TW201500483A - 以可交聯氟聚合物爲基礎之表面塗層 - Google Patents
以可交聯氟聚合物爲基礎之表面塗層 Download PDFInfo
- Publication number
- TW201500483A TW201500483A TW103108162A TW103108162A TW201500483A TW 201500483 A TW201500483 A TW 201500483A TW 103108162 A TW103108162 A TW 103108162A TW 103108162 A TW103108162 A TW 103108162A TW 201500483 A TW201500483 A TW 201500483A
- Authority
- TW
- Taiwan
- Prior art keywords
- composition
- coating
- weight
- substrate
- functional
- Prior art date
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 97
- 239000011248 coating agent Substances 0.000 title claims abstract description 74
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 17
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 46
- 239000000758 substrate Substances 0.000 claims description 39
- 239000010410 layer Substances 0.000 claims description 23
- -1 acrylate polyol Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 229920005862 polyol Polymers 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 238000004132 cross linking Methods 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 7
- 239000010408 film Substances 0.000 claims description 7
- 239000005056 polyisocyanate Substances 0.000 claims description 7
- 229920001228 polyisocyanate Polymers 0.000 claims description 7
- 230000005855 radiation Effects 0.000 claims description 7
- 230000002787 reinforcement Effects 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012790 adhesive layer Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 5
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000006120 scratch resistant coating Substances 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012963 UV stabilizer Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000012948 isocyanate Substances 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003373 anti-fouling effect Effects 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 3
- 229920001187 thermosetting polymer Polymers 0.000 claims description 3
- 239000010409 thin film Substances 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- ATOUXIOKEJWULN-UHFFFAOYSA-N 1,6-diisocyanato-2,2,4-trimethylhexane Chemical compound O=C=NCCC(C)CC(C)(C)CN=C=O ATOUXIOKEJWULN-UHFFFAOYSA-N 0.000 claims description 2
- QGLRLXLDMZCFBP-UHFFFAOYSA-N 1,6-diisocyanato-2,4,4-trimethylhexane Chemical compound O=C=NCC(C)CC(C)(C)CCN=C=O QGLRLXLDMZCFBP-UHFFFAOYSA-N 0.000 claims description 2
- WJIOHMVWGVGWJW-UHFFFAOYSA-N 3-methyl-n-[4-[(3-methylpyrazole-1-carbonyl)amino]butyl]pyrazole-1-carboxamide Chemical compound N1=C(C)C=CN1C(=O)NCCCCNC(=O)N1N=C(C)C=C1 WJIOHMVWGVGWJW-UHFFFAOYSA-N 0.000 claims description 2
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 claims description 2
- 239000012876 carrier material Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 230000002708 enhancing effect Effects 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical group CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 229920001567 vinyl ester resin Polymers 0.000 claims description 2
