JP2004143452A - Self-cleaning aqueous coating composition and self- cleaning member - Google Patents
Self-cleaning aqueous coating composition and self- cleaning member Download PDFInfo
- Publication number
- JP2004143452A JP2004143452A JP2003342361A JP2003342361A JP2004143452A JP 2004143452 A JP2004143452 A JP 2004143452A JP 2003342361 A JP2003342361 A JP 2003342361A JP 2003342361 A JP2003342361 A JP 2003342361A JP 2004143452 A JP2004143452 A JP 2004143452A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- self
- resin
- parts
- coating composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 40
- 239000008199 coating composition Substances 0.000 title claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000839 emulsion Substances 0.000 claims abstract description 45
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000011941 photocatalyst Substances 0.000 claims abstract description 36
- 229920002050 silicone resin Polymers 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000001023 inorganic pigment Substances 0.000 claims abstract description 6
- 239000004793 Polystyrene Substances 0.000 claims abstract description 4
- 229920002223 polystyrene Polymers 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 28
- 229920005989 resin Polymers 0.000 claims description 24
- 239000011347 resin Substances 0.000 claims description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 17
- 239000008119 colloidal silica Substances 0.000 claims description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 14
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 8
- 239000004925 Acrylic resin Substances 0.000 claims description 5
- 229920000178 Acrylic resin Polymers 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000004640 Melamine resin Substances 0.000 claims description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000180 alkyd Polymers 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920001225 polyester resin Polymers 0.000 claims description 3
- 239000004645 polyester resin Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 42
- 238000000576 coating method Methods 0.000 abstract description 40
- 238000009835 boiling Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 description 29
- 239000000049 pigment Substances 0.000 description 28
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- VPJOGDPLXNTKAZ-UHFFFAOYSA-N 2-methylpropanoic acid;2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)=O.CC(C)C(O)C(C)(C)CO VPJOGDPLXNTKAZ-UHFFFAOYSA-N 0.000 description 14
- 238000004040 coloring Methods 0.000 description 14
- -1 fluororesin Polymers 0.000 description 14
- 239000004606 Fillers/Extenders Substances 0.000 description 13
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 229920006310 Asahi-Kasei Polymers 0.000 description 10
- 229920004482 WACKER® Polymers 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 9
- 229910052791 calcium Inorganic materials 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 239000000377 silicon dioxide Substances 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000003973 paint Substances 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 230000000007 visual effect Effects 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 4
- 230000003373 anti-fouling effect Effects 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 230000001678 irradiating effect Effects 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- DAFHKNAQFPVRKR-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylpropanoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)C DAFHKNAQFPVRKR-UHFFFAOYSA-N 0.000 description 2
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical group 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 2
- 235000019645 odor Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005382 thermal cycling Methods 0.000 description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 2
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- AGZQGENSWWIMDF-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy-phenylsilane Chemical compound CC(C)(C)O[SiH2]c1ccccc1 AGZQGENSWWIMDF-UHFFFAOYSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 description 1
- DJCYDDALXPHSHR-UHFFFAOYSA-N 2-(2-propoxyethoxy)ethanol Chemical compound CCCOCCOCCO DJCYDDALXPHSHR-UHFFFAOYSA-N 0.000 description 1
- JDSQBDGCMUXRBM-UHFFFAOYSA-N 2-[2-(2-butoxypropoxy)propoxy]propan-1-ol Chemical compound CCCCOC(C)COC(C)COC(C)CO JDSQBDGCMUXRBM-UHFFFAOYSA-N 0.000 description 1
- WAEVWDZKMBQDEJ-UHFFFAOYSA-N 2-[2-(2-methoxypropoxy)propoxy]propan-1-ol Chemical compound COC(C)COC(C)COC(C)CO WAEVWDZKMBQDEJ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- JRGQKLFZSNYTDX-UHFFFAOYSA-N 3-(oxiran-2-ylmethoxy)propyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOCC1CO1 JRGQKLFZSNYTDX-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- UDWIZRDPCQAYRF-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl prop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C=C UDWIZRDPCQAYRF-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- LZMNXXQIQIHFGC-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CO[Si](C)(OC)CCCOC(=O)C(C)=C LZMNXXQIQIHFGC-UHFFFAOYSA-N 0.000 description 1
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 description 1
- LDMRLRNXHLPZJN-UHFFFAOYSA-N 3-propoxypropan-1-ol Chemical compound CCCOCCCO LDMRLRNXHLPZJN-UHFFFAOYSA-N 0.000 description 1
- OXKAXHPVFLEQHV-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropan-1-amine Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCN OXKAXHPVFLEQHV-UHFFFAOYSA-N 0.000 description 1
- CHPNMYQJQQGAJS-UHFFFAOYSA-N 3-tri(propan-2-yloxy)silylpropyl 2-methylprop-2-enoate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCCOC(=O)C(C)=C CHPNMYQJQQGAJS-UHFFFAOYSA-N 0.000 description 1
- URDOJQUSEUXVRP-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C(C)=C URDOJQUSEUXVRP-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- GVSGYCMWBRLEJJ-UHFFFAOYSA-N C(CCCC)C(C(=O)O)C.C(CCCC)OC(CC)=O Chemical compound C(CCCC)C(C(=O)O)C.C(CCCC)OC(CC)=O GVSGYCMWBRLEJJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- MZZINWWGSYUHGU-UHFFFAOYSA-J ToTo-1 Chemical compound [I-].[I-].[I-].[I-].C12=CC=CC=C2C(C=C2N(C3=CC=CC=C3S2)C)=CC=[N+]1CCC[N+](C)(C)CCC[N+](C)(C)CCC[N+](C1=CC=CC=C11)=CC=C1C=C1N(C)C2=CC=CC=C2S1 MZZINWWGSYUHGU-UHFFFAOYSA-J 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- IGLKFJCWZNXDIV-UHFFFAOYSA-N [1-amino-3-[tris[(2-methylpropan-2-yl)oxy]silyl]propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(N)CC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C IGLKFJCWZNXDIV-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- AUNAPVYQLLNFOI-UHFFFAOYSA-L [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O Chemical compound [Pb++].[Pb++].[Pb++].[O-]S([O-])(=O)=O.[O-][Cr]([O-])(=O)=O.[O-][Mo]([O-])(=O)=O AUNAPVYQLLNFOI-UHFFFAOYSA-L 0.000 description 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- UWMGVIKSCFGFDR-UHFFFAOYSA-N benzyl(dibromo)silane Chemical compound Br[SiH](Br)CC1=CC=CC=C1 UWMGVIKSCFGFDR-UHFFFAOYSA-N 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CJOBVZJTOIVNNF-UHFFFAOYSA-N cadmium sulfide Chemical compound [Cd]=S CJOBVZJTOIVNNF-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- BAAAEEDPKUHLID-UHFFFAOYSA-N decyl(triethoxy)silane Chemical compound CCCCCCCCCC[Si](OCC)(OCC)OCC BAAAEEDPKUHLID-UHFFFAOYSA-N 0.000 description 1
- KQAHMVLQCSALSX-UHFFFAOYSA-N decyl(trimethoxy)silane Chemical compound CCCCCCCCCC[Si](OC)(OC)OC KQAHMVLQCSALSX-UHFFFAOYSA-N 0.000 description 1
- LILGYOCNANBWTO-UHFFFAOYSA-N decyl-tri(propan-2-yloxy)silane Chemical compound CCCCCCCCCC[Si](OC(C)C)(OC(C)C)OC(C)C LILGYOCNANBWTO-UHFFFAOYSA-N 0.000 description 1
- AGUMJWWZSTXCAM-UHFFFAOYSA-N decyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CCCCCCCCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C AGUMJWWZSTXCAM-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- LIQOCGKQCFXKLF-UHFFFAOYSA-N dibromo(dimethyl)silane Chemical compound C[Si](C)(Br)Br LIQOCGKQCFXKLF-UHFFFAOYSA-N 0.000 description 1
- DBUGVTOEUNNUHR-UHFFFAOYSA-N dibromo(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Br)(Br)C1=CC=CC=C1 DBUGVTOEUNNUHR-UHFFFAOYSA-N 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- GNEPOXWQWFSSOU-UHFFFAOYSA-N dichloro-methyl-phenylsilane Chemical compound C[Si](Cl)(Cl)C1=CC=CC=C1 GNEPOXWQWFSSOU-UHFFFAOYSA-N 0.000 description 1
- ZZNQQQWFKKTOSD-UHFFFAOYSA-N diethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OCC)(OCC)C1=CC=CC=C1 ZZNQQQWFKKTOSD-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- MNFGEHQPOWJJBH-UHFFFAOYSA-N diethoxy-methyl-phenylsilane Chemical compound CCO[Si](C)(OCC)C1=CC=CC=C1 MNFGEHQPOWJJBH-UHFFFAOYSA-N 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- UYAAVKFHBMJOJZ-UHFFFAOYSA-N diimidazo[1,3-b:1',3'-e]pyrazine-5,10-dione Chemical compound O=C1C2=CN=CN2C(=O)C2=CN=CN12 UYAAVKFHBMJOJZ-UHFFFAOYSA-N 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- MABAWBWRUSBLKQ-UHFFFAOYSA-N ethenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C=C MABAWBWRUSBLKQ-UHFFFAOYSA-N 0.000 description 1
