンオリゴマーとしては、下記式(2)で表される化合物を例示することができる。 As said cyclic siloxane oligomer, the compound represented by following formula (2) can be illustrated.
(R’2SiO)m (2)
(式中、R’は、水素原子、直鎖状又は分岐状の炭素数が1〜30個のアルキル基、炭素数5〜20のシクロアルキル基、及び置換されていないか又は炭素数1〜20のアルキル基若しくは炭素数1〜20のアルコキシ基若しくはハロゲン原子で置換されている炭素数6〜20のアリール基から選ばれる少なくとも1種を表す。mは2≦m≦20の整数である。)
(R ′ 2 SiO) m (2)
(In the formula, R ′ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or substituted carbon atom having 1 to 30 carbon atoms. It represents at least one selected from an alkyl group having 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom, and m is an integer of 2 ≦ m ≦ 20. )
上記環状シロキサンオリゴマーの中で、反応性等の点からオクタメチルシクロテトラシロキサン等の環状ジメチルシロキサンオリゴマーが好ましい。 Among the cyclic siloxane oligomers, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferable from the viewpoint of reactivity.
また、本発明において、上述した加水分解性珪素化合物(b1)にチタンアルコキシド、ジルコニウムアルコキシド、及びそれらの縮合生成物、又は、それらのキレート化物を併用して用いることもできる。これらの化合物の併用により、本発明の光触媒組成物からは、耐水性、硬度等に優れた光触媒体を形成することができる。 In the present invention, the hydrolyzable silicon compound (b1) described above can be used in combination with a titanium alkoxide, a zirconium alkoxide, a condensation product thereof, or a chelated product thereof. By using these compounds in combination, a photocatalyst having excellent water resistance, hardness and the like can be formed from the photocatalyst composition of the present invention.
上記チタンアルコキシドの具体例としては、例えば、テトラメトキシチタン、テトラエトキシチタン、テトライソプロポキシチタン、テトラ−n−プロポキシチタン、テトラ−n−ブトキシチタン、テトラ−sec−ブトキシチタン、テトラ−tert−ブトキシチタン等が挙げられる。 Specific examples of the titanium alkoxide include, for example, tetramethoxy titanium, tetraethoxy titanium, tetraisopropoxy titanium, tetra-n-propoxy titanium, tetra-n-butoxy titanium, tetra-sec-butoxy titanium, tetra-tert-butoxy. Examples include titanium.
上記チタンアルコキシドが縮合生成物として使用されるとき、該縮合生成物のポリスチレン換算重量平均分子量は、好ましくは200〜5000、さらに好ましくは300〜1000である。 When the titanium alkoxide is used as a condensation product, the weight average molecular weight in terms of polystyrene of the condensation product is preferably 200 to 5,000, more preferably 300 to 1,000.
また、上記ジルコニウムアルコキシドの具体例としては、テトラメトキシジルコニウム、テトラエトキシジルコニウム、テトライソプロポキシジルコニウム、テトラ−n−プロポキシジルコニウム、テトラ−n−ブトキシジルコニウム、テトラ−sec−ブトキシジルコニウム、テトラ−tert−ブトキシジルコニウム等が挙げられる。 Specific examples of the zirconium alkoxide include tetramethoxy zirconium, tetraethoxy zirconium, tetraisopropoxy zirconium, tetra-n-propoxy zirconium, tetra-n-butoxy zirconium, tetra-sec-butoxy zirconium, tetra-tert-butoxy. Zirconium etc. are mentioned.
上記ジルコニウムアルコキシドが縮合生成物として使用されるとき、該縮合生成物のポリスチレン換算重量平均分子量は、好ましくは200〜5000、さらに好ましくは300〜1000である。 When the zirconium alkoxide is used as a condensation product, the weight average molecular weight in terms of polystyrene of the condensation product is preferably 200 to 5,000, more preferably 300 to 1,000.
また、遊離の金属化合物に配位させてキレート化物を形成するのに好ましいキレート化剤としては、ジエタノールアミン、トリエタノールアミン等のアルカノールアミン類;エチレングリコール、ジエチレングリコール、プロピレングリコール等のグリコール類;アセチルアセトン;アセト酢酸エチルなどであって分子量1万以下のものを例示することができる。これらのキレート化剤を用いることにより、加水分解性金属化合物(b1)の重合速度を制御することができ、水及び乳化剤の存在下における重合安定性を優れたものにするため非常に好ましい。この際、キレート化剤は、これを配位させる遊離の金属化合物の金属原子1モル当たり、0.1モル〜2モルの割合で用いると効果が大きく好ましい。 Further, as a preferable chelating agent for coordination with a free metal compound to form a chelate, alkanolamines such as diethanolamine and triethanolamine; glycols such as ethylene glycol, diethylene glycol and propylene glycol; acetylacetone; Examples thereof include ethyl acetoacetate having a molecular weight of 10,000 or less. By using these chelating agents, the polymerization rate of the hydrolyzable metal compound (b1) can be controlled, and this is very preferable in order to make the polymerization stability excellent in the presence of water and an emulsifier. In this case, the chelating agent is preferably used in a ratio of 0.1 mol to 2 mol per mol of the metal atom of the free metal compound that coordinates it.
本発明において、重合体エマルジョン粒子(B)の合成に用いることができる乳化剤としては、例えば、アルキルベンゼンスルホン酸、アルキルスルホン酸、アルキルスルホコハク酸、ポリオキシエチレンアルキル硫酸、ポリオキシエチレンアルキルアリール硫酸、ポリオキシエチレンジスチリルフェニルエーテルスルホン酸等の酸性乳化剤、酸性乳化剤のアルカリ金属(Li、Na、K等)塩、酸性乳化剤のアンモニウム塩、脂肪酸石鹸等のアニオン性界面活性剤や、例えばアルキルトリメチルアンモニウムブロミド、アルキルピリジニウムブロミド、イミダゾリニウムラウレート等の四級アンモニウム塩、ピリジニウム塩、イミダゾリニウム塩型のカチオン性界面活性剤、ポリオキシエチレンアルキルアリールエーテル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンオキシプロピレンブロックコポリマー、ポリオキシエチレンジスチリルフェニルエーテル等のノニオン型界面活性剤やラジカル重合性の二重結合を有する反応性乳化剤等を例示することができる。 In the present invention, examples of the emulsifier that can be used for the synthesis of the polymer emulsion particles (B) include alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, poly Acidic emulsifiers such as oxyethylene distyryl phenyl ether sulfonic acid, alkali metal (Li, Na, K, etc.) salts of acidic emulsifiers, ammonium salts of acidic emulsifiers, anionic surfactants such as fatty acid soaps, and alkyltrimethylammonium bromides, for example , Quaternary ammonium salts such as alkylpyridinium bromides and imidazolinium laurates, pyridinium salts, imidazolinium salt type cationic surfactants, polyoxyethylene alkylaryl ethers, polyoxyethylenes Nsorubitan fatty acid esters, polyoxyethylene polyoxypropylene block copolymers can be exemplified reactive emulsifier or the like having a nonionic surface active agent and a radical polymerizable double bond polyoxyethylene distyryl phenyl ether.
これらの乳化剤の中で、ラジカル重合性の二重結合を有する反応性乳化剤を選択すると、本発明の重合体エマルジョン粒子(B)の水分散安定性が非常に良好になると共に、該重合体エマルジョン粒子(B)を含有する本発明の光触媒組成物からは、耐水性、耐薬品性、光学特性、強度等に優れた光触媒体を形成することができるため、非常に好ましい。 Among these emulsifiers, when a reactive emulsifier having a radical polymerizable double bond is selected, the water dispersion stability of the polymer emulsion particles (B) of the present invention becomes very good, and the polymer emulsion The photocatalyst composition of the present invention containing the particles (B) is very preferable because a photocatalyst having excellent water resistance, chemical resistance, optical properties, strength, and the like can be formed.
上記ラジカル重合性の二重結合を有する反応性乳化剤としては、例えばスルホン酸基又はスルホネート基を有するビニル単量体、硫酸エステル基を有するビニル単量体やそれらのアルカリ金属塩、アンモニウム塩、ポリオキシエチレン等のノニオン基を有するビニル単量体、4級アンモニウム塩を有するビニル単量体等を挙げることができる。 Examples of the reactive emulsifier having a radical polymerizable double bond include a vinyl monomer having a sulfonic acid group or a sulfonate group, a vinyl monomer having a sulfate ester group, an alkali metal salt thereof, an ammonium salt, Examples include vinyl monomers having a nonionic group such as oxyethylene, and vinyl monomers having a quaternary ammonium salt.
上記反応性乳化剤の具体例として、スルホン酸基又はスルホネート基を有するビニル単量体の塩を例にとると、ラジカル重合性の二重結合を有し、かつスルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基により一部が置換された、炭素数1〜20のアルキル基、炭素数2〜4のアルキルエーテル基、炭素数2〜4のポリアルキルエーテル基、炭素数6又は10のアリール基及びコハク酸基からなる群から選ばれる置換基を有する化合物であるか、スルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基が結合しているビニル基を有するビニルスルホネート化合物である。硫酸エステル基を有するビニル単量体は、ラジカル重合性の二重結合を有し、かつ硫酸エステル基のアンモニウム塩、ナトリウム塩又はカリウム塩である基により一部が置換された、炭素数1〜20のアルキル基、炭素数2〜4のアルキルエーテル基、炭素数2〜4のポリアルキルエーテル基及び炭素数6又は10のアリール基からなる群から選ばれる置換基を有する化合物である。 As a specific example of the reactive emulsifier, taking a vinyl monomer salt having a sulfonic acid group or a sulfonate group as an example, it has a radical polymerizable double bond, and is an ammonium salt or sodium salt of a sulfonic acid group. Or an alkyl group having 1 to 20 carbon atoms, an alkyl ether group having 2 to 4 carbon atoms, a polyalkyl ether group having 2 to 4 carbon atoms, a 6 or 10 carbon atom, partially substituted with a group that is a potassium salt It is a compound having a substituent selected from the group consisting of an aryl group and a succinic acid group, or a vinyl sulfonate compound having a vinyl group to which a group which is an ammonium salt, sodium salt or potassium salt of a sulfonic acid group is bonded. . The vinyl monomer having a sulfate ester group has a radically polymerizable double bond and is partially substituted with a group that is an ammonium salt, sodium salt or potassium salt of a sulfate ester group, having 1 to 1 carbon atoms. It is a compound having a substituent selected from the group consisting of 20 alkyl groups, alkyl ether groups having 2 to 4 carbon atoms, polyalkyl ether groups having 2 to 4 carbon atoms, and aryl groups having 6 or 10 carbon atoms.