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 claims description 2
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- NAUBYZNGDGDCHH-UHFFFAOYSA-N N=C=O.N=C=O.CCCC(C)C Chemical compound N=C=O.N=C=O.CCCC(C)C NAUBYZNGDGDCHH-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 229920002098 polyfluorene Polymers 0.000 claims 1
- 238000005728 strengthening Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 238000005299 abrasion Methods 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000009472 formulation Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 10
- 239000002131 composite material Substances 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 7
- 230000007797 corrosion Effects 0.000 description 7
- 230000007774 longterm Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 230000004224 protection Effects 0.000 description 7
- 150000003077 polyols Chemical class 0.000 description 6
- 238000000465 moulding Methods 0.000 description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005240 physical vapour deposition Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000008199 coating composition Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000193 polymethacrylate Polymers 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N 2-Methylpentane Chemical compound CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004971 Cross linker Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 239000002346 layers by function Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000011877 solvent mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- SITYOOWCYAYOKL-UHFFFAOYSA-N 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(3-dodecoxy-2-hydroxypropoxy)phenol Chemical compound OC1=CC(OCC(O)COCCCCCCCCCCCC)=CC=C1C1=NC(C=2C(=CC(C)=CC=2)C)=NC(C=2C(=CC(C)=CC=2)C)=N1 SITYOOWCYAYOKL-UHFFFAOYSA-N 0.000 description 1
- MFAWEYJGIGIYFH-UHFFFAOYSA-N 2-[4-(trimethoxymethyl)dodecoxymethyl]oxirane Chemical group C(C1CO1)OCCCC(C(OC)(OC)OC)CCCCCCCC MFAWEYJGIGIYFH-UHFFFAOYSA-N 0.000 description 1
- JRXXEXVXTFEBIY-UHFFFAOYSA-N 3-ethoxypropanoic acid Chemical compound CCOCCC(O)=O JRXXEXVXTFEBIY-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 229920004041 Makrolon® 2607 Polymers 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920005375 Plexiglas® 7H Polymers 0.000 description 1
- 229920002675 Polyoxyl Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- JYMITAMFTJDTAE-UHFFFAOYSA-N aluminum zinc oxygen(2-) Chemical compound [O-2].[Al+3].[Zn+2] JYMITAMFTJDTAE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UHKJHMOIRYZSTH-UHFFFAOYSA-N ethyl 2-ethoxypropanoate Chemical compound CCOC(C)C(=O)OCC UHKJHMOIRYZSTH-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011084 recovery Methods 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
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-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
