WO2015012021A1 - 水性防汚コート剤、防汚コート層、積層体及び太陽電池モジュール - Google Patents
水性防汚コート剤、防汚コート層、積層体及び太陽電池モジュール Download PDFInfo
- Publication number
- WO2015012021A1 WO2015012021A1 PCT/JP2014/065991 JP2014065991W WO2015012021A1 WO 2015012021 A1 WO2015012021 A1 WO 2015012021A1 JP 2014065991 W JP2014065991 W JP 2014065991W WO 2015012021 A1 WO2015012021 A1 WO 2015012021A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- antifouling coating
- coating agent
- aqueous
- water
- mass
- Prior art date
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 239000003795 chemical substances by application Substances 0.000 title abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 58
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 29
- 230000000694 effects Effects 0.000 claims abstract description 25
- 230000001747 exhibiting effect Effects 0.000 claims abstract description 15
- 125000000962 organic group Chemical group 0.000 claims abstract description 6
- 230000003373 anti-fouling effect Effects 0.000 claims description 193
- 239000011248 coating agent Substances 0.000 claims description 126
- 239000011247 coating layer Substances 0.000 claims description 75
- 239000010419 fine particle Substances 0.000 claims description 54
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000002216 antistatic agent Substances 0.000 claims description 22
- 238000002834 transmittance Methods 0.000 claims description 20
- 239000011521 glass Substances 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims description 16
- 239000011164 primary particle Substances 0.000 claims description 16
- 238000009833 condensation Methods 0.000 claims description 12
- 230000005494 condensation Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 7
- 230000001737 promoting effect Effects 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 6
- 239000000470 constituent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 239000011859 microparticle Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 30
- 239000000463 material Substances 0.000 description 15
- 239000002563 ionic surfactant Substances 0.000 description 14
- 238000000576 coating method Methods 0.000 description 13
- 238000006460 hydrolysis reaction Methods 0.000 description 12
- 239000000356 contaminant Substances 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 239000002202 Polyethylene glycol Substances 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- 239000004094 surface-active agent Substances 0.000 description 9
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 7
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- -1 alkyl phosphates Chemical class 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000049 pigment Substances 0.000 description 6
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 5
- 239000013522 chelant Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000005357 flat glass Substances 0.000 description 4
- 239000012452 mother liquor Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 229920001515 polyalkylene glycol Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- 238000012719 thermal polymerization Methods 0.000 description 2
- CVBWTNHDKVVFMI-LBPRGKRZSA-N (2s)-1-[4-[2-[6-amino-8-[(6-bromo-1,3-benzodioxol-5-yl)sulfanyl]purin-9-yl]ethyl]piperidin-1-yl]-2-hydroxypropan-1-one Chemical compound C1CN(C(=O)[C@@H](O)C)CCC1CCN1C2=NC=NC(N)=C2N=C1SC(C(=C1)Br)=CC2=C1OCO2 CVBWTNHDKVVFMI-LBPRGKRZSA-N 0.000 description 1
- YOBOXHGSEJBUPB-MTOQALJVSA-N (z)-4-hydroxypent-3-en-2-one;zirconium Chemical compound [Zr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O YOBOXHGSEJBUPB-MTOQALJVSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- FDCJDKXCCYFOCV-UHFFFAOYSA-N 1-hexadecoxyhexadecane Chemical compound CCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC FDCJDKXCCYFOCV-UHFFFAOYSA-N 0.000 description 1
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical class CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- YNCDEEFMDXHURQ-UHFFFAOYSA-N aluminum;ethyl 3-oxobutanoate Chemical compound [Al].CCOC(=O)CC(C)=O YNCDEEFMDXHURQ-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RPPBZEBXAAZZJH-UHFFFAOYSA-N cadmium telluride Chemical compound [Te]=[Cd] RPPBZEBXAAZZJH-UHFFFAOYSA-N 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- UIPVMGDJUWUZEI-UHFFFAOYSA-N copper;selanylideneindium Chemical compound [Cu].[In]=[Se] UIPVMGDJUWUZEI-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021421 monocrystalline silicon Inorganic materials 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
- C09D5/1662—Synthetic film-forming substance
- C09D5/1675—Polyorganosiloxane-containing compositions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
- B32B17/10018—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising only one glass sheet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
- B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
- B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
- B32B17/10788—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing ethylene vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/10—Cleaning arrangements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2255/00—Coating on the layer surface
- B32B2255/26—Polymeric coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/02—Polysilicates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/045—Polysiloxanes containing less than 25 silicon atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/017—Additives being an antistatic agent
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Definitions
- the present invention relates to a water-based antifouling coating agent, an antifouling coating layer, and a solar cell module. Specifically, the present invention relates to an aqueous antifouling coating agent for forming an antifouling coating layer for protecting the surface of a solar cell module.
- the antifouling coating layer formed using such an aqueous antifouling coating agent is preferably used as a surface protective material for solar cell modules.
- a solar cell module generally includes a surface protective material disposed on a light receiving surface side (front surface side) on which sunlight is incident and a base material (rear surface side) disposed opposite to the light receiving surface side on which sunlight is incident (back surface side).
- a solar cell in which a solar cell element is sealed with a sealing material is sandwiched between a so-called back sheet).
- the light receiving surface of a solar cell is usually protected by a surface protective material made of glass or weather resistant resin film. Since the light receiving surface of the solar cell is a surface on which sunlight is incident, the surface protective material provided on the light receiving surface side is required to have high light transmittance. Further, the surface protective material provided on the light receiving surface is often exposed to an open-air environment, and is also required to have high weather resistance. On the other hand, surface protection materials for solar cells are susceptible to the effects of heavy dust and soot in the atmosphere, and there is a problem that contaminants tend to adhere. In the surface protective material to which the pollutant adheres, the light transmittance is lowered, which has an adverse effect on the energy conversion efficiency of the solar cell.
- Patent Document 1 discloses a hydrophilic film having high hydrophilicity and an aqueous hydrophilization treatment agent for forming such a film.
- the adhered contaminants can be removed by washing with water.
- there is no means for removing the pollutant during fine weather or dry and there is a problem that the pollutant accumulates if there is no rain.
- the light transmittance is deteriorated, which causes a problem because it adversely affects the energy conversion efficiency of the solar cell.
- the present inventors have an excellent anti-washing property and can prevent the adhesion of contaminants even in fine weather or dry conditions. Studies have been conducted for the purpose of providing an antifouling coating layer and an aqueous antifouling coating agent capable of forming such an antifouling coating layer.
- the present inventors are an aqueous antifouling coating agent having an antistatic agent, which contains a component exhibiting surface activity contained in the aqueous antifouling coating agent. It has been found that by obtaining an aqueous antifouling coating agent having a rate equal to or higher than a predetermined amount, an antifouling coating layer having both excellent water washing and antifouling properties can be formed. Furthermore, the present inventors have provided a solar cell module provided with such an antifouling coating layer in a state where the energy conversion efficiency of the solar cell is good over a long period of time without lowering the light transmittance of the surface. The present invention has been found to be able to be maintained. Specifically, the present invention has the following configuration.
- An aqueous antifouling coating agent in which a siloxane oligomer represented by the following general formula (1), a water component, an antistatic agent, and silica fine particles are mixed.
- An aqueous antifouling coating agent containing 0.01% by mass or more of an active ingredient;
- R 1 to R 4 each independently represents an organic group having 1 to 6 carbon atoms.
- N represents an integer of 2 to 20.
- Agent. [6] The aqueous antifouling coating agent according to any one of [1] to [5], wherein the antistatic agent contains fine metal oxide particles.
- An antifouling coating layer formed by applying and drying the aqueous antifouling coating agent according to any one of [1] to [9].
- the antifouling coating layer according to claim 10 wherein the surface resistance is 1 ⁇ 10 12 ⁇ / ⁇ or less.
- a laminate in which the antifouling coating layer according to any one of [10] to [13] is laminated on a glass layer.
- a solar cell module having the laminate according to [14].