上記スルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基により一部が置換されたコハク酸基を有する化合物の具体例としては、アリルスルホコハク酸塩が挙げられる。これらの具体例として、例えば、エレミノールJS−2(商品名)(三洋化成(株)製)、ラテムルS−120(商品名)、S−180A(商品名)又はS−180(商品名)(花王(株)製)等を挙げることができる。 Specific examples of the compound having a succinic acid group partially substituted with a group which is an ammonium salt, sodium salt or potassium salt of the sulfonic acid group include allylsulfosuccinate. Specific examples of these include, for example, Eleminol JS-2 (trade name) (manufactured by Sanyo Kasei Co., Ltd.), Latemul S-120 (trade name), S-180A (trade name) or S-180 (trade name) ( And Kao Corporation).
また、上記スルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基により一部が置換された、炭素数2〜4のアルキルエーテル基又は炭素数2〜4のポリアルキルエーテル基を有する化合物の具体例として、例えばアクアロンHS−10又はKH−1025(商品名)(第一工業製薬(株)製)、アデカリアソープSE−1025N(商品名)又はSR−1025(商品名)(旭電化工業(株)製)等を挙げることができる。 Further, a compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, which is partially substituted by a group which is an ammonium salt, sodium salt or potassium salt of the sulfonic acid group. As specific examples, for example, Aqualon HS-10 or KH-1025 (trade name) (Daiichi Kogyo Seiyaku Co., Ltd.), Adekaria Soap SE-1025N (trade name) or SR-1025 (trade name) (Asahi Denka Kogyo) For example).
その他、スルホネート基により一部が置換されたアリール基を有する化合物の具体例として、p−スチレンスルホン酸のアンモニウム塩、ナトリウム塩及びカリウム塩等が挙げられる。 Other specific examples of the compound having an aryl group partially substituted with a sulfonate group include ammonium salt, sodium salt and potassium salt of p-styrenesulfonic acid.
上記スルホン酸基のアンモニウム塩、ナトリウム塩又はカリウム塩である基が結合しているビニル基を有するビニルスルホネート化合物として例えば、2−スルホエチルアクリレート等のアルキルスルホン酸(メタ)アクリレートやメチルプロパンスルホン酸(メタ)アクリルアミド、アリルスルホン酸等のアンモニウム塩、ナトリウム塩及びカリウム塩が挙げられる。 Examples of the vinyl sulfonate compound having a vinyl group to which a group of ammonium salt, sodium salt or potassium salt of the sulfonic acid group is bonded include, for example, alkyl sulfonic acid (meth) acrylate such as 2-sulfoethyl acrylate, and methylpropane sulfonic acid. Examples thereof include ammonium salts such as (meth) acrylamide and allyl sulfonic acid, sodium salts, and potassium salts.
また、上記の硫酸エステル基のアンモニウム塩、ナトリウム塩又はカリウム塩により一部が置換された炭素数2〜4のアルキルエーテル基又は炭素数2〜4のポリアルキエーテル基を有する化合物としては、例えばスルホネート基により一部が置換されたアルキルエーテル基を有する化合物等がある。 Examples of the compound having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms partially substituted with the ammonium salt, sodium salt or potassium salt of the sulfate ester group include, for example, Examples include compounds having an alkyl ether group partially substituted with a sulfonate group.
また、ノニオン基を有するビニル単量体の具体例としては、α−〔1−〔(アリルオキシ)メチル〕−2−(ノニルフェノキシ)エチル〕−ω−ヒドロキシポリオキシエチレン(商品名:アデカリアソープNE−20、NE−30、NE−40等、旭電化工業(株)製)、ポリオキシエチレンアルキルプロペニルフェニルエーテル(商品名:アクアロンRN−10、RN−20、RN−30、RN−50等、第一製薬工業(株)製)等を挙げることができる。 In addition, specific examples of vinyl monomers having a nonionic group include α- [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] -ω-hydroxypolyoxyethylene (trade name: ADEKA rear soap). NE-20, NE-30, NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene alkylpropenyl phenyl ether (trade names: Aqualon RN-10, RN-20, RN-30, RN-50, etc.) , Manufactured by Daiichi Pharmaceutical Co., Ltd.).
上記乳化剤の使用量としては、重合体エマルジョン粒子(B)100質量部に対して、20質量部以下となる範囲内が適切であり、なかでも、0.001〜10質量部となる範囲内が好ましい。 As the usage-amount of the said emulsifier, the inside of the range used as 20 mass parts or less is suitable with respect to 100 mass parts of polymer emulsion particle | grains (B), Especially, within the range used as 0.001-10 mass parts. preferable.
また、上記乳化剤以外に、本発明の重合体エマルジョン粒子(B)の水分散安定性を向上させる目的で分散安定剤を使用することもできる。該分散安定剤としては、ポリカルボン酸及びスルホン酸塩からなる群から選ばれる各種の水溶性オリゴマー類や、ポリビニルアルコール、ヒドロキシエチルセルロース、澱粉、マレイン化ポリブタジエン、マレイン化アルキッド樹脂、ポリアクリル酸(塩)、ポリアクリルアミド、水溶性又は水分散性アクリル樹脂などの合成又は天然の水溶性又は水分散性の各種の水溶性高分子物質が挙げられ、これらの1種又は2種以上の混合物を使用することができる。 In addition to the above emulsifiers, a dispersion stabilizer can also be used for the purpose of improving the water dispersion stability of the polymer emulsion particles (B) of the present invention. Examples of the dispersion stabilizer include various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin, polyacrylic acid (salt ), Synthetic or natural water-soluble or water-dispersible water-soluble polymer substances such as polyacrylamide, water-soluble or water-dispersible acrylic resin, etc., and one or a mixture of two or more of these are used. be able to.
これらの分散安定剤を使用する場合、その使用量としては、重合体エマルジョン粒子(B)100質量部に対して、10質量部以下となる範囲内が適切であり、なかでも、0.001〜5質量部となる範囲内が好ましい。 When these dispersion stabilizers are used, the amount used is suitably within a range of 10 parts by mass or less with respect to 100 parts by mass of the polymer emulsion particles (B). The range of 5 parts by mass is preferable.
本発明において、加水分解性珪素化合物(b1)及びビニル単量体(b2)の重合は、重合触媒存在下で実施するのが好ましい。 In the present invention, the polymerization of the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) is preferably carried out in the presence of a polymerization catalyst.
ここで、加水分解性珪素化合物(b1)の重合触媒としては、塩酸、フッ酸等のハロゲン化水素類、酢酸、トリクロル酢酸、トリフルオロ酢酸、乳酸等のカルボン酸類、硫酸、p−トルエンスルホン酸等のスルホン酸類、アルキルベンゼンスルホン酸、アルキルスルホン酸、アルキルスルホコハク酸、ポリオキシエチレンアルキル硫酸、ポリオキシエチレンアルキルアリール硫酸、ポリオキシエチレンジスチリルフェニルエーテルスルホン酸等の酸性乳化剤類、酸性又は弱酸性の無機塩、フタル酸、リン酸、硝酸のような酸性化合物類;水酸化ナトリウム、水酸化カリウム、ナトリウムメチラート、酢酸ナトリウム、テトラメチルアンモニウムクロリド、テトラメチルアンモニウムヒドロキシド、トリブチルアミン、ジアザビシクロウンデセン、エチレンジアミン、ジエチレントリアミン、エタノールアミン類、γ−アミノプロピルトリメトキシシラン、γ−(2−アミノエチル)−アミノプロピルトリメトキシシランのような塩基性化合物類;ジブチル錫オクチレート、ジブチル錫ジラウレートのような錫化合物等を挙げることができる。 Here, as a polymerization catalyst for the hydrolyzable silicon compound (b1), hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid, sulfuric acid, and p-toluenesulfonic acid Sulfonic acids such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid, etc., acidic or weakly acidic emulsifier Acidic compounds such as inorganic salts, phthalic acid, phosphoric acid, nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicyclounde SE , Basic compounds such as ethylenediamine, diethylenetriamine, ethanolamine, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; tin such as dibutyltin octylate, dibutyltin dilaurate A compound etc. can be mentioned.
これらの中で、加水分解性珪素化合物(b1)の重合触媒としては、重合触媒のみならず乳化剤としての作用を有する酸性乳化剤類、特に炭素数が5〜30のアルキルベンゼンスルホン酸(ドデシルベンゼンスルホン酸等)が非常に好ましい。 Among these, as a polymerization catalyst for the hydrolyzable silicon compound (b1), acidic emulsifiers having an action as an emulsifier as well as a polymerization catalyst, particularly alkylbenzenesulfonic acid (dodecylbenzenesulfonic acid having 5 to 30 carbon atoms). Etc.) is highly preferred.