- 239000008096 xylene Substances 0.000 description 1
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/14—Homopolymers or copolymers of vinyl fluoride
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
- C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
- C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
-
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
-
- 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
- C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
- C09D129/10—Homopolymers or copolymers of unsaturated ethers
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
- C09D133/12—Homopolymers or copolymers of methyl methacrylate
-
- 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
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
-
- 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
-
- 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
- C09D7/48—Stabilisers against degradation by oxygen, light or heat
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
- F24S23/00—Arrangements for concentrating solar-rays for solar heat collectors
- F24S23/70—Arrangements for concentrating solar-rays for solar heat collectors with reflectors
- F24S23/82—Arrangements for concentrating solar-rays for solar heat collectors with reflectors characterised by the material or the construction of the reflector
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/049—Protective back sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
- H01L31/0547—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means comprising light concentrating means of the reflecting type, e.g. parabolic mirrors, concentrators using total internal reflection
-
- 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
- Y02E10/40—Solar thermal energy, e.g. solar towers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
- Polyurethanes Or Polyureas (AREA)
- Photovoltaic Devices (AREA)
Abstract
本發明係關於利用以包含可交聯氟聚合物之調合物為基礎之高級耐磨表面塗層處理材料以供曝露於戶外使用的技術。本發明另外關於該表面塗層之特別具體例。
Description
本發明係關於利用以包含可交聯氟聚合物之調合物為基礎之高級耐磨表面塗層處理材料以供曝露於戶外使用的技術。本發明另外關於該表面塗層之特別具體例。
材料在戶外使用時無可避免地曝露於磨蝕作用。此種磨蝕尤其是因清潔操作或風攜帶之介質諸如沙或塵粒所引起。結果,未經防護或未經充足表面塗覆的材料喪失其價值或長期黏著性。熱塑性聚合材料之耐磨性低,因此不適合或僅極有限地適合於曝露於戶外使用之材料的表面塗層。
戶外使用之材料另外明顯不利於曝露於太陽輻射之UV部分。高級表面塗層因此同樣必須確保基材對於UV輻射的顯著防護,而使其本身不會有因UV輻射而受到內在損害的可能性。
例如可撓薄膜太陽能模組及可撓OLED及顯示器材料在戶外使用時另外會有關鍵功能層腐蝕的明顯可能性。因此在這些應用方面中,高性能表面塗層同樣必須提供適當之腐蝕防護以及對水分移動之阻障性。
已知用於戶外使用之塗層的材料的實例是聚矽氧烷諸如得自SDC Technologies Inc.之Crystalcoat TM MP-100、皆得自Momentive Performance Materials之AS 400-SHP 401或UVHC3000K。然而,在戶外區中超過至少20年的長期應用中,特別是用於太陽能反射器或光伏打電池所需的,此種材料沒有顯示足夠的耐磨性。
在US 5,118,540中,係藉由黏著性施加以氟碳為底質之聚合物(諸如PVDF)之耐磨且防水的鋪片來改良表面防護。不僅UV吸收劑是該黏著層之成分,腐蝕抑制劑也是,而藉由該黏著層,該鋪片連結至該經氣相塗覆之聚酯載體膜的金屬表面。該黏著層在此可與上述(甲基)丙烯酸酯之雙塗層類似的方式由二不同層所構成,以將腐蝕抑制劑與UV吸收劑分開。然而此種塗層沒有展現足夠的長期耐刮性。
在先前技藝中之另一解決方式是無機耐刮塗層。EP 1 629 053揭示此種由直徑小於1微米之二氧化矽粒子或氧化鋁粒子構成之塗層以供用作耐風化之片的膜層合物的塗層。然而此種無機塗層之缺點是:其耐久性僅是相對短時間的,換言之,在風化條件下不超過數年。在極熱及尤其是乾燥環境中流沙、及當然地沙暴、或其他氣候狀況導致此種塗層之磨損。
EP 2 524 802揭示一種用於太陽能設施之風化防護的