- the aqueous antifouling coating agent of the present invention it is possible to form an antifouling coating layer having both excellent water washing and antifouling properties. That is, when the aqueous antifouling coating agent of the present invention is used, it is possible to obtain an antifouling coating layer in which contaminants are easily washed away by rainwater or the like during rainy weather and adhesion of contaminants is suppressed during sunny weather or drying.
- the antifouling coating layer thus obtained is preferably used as the antifouling layer on the surfaces of various substrates and particularly on the solar cell surface protective material.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the present invention relates to an aqueous antifouling coating agent in which a siloxane oligomer represented by the following general formula (1), a water component, an antistatic agent, and silica fine particles are mixed.
- the aqueous antifouling coating agent contains 0.01% by mass or more of a component exhibiting surface activity.
- a coating layer rich in antistatic properties and hydrophilicity can be formed on the surface of the target substrate. Thereby, the antifouling coating layer which has washing-washing property and antifouling property (stain adhesion resistance) can be obtained.
- R 1 to R 4 each independently represents an organic group having 1 to 6 carbon atoms.
- N represents an integer of 2 to 20.
- R 1 to R 4 each independently represents an organic group having 1 to 6 carbon atoms. Each of R 1 to R 4 may be the same or different. R 1 to R 4 may be linear or may have branches.
- the organic group represented by R 1 ⁇ R 4 is an alkyl group having 1 to 6 carbon atoms, the alkyl group represented by R 1 ⁇ R 4, for example, a methyl group, an ethyl group, a propyl group, an isopropyl Group, n-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, cyclohexyl group and the like.
- the hydrolyzability of the siloxane oligomer can be enhanced by setting the alkyl group represented by R 1 to R 4 to have 1 to 6 carbon atoms.
- the alkyl group represented by R 1 to R 4 In view of ease of hydrolysis, an alkyl group having 1 to 4 carbon atoms is more preferable, and an alkyl group having 1 or 2 carbon atoms is particularly preferable.
- n is an integer of 2 to 20.
- the viscosity of the solution containing the hydrolyzate can be adjusted to an appropriate range, and the reactivity of the siloxane oligomer can be controlled within a preferable range.
- n exceeds 20, the viscosity of the hydrolyzate solution becomes too high and the handling tends to be difficult.
- n may be 2 to 20, preferably 3 to 15, and more preferably 5 to 10.
- the siloxane oligomer used in the present invention is mixed with a water component, so that at least a part is hydrolyzed.
- a hydrolyzate of a siloxane oligomer can be obtained by reacting a siloxane oligomer with a water component and changing an alkoxy group bonded to silicon to a hydroxyl group. It is not always necessary for all alkoxy groups to react during hydrolysis, but it is preferable that as many alkoxy groups as possible be hydrolyzed in order for the coating agent to exhibit hydrophilicity after coating.
- the minimum amount of water component required for hydrolysis is equal to the molar amount of the alkoxy group of the siloxane oligomer, but it is preferable that a large excess amount of water is present to facilitate the reaction.
- This hydrolysis reaction proceeds even at room temperature, but may be heated to promote the reaction. A longer reaction time is preferable because the reaction proceeds more.
- a hydrolyzate can be obtained in about half a day in the presence of a catalyst described later.
- the hydrolysis reaction is a reversible reaction, and when water is removed from the system, the hydrolyzate of the siloxane oligomer starts to condense between the hydroxyl groups. Accordingly, when an aqueous solution of a hydrolyzate is obtained by reacting a siloxane oligomer with a large excess of water, it is preferable to use the hydrolyzate as a raw material for the coating agent as it is without forcibly isolating the hydrolyzate therefrom.
- the aqueous antifouling coating agent of the present invention has a water component as its main solvent.
- a water component as a solvent reduces the burden on workers' health and the environment during handling, and prevents the hydrolysis of the hydrolyzate of the siloxane oligomer in the liquid during storage. it can.
- the water component used by this invention contains water as a main component, Preferably, it contains 30 mass% or more of water, More preferably, it contains 40 mass% or more of water.
- the water component may contain an organic solvent or compound in addition to water. For example, you may have a hydrophilic organic solvent.
- hydrophilic organic solvent By having a hydrophilic organic solvent, it is possible to obtain uniform effects by reducing the surface tension, and the ratio of the low-boiling solvent is increased, so that drying is facilitated.
- a hydrophilic organic solvent Methanol, ethanol, isopropanol, a butanol, acetone, ethylene glycol, ethyl cellosolve etc. are mentioned. Alcohols are preferable, and ethanol or isopropanol is more preferable in view of environmental burden and burden on workers' health.
- the ratio of the solid content mass to the total mass of the aqueous antifouling coating agent of the present invention is preferably 0.1 to 30%, more preferably 0.2 to 20%, and more preferably 0.5 to 10%. More preferably.
- the content of the siloxane oligomer is preferably 3 to 70% by mass, more preferably 5 to 60% by mass, and more preferably 10 to 50% by mass with respect to the total solid content of the aqueous antifouling coating agent. % Is more preferable.
- the aqueous antifouling coating agent of the present invention has an antistatic agent.
- the antistatic agent suppresses adhesion of contaminants by imparting antistatic properties to the antifouling coating layer.
- Examples of the antistatic agent for imparting antistatic properties include ionic surfactants and metal oxide fine particles.
- the antistatic agent any one of an ionic surfactant and metal oxide fine particles may be used, or two or more of them may be used. Since the ionic surfactant has the property of segregating and acting in the vicinity of the outermost surface of the coating agent after coating, the effect can be exhibited with a smaller amount of addition.
- the metal oxide fine particles need to be added in a relatively large amount in order to provide antistatic properties, but since they are inorganic substances, the durability of the antifouling coating layer can be enhanced.
- ionic surfactants include anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, and alkyl phosphates, and cationic surfactants such as alkyl trimethyl ammonium salts and dialkyl dimethyl ammonium salts, Examples include amphoteric surfactants such as alkylcarboxybetaines.
- anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, and alkyl phosphates
- cationic surfactants such as alkyl trimethyl ammonium salts and dialkyl dimethyl ammonium salts
- amphoteric surfactants such as alkylcarboxybetaines.
- the content of the component exhibiting ionic surface activity is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, with respect to the total mass of the aqueous antifouling coating agent. Is more preferably 0.5% by mass or less.
- the metal oxide fine particles used as the antistatic agent are not particularly limited, and examples thereof include tin oxide fine particles, antimony-doped tin oxide fine particles, tin-doped indium oxide fine particles, and zinc oxide fine particles.
- metal oxide fine particles having different sizes, shapes, and materials may be mixed and used.
- the oxide particles have a large refractive index, and if the particle size is large, loss due to excessive scattering of transmitted light occurs. Therefore, the primary particle size is preferably 100 nm or less, and more preferably 50 nm or less. More preferably, it is 30 nm or less.
- the shape of the particles is not particularly limited, and may be spherical, plate-shaped, or needle-shaped.
- the primary particle size of the metal oxide fine particles may be obtained from a photograph obtained by observing the dispersed particles with a transmission electron microscope.
- the projected area of the particles is obtained, and the equivalent circle diameter is obtained therefrom, and the average particle size (average primary particle size) is obtained.
- the average particle diameter in this specification can be calculated by measuring the projected area of 300 or more particles and obtaining the equivalent circle diameter.
- the content of the metal oxide fine particles is preferably 70% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass or less with respect to the total solid mass of the aqueous antifouling coating agent. More preferably.
- the content of the metal oxide fine particles is preferably 30% by mass or less, more preferably 20% by mass or less, and more preferably 10% by mass or less with respect to the total mass of the aqueous antifouling coating agent. Is more preferable.
- the ratio of the metal oxide fine particles within the above range, the dispersibility of the metal oxide fine particles in the aqueous antifouling coating agent can be enhanced, and the antistatic property can be obtained without causing disadvantages such as agglomeration of itself. Can be granted.
- the aqueous antifouling coating agent of the present invention has silica fine particles.
- the silica fine particles have a function of enhancing the physical resistance of the antifouling coating layer formed by applying an aqueous antifouling coating agent and further exerting hydrophilicity. That is, the silica fine particles play a role as a hard filler and contribute to further hydrophilicity by the hydroxyl groups on the surface.