一方、ビニル単量体(b2)の重合触媒としては、熱又は還元性物質などによってラジカル分解してビニル単量体の付加重合を起こさせるラジカル重合触媒が好適であり、水溶性又は油溶性の過硫酸塩、過酸化物、アゾビス化合物等が使用される。その例としては、過硫酸カリウム、過硫酸ナトリウム、過硫酸アンモニウム、過酸化水素、t−ブチルヒドロパーオキシド、t−ブチルパーオキシベンゾエート、2,2−アゾビスイソブチロニトリル、2,2−アゾビス(2−ジアミノプロパン)ヒドロクロリド、2,2−アゾビス(2,4−ジメチルバレロニトリル)等があり、その量としては全ビニル単量体100質量部に対して、0.001〜5質量部の配合が好ましい。なお、重合速度の促進、及び70℃以下での低温の重合を望むときには、例えば重亜硫酸ナトリウム、塩化第一鉄、アスコルビン酸塩、ロンガリット等の還元剤をラジカル重合触媒と組み合わせて用いると有利である。 On the other hand, the polymerization catalyst for the vinyl monomer (b2) is preferably a radical polymerization catalyst that undergoes radical decomposition by heat or a reducing substance to cause addition polymerization of the vinyl monomer, and is water-soluble or oil-soluble. Persulfates, peroxides, azobis compounds and the like are used. Examples include potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyronitrile, 2,2-azobis. (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile), etc., and the amount thereof is 0.001 to 5 parts by mass with respect to 100 parts by mass of the total vinyl monomer. Is preferable. When acceleration of the polymerization rate and polymerization at a low temperature of 70 ° C. or lower are desired, it is advantageous to use a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, or longalite in combination with the radical polymerization catalyst. is there.
上述したように、本発明の光触媒組成物に用いる重合体エマルジョン粒子(B)は、水及び乳化剤の存在下に加水分解性珪素化合物(b1)及びビニル単量体(b2)を、好ましくは重合触媒存在下で重合することにより得ることができる。 As described above, the polymer emulsion particles (B) used in the photocatalyst composition of the present invention preferably polymerize the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) in the presence of water and an emulsifier. It can be obtained by polymerization in the presence of a catalyst.
ここで、加水分解性珪素化合物(b1)及びビニル単量体(b2)の重合は、別々に実施することも可能であるが、同時に実施することにより水素結合等によるミクロな有機・無機複合化が達成できるので好ましい。 Here, the polymerization of the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) can be carried out separately. Can be achieved.
また、本発明において、重合体エマルジョン粒子(B)の粒子径が10〜800nmであることが重要である。粒子径をこの様な範囲に調整し、粒子径が100nm以下の金属酸化物(A)と組み合わせて光触媒組成物とすることにより、はじめて耐候性、耐薬品性、光学特性、更には防汚性、防曇性、帯電防止性等に優れた光触媒体を形成することが可能となる。また、重合体エマルジョン粒子(B)の粒子径は50〜300nmであると、得られる塗膜の透明性が向上しより好ましい。 In the present invention, it is important that the particle diameter of the polymer emulsion particles (B) is 10 to 800 nm. By adjusting the particle diameter to such a range and combining it with a metal oxide (A) having a particle diameter of 100 nm or less to form a photocatalyst composition, weather resistance, chemical resistance, optical properties, and antifouling properties can be used for the first time. It is possible to form a photocatalyst having excellent antifogging properties and antistatic properties. Moreover, it is more preferable that the particle diameter of the polymer emulsion particles (B) is 50 to 300 nm because the transparency of the obtained coating film is improved.
このような粒子径の重合体エマルジョン粒子(B)を得る方法として、乳化剤がミセルを形成するのに十分な量の水の存在下に加水分解性金属化合物(b1)及びビニル単量体(b2)を重合する、いわゆる乳化重合が最も適した方法である。 As a method for obtaining polymer emulsion particles (B) having such a particle size, the hydrolyzable metal compound (b1) and the vinyl monomer (b2) in the presence of a sufficient amount of water for the emulsifier to form micelles. So-called emulsion polymerization is the most suitable method.
乳化重合のやり方としては、例えば、加水分解性珪素化合物(b1)及びビニル単量体(b2)は、そのまま、又は乳化した状態で、一括で若しくは分割で、又は連続的に反応容器中に滴下し、前記重合触媒の存在下で、好ましくは大気圧から必要により10MPaの圧力下で、約30〜150℃の反応温度で重合させればよい。場合によっては、これ以上の圧力で、又はこれ以下の温度条件で重合を行っても差し支えない。加水分解性珪素化合物(b1)及び全ビニル単量体量の総量と水との比率は最終固形分量が0.1〜70質量%、好ましくは1〜55質量%の範囲になるように設定するのが好ましい。また、乳化重合をするにあたり粒子径を成長又は制御させるために、予め水相中にエマルジョン粒子を存在させて重合させるシード重合法によってもよい。重合反応は、系中のpHが好ましくは1.0〜10.0、より好ましくは1.0〜6.0の範囲で進行させればよい。pHは、燐酸二ナトリウムやボラックス、又は、炭酸水素ナトリウム、アンモニアなどのpH緩衝剤を用いて調節することが可能である。 As a method of emulsion polymerization, for example, the hydrolyzable silicon compound (b1) and the vinyl monomer (b2) are dropped into the reaction vessel as they are or in an emulsified state, in a lump, in a divided manner, or continuously. In the presence of the polymerization catalyst, polymerization is preferably performed at a reaction temperature of about 30 to 150 ° C., preferably from atmospheric pressure to a pressure of 10 MPa if necessary. In some cases, the polymerization may be carried out at a higher pressure or lower temperature. The ratio of the total amount of hydrolyzable silicon compound (b1) and all vinyl monomers to water is set so that the final solid content is in the range of 0.1 to 70% by mass, preferably 1 to 55% by mass. Is preferred. Further, in order to grow or control the particle diameter in carrying out emulsion polymerization, a seed polymerization method in which emulsion particles are preliminarily present in an aqueous phase may be used. The polymerization reaction may be allowed to proceed in the range of pH in the system of preferably 1.0 to 10.0, more preferably 1.0 to 6.0. The pH can be adjusted using a pH buffer such as disodium phosphate, borax, sodium hydrogen carbonate, or ammonia.
また、本発明の重合体エマルジョン粒子(B)を得る方法として、加水分解性珪素化合物(b1)を重合させるのに必要な水及び乳化剤の存在下に、加水分解性金属化合物(b1)及びビニル単量体(b2)を、必要により溶剤存在下で重合した後、重合生成物がエマルジョンとなるまで水を添加する手法も適用できるが、上述した乳化重合方法と比べ、得られる重合体エマルジョン粒子(B)の粒子径制御が困難である。 As a method for obtaining the polymer emulsion particles (B) of the present invention, the hydrolyzable metal compound (b1) and vinyl in the presence of water and an emulsifier necessary for polymerizing the hydrolyzable silicon compound (b1). Although the monomer (b2) is polymerized in the presence of a solvent, if necessary, a method of adding water until the polymerization product becomes an emulsion can also be applied, but the resulting polymer emulsion particles are compared with the emulsion polymerization method described above. It is difficult to control the particle size of (B).
本発明において、重合体エマルジョン粒子(B)が2層以上の層から形成されるコア/シェル構造であると、該重合体エマルジョン粒子(B)を含有する光触媒組成物から機械的物性(強度と柔軟性のバランス等)に優れた光触媒体を形成することが可能となり好ましい。特に、その最内層の、加水分解性珪素化合物(b1)に対するビニル単量体(b2)の質量比(b2)/(b1)が1.0以下であり、かつ最外層の質量比(b2)/(b1)が0.1以上5.0以下であると、得られる複合体は耐候性、機械的物性が共に特に良好であり好ましい。 In the present invention, when the polymer emulsion particles (B) have a core / shell structure formed of two or more layers, mechanical properties (strength and strength) are obtained from the photocatalyst composition containing the polymer emulsion particles (B). It is possible to form a photocatalyst body excellent in flexibility balance and the like, which is preferable. In particular, the mass ratio (b2) / (b1) of the vinyl monomer (b2) to the hydrolyzable silicon compound (b1) in the innermost layer is 1.0 or less, and the mass ratio (b2) of the outermost layer. When / (b1) is 0.1 or more and 5.0 or less, the obtained composite is preferable because both weather resistance and mechanical properties are particularly good.
上記コア/シェル構造の重合体エマルジョン粒子(B)を製造する方法として、多段乳化重合が非常に有用である。 Multi-stage emulsion polymerization is very useful as a method for producing the core / shell structured polymer emulsion particles (B).
ここで、多段乳化重合とは、2種類以上の異なった組成の加水分解性珪素化合物(b1)やビニル単量体(b2)を調製し、これらを別々の段階に分けて重合することを意味する。 Here, multistage emulsion polymerization means that two or more different hydrolyzable silicon compounds (b1) and vinyl monomers (b2) having different compositions are prepared and polymerized in separate stages. To do.
以下に、多段乳化重合の中で最も単純で有用な2段乳化重合による重合体エマルジョン粒子(B)の合成を例に、本発明の多段乳化重合による重合体エマルジョン粒子(B)の合成について説明する。 Hereinafter, the synthesis of the polymer emulsion particles (B) by the multistage emulsion polymerization of the present invention will be described by taking the synthesis of the polymer emulsion particles (B) by the simplest and useful two-stage emulsion polymerization as an example. To do.
本発明において、2段乳化重合による重合体エマルジョン粒子(B)の合成として、例えば水及び乳化剤の存在下にビニル単量体(b2)及び/又は加水分解性珪素化合物(b1)を重合して得られるシード粒子の存在下に、加水分解性珪素化合物(b1)ビニル単量体(b2)を重合する方法を例示できる。 In the present invention, as the synthesis of the polymer emulsion particles (B) by two-stage emulsion polymerization, for example, the vinyl monomer (b2) and / or the hydrolyzable silicon compound (b1) is polymerized in the presence of water and an emulsifier. A method of polymerizing the hydrolyzable silicon compound (b1) vinyl monomer (b2) in the presence of the obtained seed particles can be exemplified.