塗層,其包含經異氰酸酯交聯之羥基官能的氟聚合物。這些塗層已具有極良好之耐磨性及風化穩定性。然而,問題是有限的有用性,因為這些塗層對很多基材的黏著性是有限的。用於該應用之類似系統在WO 2011/105515中發現。
WO 98/44015揭示包含聚異氰酸酯、含羥基官能之氟聚合物及羥基官能之未經氟化的多醇的組成物,其中該多醇與低分子量二醇也是聚酯、聚醚或聚碳酸酯多醇。然而,尤其鑒於其耐風化性,此種組成物是能改良的。
EP 2 298 842揭示用於汽車製造之塗層,例如由以聚醚為底質之聚異氰酸酯預聚物和不含氟之多醇所構成者。此種組成物具有極良好之耐風化性及充足之耐磨性以供汽車製造。然而對於其他在戶外的物理性曝露下的某些應用,其耐磨性不足。
該問題是將創新的表面強化物提供給塑膠或金屬表面。在戶外應用之背景中,利用此種表面強化物是意圖要確保特別良好之耐磨性、耐刮性、耐風化性及基材防護性的同時組合。
另一意圖是使此表面強化物成為透明及/或無色。再者,此表面強化物是要提供良好耐化學性、對例如水蒸汽或氧之阻障性、及拒汙性。
另一問題是與待塗覆之基材和待利用之塗覆技術相關之表面強化物應是能廣泛應用。
另一問題是提供一種容易且成本有效地製造並應用之表面強化物以供戶外應用。
未明確陳述之另外的問題可由本申請案中之描述、申請專利範圍或實例顯明。
與該先前技藝之背景及其中所述之對長期應用之有缺陷的技術解決方式相對地,在本發明中以對精於此技藝之人士並非容易明瞭之方式,成功地提供具有長時間經改良之表面品質的塗層。此種成功係利用創新之用於基材之塗層的組成物達成,該組成物包含5至70重量%(較佳是10至55重量%)之羥基官能之氟聚合物,5至70重量%(較佳是10至55重量%)之(甲基)丙烯酸酯多醇,5至35重量%(較佳10至30重量%)之聚異氰酸酯,0.001至0.2重量%(較佳是最高達1重量%)之交聯用觸媒,0.5至20重量%之較佳以三為底質之UV吸收劑及0.5至10重量%之較佳以HALS為底質之UV穩定劑及5至80重量%(較佳是最高達40重量%)之溶劑。該氟聚合物及該(甲基)丙烯酸酯多醇在此一共是該組成物的20至75重量%。再者,該氟聚合物和該(甲基)丙烯酸酯多醇一共具有介於50與400毫克KOH/克之間,較佳介於90與250毫克KOH/克之間的OH數。
特佳地,該羥基官能之氟聚合物一方面是四氟乙烯(TFE)及/或氯三氟乙烯(CTFE)之共聚物且另一方面是乙烯基酯、乙烯基醚及/或α-烯烴之共聚物。特佳地,彼是一方面是CTFE或TFE之交替型共聚合物且另一方面是其他共單體之交替型共聚物。在此種聚合物中,該羥基官能性係藉由羥基官能之乙烯醚及/或α-烯烴之共聚合而獲得。市售之羥基官能的氟聚合物的實例是藉由Asahi Glass以產品名Lumiflon®所售者、藉由Solvay Solexis以產品名FluorLin®所售者或藉由Daikin以產品名Zeffle®所售者。
因為所用之該氟聚合物以及聚(甲基)丙烯酸酯是完全非結晶的,對應之調合物和塗層具有良好之光學性及高透明性。另外,氟聚合物和聚(甲基)丙烯酸酯二者擁有極良好之極長時間的耐風化性,即使在極端條件下。本發明之塗層因此對UV是極穩定的,且再者對大氣中之氧和水(例如大氣中之溼氣形式)具有極良好之阻障性。
為建立所需之該塗層的風化穩定性以及基材防護性,另一需要是添加0.5至20重量%(較佳最高達15重量%)之較佳以三為底質之UV吸收劑及0.5至10重量%(較佳最高達7.5重量%)之較佳以HALS為底質之UV穩定劑。
該組成物也可另包含5至40重量%之羥基官能的聚矽氧樹脂。此聚矽氧樹脂具有介於50與300毫克KOH/克(較佳是介於90與200毫克KOH/克)之間的OH數。這
些種類之聚矽氧樹脂也增加該組成物之耐熱性。再者,若有相對高比例之此種成分聯同稍微較低比例之其他聚合物成分,該組成物整體之固體含量可提高。此種羥基官能之聚矽氧樹脂的實例是得自Dow Corning之Xiameter® RSN-0255。
所用之聚(甲基)丙烯酸酯包含至少60重量%之程度之以甲基丙烯酸酯為底質之單體單元。所特別討論之聚合物較佳是懸浮聚合物或溶液聚合物,其特佳是由至少70重量%之甲基丙烯酸甲酯(MMA)及/或甲基丙烯酸丁酯(BuMA)所構成。該羥基官能化在此可例如經由適合單體諸如(甲基)丙烯酸羥乙酯或(甲基)丙烯酸羥丙酯之共聚合,及/或例如藉由使用羥基官能之鏈轉移劑諸如巰基乙醇而達成。分子量是10 000至300 000克/莫耳且該玻璃轉換溫度之範圍介於10與130℃之間。
所預期之溶劑原則上包括所有適合依照本發明所利用之其他成分的溶劑及溶劑混合物。這些溶劑更特別地可以是酮類諸如丙酮或甲基乙基酮、酯類諸如乙酸乙酯、丙酯或丁酯、芳香族諸如甲苯或二甲苯、或醚類諸如***或乙氧基丙酸乙酯。
然而,更特別地,該溶劑也可以是水。令人驚訝地,已發現:特別地本發明之組成物的其他成分即使在水中也形成穩定分散液,且若以水作為溶劑,則對應之塗層材料可容易地並對環境友善地被施加。
在該組成物中之聚異氰酸酯通常是異佛酮二異氰酸酯
(IPDI)、六亞甲基二異氰酸酯(HDI)、二異氰酸基二環己基甲烷(H12MDI)、2-甲基戊烷二異氰酸酯(MPDI)、2,2,4-三甲基六亞甲基二異氰酸酯/2,4,4-三甲基六亞甲基二異氰酸酯(TMDI)及/或降烷二異氰酸酯(NBDI)。
所用之交聯用觸媒一般是二月桂酸二丁基錫、辛酸鋅、新癸酸鉍及/或三級胺,較佳是1,4-二氮雜雙環[2.2.2]辛烷。適合之此種交聯劑的實例是得自Bayer之Desmodur® BL 3175。一般而言,設定交聯劑之量以使OH基與NCO基之比率是介於0.5與1.5之間,較佳是介於0.8與1.2之間且更佳是介於0.9與1.1之間。這些例示的圖特別是關於包含HDI縮合物和DBTDL的系統。利用其他系統(其成分在各別之分子量或官能度的數目上有更明顯的偏差),所具體說明之限制範圍可因此被修正。
另外,該組成物可另包含最高達20重量%之矽烷官能的異氰酸烷酯或縮水甘油基官能之烷基矽烷。這些成分另外對該待塗覆之基材的黏合性有貢獻。一種較佳之矽烷官能的異氰酸烷酯是三甲氧基丙基矽烷基異氰酸酯,其是例如由Evonik Industries以Vestanat EP-M95之名銷售。縮水甘油基官能之烷基矽烷的較佳實例是3-縮水甘油基氧基丙基三甲氧基矽烷,其例如可由Evonik Industries以Dynasylan GLYMO之名獲得。
另外,也可特別存在無機奈米粒子,尤其是包含矽氧化物者,以供在該組成物中另外強化該耐刮性及耐磨性。
已經添加最高達40重量%(較佳是最高達30重量%)之這些奈米粒子。在此特佳是使這些奈米粒子具有折射性且使該聚合物基質不混濁。
並且,除了所述之組成物,本發明之部分也是一種以本發明之組成物塗覆之基材。在那情況中,該塗層在乾燥及交聯後較佳具有介於0.5與200微米之間的厚度,較佳介於2微米與150微米之間的厚度,且更佳介於5微米與50微米之間的厚度。
依照本發明所塗覆之基材比先前技藝之優點列述於下。