- the shape of the silica fine particles that can be used in the present invention is not particularly limited, and examples thereof include a spherical shape, a plate shape, a needle shape, and a necklace shape.
- the primary particle size of the silica fine particles is preferably 100 nm or less, more preferably 50 nm or less, More preferably, it is 30 nm or less.
- Silica fine particles having different sizes and shapes may be mixed and used.
- the primary particle size of the silica fine particles can be measured by the same measurement method as the primary particle size of the metal oxide fine particles described above.
- the content of the silica fine particles is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, and more preferably 20 to 80% by mass with respect to the total solid mass of the aqueous antifouling coating agent. Is more preferable.
- the content of the silica fine particles is preferably 30% by mass or less, more preferably 20% by mass or less, and further preferably 10% by mass or less with respect to the total mass of the aqueous antifouling coating agent. preferable.
- the proportion of silica fine particles within the above range, the dispersibility of the silica fine particles in the aqueous antifouling coating agent can be increased, and the above antifouling coating layer can be formed without causing disadvantages such as aggregation of itself. can do.
- the aqueous antifouling coating agent of the present invention contains a component exhibiting surface activity.
- the component exhibiting surface activity may be a surface active component derived from an antistatic agent.
- an antistatic agent does not have surfactant component, it is preferable to contain surfactant. That is, in the present invention, the component exhibiting surface activity includes at least one of a surfactant component derived from an antistatic agent and a surfactant component derived from a surfactant.
- any of nonionic surfactants, ionic (anionic, cationic and amphoteric) surfactants can be suitably used.
- the ionic surfactant added as the antistatic agent may work to improve wettability.
- an ionic surfactant is added in excess, the electrolytic mass in the system increases and aggregation of silica fine particles is caused. Therefore, when an ionic surfactant is used as an antistatic agent, a nonionic interface is used. It is preferable to further include a component showing activity.
- the component which shows nonionic surface activity does not need to be used together with an ionic surfactant, and the component which shows nonionic surface activity may be used independently as a surface active component.
- nonionic surfactants include polyalkylene glycol monoalkyl ethers, polyalkylene glycol monoalkyl esters, polyalkylene glycol monoalkyl esters / monoalkyl ethers, and the like. More specifically, polyethylene glycol monolauryl ether, polyethylene glycol monostearyl ether, polyethylene glycol monocetyl ether, polyethylene glycol monolauryl ester, polyethylene glycol monostearyl ester and the like can be mentioned.
- the compounds exemplified in the section of the antistatic agent can be appropriately used.
- the component exhibiting the surface activity may be contained in an amount of 0.01% by mass or more, preferably 0.02% by mass or more, based on the total mass of the aqueous antifouling coating agent. It is more preferable that 0.03 mass% or more is contained.
- the surface active component within the above range, wettability can be improved, and applicability of the aqueous antifouling coating agent can be improved.
- the amount of the surface active component is preferably 10% or less, more preferably 8% or less, and further preferably 5% or less, based on the total solid mass of the aqueous antifouling coating agent.
- the aqueous antifouling coating agent of the present invention preferably further contains a catalyst that promotes condensation of the siloxane oligomer.
- a catalyst that promotes condensation of the siloxane oligomer.
- an antifouling coating layer having excellent durability can be formed.
- the water-based antifouling coating agent is dried after being applied to remove moisture, whereby the hydroxyl groups (at least part of) of the hydrolyzate of the siloxane oligomer are condensed with each other to form a bond and form a stable film ( (Anti-fouling coat layer).
- the antifouling coating layer can be formed more rapidly by having a catalyst that promotes the condensation of the siloxane oligomer.
- the catalyst for promoting the condensation of the siloxane oligomer that can be used in the present invention is not particularly limited, and examples thereof include an acid catalyst, an alkali catalyst, and an organometallic catalyst.
- the acid catalyst include nitric acid, hydrochloric acid, sulfuric acid, acetic acid, chloroacetic acid, formic acid, oxalic acid, toluenesulfonic acid and the like.
- the alkali catalyst include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide and the like.
- organometallic catalysts include aluminum bis (ethylacetoacetate) mono (acetylacetonate), aluminum tris (acetylacetonate), aluminum chelate compounds such as aluminum ethylacetoacetate diisopropylate, zirconium tetrakis (acetylacetonate) , Zirconium chelate compounds such as zirconium bis (butoxy) bis (acetylacetonate), titanium chelate compounds such as titanium tetrakis (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate) and dibutyltin diacetate, dibutyltin dilaurate, And organotin compounds such as dibutyltin dioctiate.
- the type of the catalyst is not particularly limited, but an organometallic catalyst is preferable, and an aluminum chelate compound or a zirconium chelate compound is particularly preferable.
- the content of the catalyst for promoting the condensation of the siloxane oligomer is preferably 0.1 to 20% by mass, and preferably 0.2 to 15% by mass with respect to the total solid content of the aqueous antifouling coating agent. Is more preferably 0.3 to 10% by mass. It is possible to form an antifouling coating layer having an appropriate hardness and durability, which is preferable to keep the catalyst content within the above range. In addition, the antifouling coating layer can be formed at an appropriate speed.
- stimulates condensation of a siloxane oligomer is useful also with respect to the hydrolysis of the siloxane oligomer mentioned above.
- the hydrolysis reaction and condensation reaction of the alkoxy group bonded to silicon of the siloxane oligomer are in an equilibrium relationship, and the water proceeds in the direction of hydrolysis when the amount of water in the system is large, and the direction of condensation when the amount of water is small. Since the catalyst for promoting the condensation reaction of the alkoxy group promotes both directions of the reaction, the hydrolysis reaction can be promoted in a state where there is a lot of water in the system. The presence of the catalyst makes it possible to more reliably proceed with hydrolysis of the siloxane oligomer under milder conditions.
- the catalyst used for the hydrolysis reaction of the siloxane oligomer is kept in the system as it is to be used as a component of the aqueous antifouling coating agent and used as it is as a catalyst for condensation of the siloxane oligomer.
- the aqueous antifouling coating agent of the present invention may have additives such as preservatives as appropriate in addition to the above.
- the water-based antifouling coating agent of the present invention is characterized in that it does not require light irradiation or high-temperature heat treatment when forming a film after coating, so a photopolymerization initiator or thermal polymerization initiator corresponding to them is required. And not. Rather, in view of the storage stability of the coating agent, it is preferable not to have a photopolymerization initiator or a thermal polymerization initiator.
- the antifouling coating layer can be formed from the aqueous antifouling coating agent by a simple method.
- the antifouling coating agent of the present invention is mostly composed of silicon and oxygen and has a low carbon content.
- the carbon content for example, when the antifouling coating layer after coating and drying is placed in a harsh environment such as the surface of a solar cell, the effects of light and heat are minimized. Is possible.
- the proportion of carbon in the total solid content is preferably 3% by mass or less, more preferably 2.5% by mass or less, and further preferably 2% by mass or less. preferable.
- the carbon compound contained in the aqueous antifouling coating agent as a minimum is preferably of low molecular weight.
- the content of the organic compound having a molecular weight of 1100 or more contained in the total solid content of the aqueous antifouling coating agent is preferably 0.2% by mass or less, more preferably 0.1% by mass. Preferably, it is 0% by mass.
- the aqueous antifouling coating agent of the present invention is obtained by mixing a siloxane oligomer, a water component, an antistatic agent, and silica fine particles.
- the siloxane oligomer is preferably first mixed with a water component, and a hydrolyzate of the siloxane oligomer is preferably obtained.
- a catalyst for promoting condensation of the siloxane oligomer it is preferable to add a catalyst for promoting condensation of the siloxane oligomer. In this way, a hydrolyzate solution of siloxane oligomer is obtained.
- An antistatic agent and silica fine particles are further added to the siloxane oligomer hydrolyzate solution.
- a surfactant as a wettability improver.
- a catalyst for promoting condensation of the siloxane oligomer may be added.
- part or all of the antistatic agent and the surfactant may be added in the step of obtaining a hydrolyzate of siloxane oligomer.