上記2段乳化重合による重合体エマルジョン粒子(B)の合成は、第1系列(ビニル単量体(b2)及び/又は加水分解性金属化合物(b1))を供給して乳化重合する第1段の重合と、第1段に引き続き、第2系列(加水分解性金属化合物(b1)及びビニル単量体(b2))を供給し、水性媒体中において乳化重合する第2段の重合からなる2段階の重合工程により行われる。この際、第1系列中の固形分質量(M1)と第2系列中の固形分質量(M2)の質量比は、好ましくは(M1)/(M2)=9/1〜1/9、より好ましくは8/2〜2/8である。 The synthesis of the polymer emulsion particles (B) by the two-stage emulsion polymerization is a first stage in which emulsion polymerization is performed by supplying a first series (vinyl monomer (b2) and / or hydrolyzable metal compound (b1)). And the second stage (the hydrolyzable metal compound (b1) and the vinyl monomer (b2)) are supplied to the second stage, followed by emulsion polymerization in an aqueous medium. It is carried out by a staged polymerization process. At this time, the mass ratio of the solid content mass (M1) in the first series to the solid content mass (M2) in the second series is preferably (M1) / (M2) = 9/1 to 1/9. Preferably, it is 8/2 to 2/8.
本発明において、好ましいコア/シェル構造の重合体の特徴は、第1段の重合で得られたシード粒子の粒子径が、粒径分布(体積平均粒子径/数平均粒子径)の大きな変化なしに(好ましくは単分散の状態で)、第2段の重合によって大きくなる(粒子径の増大)ことを挙げることができる。 In the present invention, the preferred core / shell structure polymer is characterized in that the particle size of the seed particles obtained by the first stage polymerization is not greatly changed in the particle size distribution (volume average particle size / number average particle size). (Preferably in a monodispersed state) can be increased by the second stage polymerization (increase in particle diameter).
また、コア/シェル構造の確認は、例えば、透過型電子顕微鏡等による形態観察や粘弾性測定による解析等により実施することが可能である。 The core / shell structure can be confirmed by, for example, morphological observation with a transmission electron microscope, analysis by viscoelasticity measurement, or the like.
重合体エマルジョン粒子(B)を、水及び乳化剤の存在下に加水分解性珪素化合物(b1)を重合して得られるシード粒子の存在下に加水分解性珪素化合物(b1)及びビニル単量体(b2)を重合した場合は重合安定性に優れており好ましい。 In the presence of seed particles obtained by polymerizing the polymer emulsion particles (B) in the presence of water and an emulsifier, the hydrolyzable silicon compound (b1) and the vinyl monomer ( When b2) is polymerized, the polymerization stability is excellent, which is preferable.
また、上述したコア/シェル構造の重合体エマルジョン粒子(B)において、コア相のガラス転移温度(Tg)が0℃以下、すなわち上記シード粒子のガラス転移温度が0℃以下のものは、それを含有する光触媒組成物からは室温における柔軟性に優れ、割れ等が生じにくい光触媒体を形成することが可能となり、好ましい。 In the above-described polymer emulsion particles (B) having a core / shell structure, the glass transition temperature (Tg) of the core phase is 0 ° C. or lower, that is, the glass transition temperature of the seed particles is 0 ° C. or lower. It is preferable from the photocatalyst composition to be contained because it is possible to form a photocatalyst that is excellent in flexibility at room temperature and hardly cracks.
本発明において、3段以上の多段乳化重合を実施する場合は、上述した2段重合による重合体エマルジョン粒子(B)の合成例を参考に、重合する系列の数を増加させればよい。 In the present invention, when multi-stage emulsion polymerization of three or more stages is performed, the number of series to be polymerized may be increased with reference to the synthesis example of the polymer emulsion particles (B) by the two-stage polymerization described above.
また、本発明の光触媒組成物には、水素結合等による金属酸化物(A)と重合体エマルジョン粒子(B)の相互作用を制御する目的で、アルコール類を添加することもできる。アルコールの添加により、貯蔵安定性等が非常に向上する。 Moreover, alcohols can also be added to the photocatalyst composition of the present invention for the purpose of controlling the interaction between the metal oxide (A) and the polymer emulsion particles (B) due to hydrogen bonding or the like. Addition of alcohol greatly improves storage stability and the like.
上記アルコール類としては、メタノール、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、変性エタノール、グリセリン、アルキル鎖の炭素数が3〜8のモノアルキルモノグリセリルエーテル、プロピレングリコールモノメチルエーテル、ジエチレングリコールモノブチルエーテル、プロピレングリコールモノエチルエーテル、プロピレングリコールモノブチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノブチルエーテル又はジないしテトラエチレングリコールモノフェニルエーテルが好ましい。これらの中で、エタノールが環境上最も好ましい。 Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, modified ethanol, glycerin, monoalkyl monoglyceryl ether having 3 to 8 carbon atoms in the alkyl chain, and propylene glycol monomethyl. Ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether or di to tetraethylene glycol monophenyl ether are preferred. Of these, ethanol is most preferable from the environmental viewpoint.
本発明の光触媒体には、紫外線吸収剤として、ベンゾフェノン系紫外線吸収剤、ベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤からなる群から選ばれる少なくとも1種、光安定剤として、ヒンダードアミン系光安定剤からなる群から選ばれる少なくとも1種を用いることができる。紫外線吸収剤及び/又は光安定剤は、重合体エマルジョン粒子(B)の質量に対して0.1質量%〜5質量%用いることが好ましい。また、紫外線吸収剤として、分子内にラジカル重合性の二重結合を有するラジカル重合性紫外線吸収剤、光安定剤として、分子内にラジカル重合性の二重結合を有するラジカル重合性光安定剤を用いることもできる。また、紫外線吸収剤と光安定剤を併用した方が、耐候性に優れるため好ましい。 The photocatalyst of the present invention has at least one selected from the group consisting of benzophenone-based UV absorbers, benzotriazole-based UV absorbers, and triazine-based UV absorbers as UV absorbers, and hindered amine-based light stabilizers as light stabilizers. At least one selected from the group consisting of agents can be used. It is preferable to use 0.1 mass%-5 mass% of a ultraviolet absorber and / or a light stabilizer with respect to the mass of a polymer emulsion particle (B). Moreover, a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule as an ultraviolet absorber, and a radical polymerizable light stabilizer having a radical polymerizable double bond in the molecule as a light stabilizer. It can also be used. Moreover, since it is excellent in a weather resistance, it is preferable to use an ultraviolet absorber and a light stabilizer in combination.
これらの紫外線吸収剤、光安定剤は、金属酸化物(A)と重合体エマルジョン粒子(B)と単に配合することも可能であるし、重合体エマルジョン粒子(B)を合成する際に共存させることも可能である。 These ultraviolet absorbers and light stabilizers can be simply blended with the metal oxide (A) and the polymer emulsion particles (B), and are allowed to coexist when the polymer emulsion particles (B) are synthesized. It is also possible.
本発明において使用できるベンゾフェノン系紫外線吸収剤としては、具体的には、2,4−ジヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン、2−ヒドロキシ−4−メトキシベンゾフェノン−5−スルホン酸、2−ヒドロキシ−4−n−オクトキシベンゾフェノン、2−ヒドロキシ−4−n−ドデシルオキシベンゾフェノン、2−ヒドロキシ−4−ベンジルオキシベンゾフェノン、ビス(5−ベンゾイル−4−ヒドロキシ−2−メトキシフェニル)メタン、2,2’−ジヒドロキシ−4−メトキシベンゾフェノン、2,2’−ジヒドロキシ−4,4’−ジメトキシベンゾフェノン、2,2’,4,4’−テトラヒドロキシベンゾフェノン、4−ドデシルオキシ−2−ヒドロキシベンゾフェノン、2−ヒドロキシ−4−メトキシ−2’−カルボキシベンゾフェノン、2−ヒドロキシ−4−ステアリルオキシベンゾフェノンなどがある。ラジカル重合性ベンゾフェノン系紫外線吸収剤として具体的には、2−ヒドロキシ−4−アクリロキシベンゾフェノン、2−ヒドロキシ−4−メタクリロキシベンゾフェノン、2−ヒドロキシ−5−アクリロキシベンゾフェノン、2−ヒドロキシ−5−メタクリロキシベンゾフェノン、2−ヒドロキシ−4−(アクリロキシ−エトキシ)ベンゾフェノン、2−ヒドロキシ−4−(メタクリロキシ−エトキシ)ベンゾフェノン、2−ヒドロキシ−4−(メタクリロキシ−ジエトキシ)ベンゾフェノン、2−ヒドロキシ−4−(アクリロキシ−トリエトキシ)ベンゾフェノンなどがある。 Specific examples of the benzophenone-based ultraviolet absorber that can be used in the present invention include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2- Hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2 , 2′-dihydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy- - methoxy-2'-carboxy benzophenone, and the like 2-hydroxy-4-stearyloxy benzophenone. Specific examples of the radical polymerizable benzophenone ultraviolet absorber include 2-hydroxy-4-acryloxybenzophenone, 2-hydroxy-4-methacryloxybenzophenone, 2-hydroxy-5-acryloxybenzophenone, 2-hydroxy-5- Methacryloxybenzophenone, 2-hydroxy-4- (acryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-ethoxy) benzophenone, 2-hydroxy-4- (methacryloxy-diethoxy) benzophenone, 2-hydroxy-4- ( Acryloxy-triethoxy) benzophenone.