本發明之該較佳透明的塗層特別是彩色中性的且在溼氣影響下不變混濁。另外,該塗層展現優越的風化穩定性及極良好之耐化學性,例如與所有之商用清潔產品相關之耐化學性。這些方面也對長時間保持表面品質有貢獻。
本發明之材料例如也可在至少15年(較佳甚至至少20年,更佳至少25年)之極長時間中,用在具有特別強烈之太陽光的位置上(諸如在美國西南部或撒哈拉)的戶外應用中。
本發明之塗層具有極良好之性質,特別是在該表面受到物理性曝露時。這是指這些基材之使用壽命被延長,即使在經常地經歷沙暴或高塵粒含量之風的區域中或當經常使用刷子來清潔該表面時。
再者,本發明之塗層對水份(特別是與雨水、大氣中之溼氣或露水相關者)特別穩定。因此,該塗層在水份影
響下並不顯出已知之該塗層由該基材剝離的容易性。另外,以氟為底質之塗層擁有特別良好之阻水效果。再者,以氟為底質之塗層展現出特別良好之阻氧效果且因此在腐蝕控制上具有極良好性質。
此外,本發明塗層展現極佳的耐刮性及耐磨性,因此這效果另外對這些基材的使用壽命有貢獻。
除了已經描述之用於塗層的組成物之外,用於基材之塗層的方法也是本發明之部分。在此種用於基材之塗層的方法中,該基材係以如上述之本發明的組成物塗覆,且隨後將該塗層乾燥且交聯。
更特別地使用一種方法,其中本發明之組成物係與另外之作為"有機溶膠"之調合用成分一同以有機溶液形式被施加至該複合模製物,且隨後將所施加之層乾燥。塗覆在此係利用例如刮刀塗覆、輥塗覆、浸漬塗覆、簾塗覆及/或噴灑塗覆。藉由該塗層之交聯完成乾燥。
此塗覆之步驟可在塗覆單元中在預製之未經塗覆的複合模製物上進行。塗覆可直接在例如複合模製物形式之基材的製造後,選擇地且較佳地在線路中進行。該基材係例如在一具體例中藉由層合被製造成多層片。在此情況中,上述之塗覆單元係設定在線路中層合單元之後,且塗覆係在新製之基材上進行。
關於該成品,有很多具體例。在第一具體例中,塗覆
係直接在該基材上進行。
在第二具體例中,該塗覆係以配備有本發明之塗料調合物之表面塗層片形式實施在各別基材上。在此情況中,第一操作是用於本發明之塗層的調合物,其是要以牢固黏合方式塗覆在對應之膜基材上。在這之後是將此表面塗層片施加至各別的最後基材上。該表面塗層片之底面在此是塗覆有自黏性調合物或配備有熱熔物或黏著性之層。在經溫度及壓力輔助之應用的事例中,該底面之改質物係"熱塑性地"或"反應性地"貼合於該最後的基材上。
以此方式,經由該表面塗層片之物性,可實現另外之產品特性,包括例如光學種類者。再者,此類之方法是極具彈性的,且可例如在現場配合相對大之待塗覆之基材以被利用,卻不運用溶劑或高溫。
在第三變化型中,與該第二具體例類似的,該塗覆係以本發明之塗層調合物的熱轉印操作方式實施至該各別基材上。在此,在第一塗覆步驟中,所討論之膜或紙載體材料係配備有釋放層,該釋放層使在第二塗覆步驟中所施加之本發明的塗層調合物能熱轉印至該各別基材。隨意地,在此若需要,則在第三塗覆步驟中,可施加黏著性之層,以確保該熱轉移層系統適當地黏合至該各別的基材。
本發明之塗層隨後可隨意地配備有一或多個另外的功能層。所討論之層可包含例如耐刮塗層、傳導層、抗汙塗層及/或反射增加層或其他具有光學功能之層。這些另外的層可例如藉由物理氣相沉積(PVD)或化學氣相沉積
(CVD)來施加。
另外之耐刮塗層可隨意地被施加以供進一步改良耐刮性。然而一般而言,不需要此種另外之層,若本發明之複合模製物有良好品質。耐刮塗層可以是例如直接藉由PVD或CVD施加之氧化矽層。
另外,為促進清潔,該複合模製物表面可配備有排斥汙垢或破壞汙垢之塗層,稱為防汙塗層。該塗層也可藉由PVD或CVD施加。
作為另一例示的選項,相對薄之極耐磨的層也經定位在本發明之塗層上。此另外之層是一種特硬之熱固性塑膠層,厚度較佳低於5微米,更佳介於0.5與2.0微米之間。此層可例如由聚矽氮烷調合物製造。
本發明之表面塗覆技術可用於以下應用方面:
1.為供例如用於戶外應用之熱固性塑膠的塗層,以作為用於建築飾面設計之高壓層合板。
2.為供裝飾性層合物的塗層,以例如用於窗戶型材、咖啡廳家具或壁襯(wall lining)。
3. OLED(有機發光二極體):作為特別在可撓OLED上之塗層,有較好之持久性,可實現在戶外區域中防刮及長期使用性之改良。該OLED之特別的具體例是可捲型顯示器。它們尤其受到高機械應力,而利用本發明之塗層,該顯示器會具有較長使用壽
命。
4.外窗膜:外窗處理有很大部份與熱絕緣有關,特別是當外部溫度高時。特別的風化穩定性對此是很重要的。另外,在本申請案中,該塗層之高透明性是特別的因素。
5.抗腐蝕塗層(耐用塗層):這些多層塗層系統在諸如橋建築或在建築物中在利用鋼結構體的情況下是特別重要的。在此,使用本發明之塗覆技術以設計此多層塗層之上層(上塗層),藉此可獲得相對於該先前技藝明顯延長之腐蝕控制與特別改良之塗層的長期黏合。
同樣令人感興趣之用途領域是用於太陽能回收之系統的用途。尤其是:
6.薄膜太陽能電池。
在此特別相關之因素是該塗層之高抗UV性以及即使在極端風化影響(諸如沙暴)或高溫下也極佳之風化穩定性。
7.用於集中太陽輻射之鏡子,特別是用在太陽熱力集中站者。
利用這些鏡子的受矚目之處特別是在於該塗層之腐蝕控制、耐刮性、透明性和長期黏合性,以及極佳之風化穩定性。
8.光伏打背層:光伏打模組之反面塗層。在此極重要的尤其是對水、UV輻射及其他風化影響的防護。
程序:在試驗前,將樣品表面清潔。利用得自Bosch之附帶0.75毫米試驗尖端的ZHT 2092 Zehntner硬度試驗劃線器、ACC 112觸輪(trolley)和不同的壓縮彈簧以進行試驗。使用不同限定的壓縮彈簧,以不同的力,該試驗尖端直線劃過該樣品。
該彈簧的力藉由該壓縮彈簧之預先拉緊而調節,將該硬度試驗劃線器與該尖端置於該表面上,且將該試驗儀器垂直壓在該表面上以對抗該彈簧壓力。然後該觸輪以約10毫米/秒之速度直線劃過該樣品而遠離該物體。應在改變該彈簧之力的情況下重覆此操作,直至該試驗表面之輕微損傷變為可見。在該試驗循環後,應放鬆該壓縮彈簧。在刻度表上該滑動位置顯示該力(牛頓)且因此直接地顯示與該硬度對應之試驗值。在該材料中已作出可見之刻線的最低力被使用以作為結果。利用該觸覺測量儀,可隨意地測定刻劃深度。
以下之初步階段舉例描繪基材,其可被利用以作為集中太陽輻射之鏡子。
由0.125毫米之以2%之CGX 006和0.6%之Chimasorb將UV加成(additized)的PMMA Plexiglas 7H
及0.025毫米之Makrolon 2607聚碳酸酯所構成之0.15毫米厚的複合片係藉由接合器(adapter)共擠出而製造。在此之後是利用電漿輔助之濺射操作將該反射用塗層施加至該複合片之聚碳酸酯面上,該塗層經認定開始於該聚碳酸酯膜而由下述順序之各層構成:0.5奈米之ZAO(氧化鋅鋁)、100奈米之Ag和50奈米之Cu。