- the silica fine particles may aggregate depending on the pH and concentration of coexisting components. Accordingly, the silica fine particles may be added in the latter half of the preparation, preferably at the end.
- the pH of the dispersion and the pH of the coating agent are preferably both acidic or basic.
- the antifouling coating layer of the present invention can be formed by applying the aqueous antifouling coating agent described above and drying it.
- the object to which the aqueous antifouling coating agent is applied is not particularly limited, and is suitably used on the surface of various supports such as glass, resin, metal and ceramics.
- a glass layer is used as the base material, condensation of hydroxyl groups on silicon occurs even between the hydroxyl groups on the glass surface, whereby a laminate having excellent adhesion can be obtained.
- the antifouling coating layer of the present invention is preferably provided, for example, on the glass surface on the light receiving surface side of the solar cell module, and is useful as an antifouling coating layer for solar cell modules.
- the method for applying the aqueous antifouling coating agent of the present invention is not particularly limited, and examples thereof include spray coating, brush coating, roller coating, bar coating, and dip coating.
- the drying method after coating may be performed at room temperature, or may be performed at 40 to 120 ° C. for about 1 to 30 minutes.
- the surface of the antifouling coating layer is preferably antistatic and hydrophilic. Thereby, adhesion of contaminants can be suppressed, and even when contaminants adhere to the surface of the antifouling coating layer, the stains can be washed away (washed with water).
- the surface resistance of the antifouling coating layer is preferably 1 ⁇ 10 12 ⁇ / ⁇ or less, more preferably 1 ⁇ 10 11 ⁇ / ⁇ or less, and preferably 1 ⁇ 10 10 ⁇ / ⁇ or less. Further preferred. By setting the surface resistance of the antifouling coating layer within the above range, sufficient antifouling properties can be imparted to the antifouling coating layer.
- the water contact angle of the antifouling coating layer is preferably 40 ° or less, more preferably 30 ° or less, and further preferably 25 ° or less. By setting the water contact angle of the antifouling coating layer within the above range, sufficient hydrophilicity can be imparted to the antifouling coating layer.
- the antifouling coating layer of the present invention has sufficient light transmittance.
- the average integrating sphere transmittance at a wavelength ( ⁇ ) of 300 nm to 1200 nm of the antifouling coating layer of the present invention is preferably 90% or more, and more preferably 95% or more.
- the integral sphere transmittance of the antifouling coating layer was determined by measuring the integrating sphere transmittance of the glass provided with the antifouling coating layer, and the integrated sphere transmittance of the glass not provided with the antifouling coating layer as a reference.
- the integrating sphere transmittance can be measured by using a transmission spectrophotometer with an integrating sphere.
- a device in which an integrating sphere attachment device (ISR-2200, Shimadzu Corp.) is connected to an ultraviolet-visible infrared spectrophotometer (UV-3600, Shimadzu Corp.), an ultraviolet-visible infrared spectrophotometer (UV -3600, Shimadzu Corporation) and a multipurpose large sample chamber (MPC-3100, Shimadzu Corporation) can be used for measurement.
- the average transmittance of the antifouling coating layer of the present invention at a wavelength ( ⁇ ) of 300 nm to 1200 nm is preferably 70% or more, and more preferably 80% or more.
- the transmittance of the antifouling coating layer is determined by measuring the integrating sphere transmittance of the glass provided with the antifouling coating layer as the integrating sphere transmittance, and the integrating sphere transmittance of the glass not provided with the antifouling coating layer as a reference. Asked.
- the transmittance can be measured by, for example, a self-recording spectrophotometer (UV2400-PC, manufactured by Shimadzu Corporation).
- the solar cell module of the present invention has a laminate including the above-described antifouling coating layer.
- the solar cell module of the present invention is a solar cell element that converts light energy of sunlight into electrical energy, between a transparent substrate provided on the side on which sunlight is incident and a polyester film (solar cell backsheet). It is arranged and arranged.
- the substrate and the polyester film can be formed by sealing with a resin (so-called sealing agent) such as an ethylene-vinyl acetate copolymer.
- Examples of the substrate provided on the side on which sunlight is incident include a glass substrate, a transparent resin such as an acrylic resin, and the like. Among these, a glass substrate is preferably used.
- Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, and II Various known solar cell elements such as -VI group compound semiconductor systems can be applied.
- An antifouling coating agent AS-1 was produced.
- the produced aqueous antifouling coating agent was applied onto a white glass plate using a roller and dried at room temperature for 1 hour to obtain an antifouling coating layer-containing laminate.
- the surface resistance of the prepared antifouling coating layer was measured and found to be 1.7 ⁇ 10 9 ⁇ / ⁇ . Further, when the integrated sphere transmittance of the prepared antifouling coating layer was measured using white plate glass used for coating as a reference, it was 95% or more on average in the wavelength range of 300 nm to 1200 nm.
- Example 2 An aqueous antifouling coating agent AS-2 of Example 2 was prepared in the same manner as in Example 1 except that the amount of sodium di (2-ethylhexyl) sulfosuccinate was changed from 0.0011 g to 0.011 g in Example 1. .
- Example 3 An aqueous antifouling coating agent AS-3 of Example 3 was prepared in the same manner as in Example 1 except that the amount of sodium di (2-ethylhexyl) sulfosuccinate was changed from 0.0011 g to 0.11 g in Example 1. .
- Example 4 An aqueous antifouling coating agent AS-4 of Example 4 was produced in the same manner as in Example 1 except that the amount of sodium di (2-ethylhexyl) sulfosuccinate was changed from 0.0011 g to 1.1 g in Example 1. .
- Comparative Example 1 An aqueous antifouling coating agent AS-21 of Comparative Example 1 was produced in the same manner as in Example 1 except that 0.0011 g of sodium di (2-ethylhexyl) sulfosuccinate was not added in Example 1.
- the hydrophilicity was evaluated by the contact angle of water (40 ° or less passed). For stain adhesion resistance, the process of sprinkling the natural ocher pigment made by Holbein onto the antifouling coating layer and then hitting the back surface to remove it was repeated 5 times, and the amount of adhered dirt was visually evaluated (5 stages A to E). Evaluation, B or higher pass).
- B The ocher pigment adheres to 10% or less of the antifouling coating layer surface.
- C The ocher pigment adheres to 50% or less of the antifouling coating layer surface.
- D The ocher pigment adheres to almost the entire surface of the antifouling coating layer, but the transparency is maintained.
- E Ocher pigment adheres to almost the entire surface of the antifouling coating layer, and a part or all of it is opaque.
- the samples prepared using the water-based antifouling coating agents AS-1 to 3 of the examples were colorless and transparent, had a hard and uniform coating film, and were excellent in both hydrophilicity and antifouling properties (dirt adhesion resistance).
- the aqueous antifouling coating agent AS-4 an agglomerate considered to be derived from silica is generated in the state of the aqueous antifouling coating agent, and the sample prepared using AS-4 is expected to be a foreign substance
- hydrophilicity and antifouling properties were barely passed.
- the glass produced using the aqueous antifouling coating agent AS-11 of Comparative Example 1 had good hydrophilicity but insufficient antifouling properties.
- Example 5 In the same manner as in Example 1, except that 1.20 g of a 50% dispersion of tin oxide fine particles (primary particle size of 15 to 25 nm) was used instead of 0.0022 g of sodium di (2-ethylhexyl) sulfosuccinate in Example 1. An aqueous antifouling coating agent AS-5 of Example 5 was produced.
- Example 6 A 30% dispersion of zinc oxide / antimony oxide composite oxide fine particles (primary particle size 15 to 25 nm) instead of 1.20 g of a 50% dispersion of tin oxide fine particles (primary particle size 15 to 25 nm) in Example 5.
- a water-based antifouling coating agent AS-6 of Example 6 was produced in the same manner as Example 5 except that 00 g was used.
- Example 7 In Example 5, 2.00 g of a 30% dispersion of gallium-doped zinc oxide fine particles (primary particle size 20 to 40 nm) was used instead of 1.20 g of the 50% dispersion of tin oxide fine particles (primary particle size 15 to 25 nm).
- a water-based antifouling coating agent AS-7 of Example 7 was produced in the same manner as Example 5 except for the above.