- BQRPSOKLSZSNAR-UHFFFAOYSA-N ethenyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)C=C BQRPSOKLSZSNAR-UHFFFAOYSA-N 0.000 description 1
- OIKTYAIWDCKBDE-UHFFFAOYSA-N ethoxy(hexyl)silane Chemical compound CCCCCC[SiH2]OCC OIKTYAIWDCKBDE-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- MYEJNNDSIXAGNK-UHFFFAOYSA-N ethyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](CC)(OC(C)C)OC(C)C MYEJNNDSIXAGNK-UHFFFAOYSA-N 0.000 description 1
- ZVQNVYMTWXEMSF-UHFFFAOYSA-N ethyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](CC)(OC(C)(C)C)OC(C)(C)C ZVQNVYMTWXEMSF-UHFFFAOYSA-N 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- CZWLNMOIEMTDJY-UHFFFAOYSA-N hexyl(trimethoxy)silane Chemical compound CCCCCC[Si](OC)(OC)OC CZWLNMOIEMTDJY-UHFFFAOYSA-N 0.000 description 1
- DPTKSEHTOJHGOV-UHFFFAOYSA-N hexyl-tri(propan-2-yloxy)silane Chemical compound CCCCCC[Si](OC(C)C)(OC(C)C)OC(C)C DPTKSEHTOJHGOV-UHFFFAOYSA-N 0.000 description 1
- QECCXOBPOBIUMS-UHFFFAOYSA-N hexyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CCCCCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C QECCXOBPOBIUMS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- UCNNJGDEJXIUCC-UHFFFAOYSA-L hydroxy(oxo)iron;iron Chemical compound [Fe].O[Fe]=O.O[Fe]=O UCNNJGDEJXIUCC-UHFFFAOYSA-L 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HLXDKGBELJJMHR-UHFFFAOYSA-N methyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](C)(OC(C)C)OC(C)C HLXDKGBELJJMHR-UHFFFAOYSA-N 0.000 description 1
- AHQDZKRRVNGIQL-UHFFFAOYSA-N methyl-tris[(2-methylpropan-2-yl)oxy]silane Chemical compound CC(C)(C)O[Si](C)(OC(C)(C)C)OC(C)(C)C AHQDZKRRVNGIQL-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical compound [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- VPLNCHFJAOKWBT-UHFFFAOYSA-N phenyl-tri(propan-2-yloxy)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)C1=CC=CC=C1 VPLNCHFJAOKWBT-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229940116423 propylene glycol diacetate Drugs 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910003450 rhodium oxide Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- PCADGSDEFOMDNL-UHFFFAOYSA-N tri(propan-2-yloxy)-(3,3,3-trifluoropropyl)silane Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)CCC(F)(F)F PCADGSDEFOMDNL-UHFFFAOYSA-N 0.000 description 1
- MQVCTPXBBSKLFS-UHFFFAOYSA-N tri(propan-2-yloxy)-propylsilane Chemical compound CCC[Si](OC(C)C)(OC(C)C)OC(C)C MQVCTPXBBSKLFS-UHFFFAOYSA-N 0.000 description 1
- BZAROSBWJASVBU-UHFFFAOYSA-N tribromo(ethenyl)silane Chemical compound Br[Si](Br)(Br)C=C BZAROSBWJASVBU-UHFFFAOYSA-N 0.000 description 1
- KVENDAGPVNAYLY-UHFFFAOYSA-N tribromo(ethyl)silane Chemical compound CC[Si](Br)(Br)Br KVENDAGPVNAYLY-UHFFFAOYSA-N 0.000 description 1
- VRUFDMFAHKOFOT-UHFFFAOYSA-N tribromo(hexyl)silane Chemical compound CCCCCC[Si](Br)(Br)Br VRUFDMFAHKOFOT-UHFFFAOYSA-N 0.000 description 1
- KBSUPJLTDMARAI-UHFFFAOYSA-N tribromo(methyl)silane Chemical compound C[Si](Br)(Br)Br KBSUPJLTDMARAI-UHFFFAOYSA-N 0.000 description 1
- HPTIEXHGTPSFDC-UHFFFAOYSA-N tribromo(phenyl)silane Chemical compound Br[Si](Br)(Br)C1=CC=CC=C1 HPTIEXHGTPSFDC-UHFFFAOYSA-N 0.000 description 1
- RWRKNKVDHIEKHS-UHFFFAOYSA-N tribromo(propyl)silane Chemical compound CCC[Si](Br)(Br)Br RWRKNKVDHIEKHS-UHFFFAOYSA-N 0.000 description 1
- WEUBQNJHVBMUMD-UHFFFAOYSA-N trichloro(3,3,3-trifluoropropyl)silane Chemical compound FC(F)(F)CC[Si](Cl)(Cl)Cl WEUBQNJHVBMUMD-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- LFXJGGDONSCPOF-UHFFFAOYSA-N trichloro(hexyl)silane Chemical compound CCCCCC[Si](Cl)(Cl)Cl LFXJGGDONSCPOF-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- ZLGWXNBXAXOQBG-UHFFFAOYSA-N triethoxy(3,3,3-trifluoropropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCC(F)(F)F ZLGWXNBXAXOQBG-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- 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
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-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
- JIOBRIJHDZBWDE-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-(3,3,3-trifluoropropyl)silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCC(F)(F)F JIOBRIJHDZBWDE-UHFFFAOYSA-N 0.000 description 1
- WUSDGIZCXCUHAI-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)CCCOCC1CO1 WUSDGIZCXCUHAI-UHFFFAOYSA-N 0.000 description 1
- DIZPPYBTFPZSGK-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]-propylsilane Chemical compound CCC[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C DIZPPYBTFPZSGK-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 235000013799 ultramarine blue Nutrition 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- NDKWCCLKSWNDBG-UHFFFAOYSA-N zinc;dioxido(dioxo)chromium Chemical compound [Zn+2].[O-][Cr]([O-])(=O)=O NDKWCCLKSWNDBG-UHFFFAOYSA-N 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Abstract
Description
本発明は、建物の壁面等に塗布する塗料のうち、自己浄化性を発揮するものに関する発明である。 The present invention is an invention relating to a coating material applied to a wall surface of a building or the like that exhibits a self-purifying property.
近年、光触媒材料が、建物外装に被覆することで、太陽光の照射により親水化して降雨によるセルフクリーニング機能を有する材料として注目されている。また、光触媒を含んだ塗料に関しては、作業環境、周辺への影響、臭いなどの観点から、最近では溶剤系塗料よりも水系塗料（水性塗料）を用いる傾向が高まりつつある。そのため、上記建物外装等に塗布するための光触媒の水性コート剤も提案されている。 例えば、珪酸リチウムと二酸化チタンを含有する塗料を塗布し、加熱処理することで、自浄効果に優れた建材が得られている。このような場合、プラスチックや塗装鋼板などの疎水性物質を表面に有する基材に対する濡れ性が悪いため、使用の対象がガラス、木材、金属などに限定される問題があった（例えば、特許文献１参照）。
また、光触媒と重量平均分子量が６００〜５０００のオルガノシロキサン部分加水分解物を含有する防汚性シリコーンエマルジョンコーティング材組成物が提案されている。光触媒とオルガノシロキサン部分加水分解物を含有する防汚性シリコーンエマルジョンコーティング材組成物の場合、膜厚を２０μｍ程度に大きくした塗装品では、耐沸騰水性を持たせるためには光触媒に分解されるシリコーン以外の樹脂が必要となり、耐候性が犠牲になるという問題があった（例えば、特許文献２参照）。
さらに、シリコーン以外の樹脂を耐候性が維持できる程度の量導入しても、塗膜の耐洗浄性や耐冷熱サイクル性といった、塗膜と被塗装面との適合性や塗膜の機械的性質を十分に補うことができないと考えられる。
Further, an antifouling silicone emulsion coating material composition containing a photocatalyst and a partially hydrolyzed organosiloxane having a weight average molecular weight of 600 to 5,000 has been proposed. In the case of an antifouling silicone emulsion coating material composition containing a photocatalyst and an organosiloxane partial hydrolyzate, in the case of a coating product whose film thickness is increased to about 20 μm, silicone which is decomposed into a photocatalyst is required to have boiling water resistance. However, there has been a problem that a resin other than the above is required, and the weather resistance is sacrificed (for example, see Patent Document 2).
Furthermore, even if a resin other than silicone is introduced in such an amount that the weather resistance can be maintained, the compatibility between the coated film and the coated surface and the mechanical properties of the coated film, such as the wash resistance and the thermal cycling resistance of the coated film Is not considered to be sufficient.
本発明は、上記問題を解決するためになされたもので、本発明の課題は、耐久性を有し、かつ塗膜抵抗性に優れた塗膜を形成することが可能な自己洗浄性水性塗料組成物、及び自己洗浄性部材に関するものである。 The present invention has been made to solve the above problems, and an object of the present invention is to provide a self-cleaning water-based paint capable of forming a coating film having durability and excellent coating film resistance. The present invention relates to a composition and a self-cleaning member.
上記目的を達成するために請求項１記載の発明によれば、ａ）シリコーン樹脂被膜を形成可能なシリコーン樹脂前駆体の水性エマルジョンと、（ｂ）光触媒粒子又は光触媒ゾルと、（ｃ）水と、（ｄ）無機顔料とを少なくとも含んだ自己浄化性水性塗料組成物であって、前記（ａ）成分中に分散した粒子の重量平均分子量がポリスチレン換算で５０００以上とすることにより、疎水性物質を表面に有する基材に被膜を形成した場合にも基材と被膜との密着性が強固であり、耐沸騰水性にも耐久性にも優れ、かつ被膜表面は水との接触角が小さく、降雨によるセルフクリーニング機能を享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される自己浄化性水性塗料組成物、及びそれを疎水性物質を表面に有する基材に被覆した自己浄化性部材が提供可能となる。 According to the first aspect of the present invention, there is provided an aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film, (b) photocatalyst particles or a photocatalyst sol, and (c) water. And (d) a self-cleaning water-based coating composition containing at least an inorganic pigment, wherein the weight average molecular weight of the particles dispersed in the component (a) is 5,000 or more in terms of polystyrene, whereby the hydrophobic substance Even when a film is formed on a substrate having a surface on the surface, the adhesion between the substrate and the film is strong, excellent in durability against boiling water, and the surface of the film has a small contact angle with water, A self-cleaning water-based coating composition capable of enjoying a self-cleaning function by rainfall and maintaining its state for a long time by irradiating sunlight, and having the hydrophobic substance on its surface Self-cleaning member coated on wood can be provided.