將28.9重量%之Lumiflon LF-9716導入12.4重量%之乙氧基丙酸乙酯與37.3重量%之乙酸丁酯的溶劑混合物中且順序地並在攪拌下與0.0013重量%之DBTDL(二月桂酸二丁基錫;交聯用觸媒)、3.4重量%之Tinuvin 400(UV吸收劑)和1.1重量%之Tinuvin 123(HALS化合物)摻混直至形成均勻且澄清之混合物。然後,16.9重量%之Desmodur N 3300(聚異氰酸酯,交聯劑)藉由攪拌10分鐘而合併。使用40微米之線刮刀,在標準氣候條件下,將塗層材料施加至來自初步階段1之基材的PMMA面。在80℃之強制空氣爐中進行乾燥及初步固化2小時。僅10分鐘後該塗層在僅10分鐘即無黏性。隨後之硬化係在室溫下進行超過7天或在80℃下進行2小時。
在此,30重量%之該Lumiflon LF 9716係經該以甲基丙烯酸酯為底質之多醇Degalan 4800-L代替。
尤其是在滾筒對滾筒操作中,本發明之塗層的固化速率因此明顯增加(降低無黏性之時間),藉此明顯降低該塗層之成本。由於該比較昂貴之氟聚合物多醇經比較有利之甲基丙烯酸酯多醇所部分代替,調合成本也下降。再者,在所述之應用方面中該表面塗層之經顯著改善的經濟性也變為可能。其他的塗層性質仍不受影響。依照所進行之刮痕硬度測量,本實例之塗層相較於比較用實例之塗層展現出顯著較少的表面損害。
Claims (16)
- 一種用於基材之塗層的組成物,其特徵在於該組成物包含5至70重量%之羥基官能之氟聚合物,5至70重量%之(甲基)丙烯酸酯多醇,5至35重量%之聚異氰酸酯,0.001至0.2重量%之交聯用觸媒,5至80重量%之溶劑,0.5至20重量%之UV吸收劑及0.5至10重量%之UV穩定劑,該氟聚合物及該(甲基)丙烯酸酯多醇一共佔該組成物之20至75重量%且一共具有介於50與400毫克KOH/克之間的OH數。
- 如申請專利範圍第1項之組成物,其中該氟聚合物及該(甲基)丙烯酸酯多醇之OH數一共是介於90與250毫克KOH/克之間。
- 如申請專利範圍第1或2項之組成物,其中該羥基官能之氟聚合物為一方面是四氟乙烯(TFE)及/或氯三氟乙烯(CTFE)及另一方面是乙烯酯、乙烯醚及/或α-烯烴的共聚物,該羥基官能之氟聚合物係利用羥基官能之乙烯醚及/或α-烯烴之共聚合而獲得。
- 如申請專利範圍第1或2項之組成物,其中該組成物另外包含5至40重量%之羥基官能之聚矽氧樹脂,且其中該聚矽氧樹脂具有介於50與300毫克KOH/克之間的OH數。
- 如申請專利範圍第1或2項之組成物,其中該組成物包含0.5至15重量%之三作為UV吸收劑,及0.5至7.5重量%之HALS化合物作為UV穩定劑。
- 如申請專利範圍第1或2項之組成物,其中該(甲基)丙烯酸酯多醇具有介於10 000與300 000克/莫耳之間的分子量及介於10與130℃之間的玻璃轉換溫度。
- 如申請專利範圍第1或2項之組成物,其中該聚異氰酸酯是異佛酮二異氰酸酯(IPDI)、六亞甲基二異氰酸酯(HDI)、二異氰酸基二環己基甲烷(H12MDI)、2-甲基戊烷二異氰酸酯(MPDI)、2,2,4-三甲基六亞甲基二異氰酸酯/2,4,4-三甲基六亞甲基二異氰酸酯(TMDI)及/或降烷二異氰酸酯(NBDI),且其中該交聯用觸媒包含二月桂酸二丁基錫、辛酸鋅、新癸酸鉍及/或三級胺,較佳是1,4-二氮雜雙環[2.2.2]辛烷。
- 如申請專利範圍第1或2項之組成物,其中該組成物另外包含最多達20重量%之矽烷官能之異氰酸烷酯或縮水甘油基官能之烷基矽烷。
- 如申請專利範圍第1或2項之組成物,其中該溶劑是水。
- 一種基材,其特徵在於此基材係以如申請專利範圍第1至9項中任一項之組成物塗覆且該塗層在乾燥及交聯後具有介於0.5與200微米之間的厚度。
- 一種塗覆基材之方法,其特徵在於該基材係以如申請專利範圍第1至9項中任一項之組成物塗覆且隨後將該塗層乾燥及交聯。
- 如申請專利範圍第11項之方法,其中該基材是 一種表面塗層片,其在一面上以如申請專利範圍第1至9項中至少一項之組成物塗覆且在另一面上提供有具有黏著性之層,且其中此表面塗層片可以黏合至第二基材。
- 如申請專利範圍第11項之方法,其中該基材係利用熱轉印技術,以如申請專利範圍第1至9項中任一項之組成物塗覆,且其中為此目的,先將該組成物施加至一種配備有釋放層之膜或紙載體材料。
- 如申請專利範圍第11至13項中任一項之方法,其中所得之塗層額外被提供另外的耐刮塗層、傳導層、防汙塗層及/或反射強化層或其他具有光學功能之層。
- 一種如申請專利範圍第1至9項中至少一項之組成物之用途,其係用於裝飾型層合物之表面強化、OLED、熱固物、可捲型顯示器或窗外膜或用作抗腐蝕塗層,更特別是用作耐用塗層系統之上塗層。
- 一種如申請專利範圍第1至9項中至少一項之組成物之用途,其係用於薄膜太陽能電池之表面強化、集中太陽輻射用之鏡子或光伏打背層。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102013204395.3A DE102013204395A1 (de) | 2013-03-13 | 2013-03-13 | Oberflächenvergütung auf Basis von vernetzbaren Fluorpolymeren |
Publications (1)
Publication Number | Publication Date |
---|---|
TW201500483A true TW201500483A (zh) | 2015-01-01 |
Family
ID=50115865
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
TW103108162A TW201500483A (zh) | 2013-03-13 | 2014-03-10 | 以可交聯氟聚合物爲基礎之表面塗層 |
Country Status (8)
Country | Link |
---|---|
US (1) | US20160017165A1 (zh) |
EP (1) | EP2970558A1 (zh) |
JP (1) | JP2016516843A (zh) |
CN (1) | CN105073816A (zh) |
AR (1) | AR095382A1 (zh) |
DE (1) | DE102013204395A1 (zh) |
TW (1) | TW201500483A (zh) |
WO (1) | WO2014139752A1 (zh) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI621871B (zh) * | 2015-07-31 | 2018-04-21 | 三星Sdi股份有限公司 | 窗膜和包含所述窗膜的可撓性顯示器 |
US10696016B2 (en) | 2015-07-31 | 2020-06-30 | Samsung Sdi Co., Ltd. | Window film and flexible display including the same |
US11041057B2 (en) | 2016-12-13 | 2021-06-22 | Samsung Sdi Co., Ltd. | Window film, manufacturing method thereof, and display device including same |
Families Citing this family (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102011113160A1 (de) * | 2011-09-14 | 2013-03-14 | Evonik Röhm Gmbh | Polymere Materialien für Außenanwendungen mit selbstheilenden Oberflächeneigenschaften nach Verkratzen oder Abrasionsbeschädigung |
DE102013208356A1 (de) | 2013-05-07 | 2014-11-13 | Evonik Industries Ag | Vernetzung von IPMS Addukten mit Aminosilanen |
US20150299498A1 (en) * | 2014-04-17 | 2015-10-22 | E I Du Pont De Nemours And Company | Transparent fluoropolymer coated films, building structures and liquid fluoropolymer coating compositions |
DE102014218188B4 (de) | 2014-09-11 | 2023-01-19 | Evonik Operations Gmbh | Formulierung zur Beschichtung von Substraten, Verfahren zur Beschichtung von Substraten, beschichtete Substrate sowie Verwendung der Formulierung |
CN109154088B (zh) * | 2016-02-24 | 2021-06-22 | 蒂森克虏伯钢铁欧洲股份公司 | 半成品,其生产方法和应用 |
EP3339387B1 (de) | 2016-12-22 | 2020-06-24 | Evonik Operations GmbH | Verbindungen auf basis von addukten mit isocyanaten für beschichtungszusammensetzungen |
US11417857B2 (en) | 2018-01-24 | 2022-08-16 | Samsung Display Co., Ltd. | Heterocyclic compound and electronic apparatus |
EP3524651A1 (de) | 2018-02-08 | 2019-08-14 | Evonik Degussa GmbH | Wässrige polyorganosiloxanhybridharz-dispersion |
EP3719076A1 (de) | 2019-04-01 | 2020-10-07 | Evonik Operations GmbH | Wässrige polyorganosiloxanhybridharz-dispersion |
CN111013988A (zh) * | 2019-12-20 | 2020-04-17 | 江苏佰大铝业科技有限公司 | 一种幕墙用铝单板的表面处理工艺 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2830046B2 (ja) * | 1989-05-15 | 1998-12-02 | 旭硝子株式会社 | 軟質塩ビシート |
JP2808663B2 (ja) * | 1989-05-15 | 1998-10-08 | 旭硝子株式会社 | 壁 紙 |
JP2830047B2 (ja) * | 1989-05-15 | 1998-12-02 | 旭硝子株式会社 | 異型押出し品 |
JP2949738B2 (ja) * | 1989-10-11 | 1999-09-20 | 旭硝子株式会社 | 耐候性の優れたポリ塩化ビニル板の製造方法 |
US5118540A (en) | 1990-04-23 | 1992-06-02 | Solar Kinetics, Inc. | Corrosion resistant flexible reflective film for solar energy applications |
JP2852129B2 (ja) * | 1990-12-28 | 1999-01-27 | 日本ペイント株式会社 | 熱硬化性塗料組成物 |
JP3533751B2 (ja) * | 1995-04-26 | 2004-05-31 | 日本油脂Basfコーティングス株式会社 | 熱硬化性塗料組成物 |
US6001923A (en) | 1997-03-27 | 1999-12-14 | Pilkington Aerospace Inc. | Transparent fluorinated polyurethane coating compositions and methods of use thereof |
US6974850B2 (en) | 2003-05-30 | 2005-12-13 | 3M Innovative Properties Company | Outdoor weatherable photopolymerizable coatings |
CN102544149B (zh) * | 2005-11-30 | 2016-07-20 | 大金工业株式会社 | 太阳能电池以及太阳能电池的保护罩用层积膜 |
KR101274885B1 (ko) | 2008-07-01 | 2013-06-17 | 쇼와 덴코 가부시키가이샤 | 도료 조성물 및 이것을 사용한 도막 형성 방법 |
EP2513220B1 (en) * | 2009-12-16 | 2013-11-06 | Avery Dennison Corporation | Photovoltaic backsheet |
JPWO2011087046A1 (ja) | 2010-01-14 | 2013-05-20 | ダイキン工業株式会社 | 太陽電池モジュール用耐侯性シートおよび該シートを用いた製品ならびに該太陽電池モジュール用耐侯性シートの製造方法 |
MX2012009871A (es) * | 2010-02-26 | 2012-09-12 | Asahi Glass Co Ltd | Composicion de recubrimiento para reflector recolector de calor solar y reflector recolector de calor solar y procedimiento para su produccion. |
JP5540825B2 (ja) * | 2010-03-29 | 2014-07-02 | 大日本印刷株式会社 | 遮光シート、並びにそれを使用した太陽電池モジュール用バックシート及び太陽電池モジュール |
EP2698399B1 (en) * | 2011-04-13 | 2017-11-15 | LG Chem, Ltd. | Resin composition, multilayer film and photovoltaic module including same |
-
2013
- 2013-03-13 DE DE102013204395.3A patent/DE102013204395A1/de not_active Withdrawn
-
2014
- 2014-02-14 US US14/772,019 patent/US20160017165A1/en not_active Abandoned
- 2014-02-14 EP EP14705113.0A patent/EP2970558A1/de not_active Withdrawn
- 2014-02-14 JP JP2015561997A patent/JP2016516843A/ja not_active Withdrawn
- 2014-02-14 CN CN201480013873.4A patent/CN105073816A/zh active Pending
- 2014-02-14 WO PCT/EP2014/052867 patent/WO2014139752A1/de active Application Filing
- 2014-03-10 TW TW103108162A patent/TW201500483A/zh unknown
- 2014-03-13 AR ARP140100922A patent/AR095382A1/es unknown
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI621871B (zh) * | 2015-07-31 | 2018-04-21 | 三星Sdi股份有限公司 | 窗膜和包含所述窗膜的可撓性顯示器 |
US10696016B2 (en) | 2015-07-31 | 2020-06-30 | Samsung Sdi Co., Ltd. | Window film and flexible display including the same |
US11041057B2 (en) | 2016-12-13 | 2021-06-22 | Samsung Sdi Co., Ltd. | Window film, manufacturing method thereof, and display device including same |
Also Published As
Publication number | Publication date |
---|---|
EP2970558A1 (de) | 2016-01-20 |
AR095382A1 (es) | 2015-10-14 |
JP2016516843A (ja) | 2016-06-09 |
CN105073816A (zh) | 2015-11-18 |
US20160017165A1 (en) | 2016-01-21 |
DE102013204395A1 (de) | 2014-09-18 |
WO2014139752A1 (de) | 2014-09-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TW201500483A (zh) | 以可交聯氟聚合物爲基礎之表面塗層 | |
CN104245863B (zh) | 水性氟聚合物玻璃涂料 | |
TWI476223B (zh) | 防污組成物、防污膜、防污積層膜、轉印薄膜及樹脂積層體以及樹脂積層體的製造方法 | |
US8956730B2 (en) | Conductive multilayer stack, coated substrates including the same, and methods of making the same | |
CN103703570B (zh) | 在刮擦或磨损损坏之后具有自修复表面性能的供户外应用的聚合物材料 | |
CN107428972B (zh) | 用于飞机座舱盖和挡风玻璃的衬垫类型抗静电的顶涂层体系 | |
TW201333125A (zh) | 塗料、塗膜、太陽能電池模組之背板、及太陽能電池模組 | |
US20140093738A1 (en) | Coating composition for coated substrates and methods of making the same | |
JP6305983B2 (ja) | 水性フルロロポリマーコーティングを用いてガラス基材をコーティングするための方法 | |
CN115287012B (zh) | 一种超疏水自修复热固化pu胶膜制备方法及汽车保护膜 | |
EP2970710B1 (en) | Coating composition for coated substrates and methods of making the same | |
TW202311054A (zh) | 多層障壁膜、其製造及其於光伏打應用之用途 | |
US20180362794A1 (en) | Semifinished Product, Method of Production and Use Thereof | |
CN106687539B (zh) | 基于可交联的饱和聚酯树脂和含氟聚合物的表面涂层 | |
CN116686098A (zh) | 用于太阳能电池的阻挡组件 | |
WO2016175058A1 (ja) | 積層体およびその製造方法 | |
TW201345980A (zh) | 塗料、塗膜、太陽能電池模組之背板及太陽能電池模組 | |
JP2001180981A (ja) | 防眩性の塗膜を有する外装用硝子部材およびその設置方法 | |
JP2013207044A (ja) | 太陽電池表面保護シートおよびそれを用いた太陽電池モジュール |