- Example 8 In Example 5, 1.20 g of a 20% dispersion of tin oxide fine particles (average primary particle size 150 nm) was used instead of 1.20 g of a 50% dispersion of tin oxide fine particles (primary particle size 15 to 25 nm). In the same manner as in Example 5, an aqueous antifouling coating agent AS-8 of Example 8 was produced.
- the sample prepared using the aqueous antifouling coating agent AS-5 to 7 of the example had a colorless, transparent, hard and uniform coating film, and was hydrophilic and antifouling like the sample prepared using AS-1. Both sexes were excellent.
- the sample prepared using the aqueous antifouling coating agent AS-8 was slightly colored, but showed excellent performance in terms of hydrophilicity and antifouling properties.
- Example 9 An aqueous antifouling coating agent AS-9 of Example 9 was produced in the same manner as in Example 1 except that a 1% isopropanol solution of aluminum bis (ethylacetoacetate) mono (acetylacetonate) was not added in Example 1. .
- Example 10 In Example 1, the same procedure as in Example 1 was carried out except that the amount of polyethylene glycol monolauryl ether (the number of repetitions of ethylene oxide part 15) added to the coating agent mother liquor was changed from 0.0056 g to 0.11 g. The aqueous antifouling coating agent AS-10 of Example 10 was produced.
- Example 11 In Example 1, instead of 0.0056 g of polyethylene glycol monolauryl ether (ethylene oxide part repeat number 15, molecular weight 848) added to the coating agent mother liquor, stearic acid polyoxyethylene stearyl ether (ethylene oxide part repeat number) 15 and molecular weight 1210) A water-based antifouling coating agent AS-11 of Example 11 was produced in the same manner as in Example 1 except that 0.11 g was used.
- the sample produced using the aqueous antifouling coating agent AS-9 to 11 of the example had a colorless and transparent coating film although it was slightly inferior to the sample produced using AS-1. Both hydrophilicity and dirt adhesion resistance were excellent.
- the aqueous antifouling coating agent of the present invention is used, it is possible to form an antifouling coating layer having both excellent water washing and antifouling properties.
- the antifouling coating layer thus obtained is preferably used as the antifouling layer on the surfaces of various substrates and particularly on the surface protection material of solar cell modules, and has high industrial applicability.
Abstract
Description
具体的に、本発明は、以下の構成を有する。
[2]シロキサンオリゴマーの縮合を促進する触媒をさらに含む[1]に記載の水性防汚コート剤。
[3]イオン性の界面活性を示す成分を含む[1]又は[2]に記載の水性防汚コート剤。
[4]ノニオン性の界面活性を示す成分を含む[1]~[3]のいずれかに記載の水性防汚コート剤。
[5]イオン性の界面活性を示す成分の含有率は、水性防汚コート剤の全質量に対して、1.0質量%以下である[3]又は[4]に記載の水性防汚コート剤。
[6]帯電防止剤が金属酸化物微粒子を含む[1]~[5]のいずれかに記載の水性防汚コート剤。
[7]水性防汚コート剤中に含まれる全固形分中の炭素の割合が3質量%以下である[1]~[6]のいずれかに記載の水性防汚コート剤。
[8]金属酸化物微粒子の一次粒径が100nm以下である[6]又は[7]に記載の水性防汚コート剤。
[9]水性防汚コート剤中に含まれる分子量1100以上の有機化合物の含有率は、0.2質量%以下である[1]~[8]のいずれかに記載の水性防汚コート剤。
[10][1]~[9]のいずれかに記載の水性防汚コート剤を塗布・乾燥して形成する防汚コート層。
[11]表面抵抗が1×1012Ω/□以下である請求項10に記載の防汚コート層。
[12]表面における水接触角が40°以下である[10]又は[11]に記載の防汚コート層。
[13]波長300nm~1200nmにおける平均の積分球透過率が95%以上である[10]~[12]のいずれかに記載の防汚コート層。
[14][10]~[13]のいずれかに記載の防汚コート層をガラス層の上に積層した積層体。
[15][14]に記載の積層体を有する太陽電池モジュール。
本発明は、下記一般式(1)で表されるシロキサンオリゴマーと、水成分と、帯電防止剤と、シリカ微粒子とを混合した水性防汚コート剤に関する。ここで、水性防汚コート剤には、界面活性を示す成分が0.01質量%以上含まれている。本発明では、このような水性防汚コート剤を用いることにより、対象基材の表面に帯電防止性と親水性に富んだコート層を形成することができる。これにより、水洗洗浄性と防汚性(汚れ付着耐性)を兼ね備えた防汚コート層を得ることができる。
なお、加水分解反応は可逆反応であり、系から水が除かれるとシロキサンオリゴマーの加水分解物はヒドロキシル基間で縮合を開始してしまう。従って、シロキサンオリゴマーに大過剰の水を反応させて加水分解物の水溶液を得た場合、そこから加水分解物を無理に単離せずに水溶液のままコート剤の原料として用いることが好ましい。
なお、本発明で用いる水成分は、水を主成分として含むものであり、好ましくは、水を30質量%以上含むものであり、より好ましくは、水を40質量%以上含むものである。また、水成分は、水の他に有機溶媒や化合物を含有するものであってもよい。例えば、親水性の有機溶媒を有していてもよい。親水性の有機溶媒を有していることで表面張力低減により均一な塗布が可能となったり、低沸点溶媒の比率が高まるために乾燥が容易になるなどの効果が得られる。親水性有機溶媒としては特に限定されないが、メタノール、エタノール、イソプロパノール、ブタノール、アセトン、エチレングリコール、エチルセロソルブなどが挙げられる。環境負荷や作業者の健康への負荷を考えるとアルコール類が好ましく、エタノールまたはイソプロパノールがより好ましい。
また、シロキサンオリゴマーの含有率は、水性防汚コート剤の全固形分質量に対して、3~70質量%であることが好ましく、5~60質量%であることがより好ましく、10~50質量%であることがさらに好ましい。シロキサンオリゴマーの含有率を上記範囲内とすることにより、適度な硬度と耐久性を有する防汚コート層を形成することができる。
本発明の水性防汚コート剤は、帯電防止剤を有している。帯電防止剤は、防汚コート層に帯電防止性を付与することで、汚染物質の付着を抑制する。帯電防止性を付与するための帯電防止剤としては、例えばイオン性の界面活性剤や金属酸化物微粒子などが挙げられる。帯電防止剤としては、イオン性の界面活性剤や金属酸化物微粒子のいずれか1種が用いられてもよく、これらを混合した2種以上のものが用いられてもよい。
イオン性の界面活性剤は塗布後のコート剤の最表面付近に偏析して作用する性質があるため、より少量の添加で効果を発揮できる。一方、金属酸化物微粒子は帯電防止性を与えるために比較的多量の添加が必要だが、無機物であるために防汚コート層の耐久性を高めることができる。