本発明において使用できるベンゾトリアゾール系紫外線吸収剤として具体的には、2−(2’−ヒドロキシ−5’−メチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−5’−tert−ブチルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−3’,5’−ジ−tert−ブチルフェニル)ベンゾトリアゾール、2−(2−ヒドロキシ−5−tert−オクチルフェニル)ベンゾトリアゾール、2−(2−ヒドロキシ−3,5−ジ−tert−オクチルフェニル)ベンゾトリアゾール、2−〔2’−ヒドロキシ−3’,5’−ビス(α,α’−ジメチルベンジル)フェニル〕ベンゾトリアゾール)、メチル−3−〔3−tert−ブチル−5−(2H−ベンゾトリアゾール−2−イル)−4−ヒドロキシフェニル〕プロピオネートとポリエチレングリコール(分子量300)との縮合物(日本チバガイギー(株)製、商品名:TINUVIN1130)、イソオクチル−3−〔3−(2H−ベンゾトリアゾール−2−イル)−5−tert−ブチル−4−ヒドロキシフェニル〕プロピオネート(日本チバガイギー(株)製、商品名:TINUVIN384)、2−(3−ドデシル−5−メチル−2−ヒドロキシフェニル)ベンゾトリアゾール(日本チバガイギー(株)製、商品名:TINUVIN571)、2−(2’−ヒドロキシ−3’−tert−ブチル−5’−メチルフェニル)−5−クロロベンゾトリアゾール、2−(2’−ヒドロキシ−3’,5’−ジ−tert−アミルフェニル)ベンゾトリアゾール、2−(2’−ヒドロキシ−4’−オクトキシフェニル)ベンゾトリアゾール、2−〔2’−ヒドロキシ−3’−(3”,4”,5”,6”−テトラヒドロフタルイミドメチル)−5’−メチルフェニル〕ベンゾトリアゾール、2,2−メチレンビス〔4−(1,1,3,3−テトラメチルブチル)−6−(2H−ベンゾトリアゾール−2−イル)フェノール〕、2−(2H−ベンゾトリアゾール−2−イル)−4,6−ビス(1−メチル−1−フェニルエチル)フェノール(日本チバガイギー(株)製、商品名:TINUVIN900)などがある。ラジカル重合性ベンゾトリアゾール系紫外線吸収剤として具体的には、2−(2’−ヒドロキシ−5’−メタクリロキシエチルフェニル)−2H−ベンゾトリアゾール(大塚化学(株)製、商品名:RUVA−93)、2−(2’−ヒドロキシ−5’−メタクリロキシエチル−3−tert−ブチルフェニル)−2H−ベンゾトリアゾール、2−(2’−ヒドロキシ−5’−メタクリリルオキシプロピル−3−tert−ブチルフェニル)−5−クロロ−2H−ベンゾトリアゾール、3−メタクリロイル−2−ヒドロキシプロピル−3−〔3’−(2”−ベンゾトリアゾリル)−4−ヒドロキシ−5−tert−ブチル〕フェニルプロピオネート(日本チバガイギー(株)製、商品名:CGL−104)などがある。 Specific examples of the benzotriazole-based UV absorber that can be used in the present invention include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-5′-tert-butylphenyl). Benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy −3,5-di-tert-octylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] benzotriazole), methyl-3- [ 3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenyl] pro Condensation product of pionate and polyethylene glycol (molecular weight 300) (product name: TINUVIN 1130, manufactured by Ciba Geigy Japan), isooctyl-3- [3- (2H-benzotriazol-2-yl) -5-tert-butyl- 4-hydroxyphenyl] propionate (manufactured by Ciba Geigy Japan, trade name: TINUVIN 384), 2- (3-dodecyl-5-methyl-2-hydroxyphenyl) benzotriazole (manufactured by Ciba Geigy Japan, trade name: TINUVIN 571) ), 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) ) Benzotriazole, 2- (2′-hydroxy-4′-octoxy) Phenyl) benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthalimidomethyl) -5′-methylphenyl] benzotriazole, 2,2-methylenebis [4 -(1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2H-benzotriazol-2-yl) -4,6-bis (1 -Methyl-1-phenylethyl) phenol (manufactured by Nippon Ciba-Geigy Co., Ltd., trade name: TINUVIN900). Specifically, 2- (2′-hydroxy-5′-methacryloxyethylphenyl) -2H-benzotriazole (manufactured by Otsuka Chemical Co., Ltd., trade name: RUVA-93) as a radical polymerizable benzotriazole-based ultraviolet absorber. ), 2- (2′-hydroxy-5′-methacryloxyethyl-3-tert-butylphenyl) -2H-benzotriazole, 2- (2′-hydroxy-5′-methacrylyloxypropyl-3-tert- Butylphenyl) -5-chloro-2H-benzotriazole, 3-methacryloyl-2-hydroxypropyl-3- [3 '-(2 "-benzotriazolyl) -4-hydroxy-5-tert-butyl] phenylpropio Nate (Nippon Ciba-Geigy Co., Ltd., trade name: CGL-104).
本発明において使用できるトリアジン系紫外線吸収剤として具体的には、TINUVIN400(商品名、日本チバガイギー(株)製)などがある。 Specific examples of triazine-based ultraviolet absorbers that can be used in the present invention include TINUVIN400 (trade name, manufactured by Nippon Ciba-Geigy Co., Ltd.).
本発明において使用できる紫外線吸収剤としては、紫外線吸収能の高いベンゾトリアゾール系紫外線吸収剤、トリアジン系紫外線吸収剤が好ましい。 As the UV absorber that can be used in the present invention, a benzotriazole UV absorber and a triazine UV absorber having high UV absorbing ability are preferable.
本発明において使用できるヒンダードアミン系光安定剤として具体的には、ビス(2,2,6,6−テトラメチル−4−ピペリジル)サクシネート、ビス(2,2,6,6−テトラメチルピペリジル)セバケート、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)2−(3,5−ジ−tert−ブチル−4−ヒドロキシベンジル)−2−ブチルマロネート、1−〔2−〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピニルオキシ〕エチル〕−4−〔3−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピニルオキシ〕−2,2,6,6−テトラメチルピペリジン、ビス(1,2,2,6,6−ペンタメチル−4−ピペリジル)セバケートとメチル−1,2,2,6,6−ペンタメチル−4−ピペリジル−セバケートの混合物(日本チバガイギー(株)製、商品名:TINUVIN292)、ビス(1−オクトキシ−2,2,6,6−テトラメチル−4−ピペリジル)セバケート、TINUVIN123(商品名、日本チバガイギー(株)製)などがある。ラジカル重合性ヒンダードアミン系光安定剤として具体的には、1,2,2,6,6−ペンタメチル−4−ピペリジルメタクリレート、1,2,2,6,6−ペンタメチル−4−ピペリジルアクリレート、2,2,6,6−テトラメチル−4−ピペリジルメタクリレート、2,2,6,6−テトラメチル−4−ピペリジルアクリレート、1,2,2,6,6−ペンタメチル−4−イミノピペリジルメタクリレート、2,2,6,6,−テトラメチル−4−イミノピペリジルメタクリレート、4−シアノ−2,2,6,6−テトラメチル−4−ピペリジルメタクリレート、4−シアノ−1,2,2,6,6−ペンタメチル−4−ピペリジルメタクリレートなどがある。 Specific examples of hindered amine light stabilizers that can be used in the present invention include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate and bis (2,2,6,6-tetramethylpiperidyl) sebacate. Bis (1,2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [ 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2 , 2,6,6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl Mixture of 4-piperidyl-sebacate (manufactured by Ciba Geigy Japan, trade name: TINUVIN292), bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, TINUVIN123 (trade name, Japan Ciba Geigy Co., Ltd.). Specific examples of the radical polymerizable hindered amine light stabilizer include 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 1,2,2,6,6-pentamethyl-4-piperidyl acrylate, 2, 2,6,6-tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 1,2,2,6,6-pentamethyl-4-iminopiperidyl methacrylate, 2, 2,6,6, -tetramethyl-4-iminopiperidyl methacrylate, 4-cyano-2,2,6,6-tetramethyl-4-piperidyl methacrylate, 4-cyano-1,2,2,6,6- Examples include pentamethyl-4-piperidyl methacrylate.
本発明において使用できるヒンダードアミン系光安定剤としては、塩基性が低いものが好ましく、具体的には塩基定数(pKb)が8以上のものが好ましい。 As the hindered amine light stabilizer that can be used in the present invention, those having a low basicity are preferable, and specifically, those having a base constant (pKb) of 8 or more are preferable.
本発明の機能性複合体を得るのに用いられる基材としては、特に限定はされず、例えば本発明で開示した用途に使用される基材は全て用いることができる。 The substrate used for obtaining the functional composite of the present invention is not particularly limited, and for example, all substrates used for the applications disclosed in the present invention can be used.
本発明の機能性複合体を得るのに用いられる基材の具体例としては、例えば合成樹脂、天然樹脂等の有機基材や、金属、セラミックス、ガラス、石、セメント、コンクリート等の無機基材や、それらの組み合わせ等を挙げることができる。 Specific examples of the base material used to obtain the functional composite of the present invention include organic base materials such as synthetic resins and natural resins, and inorganic base materials such as metals, ceramics, glass, stone, cement, and concrete. Or combinations thereof.
本発明の機能性複合体は、例えば上記光触媒組成物を基材に塗布し、乾燥した後、所望により好ましくは20℃〜500℃、より好ましくは40℃〜250℃での熱処理や紫外線照射等を行い、基材上に光触媒皮膜を形成することにより得ることができる。上記塗布方法としては、例えばスプレー吹き付け法、フローコーティング法、ロールコート法、刷毛塗り法、ディップコーティング法、スピンコーティング法、スクリーン印刷法、キャスティング法、グラビア印刷法、フレキソ印刷法等が挙げられる。 The functional composite of the present invention, for example, after applying the photocatalyst composition to a substrate and drying it, is preferably 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C., ultraviolet irradiation, etc., if desired. And can be obtained by forming a photocatalytic film on the substrate. Examples of the coating method include spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, screen printing, casting, gravure printing, flexographic printing, and the like.