上記目的を達成するために請求項２記載の発明によれば、ａ）シリコーン樹脂被膜を形成可能なシリコーン樹脂前駆体の水性エマルジョンと、（ｂ）光触媒粒子又は光触媒ゾルと、（ｃ）水と、（ｄ）無機顔料とを少なくとも含んだ自己浄化性水性塗料組成物であって、前記（ａ）成分中に分散した粒子の平均粒子径が５００ｎｍ以上であることにより、疎水性物質を表面に有する基材に被膜を形成した場合にも基材と被膜との密着性が強固であり、耐沸騰水性にも耐久性にも優れ、かつ被膜表面は水との接触角が小さく、降雨によるセルフクリーニング機能を享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される自己浄化性水性塗料組成物、及びそれを疎水性物質を表面に有する基材に被覆した自己浄化性部材が提供可能となる。 According to the second aspect of the present invention, there is provided an aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film, (b) photocatalyst particles or a photocatalyst sol, and (c) water. And (d) a self-cleaning aqueous coating composition containing at least an inorganic pigment, wherein the particles dispersed in the component (a) have an average particle diameter of 500 nm or more, so that a hydrophobic substance Even when a coating is formed on a base material, the adhesion between the base material and the coating is strong, and it has excellent boiling water resistance and durability. A self-cleaning aqueous coating composition capable of enjoying a cleaning function and maintaining its state over a long period of time by irradiating sunlight, and coated on a substrate having a hydrophobic substance on its surface Self-purification Sexual member can be provided.
また、請求項３記載の発明によれば、前記（ａ）成分の固形分が全固形分の１０％以上とすることにより、塗膜の耐久性に効果的な無機骨格を硬化塗膜中に形成することができる。 According to the third aspect of the present invention, by setting the solid content of the component (a) to 10% or more of the total solid content, an inorganic skeleton effective for the durability of the coating film is formed in the cured coating film. Can be formed.
また、請求項４記載の発明によれば、アクリル樹脂、アクリルシリコーン樹脂、アクリルウレタン樹脂、アクリルスチレン樹脂、フッ素樹脂、ウレタン樹脂、アルキド樹脂、エポキシ樹脂、フェノール樹脂、ポリエステル樹脂、メラミン樹脂、酢酸ビニル、塩化ビニル樹脂、塩化ゴム樹脂からなる群の中から選ばれた少なくとも１種の有機樹脂を全固形分中１０重量％以上含むことを特徴とすることにより、形成した塗膜の耐洗浄性や耐冷熱サイクル性といった、塗膜と被塗装面との適合性や塗膜の機械的性質が向上する。 According to the invention of claim 4, acrylic resin, acrylic silicone resin, acrylic urethane resin, acrylic styrene resin, fluororesin, urethane resin, alkyd resin, epoxy resin, phenol resin, polyester resin, melamine resin, vinyl acetate , At least one organic resin selected from the group consisting of vinyl chloride resin and chlorinated rubber resin in a total solid content of at least 10% by weight. The compatibility between the coating film and the surface to be coated, such as resistance to thermal cycling, and the mechanical properties of the coating film are improved.
また、請求項５記載の発明によれば、コロイダルシリカを含むことを特徴とすることにより塗膜の造膜性が向上し、塗布硬化被膜の強度および表面高度を高める効果がある。 According to the fifth aspect of the present invention, by containing colloidal silica, the film forming property of the coating film is improved, and there is an effect of increasing the strength and surface height of the cured coating film.
また、請求項６記載の発明によれば、固形分濃度が２０重量％以上とすることにより、塗料として適当な膜厚である膜厚１μｍ以上の塗膜が形成可能となる。 According to the sixth aspect of the invention, by setting the solid content concentration to 20% by weight or more, it is possible to form a coating film having a film thickness of 1 μm or more, which is an appropriate film thickness as a coating material.
また、請求項７記載の発明によれば、前記（ｂ）成分の光触媒粒子が全固形分の１重量％以上であることで、被膜表面は水との接触角が小さく、降雨によるセルフクリーニング機能を享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持されるようになる。
また、光触媒粒子が全固形分の２５重量％未満であることで、光触媒粒子の酸化還元力に基づく分解力による、シリコーン樹脂被膜を形成可能なシリコーン樹脂前駆体の水性エマルジョンの硬化により得られるバインダーへの影響がなく、屋外の使用において長期に亘り、セルフクリーニング機能が維持される。
According to the seventh aspect of the present invention, since the photocatalyst particles of the component (b) account for 1% by weight or more of the total solids, the surface of the coating has a small contact angle with water, and has a self-cleaning function by rainfall. Can be enjoyed, and that state can be maintained for a long period of time by irradiation of sunlight.
Further, since the photocatalyst particles are less than 25% by weight of the total solid, a binder obtained by curing an aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film due to a decomposition force based on the redox power of the photocatalyst particles. And the self-cleaning function is maintained for a long time in outdoor use.
また、請求項８記載の発明によれば、基材の表面に、請求項１〜８に記載の自己浄化性水性塗料組成物の硬化被膜からなる塗装層を備えることにより、基材と被膜との密着性が強固であり、耐沸騰水性や耐摺動性などの塗膜抵抗性を有し、耐久性にも優れ、かつ被膜表面は水との接触角が小さく、降雨によるセルフクリーニング機能を享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される自己浄化性部材が提供可能となる。 According to the invention of claim 8, the base material and the coating film are provided on the surface of the base material by providing a coating layer composed of a cured coating film of the self-cleaning aqueous coating composition according to claims 1 to 8. The film has strong adhesion, has coating resistance such as boiling water resistance and sliding resistance, and has excellent durability.The coating surface has a small contact angle with water, and has a self-cleaning function by rainfall. It is possible to provide a self-cleaning member that can be enjoyed and whose state is maintained for a long time by irradiation of sunlight.
本発明によれば、本発明の水性塗料組成物を塗布することにより、光触媒による防汚、親水効果が発揮される。また、プラスチックなどの有機系基材表面に形成する塗膜の厚みを厚くしても、クラックが発生せず、しかも剥離強度等の塗膜の機械的性質に優れ、かつ耐候性に優れた塗膜を形成することが可能となる。 According to the present invention, by applying the aqueous coating composition of the present invention, antifouling and hydrophilic effects by a photocatalyst are exhibited. Also, even if the thickness of the coating film formed on the surface of an organic base material such as plastic is increased, cracks do not occur, and the coating film has excellent mechanical properties such as peel strength and excellent weather resistance. A film can be formed.
本発明において、「シリコーン樹脂被膜を形成可能なシリコーン樹脂前駆体の水性エマルジョン」には、例えば、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリクロシラン、メチルトリブロムシラン、メチルトリイソプロポキシシラン、メチルトリｔ−ブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、エチルトリクロルシラン、エチルトリブロムシラン、エチルトリイソプロポキシシラン、エチルトリｔ−ブトキシシラン、ｎープロピルトリメトキシシラン、ｎープロピルトリエトキシシラン、ｎープロピルトリクロシラン、ｎープロピルトリブロムシラン、ｎープロピルトリイソプロポキシシラン、ｎープロピルトリｔ−ブトキシシラン、ｎーヘキシルトリメトキシシラン、ｎーヘキシルトリエトキシシラン、ｎーヘキシルトリクロシラン、ｎーヘキシルトリブロムシラン、ｎーヘキシルトリイソプロポキシシラン、ｎーヘキシルトリｔ−ブトキシシラン、ｎーデシルトリメトキシシラン、ｎーデシルトリエトキシシラン、ｎーデシルトリクロシラン、ｎーデシルトリブロムシラン、ｎーデシルトリイソプロポキシシラン、ｎーデシルトリｔ−ブトキシシラン、ｎーオクタトリメトキシシラン、ｎーオクタトリエトキシシラン、ｎーオクタトリクロシラン、ｎーオクタトリブロムシラン、ｎーオクタトリイソプロポキシシラン、ｎーオクタトリｔ−ブトキシシラン、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、フェニルトリクロシラン、フェニルトリブロムシラン、フェニルトリイソプロポキシシラン、フェニルトリｔ−ブトキシシラン、ジメチルジクロルシラン、ジメチルジブロムシラン、ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジフェニルジクロルシラン、ジフェニルジブロムシラン、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、フェニルメチルジクロルシラン、フェニルメチルジブロムシラン、フェニルメチルジメトキシシラン、フェニルメチルジエトキシシラン、ビニルトリクロルシラン、ビニルトリブロムシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリイソプロポキシシラン、ビニルトリｔ−ブトキシシラン、トリフルオロプロピルトリクロルシラン、トリフルオロプロピルトリジブロムシラン、トリフルオロプロピルトリメトキシシラン、トリフルオロプロピルトリエトキシシラン、ビニルトリクロルシラン、トリフルオロプロピルトリイソプロポキシシラン、トリフルオロプロピルトリｔ−ブトキシシラン、γ−グリシドキシプロピルメチルジメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルトリイソプロポキシシラン、γ−グリシドキシプロピルトリｔ−ブトキシシラン、γ−メタアクリロキシプロピルメチルジメトキシシラン、γ−メタアクリロキシプロピルメチルジエトキシシラン、γ−メタアクリロキシプロピルトリメトキシシラン、γ−メタアクリロキシプロピルトリエトキシシラン、γ−メタアクリロキシプロピルトリイソプロポキシシラン、γ−メタアクリロキシプロピルトリｔ−ブトキシシラン、γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルメチルジエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリイソプロポキシシラン、γ−アミノメタアクリロキシプロピルトリｔ−ブトキシシラン、γ−メチルカプトプロピルメチルジメトキシシラン、γ−メチルカプトプロピルメチルジエトキシシラン、γ−メチルカプトプロピルトリメトキシシラン、γ−メチルカプトプロピルトリエトキシシラン、γ−メチルカプトプロピルトリイソプロポキシシラン、γ−メチルカプトプロピルトリｔ−ブトキシシラン、β−（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、β−（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の加水分解、脱水縮重合物などのエマルジョンが好適に利用できる。 In the present invention, "aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film" includes, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, methyltribromosilane, methyltriisopropoxysilane, Methyltri-t-butoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltrichlorosilane, ethyltribromosilane, ethyltriisopropoxysilane, ethyltri-t-butoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane , N-propyltrichlorosilane, n-propyltribromosilane, n-propyltriisopropoxysilane, n-propyltri-t-butoxysilane, n-hexyltrimethoxysilane, n-hexyl Ethoxysilane, n-hexyltrichlorosilane, n-hexyltribromosilane, n-hexyltriisopropoxysilane, n-hexyltri-t-butoxysilane, n-decyltrimethoxysilane, n-decyltriethoxysilane, n-decyltriclosilane N-decyltribromosilane, n-decyltriisopropoxysilane, n-decyltri-t-butoxysilane, n-octatrimethoxysilane, n-octatriethoxysilane, n-octatriclosilane, n-octatribromosilane, n-octatriisopropoxysilane, n-octatri-t-butoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, phenyltriclosilane, phenyltribromosilane, phenyltriisopropoxysilane, phenyl Tert-butoxysilane, dimethyldichlorosilane, dimethyldibromosilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldibromosilane, diphenyldimethoxysilane, diphenyldiethoxysilane, phenylmethyldichlorosilane, Phenylmethyldibromosilane, phenylmethyldimethoxysilane, phenylmethyldiethoxysilane, vinyltrichlorosilane, vinyltribromosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriisopropoxysilane, vinyltri-t-butoxysilane, trifluoro Propyltrichlorosilane, trifluoropropyltridibromosilane, trifluoropropyltrimethoxysilane, trifluoropropyltriethoxy Silane, vinyltrichlorosilane, trifluoropropyltriisopropoxysilane, trifluoropropyltri-t-butoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyl Trimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltriisopropoxysilane, γ-glycidoxypropyltri-t-butoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-meta Acryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-methacryloxypropyltriisopropoxysilane, γ-methacryloyl Cypropyltri-t-butoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ- Aminomethacryloxypropyltri-t-butoxysilane, γ-methylcaptopropylmethyldimethoxysilane, γ-methylcaptopropylmethyldiethoxysilane, γ-methylcaptopropyltrimethoxysilane, γ-methylcaptopropyltriethoxysilane, γ- Methylcaptopropyltriisopropoxysilane, γ-methylcaptopropyltri-t-butoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) Le) Hydrolysis of ethyl triethoxysilane, emulsions such as dehydration condensation polymerization product can be suitably used.