なお、イオン性の界面活性剤は過剰に加えると系内の電解質量が増えてシリカ微粒子の凝集を招くことが知られている。このため、イオン性の界面活性剤はシリカ微粒子と併用されることは避けられてきた。しかし、本発明では、驚くべきことに、このようなイオン性の界面活性剤を水性防汚コート剤に添加した場合、防汚コート層の防汚性を高め得ることが見出された。このように、本発明では、イオン性の界面活性剤を添加することにより、より効果的に、防汚性と水洗洗浄性を高めることに成功した。
金属酸化物微粒子の一次粒径は、分散した粒子を透過型電子顕微鏡により観察し、得られた写真から求めてもよい。粒子の投影面積を求め、そこから円相当径を求め平均粒径(平均一次粒径)とする。本明細書における平均粒径は、300個以上の粒子について投影面積を測定して、円相当径を求めて算出することができる。
なお、金属酸化物微粒子の形状が球状ではない場合にはその他の方法、例えば動的光散乱法を用いて求めてもよい。
一方で金属酸化物微粒子の含有率は水性防汚コート剤の全質量に対しては30質量%以下であることが好ましく、20質量%以下であることがより好ましく、10質量%以下であることがさらに好ましい。金属酸化物微粒子が占める割合を上記範囲内とすることにより水性防汚コート剤中における金属酸化物微粒子の分散性を高めることができ、自身の凝集などのデメリットを生じることなしに帯電防止性を付与することができる。
本発明の水性防汚コート剤は、シリカ微粒子を有している。シリカ微粒子は、水性防汚コート剤を塗布し形成した防汚コート層の物理耐性を高めつつ、さらに親水性を発揮させる機能を有する。すなわち、シリカ微粒子は硬いフィラーとしての役割を果たすと共に、その表面のヒドロキシル基によってさらなる親水性に寄与する。本発明で用いることができるシリカ微粒子の形状は特に限定されず、球状、板状、針状、ネックレス状などが挙げられる。
シリカ微粒子の一次粒径は、上述した金属酸化物微粒子の一次粒径と同様の測定方法で計測することができる。
一方でシリカ微粒子の含有率は水性防汚コート剤の全質量に対しては30質量%以下であることが好ましく、20質量%以下であることがより好ましく、10質量%以下であることがさらに好ましい。シリカ微粒子が占める割合を上記範囲内とすることにより水性防汚コート剤中におけるシリカ微粒子の分散性を高めることができ、自身の凝集などのデメリットを生じることなしに上記の防汚コート層を形成することができる。
本発明の水性防汚コート剤は、界面活性を示す成分を含む。本発明では、界面活性を示す成分は、帯電防止剤由来の界面活性成分であってもよい。また、帯電防止剤が界面活性成分を有さない場合は、界面活性剤を含有することが好ましい。つまり、本発明では、界面活性を示す成分は、帯電防止剤由来の界面活性成分及び界面活性剤由来の界面活性成分の少なくとも一方を含むものである。
このような界面活性成分を含有することにより、水性防汚コート剤の塗布性を高めることができる。また、界面活性成分の存在によりコート剤の表面張力が引き下げられ、より均一な塗布が可能となる。このような目的に対してはノニオン性界面活性剤、イオン性(アニオン性、カチオン性、両性)界面活性剤などいずれも好適に用いることができる。なお、上述した帯電防止剤としてイオン性界面活性剤を用いている場合には、帯電防止剤として添加したイオン性界面活性剤が濡れ性向上に対して働いてもよい。
但し、イオン性の界面活性剤は過剰に加えると系内の電解質量が増えてシリカ微粒子の凝集を招くことから、帯電防止剤としてイオン性の界面活性剤を用いる場合には、ノニオン性の界面活性を示す成分をさらに含むことが好ましい。なお、ノニオン性の界面活性を示す成分は、イオン性の界面活性剤と併用される必要はなく、界面活性成分として、ノニオン性の界面活性を示す成分が単独で用いられてもよい。
本発明の水性防汚コート剤は、シロキサンオリゴマーの縮合を促進する触媒をさらに含むことが好ましい。このような触媒を用いることにより、耐久性に優れた防汚コート層を形成することができる。なお、本発明では、水性防汚コート剤を塗布後に乾燥させて水分をなくすことによりシロキサンオリゴマーの加水分解物が持つヒドロキシル基(の少なくとも一部)が互いに縮合して結合を作り安定な皮膜(防汚コート層)となる。この際に、シロキサンオリゴマーの縮合を促進する触媒を有することで、この防汚コート層の形成をより速やかに進めることが可能となる。
この際、シロキサンオリゴマーの加水分解反応に用いた触媒をそのまま系内に留めて水性防汚コート剤の成分とし、そのままシロキサンオリゴマーの縮合用の触媒として使用すると効率が良い。
本発明の水性防汚コート剤は、上記の他に防腐剤などの添加剤を適宜有していても良い。一方で本発明の水性防汚コート剤は、塗布後の膜形成時に光照射や高温熱処理を必要としないことに特徴があることから、それらに対応した光重合開始剤や熱重合開始剤を必要としない。むしろコート剤の貯蔵安定性を考えると、逆に光重合開始剤や熱重合開始剤を有しないことが好ましい。このように、本発明では、簡便な方法で水性防汚コート剤から防汚コート層を形成すうことができる。
本発明の水性防汚コート剤は、シロキサンオリゴマーと、水成分と、帯電防止剤と、シリカ微粒子を混合することによって得られる。シロキサンオリゴマーは、まず水成分と混合することが好ましく、シロキサンオリゴマーの加水分解体を得ることが好ましい。なお、この際、シロキサンオリゴマーの縮合を促進する触媒を添加することが好ましい。このようにして、シロキサンオリゴマーの加水分解物溶液が得られる。
シロキサンオリゴマーの加水分解物溶液には、さらに、帯電防止剤とシリカ微粒子が添加される。ここでは、濡れ性向上剤として界面活性剤をさらに添加することが好ましい。なお、この際にシロキサンオリゴマーの縮合を促進する触媒を追加してもよい。また、帯電防止剤や界面活性剤の一部又は全部はシロキサンオリゴマーの加水分解体を得る工程で加えていてもよい。
本発明の防汚コート層は、上述した水性防汚コート剤を塗布し、乾燥させることによって形成することができる。水性防汚コート剤を塗布する対象は特に限定されず、ガラス、樹脂、金属、セラミックスなど各種支持体の表面に好適に用いられる。なお、基材としてガラス層を用いた場合、珪素上のヒドロキシル基の縮合がガラス表面のヒドロキシル基との間でも発生することにより、密着性に優れた積層体が得られる。このように、本発明の防汚コート層は、例えば、太陽電池モジュールの受光面側のガラス表面に設けられることが好ましく、太陽電池モジュール用防汚コート層として有用である。
本発明の水性防汚コート剤を塗布する方法としては特に限定されず、例えば、スプレー塗布、刷毛塗布、ローラー塗布、バー塗布、ディップ塗布などを挙げることができる。塗布後の乾燥法は室温で乾燥してもよく、40℃~120℃で1~30分程度の加熱を行っても良い。
本発明の防汚コート層が十分な防汚性を示すには、防汚コート層の表面が帯電防止性と親水性を有していることが好ましい。これにより、汚染物質の付着を抑制することができ、かつ、防汚コート層の表面に汚染物質が付着した場合であってもその汚れを洗い流す(水洗する)ことができる。
透過率は、例えば、自記分光光度計(UV2400-PC、島津製作所製)により測定することができる。
本発明の太陽電池モジュールは、上述した防汚コート層を含む積層体を有する。本発明の太陽電池モジュールは、太陽光の光エネルギーを電気エネルギーに変換する太陽電池素子を、太陽光が入射する側に設けられる透明性の基板とポリエステルフィルム(太陽電池用バックシート)との間に配置して構成されている。基板とポリエステルフィルムとの間は、例えばエチレン-酢酸ビニル共重合体等の樹脂(いわゆる封止剤)で封止して構成することができる。
エタノール81.07gに対して一般式(1)に示すシロキサンオリゴマー(n=5)3.06gおよびアルミニウムビス(エチルアセトアセテート)モノ(アセチルアセトナート)の1%イソプロパノール溶液0.94gを添加して混合した。得られた溶液に対してポリエチレングリコールモノラウリルエーテル(エチレンオキサイド部の繰り返し数15)0.057gを溶解させた水114.80gを徐々に加え、室温で12時間以上攪拌してシロキサンオリゴマーの加水分解を進行させてコート剤母液S-1を作製した。
次いで、コート剤母液S-1 19.99gに対してエタノール7.36g、水12.58g、ポリエチレングリコールモノラウリルエーテル(エチレンオキサイド部の繰り返し数15)0.0056gを、ジ(2-エチルヘキシル)スルホコハク酸ナトリウム0.0011gを添加して希釈した。そこにアルミニウムビス(エチルアセトアセテート)モノ(アセチルアセトナート)の1%イソプロパノール溶液0.85gおよびシリカ微粒子(一次粒径10~15nm)の33%分散液1.70gを加えて実施例1の水性防汚コート剤AS-1を作製した。作製した水性防汚コート剤は、白板ガラス板上にローラーを用いて塗布し1時間室温で乾燥して防汚コート層含有積層体を得た。作製した防汚コート層の表面抵抗を測定したところ1.7×109Ω/□であった。また作製した防汚コート層の積分球透過率を塗布に用いた白板ガラスをリファレンスとして測定したところ、波長300nm~1200nmの平均で95%以上であった。
実施例1においてジ(2-エチルヘキシル)スルホコハク酸ナトリウムの量を0.0011gから0.011gにする以外は実施例1と同様にして、実施例2の水性防汚コート剤AS-2を作製した。
実施例1においてジ(2-エチルヘキシル)スルホコハク酸ナトリウムの量を0.0011gから0.11gにする以外は実施例1と同様にして、実施例3の水性防汚コート剤AS-3を作製した。
実施例1においてジ(2-エチルヘキシル)スルホコハク酸ナトリウムの量を0.0011gから1.1gにする以外は実施例1と同様にして、実施例4の水性防汚コート剤AS-4を作製した。
実施例1においてジ(2-エチルヘキシル)スルホコハク酸ナトリウム0.0011gを添加しない以外は実施例1と同様にして、比較例1の水性防汚コート剤AS-21を作製した。
作製した水性防汚コート剤を、白板ガラス板上にローラーを用いて塗布した。1時間乾燥後に防汚コート層の親水性および汚れ付着耐性を評価した。なお、参考例1として、防汚コート層を有さない白板ガラス板の評価結果も下記表1に示している。