本発明の光触媒体を基材上に皮膜状として形成させる場合、該皮膜の厚みは0.05〜100μm、好ましくは0.1〜10μmであることが好ましい。 When the photocatalyst of the present invention is formed as a film on a substrate, the thickness of the film is 0.05 to 100 μm, preferably 0.1 to 10 μm.
なお、本明細書では、皮膜という表現を使用しているが、必ずしも連続膜である必要はなく、不連続膜、島状分散膜等の態様であっても構わない。 In the present specification, the expression “film” is used. However, the film is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.
本発明の機能性複合体の製造方法は、基材上に本発明の光触媒体皮膜を形成する場合に限定されない。基材と本発明の光触媒体を同時に成形、例えば、一体成形してもよい。また、本発明の光触媒体を成形後、基材の成形を行ってもよい。また、本発明の光触媒体と基材を個別に成形後、接着、融着等により機能性複合体としてもよい。 The method for producing the functional composite of the present invention is not limited to the case where the photocatalyst film of the present invention is formed on a substrate. The substrate and the photocatalyst of the present invention may be molded simultaneously, for example, integrally molded. Moreover, you may shape | mold a base material after shape | molding the photocatalyst body of this invention. Moreover, it is good also as a functional composite body by adhesion | attachment, melt | fusion, etc., after shape | molding the photocatalyst body and base material of this invention separately.
本発明の光触媒組成物の防汚技術分野への応用例としては、例えば建材、建物外装、建物内装、窓枠、窓ガラス、構造部材、住宅等建築設備、特に便器、浴槽、洗面台、照明器具、照明カバー、台所用品、食器、食器洗浄器、食器乾燥器、流し、調理レンジ、キッチンフード、換気扇等が挙げられる。従って本発明は、上記機能性複合体を外装に用いた建築物にも関する。本発明の光触媒組成物又は機能性複合体は、また、乗物の外装及び塗装、用途によってはその内装にも使用でき、車両用照明灯のカバー、窓ガラス、計器、表示盤等透明性が要求される部材での使用に効果があり、また、機械装置や物品の外装、防塵カバー及び塗装、表示機器、そのカバー、交通標識、各種表示装置、広告塔等の表示物、道路用、鉄道用等の遮音壁、橋梁、ガードレールの外装及び塗装、トンネル内装及び塗装、碍子、太陽電池カバー、太陽熱温水器集熱カバー等外部で使用される電子、電気機器の外装部、特に透明部材、ビニールハウス、温室等の外装、特に透明部材、また、室内にあっても汚染のおそれのある環境、たとえば医療用や体育用の施設、装置等にも用いることができる。 Examples of the application of the photocatalyst composition of the present invention to the antifouling technology field include, for example, building materials, building exteriors, building interiors, window frames, window glass, structural members, housing and other building equipment, particularly toilets, bathtubs, washstands, lighting Appliances, lighting covers, kitchen utensils, tableware, dishwashers, tableware dryers, sinks, cooking ranges, kitchen hoods, ventilation fans and the like. Therefore, the present invention also relates to a building using the functional composite as an exterior. The photocatalyst composition or the functional composite of the present invention can also be used for exterior and painting of vehicles, and for interiors depending on applications, and requires transparency of vehicle lighting lamp covers, window glass, instruments, display panels, etc. In addition, it is effective for use in parts that are used, and is used for exteriors of machinery and equipment, dust covers and coatings, display devices, covers, traffic signs, various display devices, display products such as advertising towers, roads, and railways. Sound insulation walls, bridges, guardrail exteriors and paintings, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, etc., exterior parts of electronic and electrical equipment used outside, especially transparent members, plastic houses, It can also be used for exteriors such as greenhouses, particularly transparent members, and environments that may be contaminated even in the room, such as medical and physical education facilities and equipment.
以下の実施例、参考例及び比較例により本発明を具体的に説明するが、これらは本発明の範囲を限定するものではない。 The following examples, reference examples and comparative examples will specifically explain the present invention, but these do not limit the scope of the present invention.
実施例、参考例及び比較例中において、各種の物性は下記の方法で測定した。
1.数平均粒子径
試料中の固形分含有量が1〜20質量%となるよう適宜溶媒を加えて希釈し、湿式粒度分析計(日本国日機装製マイクロトラックUPA−9230)を用いて測定した。
2.色差
色差ΔEをBYK Gardrer製カラーガイドを用いて測定した。
3.水接触角
皮膜の表面に脱イオン水の滴を乗せ、20℃で1分間放置した後、日本国協和界面科学製CA−X150型接触角計を用いて測定した。
4.耐光性
日本国オーク製作所製の紫外線照射装置(商品名「HandyUV300」)を用いて高圧水銀灯の光を光触媒塗膜に照射した。照射を開始してから15時間経過後と照射前の色差を測定して耐光性の指標とした。
5.光触媒活性
JIS R 1703−2に準拠して光触媒塗膜の湿式分解性能試験を実施し、波長664nmの吸光度から分解指数を求めた。このとき、メチレンブルーとして、和光純薬工業社製のメチレンブルー三水和物を用いた。吸光度の測定には、日本国日本分光社製紫外・可視分光光度計(商品名「V−550」)を用いた。
In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
1. Number average particle diameter A sample was appropriately diluted by adding a solvent so that the solid content in the sample was 1 to 20% by mass, and measured using a wet particle size analyzer (Microtrac UPA-9230, manufactured by Nihon Koki Co., Ltd.).
2. Color Difference Color difference ΔE was measured using a color guide manufactured by BYK Gardler.
3. Water contact angle A drop of deionized water was placed on the surface of the film, left at 20 ° C for 1 minute, and then measured using a CA-X150 contact angle meter manufactured by Kyowa Interface Science, Japan.
4). Light Resistance The photocatalyst coating film was irradiated with light from a high-pressure mercury lamp using an ultraviolet irradiation device (trade name “HandyUV300”) manufactured by Oak Manufacturing, Japan. The color difference after 15 hours from the start of irradiation and before the irradiation was measured and used as an indicator of light resistance.
5. Photocatalytic activity A wet decomposition performance test of the photocatalyst coating film was performed according to JIS R 1703-2, and a decomposition index was obtained from the absorbance at a wavelength of 664 nm. At this time, methylene blue trihydrate manufactured by Wako Pure Chemical Industries, Ltd. was used as methylene blue. For the measurement of absorbance, an ultraviolet / visible spectrophotometer (trade name “V-550”) manufactured by JASCO Corporation, Japan was used.
[参考例]
重合体エマルジョン粒子(B)水分散体の合成
[Reference example]
Polymer emulsion particles (B) Synthesis of aqueous dispersion
[参考例1]
重合体エマルジョン粒子(B−1)の水分散体の合成
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水500g、ドデシルベンゼンスルホン酸1.5gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン60g、及びフェニルトリメトキシシラン40gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル50g、フェニルトリメトキシシラン70g、テトラエトキシシラン110g、及び3−メタクリロキシプロピルトリメトキシシラン5gの混合液とジエチルアクリルアミド80g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR−1025」、旭電化(株)製、固形分25%水溶液)8g、過硫酸アンモニウムの2質量%水溶液40g、及びイオン交換水1000gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径110nmの重合体エマルジョン粒子(B−1)の水分散体を得た。
[Reference Example 1]
Synthesis of aqueous dispersion of polymer emulsion particles (B-1) After charging 500 g of ion-exchanged water and 1.5 g of dodecylbenzenesulfonic acid into a reactor having a reflux condenser, a dropping tank, a thermometer and a stirring device, The temperature was warmed to 80 ° C. with stirring. To this, a mixed solution of 60 g of dimethyldimethoxysilane and 40 g of phenyltrimethoxysilane was dropped over about 2 hours while keeping the temperature in the reaction vessel at 80 ° C., and then the temperature in the reaction vessel was 80 ° C. Stirring was continued for about 1 hour. Next, a mixed solution of 50 g of butyl acrylate, 70 g of phenyltrimethoxysilane, 110 g of tetraethoxysilane, and 5 g of 3-methacryloxypropyltrimethoxysilane, 80 g of diethylacrylamide, 3 g of acrylic acid, a reactive emulsifier (trade name “ADEKA rear soap” SR-1025 ", manufactured by Asahi Denka Co., Ltd., 25% solid content aqueous solution), a mixed solution of ammonium persulfate 2% by mass aqueous solution 40 g, and ion-exchanged water 1000 g, the temperature in the reaction vessel was kept at 80 ° C. In the state, it was dripped simultaneously over about 2 hours. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water. An aqueous dispersion of polymer emulsion particles (B-1) having a number average particle diameter of 110 nm was obtained.
[参考例2]
重合体エマルジョン粒子(B−2)の水分散体の合成
攪拌機、還流冷却器、滴下槽及び温度計を取り付けた反応器に、イオン交換水609質量部、エチレン性不飽和単量体と共重合可能な二重結合を分子中に有するスルホコハク酸ジエステルアンモニウム塩(商品名「ラテムルS−180A」、花王(株)製)の25%水溶液10質量部、メタクリル酸シクロヘキシル26質量部、メタクリル酸n−ブチル8質量部、メタクリル酸メチル14質量部、アクリル酸ブチル2.5質量部、メタクリル酸0.8質量部、アクリル酸0.8質量部、及びアクリルアミド0.4質量部を投入し、反応容器中の温度を80℃に上げてから、過硫酸アンモニウムの2%水溶液5質量部、γ−メタクリロキシプロピルトリメトキシシラン1質量部、メチルトリメトキシシラン75質
量部、及びジメチルジメトキシシラン20質量部を反応容器中へ投入した。重合開始による発熱が確認されてから反応容器中の温度を85℃にして30分間保った。次に、反応容器中の温度を80℃に保持した状態で、イオン交換水45質量部、エチレン性不飽和単量体と共重合可能な二重結合を分子中に有するスルホコハク酸ジエステルアンモニウム塩(商品名「ラテムルS−180A」、花王(株)製)の25%水溶液10質量部、メタクリル酸シクロヘキシル26質量部、メタクリル酸n−ブチル10質量部、メタクリル酸メチル12質量部、アクリル酸ブチル2.5質量部、メタクリル酸0.8質量部、アクリル酸0.8質量部、アクリルアミド0.4質量部、及び過硫酸アンモニウムの2%水溶液5質量部からなる混合液と、メチルトリメトキシシラン40質量部、及びジメチルジメトキシシラン24質量部からなる混合液とを反応容器中へ別々の滴下槽より30分かけて注入し、さらに80℃で2時間保持した。次に、反応容器中の温度を80℃に保持した状態で、イオン交換水130質量部、エチレン性不飽和単量体と共重合可能な二重結合を分子中に有するスルホコハク酸ジエステルアンモニウム塩(商品名「ラテムルS−180A」、花王(株)製)の25%水溶液50質量部、ポリオキシエチレンラウリルエーテル(商品名「エマルゲン130K」、花王(株)製)の20%水溶液7質量部、メタクリル酸シクロヘキシル100質量部、メタクリル酸n−ブチル60質量部、メタクリル酸メチル4質量部、アクリル酸ブチル79質量部、メタクリル酸4質量部、及び過硫酸アンモニウムの2%水溶液12質量部からなる混合液と、γ−メタクリロキシプロピルトリメトキシシラン2質量部、メチルトリメトキシシラン160質量部、及びジメチルジメトキシシラン78質量部からなる混合液とを反応容器中へ別々の滴下槽より2時間かけて注入し、さらに80℃で1.5時間保持した。室温まで冷却後、反応容器中の液の水素イオン濃度を測定したところpH2.8であった。25%アンモニア水溶液を反応容器中に添加して液のpHを8に調整した後、100メッシュの金網で濾過した。イオン交換水で固形分を10.0質量%に調整し、数平均粒子径126nmの重合体エマルジョン粒子(B−2)の水分散体を得た。
[Reference Example 2]
Synthesis of aqueous dispersion of polymer emulsion particles (B-2) Copolymerized with 609 parts by mass of ion-exchanged water and ethylenically unsaturated monomer in a reactor equipped with a stirrer, reflux condenser, dropping tank and thermometer. Sulfosuccinic acid diester ammonium salt having a possible double bond in the molecule (trade name “Latemul S-180A”, manufactured by Kao Corporation) 10 parts by mass of 25% aqueous solution, 26 parts by mass of cyclohexyl methacrylate, n-methacrylic acid n- 8 parts by weight of butyl, 14 parts by weight of methyl methacrylate, 2.5 parts by weight of butyl acrylate, 0.8 parts by weight of methacrylic acid, 0.8 parts by weight of acrylic acid, and 0.4 parts by weight of acrylamide were added to the reaction vessel. After raising the temperature to 80 ° C., 5 parts by mass of a 2% aqueous solution of ammonium persulfate, 1 part by mass of γ-methacryloxypropyltrimethoxysilane, Tokishishiran 75 parts by mass, and was charged with 20 parts by weight of dimethyldimethoxysilane into the reaction vessel. After the generation of heat due to the initiation of polymerization was confirmed, the temperature in the reaction vessel was raised to 85 ° C. and maintained for 30 minutes. Next, in a state where the temperature in the reaction vessel is maintained at 80 ° C., 45 parts by mass of ion exchanged water, sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule ( Trade name “Latemul S-180A”, manufactured by Kao Corporation) 10 parts by weight of 25% aqueous solution, 26 parts by weight of cyclohexyl methacrylate, 10 parts by weight of n-butyl methacrylate, 12 parts by weight of methyl methacrylate, butyl acrylate 2 0.5 parts by weight, 0.8 parts by weight of methacrylic acid, 0.8 parts by weight of acrylic acid, 0.4 parts by weight of acrylamide, and 5 parts by weight of 2% aqueous solution of ammonium persulfate, and 40 parts by weight of methyltrimethoxysilane And a mixed solution consisting of 24 parts by mass of dimethyldimethoxysilane are poured into a reaction vessel from a separate dropping tank over 30 minutes, and further 80 ° C. And held for 2 hours. Next, in a state where the temperature in the reaction vessel is maintained at 80 ° C., 130 parts by mass of ion-exchanged water, a sulfosuccinic acid diester ammonium salt having a double bond copolymerizable with an ethylenically unsaturated monomer in the molecule ( 50 parts by mass of 25% aqueous solution of trade name “Latemul S-180A” manufactured by Kao Corporation, 7 parts by mass of 20% aqueous solution of polyoxyethylene lauryl ether (trade name “Emulgen 130K” manufactured by Kao Corporation), Mixed liquid consisting of 100 parts by weight of cyclohexyl methacrylate, 60 parts by weight of n-butyl methacrylate, 4 parts by weight of methyl methacrylate, 79 parts by weight of butyl acrylate, 4 parts by weight of methacrylic acid, and 12 parts by weight of 2% aqueous solution of ammonium persulfate. Γ-methacryloxypropyltrimethoxysilane 2 parts by mass, methyltrimethoxysilane 160 parts by mass, and dimethyl And a mixture consisting dimethoxysilane 78 parts by weight was injected over a period of 2 hours from separate dropping funnel into the reaction vessel and held for 1.5 hours at 80 ° C.. After cooling to room temperature, the hydrogen ion concentration of the liquid in the reaction vessel was measured and found to be pH 2.8. A 25% aqueous ammonia solution was added to the reaction vessel to adjust the pH of the solution to 8, and then filtered through a 100 mesh wire net. The solid content was adjusted to 10.0% by mass with ion-exchanged water to obtain an aqueous dispersion of polymer emulsion particles (B-2) having a number average particle size of 126 nm.
[参考例3]
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水400g、10質量%のドデシルベンゼンスルホン酸水溶液2.57gを投入した後、撹拌下で温度を80℃に加温した。この反応器中に、ジメチルジメトキシシラン54.5g、フェニルトリメトキシシラン34.4g及びメチルトリメトキシシラン1.0gの混合液と、過硫酸アンモニウムの2質量%水溶液15.0gとを、反応器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。その後、反応器中の温度を80℃に維持した状態で約1時間撹拌を続行した。次に、アクリル酸ブチル12.3g、フェニルトリメトキシシラン13。5g、テトラエトキシシラン31.4g及び3−メタクリロキシプロピルトリメトキシシラン1.2gの混合液と、ジエチルアクリルアミド24.6g、アクリル酸1g、反応性乳化剤(商品名「アデカリアソープSR−1025」、旭電化(株)製、固形分25%水溶液)1.2g、反応性乳化剤(商品名「アクアロンKH−1025」、第一工業製薬(株)製、固形分25%水溶液)0.7g、過硫酸アンモニウムの2質量%水溶液8.5g及びイオン交換水255gの混合液とを、反応器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに、反応器中の温度を80℃に維持した状態で約2時間撹拌を続行した。その後、反応器中の液を室温まで冷却し、100メッシュの金網で濾過して、固形分12.8質量%の重合体エマルジョン水分散体を得た。そして、イオン交換水で固形分が10.0質量%となるように調整して重合体エマルジョン水分散体(B−3)を得た。重合体エマルジョン粒子の数平均粒子径は180nmであった。
[Reference Example 3]
A reactor having a reflux condenser, a dropping tank, a thermometer, and a stirring device was charged with 400 g of ion-exchanged water and 2.57 g of a 10% by mass dodecylbenzenesulfonic acid aqueous solution, and then heated to 80 ° C. with stirring. did. In this reactor, 54.5 g of dimethyldimethoxysilane, 34.4 g of phenyltrimethoxysilane, and 1.0 g of methyltrimethoxysilane and 15.0 g of a 2% by weight aqueous solution of ammonium persulfate were added to the reactor. It was dripped simultaneously over about 2 hours in the state which maintained temperature at 80 degreeC. Thereafter, stirring was continued for about 1 hour while maintaining the temperature in the reactor at 80 ° C. Next, 12.3 g of butyl acrylate, 13.5 g of phenyltrimethoxysilane, 31.4 g of tetraethoxysilane and 1.2 g of 3-methacryloxypropyltrimethoxysilane, 24.6 g of diethylacrylamide, and 1 g of acrylic acid , Reactive emulsifier (trade name “Adekaria soap SR-1025”, manufactured by Asahi Denka Co., Ltd., 25% solid content aqueous solution), 1.2 g, reactive emulsifier (trade name “AQUALON KH-1025”, Daiichi Kogyo Seiyaku (Made by Co., Ltd., 25% solid content aqueous solution) 0.7 g, a mixed solution of 2% by weight ammonium persulfate aqueous solution 8.5 g and ion-exchanged water 255 g, with the temperature in the reactor kept at 80 ° C. It was dripped simultaneously over 2 hours. Further, stirring was continued for about 2 hours while maintaining the temperature in the reactor at 80 ° C. Thereafter, the liquid in the reactor was cooled to room temperature and filtered through a 100-mesh wire mesh to obtain a polymer emulsion aqueous dispersion having a solid content of 12.8% by mass. And it adjusted so that solid content might be 10.0 mass% with ion-exchange water, and obtained the polymer emulsion water dispersion (B-3). The number average particle diameter of the polymer emulsion particles was 180 nm.
[実施例1]
参考例1で合成した重合体エマルジョン粒子(B−1)水分散体100gに、数平均粒子径12nmの水分散コロイダルシリカ(商品名「スノーテックスO」、日産化学工業(株)製、固形分20%)50g、数平均粒子径30nmの固形分10.0%に調整したルチル型酸化チタンゾル60g及び数平均粒子径4nmの水分散体コロイダルジルコニア(商品名「ナノユースZR−30BF」、日産化学工業(株)製、固形分30%、屈折率2.4)13.3gを混合して光触媒組成物を得た。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは4.2、水接触角は5.7°であった。光触媒活性は14.2であり、耐光性試験前後の色差ΔE2.7であった。
[Example 1]
To 100 g of the polymer emulsion particles (B-1) aqueous dispersion synthesized in Reference Example 1, an aqueous dispersion colloidal silica having a number average particle diameter of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content) 20%) 50 g of rutile titanium oxide sol adjusted to 10.0% solid content with a number average particle size of 30 nm and an aqueous dispersion colloidal zirconia with a number average particle size of 4 nm (trade name “Nanouse ZR-30BF”, Nissan Chemical Industries, Ltd.) Co., Ltd. product, solid content 30%, refractive index 2.4) 13.3g was mixed and the photocatalyst composition was obtained.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 4.2, and the water contact angle was 5.7 °. The photocatalytic activity was 14.2, and the color difference ΔE2.7 before and after the light resistance test was.
[実施例2]
実施例1のコロイダルジルコニアを酸化ジルコニウム−酸化イットリウム混合物コロイドジルコニア(酸化ジルコニウムの質量/酸化イットリウムの質量=9/1、固形分30%、屈折率2.4)6.6gに変更した以外は実施例1と同様に試験を実施した。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは3.7、水接触角は5.3°であった。光触媒活性は14.7であり、耐光性試験前後の色差ΔE1.3であった。
[Example 2]
Except that the colloidal zirconia of Example 1 was changed to 6.6 g of colloidal zirconia of zirconium oxide-yttrium oxide mixture (mass of zirconium oxide / mass of yttrium oxide = 9/1, solid content 30%, refractive index 2.4). The test was carried out in the same manner as in Example 1.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 3.7, and the water contact angle was 5.3 °. The photocatalytic activity was 14.7, and the color difference before and after the light resistance test was ΔE1.3.
[実施例3]
実施例1のコロイダルジルコニアを酸化ジルコニウム−酸化イットリウム混合物コロイドジルコニア(酸化ジルコニウムの質量/酸化イットリウムの質量=9/1、固形分30%、屈折率2.4)13.3gに変更した以外は実施例1と同様に試験を実施した。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは3.8、水接触角は5.5°であった。光触媒活性は14.8であり、耐光性試験前後の色差ΔE1.3であった。
[Example 3]
Except that the colloidal zirconia of Example 1 was changed to 13.3 g of colloidal zirconia of zirconium oxide-yttrium oxide mixture (mass of zirconium oxide / mass of yttrium oxide = 9/1, solid content 30%, refractive index 2.4). The test was carried out in the same manner as in Example 1.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 3.8, and the water contact angle was 5.5 °. The photocatalytic activity was 14.8 and the color difference before and after the light resistance test was ΔE1.3.
[実施例4]
実施例1のコロイダルジルコニアを酸化ジルコニウム−酸化イットリウム混合物コロイドジルコニア(酸化ジルコニウムの質量/酸化イットリウムの質量=9/1、固形分30%、屈折率2.4)19.8gに変更した以外は実施例1と同様に試験を実施した。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは3.6、水接触角は5.6°であった。光触媒活性は14.4であり、耐光性試験前後の色差ΔE1.2であった。
[Example 4]
Except that the colloidal zirconia of Example 1 was changed to 19.8 g of zirconium oxide-yttrium oxide mixture colloidal zirconia (mass of zirconium oxide / mass of yttrium oxide = 9/1, solid content 30%, refractive index 2.4). The test was carried out in the same manner as in Example 1.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 3.6, and the water contact angle was 5.6 °. The photocatalytic activity was 14.4, and the color difference before and after the light resistance test was ΔE1.2.
[実施例5]
実施例1のコロイダルジルコニアを酸化セリウムゾル(商品名「ナノユースCE−20B」、日産化学工業(株)製、固形分20%、屈折率2.2)20.0gに変更した以外は実施例1と同様に試験を実施した。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは4.4、水接触角は7.8°であった。光触媒活性は14.4であり、耐光性試験前後の色差ΔE2.9であった。
[Example 5]
Example 1 except that the colloidal zirconia of Example 1 was changed to 20.0 g of cerium oxide sol (trade name “Nanouse CE-20B”, manufactured by Nissan Chemical Industries, Ltd., solid content 20%, refractive index 2.2). A similar test was conducted.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 4.4, and the water contact angle was 7.8 °. The photocatalytic activity was 14.4, and the color difference ΔE2.9 before and after the light resistance test.
[実施例6]
実施例1のコロイダルジルコニアを酸化スズゾル(商品名「セルナックスCX−301H」、日産化学工業(株)製、固形分30%、屈折率2.0)13.3gに変更した以外は実施例1と同様に試験を実施した。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは4.1、水接触角は8.9°であった。光触媒活性は13.7であり、耐光性試験前後の色差ΔE3.2であった。
[Example 6]
Example 1 except that the colloidal zirconia of Example 1 was changed to 13.3 g of tin oxide sol (trade name “CELNAX CX-301H”, manufactured by Nissan Chemical Industries, Ltd., solid content 30%, refractive index 2.0). The test was conducted in the same manner as above.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 4.1, and the water contact angle was 8.9 °. The photocatalytic activity was 13.7, and the color difference ΔE3.2 was around before and after the light resistance test.
[実施例7]
実施例1のルチル型酸化チタンゾルを数平均粒子径20nmの固形分10.0%に調整したアナターゼ型酸化チタンゾル60gに変更した以外は実施例1と同様に試験を実施した。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは4.4、水接触角は5.6°であった。光触媒活性は17.8であり、耐光性試験前後の色差ΔE5.5であった。
[Example 7]
The test was performed in the same manner as in Example 1 except that the rutile type titanium oxide sol of Example 1 was changed to 60 g of anatase type titanium oxide sol adjusted to a solid content of 10.0% with a number average particle size of 20 nm.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 4.4, and the water contact angle was 5.6 °. The photocatalytic activity was 17.8, and the color difference before and after the light resistance test was ΔE5.5.
[実施例8]
実施例1の重合体エマルジョン粒子(B−1)を参考例2で合成した重合体エマルジョン粒子(B−2)水分散体100gに変更した以外は実施例1と同様に試験を実施した。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは4.5、水接触角は8.5°であった。光触媒活性は14.3であり、耐光性試験前後の色差ΔE3.5であった。
[Example 8]
The test was performed in the same manner as in Example 1 except that the polymer emulsion particles (B-1) of Example 1 were changed to 100 g of the polymer emulsion particles (B-2) aqueous dispersion synthesized in Reference Example 2.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 4.5, and the water contact angle was 8.5 °. The photocatalytic activity was 14.3, and the color difference before and after the light resistance test was ΔE3.5.
[比較例1]
参考例1で合成した重合体エマルジョン粒子(B−1)水分散体100gに、数平均粒子径12nmの水分散コロイダルシリカ(商品名「スノーテックスO」、日産化学工業(株)製、固形分20%)50g、数平均粒子径30nmの固形分10.0%に調整したルチル型酸化チタンゾル60gを混合して光触媒組成物を得た。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは7.8、水接触角は6.3°であった。光触媒活性は14.2であり、耐光性試験前後の色差ΔE9.1であった。
[Comparative Example 1]
To 100 g of the polymer emulsion particles (B-1) aqueous dispersion synthesized in Reference Example 1, an aqueous dispersion colloidal silica having a number average particle diameter of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content) 20%) A photocatalytic composition was obtained by mixing 60 g of a rutile titanium oxide sol adjusted to 50 g and a solid content of 10.0% having a number average particle diameter of 30 nm.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 7.8, and the water contact angle was 6.3 °. The photocatalytic activity was 14.2, and the color difference before and after the light resistance test was ΔE9.1.
[比較例2]
参考例3で合成した重合体エマルジョン粒子(B−3)水分散体100gに、数平均粒子径12nmの水分散コロイダルシリカ(商品名「スノーテックスO」、日産化学工業(株)製、固形分20%)50g、数平均粒子径30nmの固形分10.0%に調整したルチル型酸化チタンゾル65g、数平均粒子径20nmの固形分10.0%に調整したアナターゼ型酸化チタンゾル7gを混合して光触媒組成物を得た。
この光触媒組成物を黒色ガラス板上に膜厚3μになるようにスプレー塗装し、70℃で10分間焼き付けることでサンプルを得ることができた。塗装前後の色差ΔEは8.8、水接触角は5.9°であった。光触媒活性は18.7であり、耐光性試験前後の色差ΔE10.2であった。
[Comparative Example 2]
To 100 g of the polymer emulsion particles (B-3) aqueous dispersion synthesized in Reference Example 3, a water-dispersed colloidal silica having a number average particle diameter of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content) 20%) 65 g of rutile type titanium oxide sol adjusted to 10.0% solid content with a number average particle size of 30 nm and 7 g of anatase type titanium oxide sol adjusted to 10.0% solid content with a number average particle size of 20 nm were mixed. A photocatalytic composition was obtained.
This photocatalyst composition was spray-coated on a black glass plate so as to have a film thickness of 3 μm, and was baked at 70 ° C. for 10 minutes to obtain a sample. The color difference ΔE before and after coating was 8.8, and the water contact angle was 5.9 °. The photocatalytic activity was 18.7, and the color difference before and after the light resistance test was ΔE10.2.
本発明によって提供される、高いレベルでの耐候性、耐汚染性、透明性を発現する光触媒体は、建築外装、外装表示用途、自動車、ディスプレイ、レンズ等のコーティング剤として有用である。 The photocatalyst that exhibits a high level of weather resistance, stain resistance, and transparency provided by the present invention is useful as a coating agent for architectural exteriors, exterior display applications, automobiles, displays, lenses, and the like.
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