「光触媒性酸化物粒子」には、例えば、酸化チタン、酸化亜鉛、酸化錫、酸化鉄、酸化ジルコニウム、酸化タングステン、酸化クロム、酸化モリブデン、酸化ルテニウム、酸化ゲルマニウム、酸化鉛、酸化カドミウム、酸化銅、酸化バナジウム、酸化ニオブ、酸化タンタル、酸化マンガン、酸化ロジウム、酸化ニッケル、酸化レニウム、チタン酸ストロンチウム等の粒子が利用できる。
なお、酸化チタンを光触媒として用いる場合は、結晶型がアナターゼ型、またはブルッカイト型のものを用いることが、光触媒活性がもっとも強く、しかも長期間発現するので好ましい。
"Photocatalytic oxide particles" include, for example, titanium oxide, zinc oxide, tin oxide, iron oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, ruthenium oxide, germanium oxide, lead oxide, cadmium oxide, and copper oxide. Particles such as vanadium oxide, niobium oxide, tantalum oxide, manganese oxide, rhodium oxide, nickel oxide, rhenium oxide, and strontium titanate can be used.
When titanium oxide is used as the photocatalyst, it is preferable to use an anatase type or a brookite type as the crystal type, since the photocatalytic activity is the strongest and is exhibited for a long period of time.
「無機顔料」としては、例えば、無機着色顔料、無機体質顔料が利用できる。
無機着色顔料としては、酸化チタン白、チタンイエロー、スピネルグリーン、亜鉛華、ベンガラ、酸化クロム、コバルトブルー、鉄黒などの金属酸化物系、アルミナホワイト、黄色酸化鉄などの金属水酸化物系、紺青などのフェロシアン化合物系、黄鉛、ジンクロメート、モリブデンレッドなどのクロム酸鉛系、硫化亜鉛、朱、カドミウムイエロー、カドミウムレッドなどの硫化物、セレン化合物系、バライト、沈降性硫酸バリウムなどの硫酸塩系、重質炭酸カルシウム、沈降性炭酸カルシウムなどの炭酸塩系、含水珪酸塩、クレー、群青などの珪酸塩系、カーボンブラックなどの炭素系、アルミニウム粉、ブロンズ粉、亜鉛粉末などの金属粉系、雲母・酸化チタン系などのパール顔料系などが挙げられる。
また、無機体質顔料としては、酸化チタンウィスカー、炭酸カルシウムウィスカー、チタン酸カリウムウィスカー、ホウ酸アルミニウムウィスカー、マイカ、タルク、硫酸バリウム、炭酸カリウム、珪砂、珪藻土、カオリン、クレー、陶土、炭酸バリウム等が好適である。
As the “inorganic pigment”, for example, an inorganic coloring pigment and an inorganic extender can be used.
As inorganic coloring pigments, metal oxides such as titanium oxide white, titanium yellow, spinel green, zinc white, red iron oxide, chromium oxide, cobalt blue, iron black, alumina hydroxide, metal hydroxides such as yellow iron oxide, Ferrocyanide compounds such as navy blue, lead chromate such as lead, zinc chromate, molybdenum red, sulfides such as zinc sulfide, vermilion, cadmium yellow, cadmium red, selenium compounds, barite, precipitated barium sulfate, etc. Carbonates such as sulfate, heavy calcium carbonate and precipitated calcium carbonate; silicates such as hydrous silicate, clay and ultramarine blue; carbons such as carbon black; metals such as aluminum powder, bronze powder and zinc powder And pearl pigments such as powder, mica and titanium oxide.
Examples of the inorganic extender include titanium oxide whiskers, calcium carbonate whiskers, potassium titanate whiskers, aluminum borate whiskers, mica, talc, barium sulfate, potassium carbonate, silica sand, diatomaceous earth, kaolin, clay, clay, barium carbonate, and the like. It is suitable.
「有機樹脂」としては、例えば、アクリル樹脂、アクリルシリコーン樹脂、アクリルウレタン樹脂、アクリルスチレン樹脂、フッ素樹脂、ウレタン樹脂、アルキド樹脂、エポキシ樹脂、フェノール樹脂、ポリエステル樹脂、メラミン樹脂、酢酸ビニル、フタル酸樹脂、塩化ビニル樹脂、塩化ゴム樹脂からなる群の中から選ばれた少なくとも１種の有機樹脂を指す。
前記「有機樹脂」は下記（Ｘ）成分であることが好ましい。（Ｘ）一般式(I) ：ＣＨ2 ＝ＣＲ１ （ＣＯＯＲ２ ）で表される（ここでＲ１は水素原子および／またはメチル基を示す）モノマーであって、Ｒ２ が置換もしくは非置換で炭素数１〜９の１価炭化水素基である第１の（メタ）アクリル酸エステル。Ｒ２ がエポキシ基、アルコキシシリル基および／またはハロゲン化シリル基を含む炭化水素基、グリシジル基である第２の（メタ）アクリル酸エステル。上記第１、第２の（メタ）アクリル酸エステルの１種あるいは２種以上を含む共重合体であるアクリル樹脂。さらには上記第１、第２の（メタ）アクリル酸エステルの１種あるいは２種以上と、上記以外の（メタ）アクリル酸エステルの中から選ばれた１種あるいは２種以上を含む共重合体であるアクリル樹脂や（Ｘ）成分で表される第一、第二の（メタ）アクリル酸エステルの１種あるいは２種以上とスチレンとの共重合体からなる樹脂であることが好ましい。
なお、本明細書中、（メタ）アクリル酸エステルは、アクリル酸エステルおよびメタクリル酸エステルのいずれか一方または両方を指す。
As the "organic resin", for example, acrylic resin, acrylic silicone resin, acrylic urethane resin, acrylic styrene resin, fluororesin, urethane resin, alkyd resin, epoxy resin, phenol resin, polyester resin, melamine resin, vinyl acetate, phthalic acid It refers to at least one organic resin selected from the group consisting of resin, vinyl chloride resin, and chlorinated rubber resin.
The “organic resin” is preferably the following component (X). (X) A monomer represented by the general formula (I): CH 2 ＣＲCR 1 (COOR 2) (where R 1 represents a hydrogen atom and / or a methyl group), wherein R 2 is substituted or unsubstituted and has 1 to 1 carbon atoms. 9. The first (meth) acrylic acid ester which is a monovalent hydrocarbon group of No. 9. A second (meth) acrylic ester wherein R2 is a hydrocarbon group containing an epoxy group, an alkoxysilyl group and / or a halogenated silyl group, or a glycidyl group; An acrylic resin which is a copolymer containing one or more of the first and second (meth) acrylates. Further, a copolymer containing one or more of the first and second (meth) acrylates and one or two or more selected from the other (meth) acrylates And a resin comprising a copolymer of styrene and one or more of the first and second (meth) acrylates represented by the component (X).
In addition, in this specification, (meth) acrylic acid ester points out any one or both of acrylic acid ester and methacrylic acid ester.
「コロイダルシリカ」としては、特に限定はされないが、溶媒として水を含むものが望ましい。また、シリカ表面をアルミ等で被覆した各種被覆シリカ、及び樹脂粒子や金属酸化物ゾル等の表面をシリカ被覆した粒子、シリカの形状としては球状、棒状、球状シリカが連結したネックレス状シリカ、等をコロイド粒子として分散したものが利用できる。 The “colloidal silica” is not particularly limited, but preferably contains water as a solvent. In addition, various types of coated silica having a silica surface coated with aluminum or the like, and particles having a silica coated surface such as resin particles and metal oxide sols, and the shape of the silica is spherical, rod-shaped, necklace-shaped silica in which spherical silica is connected, and the like. Can be used as colloidal particles.
また、本発明の自己浄化性水性塗料組成物は、表面が疎水性である基材であっても塗布、硬化させることで塗膜を形成することができる。塗膜形成直後から降雨によるセルフクリーニング機能を享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持される自己浄化性部材が得られる。ここで、硬化は常温で行うのが、現場施工等には有利である。 Also, the self-cleaning aqueous coating composition of the present invention can form a coating film by applying and curing even a substrate having a hydrophobic surface. It is possible to obtain a self-cleaning member that can enjoy the self-cleaning function by rainfall immediately after the formation of the coating film, and that state can be maintained for a long time by irradiating sunlight. Here, curing at room temperature is advantageous for on-site construction and the like.
「疎水性物質を表面に有する基材」は、例えば、プラスチック、有機物の繊維、有機物の布帛、塗装鋼板等の塗装体等が挙げられる。 The “substrate having a hydrophobic substance on its surface” includes, for example, plastics, organic fibers, organic cloths, and painted bodies such as painted steel plates.
本発明の自己浄化性水性塗料組成物には、さらに、Ag、Cu、Znのような金属やZnOのような金属酸化物を添加することができる。このような金属及び金属酸化物が添加された表面層は、表面に付着した細菌や黴や藻を暗所でも死滅させることができ、よって防汚性をより向上させることができる。 金属 A metal such as Ag, Cu, Zn or a metal oxide such as ZnO can be further added to the self-cleaning aqueous coating composition of the present invention. The surface layer to which such a metal and a metal oxide are added can kill bacteria, mold, and algae attached to the surface even in a dark place, and thus can further improve antifouling properties.
本発明の自己浄化性水性塗料組成物には、さらに、Pt、Pd、Ru、Rh、Ir、Osのような白金族金属を添加することができる。このような金属を添加することで、光触媒の酸化還元活性を増強でき、有機物汚れの分解性、有害気体や悪臭の分解性を向上させることができる。 白金 A platinum group metal such as Pt, Pd, Ru, Rh, Ir, and Os can be further added to the self-cleaning aqueous coating composition of the present invention. By adding such a metal, the redox activity of the photocatalyst can be enhanced, and the decomposability of organic contaminants and the decomposability of harmful gases and odors can be improved.
本発明のコーティング剤には、さらに、疎水性樹脂エマルジョンの基材への造膜性を向上させるために造膜助剤を使用することが可能である。造膜助剤は、大部分の水分が気化した後も塗膜中に残存し、エマルション粒子どうしの融合を促進させる機能をもつものである。具体的には、沸点が１００℃以上の有機化合物が挙げられる。以下に具体例を示す。
エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノプロピルエーテル、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノヘキシルエーテル、エチレングリコールエチルエーテルアセテート、ジエチレングリコールモノブチルエーテルアセテート、等のエチレン系グリコールエーテル類。
プロピレングリコールモノメチルエーテル、プロピレングリコールモノブチルエーテル、プロピレングリコールモノプロピルエーテル、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メチルエーテル、
ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノブチルエーテル、トリプロピレングリコールモノメチルエーテル、トリプロピレングリコールモノブチルエーテル、ポリプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールジアセテート、プロピレングリコールフェニルエーテル、等のプロピレン系グリコールエーテル類。
２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレート、ｎ−ペンシルプロピオネ−ト（n-PENTYL PROPIONATE）、フタル酸ジブチル等のエステル類などが挙げられる。
そのうち、エステル類の一種である２，２，４−トリメチル−１，３−ペンタンジオールモノイソブチレートは、フッ素樹脂エマルジョンへの浸透能力が高いこと、最低造膜温度（MFT）の低下効果が高いことから、その使用は好ましい。逆にエチレン系グリコールエーテル類は人体への毒性が強いので、その使用は好ましくない。
In the coating agent of the present invention, it is possible to further use a film forming aid for improving the film forming property of the hydrophobic resin emulsion on the substrate. The film-forming aid has a function of remaining in the coating film even after most of the water is vaporized, and promoting the fusion of the emulsion particles. Specifically, an organic compound having a boiling point of 100 ° C. or higher can be used. Specific examples are shown below.
Ethylene glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like.
Propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether,
Propylene glycol ethers such as dipropylene glycol dimethyl ether, dipropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, polypropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol diacetate, propylene glycol phenyl ether, etc. Kind.
Esters such as 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, n-pentyl propionate (n-PENTYL PROPIONATE) and dibutyl phthalate are exemplified.
Among them, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, which is a kind of esters, has a high ability to penetrate into a fluororesin emulsion and has the effect of lowering the minimum film formation temperature (MFT). Due to its high cost, its use is preferred. Conversely, ethylene glycol ethers are highly toxic to the human body, so their use is not preferred.
（塗料組成物の調製）
以下、実施例及び比較例によって本発明を詳細に説明する。重量平均分子量は、ＧＰＣ（ゲルパーミエーションクロマトグラフィー）により、測定機種として東ソー（株）のＨＬＣ８１２０を用いて、標準ポリスチレンで検量線を作成し、測定したものである。また、粒子径の測定は、光子相関分光法（ＰＣＳ）により、測定機種としてＭＡＬＶＥＲＮ社のＺＥＴＡＳＩＺＥＲ ３０００ＨＳ を用いて測定した。なお、粒径は体積平均値である。以下、実施例及び比較例によって本発明を詳細に説明する。なお、本発明は、下記実施例に限定されない。
(Preparation of coating composition)
Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. The weight average molecular weight was measured by GPC (gel permeation chromatography) using a standard polystyrene calibration curve with HLC8120 manufactured by Tosoh Corporation as a measurement model. The particle diameter was measured by photon correlation spectroscopy (PCS) using ZETASIZER 3000HS of MALVERN as a measurement model. The particle size is a volume average value. Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. In addition, this invention is not limited to a following example.
実施例１
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２５重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）１４重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）２１重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２３重量部、体質顔料（大塚化学株式会社製、商品名ＨＴ−３００）１７重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）１．９重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 1
Photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name MF1000PC) 25 parts by weight, colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50) 14 parts by weight, silicone emulsion (Asahi Kasei Wacker Silicone Co., Ltd.) 21 parts by weight, trade name BS45, weight average molecular weight 10,000, average particle diameter 1400 nm), 23 parts by weight of a coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF color MF5160), extender pigment (manufactured by Otsuka Chemical Co., Ltd.) HT-300) and 1.9 parts by weight of a film-forming assistant (trade name: CS-12, manufactured by Chisso Corporation) were prepared. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
実施例２
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）２４重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）１０重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 2
24 parts by weight of a photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) 24 parts by weight, trade name BS45, weight average molecular weight 10,000, average particle diameter 1400 nm), 10 parts by weight of fluororesin emulsion (manufactured by Asahi Glass Co., Ltd., trade name Lumiflon FE4300), coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd.) MF color MF5765) 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name Tismo D) 3 parts by weight, and a film forming aid (Chisso Corporation, trade name CS-12) 4 parts by weight It was adjusted. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
実施例３
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）２４重量部、アクリルシリコーン樹脂エマルジョン（大日本インキ工業株式会社製、商品名ＳＡ６３００）１２重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 3
24 parts by weight of photocatalytic oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) 24 parts by weight, trade name BS45, weight average molecular weight 10,000, average particle diameter 1400 nm), 12 parts by weight of acrylic silicone resin emulsion (manufactured by Dainippon Ink Industries, Ltd., trade name: SA6300), coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd.) MF Color MF5765), 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name: Tismo D), 3 parts by weight, coating aid (Chisso Corporation, trade name: CS-12), 4 parts by weight The composition was prepared. At this time, the water content was 147 parts by weight with respect to the total of 100 parts by weight of the solid content.
実施例４
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）１７重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）２４重量部、アクリルウレタン樹脂エマルジョン（大日本インキ工業株式会社製、商品名ＣＧ５０３０）１７重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 4
17 parts by weight of photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) 24 parts by weight, trade name BS45, weight average molecular weight 10,000, average particle diameter 1400 nm), acrylic urethane resin emulsion (manufactured by Dainippon Ink Industries, Ltd., trade name CG5030) 17 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd.) MF Color MF5765), 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name: Tismo D), 3 parts by weight, coating aid (Chisso Corporation, trade name: CS-12), 4 parts by weight The composition was prepared. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
実施例５
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）１７重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）２４重量部、アクリルスチレン樹脂エマルジョン（ＢＡＳＦ株式会社製、商品名ＹＪ６２２１Ｄ）１７重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 5
17 parts by weight of photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (Trade name: BS45, weight average molecular weight: 10,000, average particle size: 1400 nm), 24 parts by weight, acrylic styrene resin emulsion (manufactured by BASF Co., Ltd., trade name: YJ6221D), 17 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name) MF color MF5765) 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name Tismo D) 3 parts by weight, and a film forming aid (Chisso Corporation, trade name CS-12) 4 parts by weight It was adjusted. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
実施例６
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）１０重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）２４重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 6
24 parts by weight of a photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) , Trade name BS45, weight average molecular weight 10,000, average particle diameter 1400 nm) 10 parts by weight, fluororesin emulsion (manufactured by Asahi Glass Co., Ltd., trade name Lumiflon FE4300) 24 parts by weight, color pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name) MF color MF5765) 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name Tismo D) 3 parts by weight, and a film forming aid (Chisso Corporation, trade name CS-12) 4 parts by weight It was adjusted. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
実施例７
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）１２重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）１０重量部、アクリルシリコーン樹脂エマルジョン（大日本インキ工業株式会社製、商品名ＳＡ６３００）２７重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 7
12 parts by weight of a photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) (Product name: BS45, weight average molecular weight: 10,000, average particle diameter: 1400 nm), 10 parts by weight, acrylic silicone resin emulsion (manufactured by Dainippon Ink Industries, Ltd., trade name: SA6300), 27 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd.) MF Color MF5765), 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name: Tismo D), 3 parts by weight, coating aid (Chisso Corporation, trade name: CS-12), 4 parts by weight The composition was prepared. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
実施例８
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）１０重量部、アクリルウレタン樹脂エマルジョン（大日本インキ工業株式会社製、商品名ＣＧ５０３０）２４重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 8
24 parts by weight of a photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) 10 parts by weight, trade name BS45, weight average molecular weight 10,000, average particle diameter 1400 nm), 24 parts by weight of an acrylic urethane resin emulsion (manufactured by Dainippon Ink Industries, Ltd., trade name: CG5030), coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd.) MF Color MF5765), 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name: Tismo D), 3 parts by weight, coating aid (Chisso Corporation, trade name: CS-12), 4 parts by weight The composition was prepared. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
実施例９
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＢＳ４５、重量平均分子量１００００、平均粒子径１４００ｎｍ）１０重量部、アクリルスチレン樹脂エマルジョン（ＢＡＳＦ株式会社製、商品名ＹＪ６２２１Ｄ）２４重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Example 9
24 parts by weight of a photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) , Trade name BS45, weight average molecular weight 10,000, average particle diameter 1400 nm) 10 parts by weight, acrylic styrene resin emulsion (manufactured by BASF Corporation, trade name YJ6221D) 24 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name) MF color MF5765) 17 parts by weight, extender pigment (manufactured by Maruo Calcium Co., Ltd., trade name Tismo D) 3 parts by weight (above indicated by solid content), film forming aid (Chisso Corporation, trade name CS-12) 4 A part by weight coating composition was prepared. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
比較例１
光触媒酸化物ゾル（石原産業株式会社製、商品名ＳＴＳ−２１）１０．４重量部、コロイダルシリカ（日本化学工業株式会社製、商品名シリカドール３０Ｂ）４１．３重量部、シリコーンエマルジョン（ＴＯＴＯ調整品、重量平均分子量２０００）３１．４重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)１６．９重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）１．９重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して２５０重量部であった。
なお、ここで用いたシリコーンエマルジョンの調製は、以下の通り行った。
水１０００重量部とアセトン５０重量部の混合液中に、メチルトリクロロシラン４５重量部、ジメチルジクロロシラン３９重量部、フェニルトリクロロシラン８５重量部、トルエン２００重量部の溶液を滴下して６０℃で加水分解した。塩酸、水、トルエンを除去し、シラノール基含有オルガノポリシロキサンのトルエン５０％溶液を得た。この溶液１００重量部とメチルトリメトキシシラン５重量部とジメチルジメトキシシラン５重量部の混合液中に、ジブチルスズジラウレート０．６重量部とトルエン１０重量部の溶液を滴下してシラノール基のアルコキシ化を６０℃で行った。ジブチルスズジラウレート、メタノール、トルエンを除去して重量平均分子量２０００のオルガノシロキサン部分加水分解物の８０％トルエン溶液を得た。この溶液５０重量部に重合抑制剤ポリオキシエチレンノニルフェニルエーテル２重量部を添加し、ロータリーエバポレーターで溶媒を除去した後、ポリオキシエチレンノニルフェニルエーテル５重量部を添加して均一に攪拌した。これに水１５３重量部を攪拌下で加え、シリコーンエマルジョンを得た。
Comparative Example 1
10.4 parts by weight of photocatalyst oxide sol (manufactured by Ishihara Sangyo Co., Ltd., trade name: STS-21), 41.3 parts by weight of colloidal silica (manufactured by Nippon Chemical Industry Co., Ltd., trade name: Silica Doll 30B), silicone emulsion (TOTO adjustment) Product, weight average molecular weight 2000) 31.4 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name MF Color MF5160) 16.9 parts by weight (above indicated by solid content), film forming aid (Chisso Corporation) Company name, trade name CS-12) 1.9 parts by weight of a coating composition was prepared. The water content at this time was 250 parts by weight with respect to the total of 100 parts by weight of the solid content.
The silicone emulsion used here was prepared as follows.
In a mixture of 1000 parts by weight of water and 50 parts by weight of acetone, a solution of 45 parts by weight of methyltrichlorosilane, 39 parts by weight of dimethyldichlorosilane, 85 parts by weight of phenyltrichlorosilane, and 200 parts by weight of toluene was added dropwise at 60 ° C. Decomposed. Hydrochloric acid, water and toluene were removed to obtain a 50% toluene solution of a silanol group-containing organopolysiloxane. In a mixture of 100 parts by weight of this solution, 5 parts by weight of methyltrimethoxysilane and 5 parts by weight of dimethyldimethoxysilane, a solution of 0.6 parts by weight of dibutyltin dilaurate and 10 parts by weight of toluene was dropped to carry out alkoxylation of silanol groups. Performed at 60 ° C. Dibutyltin dilaurate, methanol and toluene were removed to obtain an 80% toluene solution of a partially hydrolyzed organosiloxane having a weight average molecular weight of 2,000. To 50 parts by weight of this solution, 2 parts by weight of a polymerization inhibitor polyoxyethylene nonyl phenyl ether was added, and after removing the solvent by a rotary evaporator, 5 parts by weight of polyoxyethylene nonyl phenyl ether was added and stirred uniformly. To this, 153 parts by weight of water was added under stirring to obtain a silicone emulsion.
比較例２
フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）６７．８重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５１６０)２６．７重量部、体質顔料（大塚化学株式会社製、商品名ティスモ−Ｎ）５．５重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）１４．７重量部である水性塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して８５重量部であった。
Comparative Example 2
67.8 parts by weight of a fluororesin emulsion (manufactured by Asahi Glass Co., Ltd., trade name: Lumiflon FE4300), 26.7 parts by weight of a coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF Color MF5160), extender pigment (Otsuka Chemical Co., Ltd.) Aqueous coating composition comprising 5.5 parts by weight (manufactured by Tismo-N) and 14.7 parts by weight of a film forming aid (trade name: CS-12, manufactured by Chisso Corporation) did. At this time, the water content was 85 parts by weight with respect to the total of 100 parts by weight of the solid content.
比較例３
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（重量平均分子量２０００）２４重量部、アクリルシリコーン樹脂エマルジョン（大日本インキ工業株式会社製、商品名ＳＡ５８００）１２重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１６．９重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）１．９重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Comparative Example 3
24 parts by weight of a photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), 24 parts by weight of silicone emulsion (weight average molecular weight 2000) Parts, 12 parts by weight of an acrylic silicone resin emulsion (manufactured by Dainippon Ink Industries, Ltd., trade name: SA5800), 16.9 parts by weight of a color pigment (manufactured by Dainichi Seika Industry Co., Ltd., trade name: MF Color MF5765) 1.9 parts by weight of a coating composition (shown) and a film-forming auxiliary (trade name: CS-12, manufactured by Chisso Corporation). At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
比較例４
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、シリコーンエマルジョン（旭化成ワッカーシリコーン（株）製、商品名ＭＰ４２Ｅ、平均粒子径３８５ｎｍ）２４重量部、アクリルシリコーン樹脂エマルジョン（大日本インキ工業株式会社製、商品名ＳＡ６３００）１２重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１６．９重量部（以上固形分で表示）、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）１．９重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Comparative Example 4
24 parts by weight of a photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), silicone emulsion (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) 24 parts by weight, trade name: MP42E, average particle size: 385 nm), 12 parts by weight of acrylic silicone resin emulsion (trade name: SA6300, manufactured by Dainippon Ink Industries, Ltd.), coloring pigment (trade name: MF Color, manufactured by Dainichi Seika Kogyo Co., Ltd.) MF5765) (16.9 parts by weight (in terms of solid content)) and a film forming aid (Chisso Corporation, trade name CS-12) of 1.9 parts by weight were prepared. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
比較例５
光触媒酸化物ゾル（大日精化工業株式会社製、商品名ＭＦ１０００ＰＣ）２４重量部、コロイダルシリカ（日産化学株式会社製、商品名スノーテックス５０）６重量部、フッ素樹脂エマルジョン（旭硝子株式会社製、商品名ルミフロンＦＥ４３００）３４重量部、着色顔料(大日精化工業株式会社製、商品名ＭＦカラーＭＦ５７６５)１７重量部、体質顔料（丸尾カルシウム株式会社製、商品名ティスモＤ）３重量部、造膜助剤（チッソ株式会社製、商品名ＣＳ−１２）４重量部の塗料組成物を調整した。このときの水分量は固形分の合計１００重量部に対して１４７重量部であった。
Comparative Example 5
24 parts by weight of photocatalyst oxide sol (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: MF1000PC), 6 parts by weight of colloidal silica (manufactured by Nissan Chemical Co., Ltd., trade name: Snowtex 50), fluororesin emulsion (manufactured by Asahi Glass Co., Ltd., product Lumiflon FE4300) 34 parts by weight, coloring pigment (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name MF color MF5765) 17 parts by weight, extender pigment (Maruo Calcium Co., Ltd., trade name Tismo D) 3 parts by weight, film forming aid 4 parts by weight of a coating composition (trade name: CS-12, manufactured by Chisso Corporation) was prepared. At this time, the water content was 147 parts by weight with respect to 100 parts by weight of the total solid content.
（基材への塗布方法）
１５０ｍｍ×６５ｍｍに裁断した１５０ｍｍ×６５ｍｍに裁断した繊維強化セメント板（ＪＩＳ Ａ５４３０に準拠したもの）にアクリル樹脂エマルジョン系下塗り剤（ジャパンハイドロテクトコーティングス株式会社、商品名ＳＲ１１）をローラー塗布し、室温で２４時間乾燥させた。続いて、前記で調製した実施例１の塗料組成物をローラー塗りした。実施例２〜９、比較例１〜４の塗料組成物についても、前記塗布方法にしたがい塗布を行った。最後に、上記被塗装物を室温で７日間乾燥させて試験片１〜１３を得た。
実施例中に記載のａ成分〜ｄ成分は前記内容を示す。ａ′成分、ａ″成分を下記する。
ａ′成分：シリコーン樹脂被膜を形成可能なシリコーン樹脂前駆体の水性エマルジョン、スチレン換算の重量平均分子量が２０００
ａ″成分：シリコーン樹脂被膜を形成可能なシリコーン樹脂前駆体の水性エマルジョン、平均粒子径が３８５ｎｍ
(Method of coating on substrate)
An acrylic resin emulsion-based primer (Japan Hydrotect Coatings Co., Ltd., trade name SR11) is roller-coated on a fiber reinforced cement board (conforming to JIS A5430) cut into 150 mm x 65 mm cut into 150 mm x 65 mm, and then room temperature. Dry for 24 hours. Subsequently, the coating composition of Example 1 prepared above was applied by roller. The coating compositions of Examples 2 to 9 and Comparative Examples 1 to 4 were also applied according to the above-mentioned application method. Finally, the object to be coated was dried at room temperature for 7 days to obtain test pieces 1 to 13.
The components a to d described in the examples show the above contents. The components a 'and a "are described below.
Component a ': an aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film, having a weight average molecular weight in terms of styrene of 2,000
a ″ component: an aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film, having an average particle size of 385 nm
次に、上記各試験片について、耐沸騰水性、密着性、耐洗浄性、耐アルカリ性、耐水性、耐熱冷サイクル性、親水性（屋外曝露後の接触角を測定）、耐候性（促進曝露後に白亜化度を測定）の評価を行った。その結果を（表３、表4）に示す。 Next, for each of the above test pieces, boiling water resistance, adhesion, washing resistance, alkali resistance, water resistance, heat and cold cycle resistance, hydrophilicity (measure the contact angle after outdoor exposure), weather resistance (after accelerated exposure) The degree of chalking was measured). The results are shown in Tables 3 and 4.
評価方法は以下の通りである。
耐沸騰水性：９５℃以上の沸騰水中に２時間浸漬し、取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なった。
密着性：ＪＩＳ Ｋ５６００に基づく碁盤目試験法を行った。すなわち、作製した試験片の塗膜の上からカッターで２ｍｍ幅の碁盤目の切込みを入れた。大きさは１ｃｍ角にし、碁盤目の数を２５個とした。その後その碁盤目を完全に覆うようにセロハンテープを貼り付けた。その後、すばやく引き剥がして付着して残っている碁盤目の数を数えた。
耐洗浄性：ＪＩＳ Ｋ５６００に基づき、ブラシ摺動試験を行い、蒸留水にて洗浄後、十分乾燥させた後、目視外観にて評価を行なった。
耐アルカリ性：ＪＩＳ Ｋ５６００に基づき、水酸化カルシウム飽和水溶液に室温で２日間浸漬し、取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なった。
耐水性：ＪＩＳ Ｋ５６００に基づき、水中に室温で４日間浸漬し、十分乾燥させた後、目視外観にて評価を行なった。
熱冷サイクル試験：５０℃の恒温槽に３時間、次いで、−２０℃の恒温槽に３時間、次いで２５℃の恒温水槽に１８時間を１サイクルとして１０サイクル繰り返した。取り出した後蒸留水にて洗浄し、十分乾燥させた後、目視外観にて評価を行なった。
親水性（接触角）：試験片表面の水との接触角を、協和界面科学製ＣＸ-150を用いて測定した。
屋外暴露：作製した試験片を南側に向け、鉛直に対して４５°傾斜させ曝露を行った。暴露1ヶ月後、暴露2ヶ月後の接触角を測定した。
耐候性試験：ＪＩＳ Ｋ５４００ ９．８に従い、サンシャインカーボンアーク灯式に基づいて促進曝露試験を１０００時間行った後、ＪＩＳ Ｋ５６００に基づいて白亜化度評価を行った。白亜化度判定 １０点を○ ９点、８点を△ ７点以下を× とした。
The evaluation method is as follows.
Boiling water resistance: The film was immersed in boiling water of 95 ° C. or more for 2 hours, taken out, washed with distilled water, dried sufficiently, and evaluated by visual appearance.
Adhesion: A cross-cut test based on JIS K5600 was performed. That is, a 2 mm-width grid cut was made from above the coating film of the prepared test piece with a cutter. The size was 1 cm square, and the number of grids was 25. Then, cellophane tape was stuck so as to completely cover the grid. Thereafter, the number of grids remaining after being quickly peeled off and adhered was counted.
Washing resistance: Based on JIS K5600, a brush sliding test was performed, washed with distilled water, dried sufficiently, and evaluated by visual appearance.
Alkali resistance: Based on JIS K5600, it was immersed in a saturated aqueous solution of calcium hydroxide for 2 days at room temperature, taken out, washed with distilled water, dried sufficiently, and evaluated by visual appearance.
Water resistance: Based on JIS K5600, immersed in water at room temperature for 4 days, dried sufficiently, and evaluated by visual appearance.
Thermal-cooling cycle test: 10 cycles were repeated with 3 hours in a 50 ° C constant temperature bath, 3 hours in a -20 ° C constant temperature bath, and then 18 hours in a 25 ° C constant temperature water bath. After taking out, it was washed with distilled water and dried sufficiently, and then evaluated by visual appearance.
Hydrophilicity (contact angle): The contact angle of the test piece surface with water was measured using CX-150 manufactured by Kyowa Interface Science.
Outdoor exposure: The produced test piece was directed to the south side and exposed at an angle of 45 ° with respect to the vertical. The contact angle was measured one month after the exposure and two months after the exposure.
Weather resistance test: According to JIS K5400 9.8, an accelerated exposure test was performed for 1000 hours based on a sunshine carbon arc lamp system, and then a degree of chalking was evaluated based on JIS K5600. Judgment of the degree of chalking: 10 points were evaluated as 9 points, 8 points were evaluated as 7 points or less, and x was evaluated.
実施例１〜９においては、耐沸騰水性、密着性、耐洗浄性、耐アルカリ性、耐水性を備えており、リコート性も優れており、塗膜と被塗装面との適合性や塗膜の機械的性質に優れた塗膜が得られている。また、実施例２〜９においては屋外曝露２ヶ月後の水接触角が１０°を下回り、自己洗浄性が発揮されている。さらに実施例１〜７において、耐候性に優れていることが確認できた。実施例２〜７では全ての評価を満足しており、基材と被膜との密着性が強固であり、耐沸騰水性にも耐久性にも優れ、かつ被膜表面は水との接触角が小さく、降雨によるセルフクリーニング機能を享受することが可能であり、かつその状態が太陽光の照射により長期に亘って維持することができる。
比較例５ではフッ素樹脂エマルジョンを用いて塗料化したが、耐候性評価でチョーキングが見られた。無機バインダーとなるシリコーン樹脂を含まないため、光触媒によりフッ素樹脂が分解されたと考えられる。
比較例１、比較例３ではシリコーン樹脂エマルジョンのスチレン換算の重量平均分子量が２０００と小さいこと、比較例４ではシリコーン樹脂エマルジョンの平均粒子径が３８５ｎｍと小さいことから、塗膜の機械的性質が不足し、耐沸騰水性試験で塗膜のハガレやクラックが発生した。また、比較例２では屋外曝露２ヶ月後の水接触角が７７°と大きく自己浄化性を満足していない。
In Examples 1 to 9, it has boiling water resistance, adhesion, washing resistance, alkali resistance, and water resistance, and has excellent recoating properties. A coating film having excellent mechanical properties is obtained. In Examples 2 to 9, the water contact angle after two months of outdoor exposure was less than 10 °, and the self-cleaning property was exhibited. Further, in Examples 1 to 7, it was confirmed that the weather resistance was excellent. In Examples 2 to 7, all the evaluations were satisfied, the adhesion between the substrate and the coating was strong, the durability was excellent even in boiling water resistance, and the contact angle of water on the coating surface was small. In addition, it is possible to enjoy a self-cleaning function by rainfall, and the state can be maintained for a long time by irradiating sunlight.
In Comparative Example 5, coating was performed using a fluororesin emulsion, but choking was observed in the weather resistance evaluation. It is considered that the fluorine resin was decomposed by the photocatalyst because it did not contain the silicone resin serving as the inorganic binder.
In Comparative Examples 1 and 3, the silicone resin emulsion had a small styrene-equivalent weight average molecular weight of 2000, and in Comparative Example 4, the silicone resin emulsion had a small average particle size of 385 nm. However, peeling and cracking of the coating film occurred in the boiling water resistance test. In Comparative Example 2, the water contact angle after two months of outdoor exposure was as large as 77 °, and did not satisfy the self-purifying property.
Claims (8)
（ｂ）光触媒粒子又は光触媒ゾルと、
（ｃ）水と、
（ｄ）無機顔料と、
を少なくとも含んだ自己浄化性水性塗料組成物であって、
前記（ａ）成分中に分散した粒子の重量平均分子量がポリスチレン換算で５０００以上であることを特徴とする自己浄化性水性塗料組成物。 (A) an aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film;
(B) photocatalyst particles or photocatalyst sol;
(C) water;
(D) an inorganic pigment;
A self-cleaning aqueous coating composition containing at least
The self-cleaning aqueous coating composition, wherein the weight average molecular weight of the particles dispersed in the component (a) is 5,000 or more in terms of polystyrene.
（ｂ）光触媒粒子又は光触媒ゾルと、
（ｃ）水と、
（ｄ）無機顔料と、
を少なくとも含んだ自己浄化性水性塗料組成物であって、
前記（ａ）成分中に分散した粒子の平均粒子径が５００ｎｍ以上であることを特徴とする自己浄化性水性塗料組成物。 (A) an aqueous emulsion of a silicone resin precursor capable of forming a silicone resin film;
(B) photocatalyst particles or photocatalyst sol;
(C) water;
(D) an inorganic pigment;
A self-cleaning aqueous coating composition containing at least
A self-cleaning aqueous coating composition, wherein the particles dispersed in the component (a) have an average particle diameter of 500 nm or more.
A self-cleaning member comprising a coating layer comprising a cured film of the self-cleaning aqueous coating composition according to any one of claims 1 to 7 on a surface of a substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003342361A JP2004143452A (en) | 2002-09-30 | 2003-09-30 | Self-cleaning aqueous coating composition and self- cleaning member |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002285370 | 2002-09-30 | ||
| JP2003342361A JP2004143452A (en) | 2002-09-30 | 2003-09-30 | Self-cleaning aqueous coating composition and self- cleaning member |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2004143452A true JP2004143452A (en) | 2004-05-20 |
Family
ID=32473246
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2003342361A Pending JP2004143452A (en) | 2002-09-30 | 2003-09-30 | Self-cleaning aqueous coating composition and self- cleaning member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2004143452A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225629A (en) * | 2005-01-24 | 2006-08-31 | Shin Etsu Chem Co Ltd | Organosilicone resin emulsion composition and article having formed film of the same composition |
| JP2009084338A (en) * | 2007-09-28 | 2009-04-23 | Dainippon Printing Co Ltd | Water-based paint |
| JP2009279566A (en) * | 2008-05-26 | 2009-12-03 | Asahi Kasei Chemicals Corp | Composition containing photocatalyst |
| KR100987356B1 (en) * | 2008-05-30 | 2010-10-12 | 충북대학교 산학협력단 | Silicone Hybrid Hard Coating Composition for Platic Substrate Comprising Photocatalyst |
| KR100988599B1 (en) | 2008-04-28 | 2010-10-18 | 고경일 | Coating Composite for Imitational Pearl Containing Photocatalyst, Producing Method and Coating Method thereof |
| WO2010150906A1 (en) * | 2009-06-26 | 2010-12-29 | Toto株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| JP2011000717A (en) * | 2009-06-16 | 2011-01-06 | Sumitomo Light Metal Ind Ltd | Aluminum material for interior and exterior and method of manufacturing the same |
| JP2011020061A (en) * | 2009-07-16 | 2011-02-03 | Toto Ltd | Photocatalyst-coated body and photocatalyst coating liquid |
| JP2011020019A (en) * | 2009-07-14 | 2011-02-03 | Toto Ltd | Photocatalyst-coated body and photocatalyst coating liquid |
| US8512855B2 (en) | 2009-06-01 | 2013-08-20 | Toto Ltd. | Self-cleaning member and coating composition |
| TWI483777B (en) * | 2011-11-25 | 2015-05-11 | Nippon Soda Co | A structure for supporting a photocatalyst |
| WO2015133316A1 (en) * | 2014-03-03 | 2015-09-11 | 株式会社鯤コーポレーション | Photocatalyst coating liquid and photocatalyst film using same |
| JP2017036444A (en) * | 2015-08-07 | 2017-02-16 | ダイキン工業株式会社 | Paint and laminate |
| JP2017048509A (en) * | 2015-08-31 | 2017-03-09 | 株式会社鯤コーポレーション | Shroud |
| CN112680064A (en) * | 2020-12-24 | 2021-04-20 | 浩力森涂料（上海）有限公司 | Hollow microsphere fluorocarbon emulsion modified waterborne epoxy resin coating and preparation method thereof |
-
2003
- 2003-09-30 JP JP2003342361A patent/JP2004143452A/en active Pending
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006225629A (en) * | 2005-01-24 | 2006-08-31 | Shin Etsu Chem Co Ltd | Organosilicone resin emulsion composition and article having formed film of the same composition |
| JP2009084338A (en) * | 2007-09-28 | 2009-04-23 | Dainippon Printing Co Ltd | Water-based paint |
| KR100988599B1 (en) | 2008-04-28 | 2010-10-18 | 고경일 | Coating Composite for Imitational Pearl Containing Photocatalyst, Producing Method and Coating Method thereof |
| JP2009279566A (en) * | 2008-05-26 | 2009-12-03 | Asahi Kasei Chemicals Corp | Composition containing photocatalyst |
| KR100987356B1 (en) * | 2008-05-30 | 2010-10-12 | 충북대학교 산학협력단 | Silicone Hybrid Hard Coating Composition for Platic Substrate Comprising Photocatalyst |
| US8512855B2 (en) | 2009-06-01 | 2013-08-20 | Toto Ltd. | Self-cleaning member and coating composition |
| JP2011000717A (en) * | 2009-06-16 | 2011-01-06 | Sumitomo Light Metal Ind Ltd | Aluminum material for interior and exterior and method of manufacturing the same |
| JP5569523B2 (en) * | 2009-06-26 | 2014-08-13 | Ｔｏｔｏ株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| JP2011025234A (en) * | 2009-06-26 | 2011-02-10 | Toto Ltd | Photocatalyst-coated body and photocatalyst coating liquid |
| CN102470358A (en) * | 2009-06-26 | 2012-05-23 | Toto株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| WO2010150906A1 (en) * | 2009-06-26 | 2010-12-29 | Toto株式会社 | Photocatalyst-coated body and photocatalyst coating liquid |
| JP2011020019A (en) * | 2009-07-14 | 2011-02-03 | Toto Ltd | Photocatalyst-coated body and photocatalyst coating liquid |
| JP2011020061A (en) * | 2009-07-16 | 2011-02-03 | Toto Ltd | Photocatalyst-coated body and photocatalyst coating liquid |
| TWI483777B (en) * | 2011-11-25 | 2015-05-11 | Nippon Soda Co | A structure for supporting a photocatalyst |
| US9925531B2 (en) | 2011-11-25 | 2018-03-27 | Nippon Soda Co., Ltd. | Photocatalyst-supporting structure |
| US9919301B2 (en) | 2011-11-25 | 2018-03-20 | Nippon Soda Co., Ltd. | Photocatalyst-supporting structure |
| JPWO2015133316A1 (en) * | 2014-03-03 | 2017-04-06 | 株式会社鯤コーポレーション | Photocatalyst coating liquid and photocatalyst film using the same |
| JP2017042683A (en) * | 2014-03-03 | 2017-03-02 | 株式会社鯤コーポレーション | Photocatalyst coating liquid, and photocatalyst film using the same |
| CN106133078A (en) * | 2014-03-03 | 2016-11-16 | 株式会社鲲 | Photocatalyst coating liquid and use its photocatalyst film |
| WO2015133316A1 (en) * | 2014-03-03 | 2015-09-11 | 株式会社鯤コーポレーション | Photocatalyst coating liquid and photocatalyst film using same |
| WO2017026418A1 (en) * | 2015-08-07 | 2017-02-16 | ダイキン工業株式会社 | Coating material and laminate |
| JP2017036444A (en) * | 2015-08-07 | 2017-02-16 | ダイキン工業株式会社 | Paint and laminate |
| JP2017048509A (en) * | 2015-08-31 | 2017-03-09 | 株式会社鯤コーポレーション | Shroud |
| CN112680064A (en) * | 2020-12-24 | 2021-04-20 | 浩力森涂料（上海）有限公司 | Hollow microsphere fluorocarbon emulsion modified waterborne epoxy resin coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101082721B1 (en) | Photocatalytic coating material, photocatalytic composite material and process for producing the same, self-cleaning water-based coating comopsitions, and self-cleaning member | |
| JP5589267B2 (en) | Self-cleaning coating composition | |
| JP2004143452A (en) | Self-cleaning aqueous coating composition and self- cleaning member | |
| WO2014097309A1 (en) | Stimuli responsive self cleaning coating | |
| WO1998025711A1 (en) | Functional coated articles, method of their production, and application thereof | |
| WO1998041589A1 (en) | Antifouling silicone emulsion coating composition, process for producing the same and antifouling article coated therewith | |
| JP4395886B2 (en) | Water-based paint composition, antibacterial member and coating film forming method | |
| JP3717868B2 (en) | Photocatalytic coating agent, photocatalytic composite material and production method thereof | |
| JP4812902B1 (en) | Antifouling paint composition and method for forming antifouling coating film | |
| JP2009541544A (en) | Antifouling coating containing nanoscale hydrophobic particles and method for producing the same | |
| JP4823045B2 (en) | Water-based photocatalytic composition | |
| JP3985164B2 (en) | Functional coating material, functional composite material and method for producing the same | |
| JP5368720B2 (en) | Photocatalyst coating film and photocatalyst composition | |
| JP2005179686A (en) | Photocatalytic coating agent, photocatalytic composite material and method for producing the same | |
| JP2003342526A (en) | Self-cleaning aqueous coating composition and self- cleaning member | |
| JP2006008902A (en) | Photocatalytic coating composition | |
| KR20030096098A (en) | Polymeric nanoparticle formulations and their use for improving the dirt pick up resistance of a coating | |
| JP2000204287A (en) | Paint composition with low pollution properties | |
| JP5411024B2 (en) | Waterproof material and waterproof layer repair method | |
| JP2005120212A (en) | Functional coating material, functional composite material and method for producing the same | |
| JP4148835B2 (en) | Functional wood | |
| JP2004105920A (en) | Photocatalyst-carrying structural body | |
| JP3860535B2 (en) | Photocatalyst paint | |
| JP3640228B2 (en) | Joint-coated porcelain tile panel and manufacturing method thereof | |
| KR20030096094A (en) | Polymeric nanoparticle formulations and their use in microbe repellent coating applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20060414 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20090810 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091009 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20091109 |