A:防汚コート層表面に黄土顔料が付着せず無色透明である。
B:防汚コート層表面の10%以下に黄土顔料が付着している。
C:防汚コート層表面の50%以下に黄土顔料が付着している。
D:防汚コート層表面のほぼ全面に黄土顔料が付着しているが、透明性は維持している。
E:防汚コート層表面のほぼ全面に黄土顔料が付着し、一部または全部が不透明である。
実施例1においてジ(2-エチルヘキシル)スルホコハク酸ナトリウム0.0022gの代わりに酸化スズ微粒子(一次粒径15~25nm)の50%分散液1.20gを用いた以外は実施例1と同様にして、実施例5の水性防汚コート剤AS-5を作製した。
実施例5において酸化スズ微粒子(一次粒径15~25nm)の50%分散液1.20gの代わりに酸化亜鉛・酸化アンチモン複合酸化物微粒子(一次粒径15~25nm)の30%分散液2.00gを用いた以外は実施例5と同様にして、実施例6の水性防汚コート剤AS-6を作製した。
実施例5において酸化スズ微粒子(一次粒径15~25nm)の50%分散液1.20gの代わりにガリウムドープ酸化亜鉛微粒子(一次粒径20~40nm)の30%分散液2.00gを用いた以外は実施例5と同様にして、実施例7の水性防汚コート剤AS-7を作製した。
実施例5において、酸化スズ微粒子(一次粒径15~25nm)の50%分散液1.20gの代わりに酸化スズ微粒子(平均一次粒径150nm)の20%分散液1.20gを用いた以外は実施例5と同様にして、実施例8の水性防汚コート剤AS-8を作製した。
作製した水性防汚コート剤を、白板ガラス板上にローラーを用いて塗布した。1時間乾燥後にサンプルの親水性および汚れ付着耐性を評価した。
実施例1においてアルミニウムビス(エチルアセトアセテート)モノ(アセチルアセトナート)の1%イソプロパノール溶液を添加しない以外は実施例1と同様にして、実施例9の水性防汚コート剤AS-9を作製した。
実施例1において、コート剤母液に追加で添加するポリエチレングリコールモノラウリルエーテル(エチレンオキサイド部の繰り返し数15)の量を0.0056gから0.11gにする以外は実施例1と同様にして、実施例10の水性防汚コート剤AS-10を作製した。
実施例1において、コート剤母液に追加で添加するポリエチレングリコールモノラウリルエーテル(エチレンオキサイド部の繰り返し数15、分子量848)0.0056gの代わりにステアリン酸ポリオキシエチレンステアリルエーテル(エチレンオキサイド部の繰り返し数15、分子量1210)0.11gを用いる以外は実施例1と同様にして、実施例11の水性防汚コート剤AS-11を作製した。
作製した水性防汚コート剤を、白板ガラス板上にローラーを用いて塗布した。1時間乾燥後にサンプルの親水性および汚れ付着耐性を評価した。
Claims (15)
- シロキサンオリゴマーの縮合を促進する触媒をさらに含む請求項1に記載の水性防汚コート剤。
- イオン性の界面活性を示す成分を含む請求項1又は2に記載の水性防汚コート剤。
- ノニオン性の界面活性を示す成分を含む請求項1~3のいずれか1項に記載の水性防汚コート剤。
- 前記イオン性の界面活性を示す成分の含有率は、前記水性防汚コート剤の全質量に対して、1.0質量%以下である請求項3又は4に記載の水性防汚コート剤。
- 前記帯電防止剤が金属酸化物微粒子を含む請求項1~5のいずれか1項に記載の水性防汚コート剤。
- 前記水性防汚コート剤中に含まれる全固形分中の炭素の割合が3質量%以下である請求項1~6のいずれか1項に記載の水性防汚コート剤。
- 前記金属酸化物微粒子の一次粒径が100nm以下である請求項6又は7に記載の水性防汚コート剤。
- 前記水性防汚コート剤中に含まれる分子量1100以上の有機化合物の含有率は、0.2質量%以下である請求項1~8のいずれか1項に記載の水性防汚コート剤。
- 請求項1~9のいずれか1項に記載の水性防汚コート剤を塗布・乾燥して形成する防汚コート層。
- 表面抵抗が1×1012Ω/□以下である請求項10に記載の防汚コート層。
- 表面における水接触角が40°以下である請求項10又は11に記載の防汚コート層。
- 波長300nm~1200nmにおける平均の積分球透過率が95%以上である請求項10~12のいずれか1項に記載の防汚コート層。
- 請求項10~13のいずれか1項に記載の防汚コート層をガラス層の上に積層した積層体。
- 請求項14に記載の積層体を有する太陽電池モジュール。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020167000115A KR101846959B1 (ko) | 2013-07-24 | 2014-06-17 | 수성 방오 코트제, 방오 코트층, 적층체 및 태양 전지 모듈 |
CN201480041181.0A CN105408434B (zh) | 2013-07-24 | 2014-06-17 | 水性防污镀剂、防污镀层、层叠体以及太阳电池模块 |
EP14829964.7A EP3025860A1 (en) | 2013-07-24 | 2014-06-17 | Water-based anti-soiling agent, anti-soiling layer, layered body, and solar battery module |
US15/001,258 US20160130447A1 (en) | 2013-07-24 | 2016-01-20 | Water-based anti-soiling agent, anti-soiling layer, layered body, and solar battery module |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2013153749A JP6099510B2 (ja) | 2013-07-24 | 2013-07-24 | 水性防汚コート剤、防汚コート層及び太陽電池モジュール |
JP2013-153749 | 2013-07-24 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US15/001,258 Continuation US20160130447A1 (en) | 2013-07-24 | 2016-01-20 | Water-based anti-soiling agent, anti-soiling layer, layered body, and solar battery module |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015012021A1 true WO2015012021A1 (ja) | 2015-01-29 |
Family
ID=52393074
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2014/065991 WO2015012021A1 (ja) | 2013-07-24 | 2014-06-17 | 水性防汚コート剤、防汚コート層、積層体及び太陽電池モジュール |
Country Status (7)
Country | Link |
---|---|
US (1) | US20160130447A1 (ja) |
EP (1) | EP3025860A1 (ja) |
JP (1) | JP6099510B2 (ja) |
KR (1) | KR101846959B1 (ja) |
CN (1) | CN105408434B (ja) |
TW (1) | TWI630246B (ja) |
WO (1) | WO2015012021A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015141240A1 (ja) * | 2014-03-17 | 2015-09-24 | 富士フイルム株式会社 | 水性コート剤、膜、膜の製造方法、積層体、及び太陽電池モジュール |
WO2016136041A1 (ja) * | 2015-02-27 | 2016-09-01 | 富士フイルム株式会社 | 親水性膜及びその製造方法、積層体、監視カメラ用保護材、並びに監視カメラ |
WO2017217513A1 (ja) * | 2016-06-17 | 2017-12-21 | 富士フイルム株式会社 | 膜形成用組成物、積層体、及び積層体の製造方法 |
WO2017217474A1 (ja) * | 2016-06-17 | 2017-12-21 | 富士フイルム株式会社 | 膜形成用組成物、及び積層体の製造方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019207899A (ja) * | 2016-09-29 | 2019-12-05 | 富士フイルム株式会社 | 太陽電池用フロントシート及びその製造方法並びに太陽電池モジュール |
DE102022109298A1 (de) * | 2022-04-14 | 2023-10-19 | Gelita Ag | Verfahren zur Erhöhung des Wirkungsgrades eines Solarmoduls oder eines Solarkollektors |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07196985A (ja) * | 1993-12-28 | 1995-08-01 | Kansai Paint Co Ltd | 帯電防止用塗料組成物及びその塗膜形成方法 |
JP2001038219A (ja) * | 1999-07-30 | 2001-02-13 | Toto Ltd | 水性の光触媒性親水性組成物、光触媒用水性プライマー及び、それらを用いた光触媒性親水性複合材 |
JP2004307743A (ja) * | 2003-04-10 | 2004-11-04 | Nippon Tokushu Toryo Co Ltd | 帯電防止塗料およびその塗膜の形成方法 |
JP2006052352A (ja) | 2004-08-13 | 2006-02-23 | Nippon Paint Co Ltd | 水性親水化処理剤 |
JP2008500433A (ja) * | 2004-05-28 | 2008-01-10 | ピーピージー インダストリーズ オハイオ, インコーポレイテッド | 親水性組成物、その生成のための方法、およびそのような組成物でコーティングされた基材 |
JP2008052088A (ja) * | 2006-08-25 | 2008-03-06 | Bridgestone Corp | ディスプレイ用反射防止フィルム、および、これを用いたディスプレイ |
JP2011246603A (ja) * | 2010-05-26 | 2011-12-08 | Panasonic Electric Works Co Ltd | 防汚性を付与する塗料組成物とそれを用いた塗装品ならびに塗装品の製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5518299B2 (ja) * | 2008-04-10 | 2014-06-11 | 旭化成イーマテリアルズ株式会社 | 太陽電池用コーティング組成物 |
TWI553065B (zh) * | 2009-03-11 | 2016-10-11 | 旭化成電子材料股份有限公司 | 塗覆組成物、塗膜、積層體及積層體之製造方法 |
-
2013
- 2013-07-24 JP JP2013153749A patent/JP6099510B2/ja active Active
-
2014
- 2014-06-17 KR KR1020167000115A patent/KR101846959B1/ko active IP Right Grant
- 2014-06-17 CN CN201480041181.0A patent/CN105408434B/zh active Active
- 2014-06-17 EP EP14829964.7A patent/EP3025860A1/en not_active Withdrawn
- 2014-06-17 WO PCT/JP2014/065991 patent/WO2015012021A1/ja active Application Filing
- 2014-07-10 TW TW103123726A patent/TWI630246B/zh active
-
2016
- 2016-01-20 US US15/001,258 patent/US20160130447A1/en not_active Abandoned
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH07196985A (ja) * | 1993-12-28 | 1995-08-01 | Kansai Paint Co Ltd | 帯電防止用塗料組成物及びその塗膜形成方法 |
JP2001038219A (ja) * | 1999-07-30 | 2001-02-13 | Toto Ltd | 水性の光触媒性親水性組成物、光触媒用水性プライマー及び、それらを用いた光触媒性親水性複合材 |
JP2004307743A (ja) * | 2003-04-10 | 2004-11-04 | Nippon Tokushu Toryo Co Ltd | 帯電防止塗料およびその塗膜の形成方法 |
JP2008500433A (ja) * | 2004-05-28 | 2008-01-10 | ピーピージー インダストリーズ オハイオ, インコーポレイテッド | 親水性組成物、その生成のための方法、およびそのような組成物でコーティングされた基材 |
JP2006052352A (ja) | 2004-08-13 | 2006-02-23 | Nippon Paint Co Ltd | 水性親水化処理剤 |
JP2008052088A (ja) * | 2006-08-25 | 2008-03-06 | Bridgestone Corp | ディスプレイ用反射防止フィルム、および、これを用いたディスプレイ |
JP2011246603A (ja) * | 2010-05-26 | 2011-12-08 | Panasonic Electric Works Co Ltd | 防汚性を付与する塗料組成物とそれを用いた塗装品ならびに塗装品の製造方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3025860A4 |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2015141240A1 (ja) * | 2014-03-17 | 2015-09-24 | 富士フイルム株式会社 | 水性コート剤、膜、膜の製造方法、積層体、及び太陽電池モジュール |
JP2015174972A (ja) * | 2014-03-17 | 2015-10-05 | 富士フイルム株式会社 | 水性コート剤、膜、膜の製造方法、積層体、及び太陽電池モジュール |
WO2016136041A1 (ja) * | 2015-02-27 | 2016-09-01 | 富士フイルム株式会社 | 親水性膜及びその製造方法、積層体、監視カメラ用保護材、並びに監視カメラ |
WO2017217513A1 (ja) * | 2016-06-17 | 2017-12-21 | 富士フイルム株式会社 | 膜形成用組成物、積層体、及び積層体の製造方法 |
WO2017217474A1 (ja) * | 2016-06-17 | 2017-12-21 | 富士フイルム株式会社 | 膜形成用組成物、及び積層体の製造方法 |
JPWO2017217474A1 (ja) * | 2016-06-17 | 2019-02-14 | 富士フイルム株式会社 | 膜形成用組成物、及び積層体の製造方法 |
US10640670B2 (en) | 2016-06-17 | 2020-05-05 | Fujifilm Corporation | Film-forming composition and manufacturing method of laminate |
Also Published As
Publication number | Publication date |
---|---|
EP3025860A4 (en) | 2016-06-01 |
EP3025860A1 (en) | 2016-06-01 |
CN105408434B (zh) | 2017-10-20 |
CN105408434A (zh) | 2016-03-16 |
JP6099510B2 (ja) | 2017-03-22 |
TWI630246B (zh) | 2018-07-21 |
JP2015025030A (ja) | 2015-02-05 |
KR101846959B1 (ko) | 2018-04-09 |
KR20160015368A (ko) | 2016-02-12 |
TW201504369A (zh) | 2015-02-01 |
US20160130447A1 (en) | 2016-05-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6099587B2 (ja) | 水性コート剤、膜、膜の製造方法、積層体、及び太陽電池モジュール | |
JP6099510B2 (ja) | 水性防汚コート剤、防汚コート層及び太陽電池モジュール | |
US10297698B2 (en) | Articles, coating compositions, and methods | |
US9944822B2 (en) | Coating composition and method of making and using the same | |
KR101816093B1 (ko) | 반사방지용 코팅 조성물 | |
KR101774051B1 (ko) | 보호 필름 및 태양 전지용 프론트 시트 | |
JP2012246440A (ja) | 無機コーティング組成物 | |
WO2016056489A1 (ja) | 防汚層付積層体、監視カメラ用保護材、及び監視カメラ | |
JP5734739B2 (ja) | 反射防止膜の製造方法、および反射防止膜付き太陽電池モジュールの製造方法 | |
JP2019117906A (ja) | 太陽電池用保護シート、及び、太陽電池モジュール | |
KR101921328B1 (ko) | 반사방지용 코팅 조성물 | |
EP3406673B1 (en) | Anti-reflection coating composition and anti-reflection film utilizing same | |
KR102174467B1 (ko) | 반사방지용 코팅 조성물 | |
JP7394438B2 (ja) | 太陽電池モジュールの防汚・防カビ処理方法及び防汚・防カビ性塗料 | |
WO2018185865A1 (ja) | 親水性付与剤、親水性被膜形成方法、親水性被膜、及び太陽光パネル | |
JPWO2019167944A1 (ja) | 積層体、太陽電池用保護シート、及び太陽電池モジュール |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 201480041181.0 Country of ref document: CN |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 14829964 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20167000115 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2014829964 Country of ref document: EP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |