KR101282028B1 - Particles of Fluoropolymer-Acrylic Containing Perfluoroalkyl Groups Useful for Weatherable Coating of Backsheet in Photovoltaic Modules - Google Patents
Particles of Fluoropolymer-Acrylic Containing Perfluoroalkyl Groups Useful for Weatherable Coating of Backsheet in Photovoltaic Modules Download PDFInfo
- Publication number
- KR101282028B1 KR101282028B1 KR1020110035796A KR20110035796A KR101282028B1 KR 101282028 B1 KR101282028 B1 KR 101282028B1 KR 1020110035796 A KR1020110035796 A KR 1020110035796A KR 20110035796 A KR20110035796 A KR 20110035796A KR 101282028 B1 KR101282028 B1 KR 101282028B1
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- KR
- South Korea
- Prior art keywords
- fluoropolymer
- perfluoroalkyl group
- particles
- fluorine
- weight
- Prior art date
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- 239000002245 particle Substances 0.000 title claims abstract description 86
- 238000000576 coating method Methods 0.000 title claims abstract description 40
- 239000011248 coating agent Substances 0.000 title claims abstract description 35
- 125000005010 perfluoroalkyl group Chemical group 0.000 title claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 53
- 239000011737 fluorine Substances 0.000 claims abstract description 53
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 52
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 52
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000178 monomer Substances 0.000 claims abstract description 33
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 32
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 8
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 8
- 230000000379 polymerizing effect Effects 0.000 claims description 7
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 6
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000007334 copolymerization reaction Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 abstract description 37
- 239000004446 fluoropolymer coating Substances 0.000 abstract description 7
- 229920001519 homopolymer Polymers 0.000 abstract description 2
- 229920002313 fluoropolymer Polymers 0.000 description 53
- 239000004811 fluoropolymer Substances 0.000 description 42
- 239000006185 dispersion Substances 0.000 description 35
- -1 fluorine (meth) acrylic acid esters Chemical class 0.000 description 20
- 238000004519 manufacturing process Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 229920002620 polyvinyl fluoride Polymers 0.000 description 17
- 239000000203 mixture Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 16
- 239000002904 solvent Substances 0.000 description 14
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
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- 238000006243 chemical reaction Methods 0.000 description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
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- 230000000704 physical effect Effects 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 125000000524 functional group Chemical group 0.000 description 6
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 6
- 239000003505 polymerization initiator Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 5
- 239000002998 adhesive polymer Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 239000012986 chain transfer agent Substances 0.000 description 4
- 238000012674 dispersion polymerization Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000005001 laminate film Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
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- 239000002736 nonionic surfactant Substances 0.000 description 3
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical class [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
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- 238000011156 evaluation Methods 0.000 description 2
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- 230000014759 maintenance of location Effects 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
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- 239000007921 spray Substances 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 description 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- PAOHAQSLJSMLAT-UHFFFAOYSA-N 1-butylperoxybutane Chemical compound CCCCOOCCCC PAOHAQSLJSMLAT-UHFFFAOYSA-N 0.000 description 1
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
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- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- ZZEMEJKDTZOXOI-UHFFFAOYSA-N digallium;selenium(2-) Chemical compound [Ga+3].[Ga+3].[Se-2].[Se-2].[Se-2] ZZEMEJKDTZOXOI-UHFFFAOYSA-N 0.000 description 1
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- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
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- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- DVEKCXOJTLDBFE-UHFFFAOYSA-N n-dodecyl-n,n-dimethylglycinate Chemical compound CCCCCCCCCCCC[N+](C)(C)CC([O-])=O DVEKCXOJTLDBFE-UHFFFAOYSA-N 0.000 description 1
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- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
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- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 238000007761 roller coating Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 229940079827 sodium hydrogen sulfite Drugs 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 235000019187 sodium-L-ascorbate Nutrition 0.000 description 1
- 239000011755 sodium-L-ascorbate Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical class FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
본 발명은 태양전지 모듈의 백쉬트의 내후성 코팅재로 적합한 상호침투 네트웍(interpenetrating network)구조를 갖는 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 제공하며, 이는 비닐리덴 플루오라이드(VDF) 단독 중합 또는 공중합하여 불소고분자 씨드(Seed)를 제조한 후 여기에 불소함유 (메타)아크릴산 에스테르, 비불소계 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체를 중합하여 제조되고, 이는 기존 사용하고 있는 PVF 필름을 대체할 수 있는 새로운 내후성 불소고분자 코팅재로 유용하다.The present invention provides an acrylic particle containing a fluoropolymer-perfluoroalkyl group having an interpenetrating network structure suitable as a weatherproof coating of a back sheet of a solar cell module, which is polymerized or copolymerized with vinylidene fluoride (VDF) homopolymer. To produce a fluorine polymer seed (Seed) and then polymerize the fluorine-containing (meth) acrylic acid ester, non-fluorine-based (meth) acrylic acid ester and acrylamide-based monomer, which can replace the PVF film in use New weather resistant fluoropolymer coatings.
Description
본 발명은 태양전지 모듈 백쉬트의 고도의 내후성(weatherability) 코팅재로서 유용한 불소고분자-퍼플루오로알킬기 함유 아크릴 입자에 관한 것이다. 더욱 상세하게 말하면 본 발명은 비닐리덴 플루오라이드(VDF) 단독 중합 또는 VDF와 비닐 플루오라이드(VF), 트리 플루오로에틸렌(TrFE), 클로로트리플루오로에틸렌(CTFE), 테트라플루오로에틸렌(TFE), 헥사플루오로에틸렌(HFE) 및 헥사플루오로프로필렌(HFP) 중에서 선택된 하나 또는 둘 이상의 불소단량체를 공중합하여 불소고분자 씨드(Seed)를 제조한 후 여기에 불소(메타)아크릴산 에스테르와 비불소(메타)아크릴산 에스테르를 중합(Seed Polymerization)하여 제조된 불소고분자-퍼플루오로알킬기 함유 아크릴 입자에 관한 것이다. 이 불소고분자-퍼플루오로알킬기 함유 아크릴입자는 상호침투 네트웍(interpenetrationg network) 구조를 갖는다. 본 발명의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자는 코팅, 필름 및 기타 제조품의 내후성 및 내습성 성분으로 유용하다. 본 발명의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 코팅재로 사용하여 제조된 태양전지 백쉬트층은 주위 환경에 노출되어 내화학성, 내습성, 전기절연성 및 UV 광선 보호성 등이 탁월하여 고도의 내후성을 갖는다. The present invention relates to fluoropolymer-perfluoroalkyl group-containing acrylic particles useful as highly weatherable coatings for solar cell module backsheets. More specifically, the present invention is a vinylidene fluoride (VDF) homopolymerization or VDF and vinyl fluoride (VF), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) Copolymerized with one or two or more fluorine monomers selected from hexafluoroethylene (HFE) and hexafluoropropylene (HFP) to prepare fluorinated polymer seeds (Seed), followed by fluorine (meth) acrylic acid esters and non-fluorine (meta). The present invention relates to a fluoropolymer-perfluoroalkyl group-containing acrylic particle produced by polymerizing an acrylic ester. This fluoropolymer-perfluoroalkyl group-containing acrylic particle has an interpenetrationg network structure. The fluoropolymer-perfluoroalkyl group-containing acrylic particles of the present invention are useful as weather and moisture resistant components of coatings, films and other articles of manufacture. The solar cell backsheet layer manufactured by using the fluoropolymer-perfluoroalkyl group-containing acrylic particles of the present invention as a coating material has excellent chemical resistance, moisture resistance, electrical insulation, and UV light protection due to exposure to the surrounding environment. It has weather resistance.
태양전지 모듈은 외각 유리재료, 일반적으로 투명한 보호 포장으로 캡슐화된 태양전지 및 배면의 백쉬트(Backsheet)로 구성된다. 태양전지는 태양광 포집용도의 실리콘, CIS(cadimium indium selenide), CIGS(cadmium indium galliumselenide), 양자점(quantom dot)등을 포함하는 재료로 만들어진다. 태양전지 모듈은 옥외에서 사용되기 때문에 그 구성과 재질 구조 등에 있어서 충분한 내구성과 내후성이 요구된다. 특히, 태양전지 모듈 배면의 환경에 노출되는 백쉬트의 역할은 태양전지가 가혹한 환경에서도 25년 이상의 장기간 특성을 유지할 수 있도록 하는 것이다. 따라서 백쉬트는 장기 내후성이 우수해야 한다. 백쉬트는 내후성과 더불어 수증기와 산소의 차단성 및 UV 저항성이 우수해야 한다. 백쉬트는 수분, 산소 또는 UV 광선 등과의 반응으로 유발되는 실리콘 웨이퍼(태양전지)의 성능저하로부터 보호하는 중요한 역할을 한다.The solar cell module consists of an outer glass material, typically a solar cell encapsulated in a transparent protective packaging and a backsheet on the back. Solar cells are made of materials that contain silicon for solar capture, cadimium indium selenide (CIS), cadmium indium gallium selenide (CIGS), quantum dots, and the like. Since the solar cell module is used outdoors, sufficient durability and weather resistance are required in its configuration and material structure. In particular, the role of the backsheet exposed to the environment behind the solar cell module is to allow the solar cell to maintain its long-term characteristics for more than 25 years even in harsh environments. Therefore, the backsheet should have excellent long-term weather resistance. In addition to weather resistance, the backsheet should have excellent water and oxygen barrier and UV resistance. The backsheet plays an important role in protecting against the degradation of the silicon wafer (solar cell) caused by reaction with moisture, oxygen or UV light.
일반적으로 백쉬트는 3개의 기능층으로 적층된 필름 형태로 수증기와 산소 차단성이 우수한 폴리에스테르 기재 필름을 내후성이 뛰어난 불소고분자 필름으로 양면에서 감싸는(encapsulate) 형태의 구조로 되어 있다. 기재 필름은 폴리에틸렌 테레프탈레이트(PET)가 주로 사용되어 왔고, 내후성 불소고분자 필름으로는 미국 듀퐁사의 폴리비닐 플루오라이드(PVF) 필름인 Tedlar(상품명)(미국 특허 6,646,196)가 주로 사용되어 왔다. PET는 수증기 차단성이 우수하고 비교적 저렴한 고분자이지만, UV 광선, IR 광선과 오존과 같은 환경적 영향에 의하여 성능저하가 쉽게 일어난다. 현재 사용되는 백쉬트에서 PET는 내후성이 우수한 Tedlar(PVF)에 의해서 보호된다. 그러나 Tedlar 필름은 비교적 고가이고 수증기에 대한 저항성이 양호하지 않다. 따라서 Tedlar 필름과 PET의 조합은 우수한 백쉬트 재료를 제공한다. 전형적인 태양전지 백쉬트는 PVF/PET/PVF 층의 라미네이트 필름으로 제조된다. 그러나 이 구조는 PVF의 PET에 대한 부착성이 나쁘다는 결점을 지닌다. 부착성은 전형적으로 코로나 방전이나 유사한 기술로 고분자 표면을 처리하여 향상시킨다. 또한 부착성을 증가시키기 위하여 PET상에 접착제를 도포하여 사용한다.In general, the back sheet has a structure in which a polyester base film having excellent water vapor and oxygen barrier properties is encapsulated on both sides with a fluoropolymer film having excellent weather resistance in the form of a film laminated with three functional layers. As the base film, polyethylene terephthalate (PET) has been mainly used, and as a weather resistant fluoropolymer film, Tedlar (trade name) (US Pat. No. 6,646,196), which is a polyvinyl fluoride (PVF) film of DuPont, USA, has been mainly used. PET is a relatively inexpensive polymer with excellent water vapor barrier, but its performance easily occurs due to environmental effects such as UV light, IR light and ozone. In today's backsheets, PET is protected by Tedlar (PVF), which has excellent weather resistance. However, Tedlar films are relatively expensive and have poor resistance to water vapor. The combination of Tedlar film and PET thus provides a good backsheet material. Typical solar cell backsheets are made of laminate films of PVF / PET / PVF layers. However, this structure has the drawback of poor adhesion of PVF to PET. Adhesion is typically improved by treating the polymer surface with corona discharge or similar techniques. It is also used by applying an adhesive on PET to increase the adhesion.
이와 같은 PVF/PET/PVF 라미네이트 필름 복합체들은 종래에는 폴리에스테르 기재에 부착된 불소고분자, 특히 PVF의 미리 형성된 필름으로부타 제조되어 왔다. 그러나 미리 형성된 불소고분자 필름을 고분자 기재 위에 접착제를 이용하여 라미네이트를 하는 것은 제조공정이 복잡하고, 수년간 옥외 노출 후에는 라미네이트가 다시 분리되는 단점이 있다. 미국 특허 3,133,854, 5,139,878과 6,632,518 등에는 미리 형성된 필름으로 내구성 라미네이트 구조를 만들 수 있는 프라이머와 접착제를 개시하고 있다. 그러나 이들 공정은 실제의 라미네이션 단계 이전에 적어도 하나의 접착제층, 또는 하나의 프라이머와 하나의 접착제 층을 형성시켜야 한다. 라미네이션 불소고분자 필름을 사용하는 라미네이트는 제조하는데 많은 비용이 소요되며 많은 투자비가 요구된다. 미리 형성된 불소고분자 필름은 제조과정과 후속과정에서 요구되는 강도를 부여하기 위하여 충분한 두께를 가져야만 한다. 이로 인하여 라미네이트는 효율적인 보호층으로 요구되는 두께 이상으로 두꺼운 불소고분자 층을 함유할 수 있다. 미국특허 출원번호 (US Pat. Appl. No) 2009/0260677Al에서는 상기의 미리 제조된 불소고분자 필름으로 라미네이트를 제조하는 공정의 단점을 개선할 수 있는 불소고분자가 코팅된 필름을 제조하는데 필요한 불소고분자 코팅소재를 개시하였다.Such PVF / PET / PVF laminate film composites have conventionally been produced from preformed films of fluoropolymers, in particular PVF, attached to a polyester substrate. However, laminating a preformed fluoropolymer film using an adhesive on a polymer substrate has a disadvantage in that the manufacturing process is complicated and the laminate is separated again after many years of outdoor exposure. U.S. Patents 3,133,854, 5,139,878 and 6,632,518, etc. disclose primers and adhesives that can make durable laminate structures from preformed films. However, these processes must form at least one adhesive layer, or one primer and one adhesive layer, before the actual lamination step. Lamination Laminates using fluoropolymer films are expensive to manufacture and require a large investment. The preformed fluoropolymer film must have a sufficient thickness to impart the strength required in the manufacturing and subsequent processes. This may cause the laminate to contain a fluoropolymer layer thicker than the thickness required for an efficient protective layer. US Pat. Appl. No. 2009/0260677 Al discloses a fluorine polymer coating required to prepare a fluorine polymer coated film that can improve the disadvantages of the process of making a laminate with the prefabricated fluoropolymer film. The material is disclosed.
불소고분자 기반 내후성 코팅소재에 관한 선행 특허 기술들을 요약하여 기술하면 하기와 같다. 미국 특허 7,803,867에는 향상된 내구성, 내오염성, 발수성, 향상된 햇빛 반사성 등의 물성을 부여하는 수성 불소고분자 코팅 조성물을 개시하였다. 이 기술은 아크릴 변성 불소고분자(acrylic-modified fluoropolymer)의 수성 불소고분자 코팅에 관한 것이다. 수성 불소고분자는 아크릴 변성 불소고분자 형태의 분산액으로서 상호침투 네트웍(interpenetrationg network)형 모포로지를 가진다. 특히 50~95 중량%의 폴리비닐리덴 플루오라이드(PVDF)고분자와 PVDF와 열역학적으로 용해되는 아크릴 조성물의 블렌드이다. 미국 특허 6,635,714에는 고내후성을 갖는 불소고분자-아크릴(fluoropolymer-acrylic) 조성물이 개시되어 있다. 비닐리덴 플루오라이드(VDF)와 선택적으로 퍼할로젠화(perhalogenated) 공단량체를 중합하여 제조된 불소고분자와 아크릴 공중합체로 구성되는 조성물에 관한 것이다. 이 조성물은 코팅, 필름 및 기타 제조품의 내후성 성분으로 유용하다. 미국 특허 5,646,201에는 내후성과 기계적 물성이 탁월하고 고도의 광택성 코팅을 제공할 수 있는 불소고분자 수분산액을 개시하였다. VDF와 클로로트리플루우로에틸렌(CTFE)을 공중합하여 제조된 씨드 입자의 존재 하에 (메타)아크릴산 에스테르를 중합하여 얻어지는 불소함유 공중합체의 수분산액에 관한 것이다.Summarizing prior arts related to fluoropolymer based weather resistant coating materials are as follows. US Pat. No. 7,803,867 discloses an aqueous fluoropolymer coating composition that confers physical properties such as improved durability, fouling resistance, water repellency, improved sunlight reflectivity, and the like. This technology relates to aqueous fluoropolymer coatings of acrylic-modified fluoropolymers. Aqueous fluoropolymers are dispersions in the form of acrylic modified fluoropolymers and have interpenetrationg network type morphologies. In particular, it is a blend of 50-95% by weight of polyvinylidene fluoride (PVDF) polymer with an acrylic composition thermodynamically dissolved with PVDF. U.S. Patent 6,635,714 discloses fluoropolymer-acrylic compositions with high weatherability. A composition comprising a fluoropolymer and an acrylic copolymer prepared by polymerizing vinylidene fluoride (VDF) and optionally perhalogenated comonomer. This composition is useful as a weather resistant component of coatings, films and other articles of manufacture. U. S. Patent No. 5,646, 201 discloses an aqueous fluoropolymer dispersion which is excellent in weatherability and mechanical properties and can provide a highly glossy coating. It relates to an aqueous dispersion of a fluorine-containing copolymer obtained by polymerizing a (meth) acrylic acid ester in the presence of seed particles prepared by copolymerizing VDF and chlorotrifluoroethylene (CTFE).
전 세계적으로 태양전지 수요가 급신장하면서 기존 사용하고 있는 백쉬트용 내후성 불소고분자 라미네이트 소재(PVF 필름)를 대체할 수 있는 내후성 불소고분자 코팅 소재에 대한 요구가 매우 크지만 아직 만족할만한 수준의 소재가 개발되지 않고 있다.The demand for weather-resistant fluoropolymer coating material that can replace the weather-resistant fluoropolymer laminate material (PVF film) for backsheet, which is already used due to the rapid growth of solar cell demand in the world, is still satisfactory. It is not developed.
본 발명자들은 본래의 불소고분자의 벌크 물성을 변화시키지 않으면서 내후성과 내습성이 향상된 불소고분자 코팅소재를 제조하는 방법으로서 상호침투 네트웍 구조를 갖는 VDF 중합체의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 제조하는 기술을 발견하여 본 발명을 완성하게 되었다. 본 발명에 따르는 VDF 중합체 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 사용하는 경우 종래의 라미네이트 기술에 비하여 백쉬트의 제조공정을 단축할 수 있으며 제조비용을 개선할 수 있다. MEANS TO SOLVE THE PROBLEM The present inventors made the fluoropolymer-perfluoroalkyl group containing acrylic particle of the VDF polymer which has an interpenetrating network structure as a method of manufacturing the fluoropolymer coating material which improved weatherability and moisture resistance, without changing the bulk physical property of the original fluoropolymer. Discovering the technology to manufacture has been completed the present invention. In the case of using the VDF polymer fluoropolymer-perfluoroalkyl group-containing acrylic particles according to the present invention, the manufacturing process of the backsheet can be shortened and the manufacturing cost can be improved as compared with the conventional laminate technology.
태양전지 모듈의 백쉬트는 일반적으로 수증기와 산소차단성이 우수한 폴리에스테르 기재 필름을 내후성 불소고분자 라미네이트 필름으로 양면에서 감싸는 형태의 구조로 되어있다. 불소고분자 라미네이트 필름은 주로 PVF 필름을 사용하고 있다. 세계시장에서 기존의 PVF 필름보다 내후성을 나타내면서 저렴한 불소고분자 코팅 소재에 대한 요구가 매우 크다. 본 발명의 목적은 태양전지 모듈의 백쉬트 제조에 있어서 기존 사용하고 있는 PVF 필름을 대체할 수 있는 새로운 내후성 VDF 중합체 코팅재를 제공하는 것이다. 보다 구체적으로, 본 발명의 목적은 태양전지 백쉬트용 코팅재로서 필름 형성물성이 우수하며, 내후성과 내습성이 우수한 코팅을 형성할 수 있는 불소고분자 입자를 제공하는 것이다. The back sheet of a solar cell module generally has a structure in which a polyester base film having excellent water vapor and oxygen barrier properties is wrapped on both sides with a weather resistant fluoropolymer laminate film. Fluoropolymer laminate film mainly uses PVF film. There is a great demand for inexpensive fluoropolymer coating material in the world market which shows weather resistance than conventional PVF film. An object of the present invention is to provide a new weather-resistant VDF polymer coating material that can replace the PVF film currently used in the manufacture of a back sheet of a solar cell module. More specifically, an object of the present invention is to provide a fluorinated polymer particle capable of forming a coating having excellent film forming properties and excellent weatherability and moisture resistance as a coating material for a solar cell back sheet.
본 발명자들은 본래의 불소고분자의 벌크 물성을 변화시키지 않으면서 내후성과 내습성이 향상된 불소고분자 코팅재를 제조하는 방법으로서, 상호침투 네트웍 구조를 갖는 VDF 중합체의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 제조하는 기술을 발견하여 본 발명을 완성하게 되었다.MEANS TO SOLVE THE PROBLEM The present invention is a method of manufacturing the fluoropolymer coating material which improved the weatherability and moisture resistance, without changing the bulk physical property of the original fluoropolymer, Comprising: The fluoropolymer-perfluoroalkyl group containing acrylic particle of the VDF polymer which has an interpenetrating network structure is carried out. Discovering the technology to manufacture has been completed the present invention.
본 발명의 VDF 중합체는 VDF 단독중합체 또는 이의 공중합체를 포함한다.VDF polymers of the present invention include VDF homopolymers or copolymers thereof.
본 발명자들은 VDF 중합체를 씨드로 하는 분산액 속에서 퍼플르오로알킬기 함유 (메타)아크릴산 에스테르와 비불소계(메타)아크릴산 에스테르를 중합하여 분자수준에서 상용성이 있는 입자를 얻을 수 있으며, 이 입자가 내후성과 내습성이 매우 우수하다는 것을 발견하여, 본 발명을 완성하게 되었다. 본 발명에 따르는 VDF 중합체의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 사용하는 경우 종래의 라미네이트 기술에 비하여 백쉬트의 제조공정을 단축할 수 있으며 제조비용을 개선할 수 있다. The present inventors can polymerize perfluoroalkyl group-containing (meth) acrylic acid esters and non-fluorine-based (meth) acrylic acid esters in a dispersion containing a VDF polymer as a seed, thereby obtaining particles compatible with each other at the molecular level. It was found that the moisture resistance and the moisture resistance was very excellent, and thus the present invention was completed. In the case of using the fluorinated polymer-perfluoroalkyl group-containing acrylic particles of the VDF polymer according to the present invention, the manufacturing process of the backsheet can be shortened and the manufacturing cost can be improved as compared with the conventional laminate technology.
상기 목적을 달성하기 위하여, 본 발명은 태양전지 모듈 백쉬트의 내후성 코팅재로 사용하는 VDF 중합체의 불소고분자-퍼플루오로 알킬기 함유 아크릴 입자를 제공한다. In order to achieve the above object, the present invention provides a fluoropolymer-perfluoro alkyl group-containing acrylic particles of the VDF polymer used as a weather-resistant coating of the solar cell module backsheet.
보다 구체적으로 본 발명은More specifically, the present invention
a) 비닐리덴 플루오라이드(VDF) 단독중합 또는 비닐리덴 플루오라이드(VDF)와 공단량체를 공중합하여 씨드 입자를 제조하는 단계; 및a) vinylidene fluoride (VDF) homopolymerization or copolymerization of vinylidene fluoride (VDF) with a comonomer to produce seed particles; And
b) 상기 씨드 입자의 존재 하에, 불소함유 (메타)아크릴산 에스테르, 비불소계 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체를 중합하는 단계;b) polymerizing a fluorine-containing (meth) acrylic acid ester, a non-fluorine-based (meth) acrylic acid ester and an acrylamide monomer in the presence of the seed particles;
를 포함하여 제조하는 불소고분자-퍼플루오로알킬기 함유 아크릴 입자에 관한 것이다.It relates to a fluoropolymer-perfluoroalkyl group-containing acrylic particles prepared to include.
또한 본 발명은 상기 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 포함하는 내후성 또는 내습성 코팅재도 본 발명의 범위에 포함된다.In addition, the present invention also includes a weather-resistant or moisture-resistant coating material containing the fluorine-polymer-perfluoroalkyl group-containing acrylic particles in the scope of the present invention.
또한, 상기 코팅재를 포함하는 태양전지 백쉬트도 본 발명의 범위에 포함된다.In addition, the solar cell backsheet including the coating material is also included in the scope of the present invention.
이하는 본 발명의 구성에 대하여 보다 구체적으로 설명한다.Hereinafter, the configuration of the present invention will be described in more detail.
먼저, 본 발명의 a)단계에 대하여 설명하면,First, with reference to step a) of the present invention,
상기 단독중합은 VDF의 단독중합이고, VDF와 공중합하는 공단량체는 비닐 플루오라이드(VF), 트리플루오로에틸렌(TrFE), 클로로트리플루오로에틸렌(CTFE), 테트라플루오로에틸렌(TFE) 및 헥사플루오로프로필렌(HFP) 중에서 선택된 하나 또는 둘 이상인 불소고분자-퍼플루오로알킬기 함유 아크릴 입자이다. The homopolymerization is a homopolymerization of VDF, and the comonomers copolymerized with VDF are vinyl fluoride (VF), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) and hexa It is an acrylic particle containing fluoropolymer-perfluoroalkyl group which is one or two or more selected from fluoropropylene (HFP).
VDF 공중합체는 상기 공단량체 1 ~ 30 중량%를 사용하는 것이 적합하다. VDF가 70 중량% 미만인 경우에 VDF 중합체인, 불소고분자 씨드 입자는 퍼플루오로알킬기 함유 아크릴 고분자와의 상용성이 저하되어 코팅 필름의 내후성과 내습성 등의 물성이 저하된다.VDF copolymer is suitable to use 1 to 30% by weight of the comonomer. When the VDF is less than 70% by weight, the fluorinated polymer seed particles, which are VDF polymers, have low compatibility with the perfluoroalkyl group-containing acrylic polymer, thereby deteriorating physical properties such as weatherability and moisture resistance of the coating film.
본 발명에서 "불소고분자 씨드" 및 "불소고분자 씨드 입자"는 VDF 중합체 씨드를 의미한다. In the present invention, "fluorine polymer seed" and "fluorine polymer seed particle" mean VDF polymer seed.
본 발명에 따른 불소고분자 씨드 입자의 제조에 있어서, 상기 불소계 단량체의 수분산 중합은 종래에 사용되고 있는 통상적인 방법에 따라 수행된다. 유화중합의 경우에는 통상적으로 사용하는 불소계 계면활성제를 사용하여 불소계 단량체를 수분산시킨다. 불소계 계면활성제의 양은 제조된 불소고분자 씨드의 고체함량과 입자크기 등과 같은 요구물성에 따라 달라지나, 불소고분자 씨드의 양호한 물성을 위하여 불소고분자 씨드 양을 기준으로 0.01~2중량%인 것이 바람직하다.In the preparation of the fluoropolymer seed particles according to the present invention, the water dispersion polymerization of the fluorine-based monomer is carried out according to a conventional method used conventionally. In the case of emulsion polymerization, a fluorine-based monomer is used to disperse the fluorine-based monomer which is commonly used. The amount of the fluorine-based surfactant depends on the required physical properties, such as the solid content and particle size of the prepared fluorinated polymer seeds, but in order to have good physical properties of the fluorinated polymer seeds, it is preferably 0.01 to 2% by weight based on the amount of fluorinated polymer seeds.
불소고분자 씨드 입자의 크기는 상기 b)단계의 중합 후의 고분자 입자 크기와 밀접한 관계가 있다. 상기 b)단계의 중합 후에 고분자의 입자크기를 500nm이하로 만들기 위해서는 씨드 입자의 크기는 400nm이하, 바람직하게는 300nm이하인 것이 적합하다. 씨드 입자로 사용하는 불소고분자는 보통의 유화중합에 의하여 얻는다. 입자 크기가 400nm이하인 씨드 입자를 함유하는 수분산액은 물 중량기준으로 0.5중량% 이하의 불소계 계면활성제의 존재 하에서 불소단량체를 유화중합(에멀전중합)하여 제조할 수 있다.The size of the fluoropolymer seed particles is closely related to the size of the polymer particles after the polymerization in step b). In order to make the particle size of the polymer 500 nm or less after the polymerization of step b), the size of the seed particles is preferably 400 nm or less, preferably 300 nm or less. Fluorine polymers used as seed particles are obtained by ordinary emulsion polymerization. An aqueous dispersion containing seed particles having a particle size of 400 nm or less may be prepared by emulsion polymerization (emulsion polymerization) of a fluorine monomer in the presence of 0.5 wt% or less of a fluorine-based surfactant based on water weight.
본 발명에 따른 불소고분자 씨드 입자의 유화중합에 사용하는 유화제는 특별히 제한되지 않지만 불소계 계면활성제로 사용하는 경우 내후성, 내습성이 더욱 증가되는 특수한 효과를 가진다. 불소계 계면활성제는 특별하게 제한되지 않는데, 퍼플루오로 옥탄산 암모니움 염, 퍼플루오로 노난산 암모니움 염 등과 같은 현재 상업적으로 사용하는 다양한 불소계 계면활성제를 사용할 수 있다. 얻어지는 수분산액은 400nm이하의 씨드 입자를 30-50중량% 함유할 수 있다. 중합 온도는 30-120℃이나, 50-90℃가 보다 양호하다. 30℃이하인 경우에는 생성된 라텍스의 안정성이 저하되는 경향이 있고, 120℃ 이상이면 중합속도가 사슬 전이 반응으로 인하여 저하되는 경향이 있다. 본 발명의 불소고분자 씨드 입자의 수분산 중합은 20~120℃의 온도 범위 및 5~50bar의 압력 범위에서 수행되는 것이 바람직하다. 또한, 수분산 중합을 위한 반응물의 pH는 5~10인 것이 바람직하다. 중합 후 얻어지는 수분산액은 10-50중량%의 불소고분자 씨드를 함유한다.The emulsifier used in the emulsion polymerization of the fluoropolymer seed particles according to the present invention is not particularly limited, but when used as a fluorine-based surfactant, it has a special effect of further increasing weather resistance and moisture resistance. Fluorine-based surfactants are not particularly limited, and various commercially available fluorine-based surfactants such as perfluoro octanoic acid ammonium salts, perfluoro nonanoic acid ammonium salts, and the like can be used. The resulting aqueous dispersion may contain 30-50% by weight of seed particles of 400 nm or less. Although polymerization temperature is 30-120 degreeC, 50-90 degreeC is more preferable. If it is 30 ° C. or less, the stability of the resulting latex tends to be lowered, and if it is 120 ° C. or more, the polymerization rate tends to be lowered due to the chain transfer reaction. The water dispersion polymerization of the fluoropolymer seed particles of the present invention is preferably carried out in a temperature range of 20 ~ 120 ℃ and a pressure range of 5 ~ 50bar. In addition, the pH of the reactant for water dispersion polymerization is preferably 5-10. The aqueous dispersion obtained after the polymerization contains 10-50% by weight of fluoropolymer seeds.
본 발명에 따른 불소고분자 씨드의 제조방법에 있어서, 상기 수분산 에멀젼 중합은 불소단량체의 자유 라디칼 중합을 개시하기 위하여 개시제를 사용한다. 이때, 적합한 개시제로는 일반적으로 사용하는 과산화물(peroxide), 아조화합물, 및 레독스(redox) 기반 개시제를 포함할 수 있다. 개시제의 양은 불소고분자 양을 기준으로 0.05~0.5 중량%인 것이 바람직하다.In the method for producing a fluoropolymer seed according to the present invention, the water dispersion emulsion polymerization uses an initiator to initiate free radical polymerization of the fluorine monomer. In this case, suitable initiators may include peroxides, azo compounds, and redox based initiators that are generally used. The amount of the initiator is preferably 0.05 to 0.5% by weight based on the amount of fluoropolymer.
또한, 본 발명에 따른 불소고분자 씨드의 제조방법에 있어서, 상기 수분산 중합은 사슬 이동제(chain transfer agent)를 사용할 수 있다. 사슬이동제의 예로는 디에틸말론네이트와 같은 에스테르, 디메틸에테르, 메틸 t-부틸 에테르와 같은 에테르, 에탄, 프로판과 n-펜탄 등과 같은 알칸, CCl4, CHCl3과 CH2Cl2등과 같은 할로겐화 탄화수소, CH2FCF3(HCFC-134a)과 같은 탄소불화화합물, 도데실머켑탄 등을 포함한다.
In addition, in the method for producing a fluoropolymer seed according to the present invention, the water dispersion polymerization may use a chain transfer agent (chain transfer agent). Examples of chain transfer agents include esters such as diethylmalonate, dimethyl ether, ethers such as methyl t-butyl ether, alkanes such as ethane, propane and n-pentane, halogenated hydrocarbons such as CCl 4 , CHCl 3 and CH 2 Cl 2, and the like. Carbon fluoride compounds such as CH 2 FCF 3 (HCFC-134a), dodecyl merethane, and the like.
다음으로 본 발명의 b)단계에 대하여 보다 구체적으로 설명한다.Next, step b) of the present invention will be described in more detail.
본 발명에서 상기 b)단계는 a)단계에서 제조된 씨드입자의 존재 하에, 불소함유 (메타)아크릴산 에스테르, 비불소계 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체를 중합하여 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 제조하는 단계이다.In the present invention, step b) is a fluoropolymer-perfluoroalkyl group by polymerizing a fluorine-containing (meth) acrylic acid ester, a non-fluorine-based (meth) acrylic acid ester, and an acrylamide monomer in the presence of the seed particles prepared in step a). It is a step of preparing the containing acrylic particles.
본 발명에서 상기 "불소함유 (메타)아크릴산 에스테르"란 퍼플루오로알킬기를 함유하는 (메타)아크릴산 에스테르를 의미하며, 보다 구체적으로는 탄소원자수 4-20인 퍼플루오로알킬기 함유 (메타)아크릴산 에스테르를 의미한다. 구체적으로 예를 들면 In the present invention, the "fluorine-containing (meth) acrylic acid ester" means a (meth) acrylic acid ester containing a perfluoroalkyl group, and more specifically, a perfluoroalkyl group-containing (meth) acrylic acid ester having 4-20 carbon atoms. Means. Specifically
본 발명의 탄소원자 4-20개의 퍼플루오로알킬기 함유 (메타)아크릴산 에스테르는 다음과 같은 화학식 1 ~ 6 으로 표시되는 것 중에서 선택된 하나 또는 둘 이상의 화합물이다.
The perfluoroalkyl group-containing (meth) acrylic acid ester having 4-20 carbon atoms of the present invention is one or two or more compounds selected from the following formulas (1) to (6).
[화학식 1][Formula 1]
Rf(CH2)jOCOCR1=CH2 R f (CH 2 ) j OCOCR 1 = CH 2
[화학식 2] [Formula 2]
Rf(CH2)kOCOOCR1=CH2 R f (CH 2 ) kOCOOCR 1 = CH 2
[화학식 3] (3)
RfCH2C(OH)HCH2OCOR1=CH2 R f CH 2 C (OH) HCH 2 OCOR 1 = CH 2
[화학식 4] [Formula 4]
RfCON(R2)R3OCOR1=CH2 R f CON (R 2 ) R 3 OCOR 1 = CH 2
[화학식 5] [Chemical Formula 5]
RfSO2N(R2)R3OCOR1=CH2 R f SO 2 N (R 2 ) R 3 OCOR 1 = CH 2
[화학식 6] [Formula 6]
RfCH2C(OCOR4)HCH2OCOR1=CH2 R f CH 2 C (OCOR 4 ) HCH 2 OCOR 1 = CH 2
(화학식 1 ~ 6 에서 Rf는 각각 탄소원자 4-20개의 퍼플루오로알킬기(CnF2n+1: n=4-20); R1은 각각 H 또는 CH3; R2=탄소원자 1-10개의 알킬렌기 ; R3은 각각 H 또는 탄소원자 1-10개의 알킬기 ; R4은 탄소원자 1-17개의 알킬기 ; j=1-10, j는 정수 ; k=0-10, k는 정수)In Formulas 1 to 6, R f is a perfluoroalkyl group having 4 to 20 carbon atoms (C n F 2n + 1: n = 4-20); and R 1 is each H or CH 3 ; R 2 = alkylene group of 1-10 carbon atoms; R 3 is each H or an alkyl group of 1-10 carbon atoms; R 4 is an alkyl group of 1-17 carbon atoms; j = 1-10, j is an integer; k = 0-10, k is an integer)
또한 상기 "비불소계 (메타)아크릴산 에스테르"는 측쇄의 탄소 원자 수가 작을수록 불소고분자 씨드와의 상용성이 향상되기 때문에 1-3개의 탄소원자를 갖는 메타크릴산 에스테르가 보다 적합하다. 불소고분자 씨드와의 상용성의 관점에서는 아크릴산 에스테르로서 에틸 아크릴레이트와 메타크릴산 에스테르로서 메틸 메타크릴레이트가 보다 적합하고 이 중의 하나 또는 두개를 조합하여 사용하는 것이 좋다. In addition, the "non-fluorine-based (meth) acrylic acid ester" is more suitable for methacrylic acid ester having 1-3 carbon atoms because the smaller the number of carbon atoms in the side chain improves the compatibility with the fluorine polymer seed. From the viewpoint of compatibility with the fluoropolymer seed, ethyl acrylate as the acrylic acid ester and methyl methacrylate as the methacrylic acid ester are more suitable, and one or two thereof may be used in combination.
본 발명에서는 퍼플루오로알킬기 함유 아크릴산 에스테르, 비불소계 (메타)아크릴레이트 에스테르 및 아크릴 아미드계 단량체가 상기의 불소고분자 씨드 입자 존재 하에서 중합되어 본 발명의 상호침투 네트웍 구조의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자가 제조된다.In the present invention, the perfluoroalkyl group-containing acrylic acid ester, non-fluorine-based (meth) acrylate ester and acrylamide monomer are polymerized in the presence of the above-mentioned fluorinated polymer seed particles to form a fluoropolymer-perfluoroalkyl group of the interpenetrating network structure of the present invention. Containing acrylic particles are prepared.
본 발명의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자의 퍼플루오로알킬기 함유 아크릴 고분자 성분은 다음과 같은 단량체들을 구성성분으로 사용하여 제조될 수 있다.The perfluoroalkyl group-containing acrylic polymer component of the fluoropolymer-perfluoroalkyl group-containing acrylic particles of the present invention can be prepared using the following monomers as components.
(a) 2 내지 70 중량%의 탄소원자수 4-20인 퍼플루오로알킬기 함유 (메타)아크릴산 에스테르 (a) perfluoroalkyl group containing 2 to 70% by weight of carbon atoms (meth) acrylic acid ester
(b) 25 내지 97 중량%의 비불소계 (메타)아크릴산 에스테르(b) 25 to 97% by weight of non-fluorine-based (meth) acrylic acid ester
(c) 0.1 내지 5 중량%의 아크릴 아미드계 단량체(c) 0.1 to 5% by weight of acrylamide monomer
를 포함한다..
보다 구체적으로 설명하면 본 발명의 -퍼플루오로알킬기 함유 아크릴 입자의 불소함유 (메타)아크릴산 에스테르는 불소함유 (메타)아크릴산 에스테르, 비불소계 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체 100 중량%를 기준으로 2 ~ 70 중량%를 사용하여 제조하는 것이 적합하다. 2중량% 미만을 사용하는 경우에는 원하는 내후성 향상 효과를 얻을 수 없다. 70중량% 를 초과하는 경우에는 불소고분자 씨드와의 상용성이 저하되어 균일하게 혼합된 상호침투 네트웍 구조의 -퍼플루오로알킬기 함유 아크릴 입자를 얻을 수 없고, 이로 인하여 원하는 내후성 향상 효과를 기대할 수 없다.More specifically, the fluorine-containing (meth) acrylic acid esters of the -perfluoroalkyl group-containing acrylic particles of the present invention are based on 100% by weight of fluorine-containing (meth) acrylic acid esters, non-fluorine-based (meth) acrylic acid esters, and acrylamide monomers. It is suitable to prepare using 2 to 70% by weight. When less than 2% by weight is used, the desired weather resistance improvement effect cannot be obtained. When it exceeds 70% by weight, the compatibility with the fluoropolymer seeds is lowered, so that -perfluoroalkyl group-containing acrylic particles having a uniformly mixed interpenetrating network structure cannot be obtained, and thus, a desired weather resistance improvement effect cannot be expected. .
또한 본 발명의 -퍼플루오로알킬기 함유 아크릴 입자의 비불소계 (메타)아크릴산 에스테르는 불소함유 (메타)아크릴산 에스테르, 비불소계 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체 100 중량%를 기준으로 25 내지 97 중량%인 것이 적합하다. 25 중량% 미만인 경우에는 불소고분자 씨드와의 상용성이 저하된다. 97 중량% 를 초과하는 경우에는 원하는 내후성 향상 효과를 얻을 수 없다.In addition, the non-fluorine (meth) acrylic acid ester of the perfluoroalkyl group-containing acrylic particles of the present invention is 25 to 97 based on 100% by weight of fluorine-containing (meth) acrylic acid ester, non-fluorine (meth) acrylic acid ester, and acrylamide monomer. It is suitably in weight percent. If it is less than 25% by weight, the compatibility with the fluoropolymer seeds is lowered. When it exceeds 97 weight%, the desired weather resistance improvement effect cannot be acquired.
또한 아크릴 아미드계 단량체는 전체 아크릴 고분자 성분의 0.1 ~ 5 중량%를 사용하는 것이 좋다. 아크릴 아미드계 단량체로는 아크릴아미드, 메타크릴아미드, N-메틸아크릴아미드, N-메틸롤아크릴아미드, N-부톡시메틸아크릴아미드, N-메틸롤메타크릴아미드와 N-메틸메타크릴아미드 등이 있다. 그밖에도 기능성기를 갖는 단량체와 비닐 화합물을 더 포함할 수 있다. 기능성기를 갖는 단량체의 예로는 예를들면 아크릴산, 메타크릴산, 말레인산, 말레인산과 크로토닉산과 같은 불포화 카복실산, 하이드록시에틸 아크릴레이트, 하이드록시에틸 메타크릴레이트, 하이드록시프로필 아크릴레이트와 하이드로프로필 메타크릴레이트 등과 같은 하이드록시기 함유 단량체, 글리시딜 아크릴레이트와 글리시딜 메타크릴레이트와 같은 에폭시기 함유 단량체 등이다. 비닐 화합물로는 스틸렌, 아크릴로니트릴 등이 예이다.In addition, the acrylamide-based monomer is preferably used 0.1 to 5% by weight of the total acrylic polymer component. Acrylamide monomers include acrylamide, methacrylamide, N-methylacrylamide, N-methylol acrylamide, N-butoxymethylacrylamide, N-methylol methacrylamide and N-methylmethacrylamide. have. In addition, it may further include a monomer and a vinyl compound having a functional group. Examples of monomers having functional groups include, for example, acrylic acid, methacrylic acid, maleic acid, unsaturated carboxylic acids such as maleic acid and crotonic acid, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate and hydropropyl methacrylate. Hydroxy group-containing monomers such as late, and epoxy group-containing monomers such as glycidyl acrylate and glycidyl methacrylate. Examples of the vinyl compound include styrene and acrylonitrile.
또한 본 발명의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자에서 불소함유 (메타)아크릴산 에스테르, 비불소계 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체는 불소고분자 씨드 100중량부를 기준으로 20-100중량부인 것이 적합하다. 20 중량부 미만인 경우에는 코팅의 투명도와 광택이 저하되는 경향이 있다. 100 중량부를 초과하는 경우에는 원하는 내후성 향상 효과를 얻을 수 없다.In addition, the fluorine-containing (meth) acrylic acid ester, the non-fluorine-based (meth) acrylic acid ester, and the acrylamide-based monomer in the fluoropolymer-perfluoroalkyl group-containing acrylic particles of the present invention are 20-100 parts by weight based on 100 parts by weight of the fluoropolymer seed. Suitable. If it is less than 20 parts by weight, the transparency and gloss of the coating tends to be lowered. If it exceeds 100 parts by weight, the desired weather resistance improvement effect cannot be obtained.
퍼플루오로알킬기 함유 아크릴 입자의 중합은 통상의 유화중합에서 사용하는 조건과 동일한 조건하에서 실시될 수 있다. 예를 들면, 중합반응은 20-120℃의 온도에서 계면활성제, 중합개시제, 사슬이동제와, 필요하면 킬레이트제, pH조절제, 용매 등을 불소고분자 씨드 입자를 함유하는 수분산액에 첨가하여 수행할 수 있다. 중합온도는 30-90℃이고, 40-70℃가 보다 적합하다.The polymerization of the perfluoroalkyl group-containing acrylic particles can be carried out under the same conditions as those used in ordinary emulsion polymerization. For example, the polymerization can be carried out by adding a surfactant, a polymerization initiator, a chain transfer agent, and a chelating agent, a pH adjuster, a solvent, and the like to an aqueous dispersion containing fluoropolymer seed particles at a temperature of 20-120 ° C. have. Polymerization temperature is 30-90 degreeC, and 40-70 degreeC is more suitable.
상기 중합에 있어서 VDF 중합체인, 불소고분자 씨드 입자 존재하에 단량체 모두를 한꺼번에 반응시스템에 투입하는 방법, 반응을 위한 단량체의 일부를 투입하고 나머지 부분을 연속적으로 또는 나누어서 투입하는 방법과 단량체 모두를 연속적으로 투입하는 방법 등에서 어느 하나를 선택하여 사용할 수 있다.In the polymerization, in the presence of fluorinated polymer seed particles, which are VDF polymers, a method of introducing all of the monomers into the reaction system at a time, a method of adding a portion of the monomers for the reaction and continuously or dividedly adding the monomers and all of the monomers in succession Any method can be selected and used.
VDF 중합체인, 불소고분자 씨드 입자 존재 하에서 비불소계 (메타)아크릴산 에스테르, 불소함유 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체를 유화중합에 의하여 중합을 하는 경우에, 처음에는 불소고분자 씨드 입자가 비불소계 (메타)아크릴산 에스테르, 불소함유 (메타)아크릴산 에스테르 및 아크릴 아미드계 단량체 내에 스웰링(swelling)하는 현상이 발생하고, 이 시점부터 수분산액은 씨드 입자가 단량체 내에 균일하게 용해 또는 분산된 상태가 된다. 그 후 단량체들은 중합 개시제의 첨가에 의하여 중합하여 분자 사슬이 서로 교차하는 상호침투 네트웍 구조의 고분자 블렌드 입자를 형성하게 된다.When polymerizing non-fluorinated (meth) acrylic acid esters, fluorine-containing (meth) acrylic acid esters, and acrylamide monomers in the presence of fluorinated polymer seed particles, which are VDF polymers, by emulsion polymerization, the fluorinated polymer seed particles are initially non-fluorinated. The phenomenon of swelling in the (meth) acrylic acid ester, the fluorine-containing (meth) acrylic acid ester, and the acrylamide monomer occurs. From this point, the aqueous dispersion becomes a state in which the seed particles are uniformly dissolved or dispersed in the monomer. . The monomers are then polymerized by the addition of a polymerization initiator to form polymer blend particles of interpenetrating network structure in which molecular chains cross each other.
본 발명의 불소고분자 씨드를 이용한 중합에서 계면활성제는 특별하게 제한되지 않으며 음이온 계면활성제, 비이온 계면활성제, 이들의 조합 또는 양성 계면활성제를 사용할 수 있다. 음이온 계면활성제로는 에스테르의 고급 알코올 설페이트, 예를 들어, 소디움 알킬설폰네이트, 소디움 알킬벤젠설폰네이트, 소디움 석시네이트 디알킬에스테르설폰네이트, 소디움 알킬디페닐에스테르 디설폰네이트 등을 사용할 수 있다. 비이온 계면활성제로는 폴리옥시에틸렌 알킬 에테르, 폴리옥시에틸렌 알킬 페닐 에테르, 폴리옥시에틸렌 알킬 에스테르, 폴리옥시에틸렌 알킬 페닐에스테르, 솔비탄 알킬 에스테르, 글리세롤 에스테르와 이들의 유도체 등을 사용할 수 있다. 양이온 계면활성제로는 라우릴 베타인 등을 사용할 수 있다. 계면활성제의 양은 일반적으로 모든 단량체의 합을 100 중량% 기준으로 0.05-0.3 중량%가 적합하다.In the polymerization using the fluoropolymer seed of the present invention, the surfactant is not particularly limited, and anionic surfactants, nonionic surfactants, combinations thereof, or amphoteric surfactants can be used. As the anionic surfactant, higher alcohol sulfates of esters such as sodium alkylsulfonate, sodium alkylbenzenesulfonate, sodium succinate dialkylestersulfonate, sodium alkyldiphenylester disulfonate and the like can be used. As the nonionic surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ester, polyoxyethylene alkyl phenyl ester, sorbitan alkyl ester, glycerol ester and derivatives thereof and the like can be used. Lauryl betaine etc. can be used as a cationic surfactant. The amount of surfactant is generally suitable for 0.05-0.3% by weight based on 100% by weight of all monomers.
중합 개시제는 특별하게 제한되지 않으며 수매체 내에서 30-120℃에서 자유 라디칼 반응에 사용할 수 있는 라디칼을 생성할 수 있어야 한다. 필요한 경우에 개시제는 환원제와 조합하여 사용될 수 있다. 일반적으로 수용해성 중합 개시제의 예는 퍼설페이트와 과산화수소이며 환원제의 예로는 소디움 파이로설파이트(pyrosulfite), 소디움 하이드로젠 설파이트, 소디옴 L-아스코르베이트 등이다. 유용해성 중합 개시제의 예는 디이소프로필 퍼옥시디카보네이트, 벤조일 퍼옥사이드, 디부틸 퍼옥사이드, 아조비스이소부틸로니트릴 등이다. 중합 개시제의 양은 일반적으로 모든 단량체의 합을 100 기준으로 0.01-0.5이 적합하다.The polymerization initiator is not particularly limited and should be capable of producing radicals which can be used for free radical reactions at 30-120 ° C. in the aqueous medium. If necessary the initiator can be used in combination with a reducing agent. In general, examples of the water-soluble polymerization initiator are persulfate and hydrogen peroxide, and examples of the reducing agent are sodium pyrosulfite, sodium hydrogen sulfite, sodium L-ascorbate, and the like. Examples of oil-soluble polymerization initiators are diisopropyl peroxydicarbonate, benzoyl peroxide, dibutyl peroxide, azobisisobutylonitrile and the like. The amount of polymerization initiator is generally suitably 0.01-0.5 based on the sum of all monomers of 100.
용매로 메틸 에틸 케톤, 아세톤, 트리클로로트리플루오로에탄, 메틸 이소부틸케톤, 에틸 아세테이트 등을 작업성, 안전성, 환경성 등을 손상시키지 않을 정도로 소량 사용할 수 있다. 용매를 첨가함으로써 단량체의 씨드 입자에 대한 스웰링 능력을 개선시키는 경우도 있다.As a solvent, methyl ethyl ketone, acetone, trichlorotrifluoroethane, methyl isobutyl ketone, ethyl acetate, and the like can be used in a small amount so as not to impair workability, safety, or environmental performance. By adding a solvent, the swelling ability of the monomer to the seed particles may be improved in some cases.
본 발명에서 불소고분자 씨드를 이용한 중합을 통해 얻어지는 불소고분자-퍼플루오로 알킬기 함유 아크릴 입자의 평균 크기는 100-500nm가 적합하다. 입자 크기가 100nm 이하인 경우에는 수분산액의 점도가 증가하여 고농도의 수분산액을 얻을 수 없다. 또한 500nm 이상인 경우에는 수분산액을 저장할 때 고분자 입자의 침전과 응집이 발생하며, 형성된 필름의 광택이 나타나지 않는다. 본 발명의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자는 고체 형태를 원하는 경우에 응집에 의하여 분산상으로부터 분리해 낼 수 있다.In the present invention, the average size of the acrylic particles containing fluoropolymer-perfluoroalkyl group obtained through polymerization using a fluoropolymer seed is preferably 100-500 nm. When the particle size is 100 nm or less, the viscosity of the aqueous dispersion increases, and a high concentration of the aqueous dispersion cannot be obtained. In addition, in the case of 500 nm or more, precipitation and aggregation of polymer particles occur when the aqueous dispersion is stored, and the gloss of the formed film does not appear. The fluoropolymer-perfluoroalkyl group-containing acrylic particles of the present invention can be separated from the dispersed phase by agglomeration if a solid form is desired.
본 발명에 적합한 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 사용하는 코팅 조성물은 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 분산액(dispersion)형태로 함유한다. 전형적인 분산액은 필름형성. 건조 과정 중에서 기포발생을 피할 수 있는 정도의 높은 비점을 갖는 용매를 사용하여 제조된다. 분산액 형태로 존재하는 고분자에 대해서는 응결(coalescence)를 돕는 용매가 필요하다. 코팅 조성물의 고분자 농도는 작업성이 좋은 점도를 가지도록 조절되어야 하며, 특정의 고분자, 조성물의 다른 성분과 사용하는 공정장치와 조건에 따라 달라진다. 불소고분자-퍼플루오로알킬기 함유 아크릴 입자가 분산된 코팅 조성물의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자는 총중량 기준 10-25 중량%가 적합하다. 용매의 적합한 예로는 아세톤, 메틸에틸케톤(MEK), 테트라하이드로푸란(THF), 이소포론(isophrone), 디메틸 아세트아미드, 프로필렌 카보네이트, y-부틸로락톤, N-메틸피롤리돈과 디메틸설포옥사이드 등을 포함한다. 분산액 형태로 코팅 조성물을 제조하기 위하여 불소고분자-퍼플루오로알킬기 함유 아크릴 입자와 상용성 접착 고분자 그리고, 선택적으로 하나 이상의 분산제 및/또는 안료 등을 일반적으로 한 번에 적합한 용매 내에서 분산한다. 다른 방법으로는 여러 가지 성분을 각각 분산하고 별도로 혼합할 수 있다. 상용 접착제 고분자와 같이 용매에 용해되는 성분은 용해하여 사용한다. 또한 분산하는 경우에는 다양한 분쇄기를 사용하여 균일하게 분산할 수 있다. 전형적으로 볼밀을 사용한다. 코팅 조성물 내의 접착제 고분자의 함량은 고분자 기재 필름에 원하는 부착력을 줄 수 있을 정도로 충분한 수준이어야 하고 불소고분자-퍼플루오로알킬기 함유 아크릴입자의 원하는 물성에 심각한 역효과를 주지 않는 수준 이하여야 한다. 일반적으로 1~40중량% 범위가 적합하다.Coating compositions using fluoropolymer-perfluoroalkyl group-containing acrylic particles suitable for the present invention contain fluoropolymer-perfluoroalkyl group-containing acrylic particles in the form of dispersions. Typical dispersions are film forming. It is prepared using a solvent having a high boiling point such that foaming can be avoided during the drying process. For the polymer present in the form of a dispersion, a solvent that helps coalescence is required. The polymer concentration of the coating composition should be adjusted to have a good viscosity for workability, depending on the particular polymer, the other components of the composition and the process equipment and conditions used. The fluoropolymer-perfluoroalkyl group-containing acrylic particles of the coating composition in which the fluoropolymer-perfluoroalkyl group-containing acrylic particles are dispersed are preferably 10 to 25% by weight based on the total weight. Suitable examples of solvents include acetone, methyl ethyl ketone (MEK), tetrahydrofuran (THF), isophorone (isophrone), dimethyl acetamide, propylene carbonate, y-butylolactone, N-methylpyrrolidone and dimethylsulfooxide And the like. In order to prepare the coating composition in the form of a dispersion, fluoropolymer-perfluoroalkyl group-containing acrylic particles and compatible adhesive polymers and, optionally, one or more dispersants and / or pigments and the like are generally dispersed in one suitable solvent. Alternatively, the various components can be dispersed separately and mixed separately. Components dissolved in a solvent, such as a commercial adhesive polymer, are used by dissolving them. In addition, in the case of dispersion, it may be uniformly dispersed using various grinders. Typically ball mills are used. The content of the adhesive polymer in the coating composition should be at a level sufficient to give a desired adhesion to the polymer base film and should be below a level that does not adversely affect the desired physical properties of the fluoropolymer-perfluoroalkyl group-containing acrylic particles. Generally 1 to 40% by weight is suitable.
본 발명에 적합한 불소고분자-퍼플루오로알킬기 함유 아크릴 코팅막을 제조하기 위한 조성은 미리 형성된 필름을 제조할 필요 없이 종래의 코팅방법으로 적합한 기재에 액상으로 적용할 수 있다. 코팅방법은 캐스팅, 침적, 스프레이와 도포 등이 있다. 코팅이 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 분산상 형태로 포함하는 경우에는 전형적으로 스프레이, 롤러, 나이프, 커튼, 그라뷔어 코팅장치 등과 같은 종래의 방법을 이용하여 기재 필름 위에 분산액을 코팅한다. 나이프, 스프레이와 롤러 코팅방법이 편리한 방법이다. 캐스트 분산액의 건조 코팅 두께는 2.5㎛에서 250㎛까지의 범위가 적합하다.The composition for producing a fluoropolymer-perfluoroalkyl group-containing acrylic coating film suitable for the present invention can be applied in a liquid phase to a suitable substrate by a conventional coating method without the need to prepare a preformed film. Coating methods include casting, depositing, spraying and applying. When the coating comprises fluoropolymer-perfluoroalkyl group-containing acrylic particles in the form of a dispersed phase, the dispersion is typically coated on the base film using conventional methods such as sprays, rollers, knives, curtains, gravure coating equipment and the like. Knife, spray and roller coating are convenient methods. The dry coating thickness of the cast dispersion suitably ranges from 2.5 μm to 250 μm.
코팅막이 형성된 기재필름은 용매를 제거하여 건조하고 가열하여 제조한다. 건조 온도는 약 25℃(상온)에서 200℃범위이다. 사용하는 온도는 불소고분자-퍼플루오로알킬기 함유 아크릴 코팅이 기재필름에 완전히 부착하도록 하기 위하여 접착제 고분자와의 기능성기와 고분자 기재 필름의 기능성기의 상호 작용을 촉진할 정도로 충분해야 한다. 건조온도는 접착제 고분자와 기재 필름의 기능성기에 따라 크게 변하는데, 분산액 형태의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자가 건조되어 형성되는데 필요한 온도보다 높아야 한다.The base film on which the coating film is formed is prepared by removing the solvent, drying and heating. Drying temperatures range from about 25 ° C. (room temperature) to 200 ° C. The temperature used should be sufficient to facilitate the interaction of the functional group with the adhesive polymer and the functional group of the polymer base film in order for the fluoropolymer-perfluoroalkyl group-containing acrylic coating to adhere completely to the base film. The drying temperature varies greatly depending on the functional group of the adhesive polymer and the base film, and should be higher than the temperature required for the fluorine polymer-perfluoroalkyl group-containing acrylic particles in the form of dispersion to be dried and formed.
코팅 조성물 내의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자가 분산액 형태인 경우에는 용매를 제거하고 입자들이 연속적인 필름으로 응결하도록 충분하게 높은 온도로 가열하는 것이 필요하다. 건조 온도는 제한하지 않으나 좋게는 약 150℃에서 250℃까지 가열하는 것이 좋다. 사용하는 용매는 응결을 도와 용매를 사용하지 않는 경우에 비하여 보다 낮은 온도에서 응결하게 한다. 따라서 고분자를 응결시키는 조건은 사용하는 불소고분자-퍼플루오로알킬기 함유 아크릴 입자, 코팅 분산액과 기재 필름의 두께 그리고 다른 운전 조건에 따라 변하게 된다. 본 발명의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자의 코팅에서 체류시간이 약 1~10분인 경우 필름을 응결시키기 위하여 오븐 온도는 150℃에서 250℃까지 사용할 수 있다. 약 160℃에서 220℃까지의 온도가 더욱 좋다. If the fluoropolymer-perfluoroalkyl group-containing acrylic particles in the coating composition are in the form of a dispersion, it is necessary to remove the solvent and heat them to a sufficiently high temperature so that the particles congeal into a continuous film. Drying temperature is not limited but preferably heating from about 150 ° C. to 250 ° C. The solvent used aids condensation and causes condensation at lower temperatures than when no solvent is used. Therefore, the conditions for coagulating the polymer will vary depending on the fluoropolymer-perfluoroalkyl group-containing acrylic particles used, the thickness of the coating dispersion and the base film, and other operating conditions. When the residence time in the coating of the fluoropolymer-perfluoroalkyl group-containing acrylic particles of the present invention is about 1 to 10 minutes, the oven temperature may be used from 150 ° C to 250 ° C to condense the film. Temperatures from about 160 ° C. to 220 ° C. are better.
본 발명에 따르는 상호침투 네트웍 구조의 VDF 중합체의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자는 표면에너지가 극히 낮은 기능성기인 퍼플루오로알킬기를 함유한다. VDF 중합체의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 구성 성분으로 하는 코팅 조성물을 사용하여 제조된 코팅막은 퍼플루오로알킬기가 최외각에 배향하여 우수한 저표면에너지 특성과 방수/방오 특성을 나타낸다. 이러한 특성을 갖는 코팅막은 기존의 불소고분자 필름에 비하여 내후성과 내습성이 크게 향상된다. 또한, 본 발명에 따르는 VDF 중합체의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 함유하는 조성물을 사용하는 코팅막 제조과정은 기존의 불소고분자 필름을 형성시키기 위한 라미네이션 공정에 비하여 소요되는 에너지 비용을 절감할 수 있으며 공정을 단축할 수 있다. 또한, 본 발명에 따르는 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 함유하는 조성물을 사용하는 코팅은 불소고분자 필름을 사용하는 경우와 달리 코팅막의 두께를 용이하게 조절할 수 있으므로 고가의 불소고분자의 사용량을 최적화하여 백쉬트의 제조비용을 개선할 수 있다. The fluoropolymer-perfluoroalkyl group-containing acrylic particles of the VDF polymer of the interpenetrating network structure according to the present invention contain perfluoroalkyl groups which are functional groups having extremely low surface energy. The coating film prepared by using the coating composition containing fluorine polymer-perfluoroalkyl group-containing acrylic particles of the VDF polymer as its component exhibits excellent low surface energy characteristics and waterproof / antifouling properties with the perfluoroalkyl group oriented at the outermost side. The coating film having these characteristics is significantly improved in weatherability and moisture resistance compared to the conventional fluoropolymer film. In addition, the coating film manufacturing process using the composition containing the fluorine polymer-perfluoroalkyl group-containing acrylic particles of the VDF polymer according to the present invention can reduce the energy cost required compared to the lamination process for forming a conventional fluoropolymer film Can shorten the process. In addition, the coating using the composition containing the fluoropolymer-perfluoroalkyl group-containing acrylic particles according to the present invention can easily control the thickness of the coating film, unlike when using a fluoropolymer film, so that the amount of expensive fluorine polymer Optimization can improve the manufacturing cost of the backsheet.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시한다. 그러나 하기의 실시예는 본 발명을 보다 쉽게 이해하기 위하여 제공되는 것일 뿐, 이에 의해 본 발명의 내용이 한정되는 것은 아니다.Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are merely provided to more easily understand the present invention, and the contents of the present invention are not limited thereto.
<평가><Evaluation>
본 발명의 불소고분자-퍼플루오로알킬기 함유 아크릴 입자를 사용하는 코팅의 장기적 내후성과 내습성을 평가하기 위하여 다음과 같은 평가 방법들을 실시하였다.In order to evaluate the long-term weatherability and moisture resistance of the coating using the fluoropolymer-perfluoroalkyl group-containing acrylic particles of the present invention, the following evaluation methods were performed.
(1) 광택(Gloss) 측정 (측정각: 60°)(1) Gloss measurement (Measuring angle: 60 °)
내후성 시험과 내습성 시험을 실시한 코팅의 광택 측정기(Gloss meter; Suga Shikenki Kabushiki Kaisha)를 이용하여 측정한다. 시험 실시 전의 광택 대비 시험 후 유지된 광택의 비율로 측정 결과를 나타낸다. It is measured by using a gloss meter (Gloss meter; Suga Shikenki Kabushiki Kaisha) of the coating subjected to weather resistance test and moisture resistance test. The measurement result is shown by the ratio of the gloss maintained after a test to the gloss before a test execution.
(2) 내후성 시험(Weather Resistance Test)(2) Weather Resistance Test
코팅을 내후성 시험장치(Sunshine Weather-o-meter; Suga Shikenki Co.) 내에 넣어 Xenon 램프 광( 노출 강도: 3 SUN, 환경: 검정 판넬(Black panel) 온도 85℃/습도 50% RH) 노출 하에서 매 2 시간마다 8분간 샤워(shower)를 반복하면서 촉진 내후성 시험을 실시하고 1000 시간 후에 광택 측정기를 이용하여 광택의 변화를 측정한다. 광택 측정 결과에 따라 다음과 같이 판정한다. The coating is placed in a weather tester (Sunshine Weather-o-meter; Suga Shikenki Co.) and exposed to Xenon lamp light (exposure intensity: 3 SUN, environment: black panel temperature 85 ° C / humidity 50% RH). The accelerated weathering test is carried out with a repeated shower for 8 minutes every 2 hours and after 1000 hours the change in gloss is measured using a gloss meter. It determines as follows according to the glossiness measurement result.
○: 광택 유지 비율 90% 이상○: more than 90% gloss ratio
△: 광택 유지 비율 80-90%△: glossiness retention rate 80-90%
X : 광택 유지 비율 70% 이하X: gloss retention rate 70% or less
(3) 내습성 시험(Humidity Resistance Test)(3) Humidity Resistance Test
코팅을 환경 시험 장치(Environmental test machine)에 넣어 온도 85℃/습도 85% RH 조건 하에서 1000 시간 유지한 후 표면에 형성된 핀홀의 개수를 측정한다. 핀홀의 개수에 따라 다음과 같이 판정한다. The coating is placed in an environmental test machine and held for 1000 hours under a temperature of 85 ° C./85% RH, and the number of pinholes formed on the surface is measured. The number of pinholes is determined as follows.
○: 핀홀 없음.○: no pinhole.
△: 핀홀 1-5 개△: 1-5 pinholes
X : 핀홀 5 개 이상X: 5 or more pinholes
(4) 고체 함량 시험(4) solid content test
수분산액의 일부를 진공 건조기 내에서 150℃내에서 1시간 동안 건조시켰다. 건조 후의 무게를 수분산액의 무게에 대한 백분율로 나타내었다.A portion of the aqueous dispersion was dried in a vacuum drier at 150 ° C. for 1 hour. The weight after drying is expressed as a percentage of the weight of the aqueous dispersion.
(5) 평균 입자 크기 시험(5) average particle size test
레이저 광산란 입자 크기 분석기((Laser Beam Scattering Particle Size Analyzer; ELS-3000, Otsuka Denshi Kabushiki Kaisha)
Laser Light Scattering Particle Size Analyzer (ELS-3000, Otsuka Denshi Kabushiki Kaisha)
<제조예 1 불소 고분자 씨드 입자의 제조>Preparation Example 1 Preparation of Fluorine Polymer Seed Particles
교반기가 장착된 1L 압력 반응기에 500ml 탈이온수와 0.5g 퍼플루오로옥탄산 암모니움 염을 투입하였다. 질소가스를 이용하여 6atm으로 가압 후 진공으로 탈기하는 작업을 6회 반복 실시하여 용존산소를 제거하였다. 반응기의 온도를 80℃로 올린 후, 비닐리덴 플루오라이드(VDF)와 헥사플루오로프로필렌(HFP)이 90/10 몰 비율로 혼합된 불소단량체 혼합물를 투입하여 압력을 300psig로 올렸다. 2g/L 암모니움 퍼셀페이트(APS) 수용액 160ml를 투입하였다. 반응 초기에 5psi 압력 강하가 있은 후에 상기의 불소단량체 혼합물을 투입하기 시작하여 반응압력을 300psig로 유지하면서 260g을 연속적으로 투입하였다. 이후 불소단량체 혼합물의 투입을 중단하고 1시간 동안 반응시켰다. 반응 시스템을 상온, 상압으로 낮추고 중합 반응을 종료하였다. 이와 같은 방법으로 생성된 VDF/HFP 불소고분자 씨드 입자를 함유하는 수분산액을 다음과 같은 측정방법으로 분석하였다. 그 결과는 표 1과 같다.
500 ml deionized water and 0.5 g perfluorooctanoic acid ammonium salt were added to a 1 L pressure reactor equipped with a stirrer. After pressurizing to 6atm using nitrogen gas, degassing was carried out six times to remove dissolved oxygen. After raising the temperature of the reactor to 80 ℃, the fluorinomer mixture mixed with vinylidene fluoride (VDF) and hexafluoropropylene (HFP) in a 90/10 molar ratio was introduced to raise the pressure to 300 psig. 160 ml of 2 g / L ammonium percellate (APS) aqueous solution was added thereto. After the 5 psi pressure drop at the beginning of the reaction, the fluorine monomer mixture was started to be introduced, and 260 g was continuously added while maintaining the reaction pressure at 300 psig. After stopping the addition of the fluoromonomer mixture and reacted for 1 hour. The reaction system was lowered to room temperature and atmospheric pressure to terminate the polymerization reaction. The aqueous dispersion containing the VDF / HFP fluoropolymer seed particles produced by the above method was analyzed by the following measuring method. The results are shown in Table 1.
<제조예 2 ~ 4><Production example 2-4>
불소 단량체 혼합물의 조성(몰 비율을 변화시키는 것)을 제외하고 <제조예 1>과 동일한 방법으로 불소고분자 씨드 입자를 함유하는 수분산액을 제조하였고 이를 하기 표 1 에 나타내었다.Except for changing the composition (molar ratio) of the fluorine monomer mixture, an aqueous dispersion containing fluoropolymer seed particles was prepared in the same manner as in <Preparation Example 1>, and is shown in Table 1 below.
<표 1>TABLE 1
<실시예 1>≪ Example 1 >
40g 퍼플루오로알킬 에틸아크릴레이트(FA, CnF2n+1CH2CH2COOCH=CH2, n=4, 6, 8, 10, 12, 14(평균 n=8)), 30g 메틸메타크릴레이트(MMA), 27.5g 에틸아크릴레이트(EA)와 2.5g N-메틸롤 아크릴아미드(N-MAM), 계면활성제 혼합물(2.5g 라우릴 트리메틸 암모니움 클로라이드(양이온 계면활성제), 6.5g 폴리옥시에틸렌(8몰) 디스테아레이트(비이온 계면활성제, HLB=8.5)), 용매(30g 메틸에틸케톤), 사슬이동제(0.6g 도데실퍼켑탄)를 190g 물에 투입하여 호모믹서로 교반시킨 후 초음파 유화기로 유화시켜 FA/MA/EA/n-MAM 함유 수분산액(수분산액 내 아크릴 단량체 함량 30.3 중량%)을 제조하였다.40 g perfluoroalkyl ethylacrylate (FA, C n F 2n + 1 CH 2 CH 2 COOCH = CH 2 , n = 4, 6, 8, 10, 12, 14 (average n = 8)), 30 g methylmetha Acrylate (MMA), 27.5 g ethyl acrylate (EA) and 2.5 g N-methylol acrylamide (N-MAM), surfactant mixture (2.5 g lauryl trimethyl ammonium chloride (cationic surfactant), 6.5 g poly Oxyethylene (8 moles) distearate (nonionic surfactant, HLB = 8.5)), a solvent (30 g methyl ethyl ketone), and a chain transfer agent (0.6 g dodecyl furpentane) were added to 190 g water, followed by stirring with a homomixer. Emulsification with an ultrasonic emulsifier produced an aqueous dispersion containing FA / MA / EA / n-MAM (30.3 wt% of acrylic monomer content in the aqueous dispersion).
교반기, 냉각관과 온도계가 장착된 500ml 플라스크에 제조예1에 제조한 불소고분자 씨드 분산액 175g을 투입하고, 여기에 소디움 도데실벤젠설포네이트와 트리톤(Triton) X100(Union Carbide Co., Ltd)을 각각 고체 기준으로 0.5중량%를 투입하였다. 교반하면서 수조 내에서 반응기를 가열하여 80℃로 승온시켰다. 이 온도에서 앞에서 제조한 FA/MMA/EA/n-MAM 함유 수분산액 70g(표 2의 실시예1에 수분산액 투입량 명시)을 1시간 동안 서서히(dropwise) 투입하였다. 투입 완료 후 곧바로 2 중량%의 암모니움 퍼셀페이트 수용액 2.5ml를 첨가하여 반응을 개시하였다. 반응 개시 후 3시간 시점에서 수조의 내부 온도를 85℃로 승온하고 이 온도에서 1시간 동안 유지한 후에 상온으로 냉각하였다. 단량체의 농도를 GC로 분석하여 반응 종결점을 확인하였다. 암모니아 수용액을 이용하여 반응물의 pH를 7로 조정한 다음 300 메쉬 금속망으로 여과하여 불소고분자-퍼플루오로알킬기 함유 아크릴 고분자의 수분산액을 얻었다. 얻어진 입자체를 표2에 수록하였다. <표 2>의 불소고분자/아크릴고분자함량비(%)는 다음과 같이 계산하였다. Into a 500 ml flask equipped with a stirrer, a cooling tube, and a thermometer, 175 g of the fluoropolymer seed dispersion prepared in Preparation Example 1 was added, and sodium dodecylbenzenesulfonate and Triton X100 (Union Carbide Co., Ltd) were added thereto. 0.5% by weight of each solid was added. The reactor was heated to 80 ° C. in a water bath with stirring. At this temperature, 70 g of FA / MMA / EA / n-MAM-containing aqueous dispersion prepared above (specified amount of aqueous dispersion in Example 1 of Table 2) was added dropwise for 1 hour. Immediately after the addition was completed, 2.5 ml of an aqueous solution of 2% by weight of ammonium percellate was added to initiate the reaction. 3 hours after the start of the reaction, the internal temperature of the water bath was increased to 85 ° C. and maintained at this temperature for 1 hour, followed by cooling to room temperature. The concentration of monomer was analyzed by GC to identify the end point of the reaction. The pH of the reactant was adjusted to 7 using an aqueous ammonia solution and then filtered through a 300 mesh metal network to obtain an aqueous dispersion of an acrylic polymer containing a fluoropolymer-perfluoroalkyl group. The obtained particle bodies are listed in Table 2. The fluorine polymer / acrylic polymer content ratio (%) of <Table 2> was calculated as follows.
*아크릴 고분자 함량(%)* Acrylic polymer content (%)
*불소고분자 함량(%)* Fluoropolymer content (%)
69.3(%) = 100-30.7(아크릴고분자 함량%)
69.3 (%) = 100-30.7 (acrylic polymer content%)
불소고분자-퍼플루오로알킬기 함유 아크릴 고분자의 분산액을 같은 양의 탈이온수로 희석한 후 냉동시켜 응집하였다. 응집된 불소고분자 고체를 여과하여 회수 한 후 1000ml의 탈이온수로 3회 세정한 수 50℃로 건조하였다. 이 분말 고체를 이소포론 용매에 현탁시켜 25 중량%의 불소고분자-퍼플루오로알킬기 함유 아크릴 고분자의 코팅막을 제조하였다.The dispersion of the fluoropolymer-perfluoroalkyl group-containing acrylic polymer was diluted with the same amount of deionized water and then frozen and coagulated. The agglomerated fluoropolymer solid was collected by filtration and then washed three times with 1000 ml of deionized water and dried at 50 ° C. This powder solid was suspended in an isophorone solvent to prepare a coating film of an acrylic polymer containing 25% by weight of a fluoropolymer-perfluoroalkyl group.
이와 같이 제조된 불소고분자-퍼플루오로알킬기 함유 아크릴 고분자의 코팅막에 대하여 상기에서 기술한 방법으로 내후성 시험과 내습성 시험을 실시하였다. 내후성 시험 후의 광택은 시험 전 광택의 97%로 측정되었다. 내습성 시험 후의 시편은 핀홀이 없었으며 시험 전과 겉모습의 차이가 나지 않았다. 이로부터 내후성과 내습성이 양호함을 확인할 수 있었다.
The coating film of the fluoropolymer-perfluoroalkyl group-containing acrylic polymer thus prepared was subjected to the weather resistance test and the moisture resistance test by the method described above. The gloss after the weathering test was measured at 97% of the gloss before the test. The specimens after the moisture resistance test had no pinholes and no difference in appearance from the test. From this, it was confirmed that weather resistance and moisture resistance were good.
<실시예 2 - 12><Examples 2-12>
실시예 1과 동일한 방법으로 불소고분자 씨드 입자<표 1>, 아크릴 단량체 함량<표 2> 및 아크릴 단량체 수분산액 투입량<표 2>을 변화시켜 불소고분자-퍼플루오로알킬기 함유 아크릴 고분자를 제조하였고, 이를 이용하여 실시예 1과 동일한 방법으로 코팅막을 제조하여 내후성과 내습성을 평가하였다. 그 결과를 하기 표 2에 나타내었다.In the same manner as in Example 1, a fluoropolymer-perfluoroalkyl group-containing acrylic polymer was prepared by changing the fluorinated polymer seed particles <Table 1>, the acrylic monomer content <Table 2> and the acrylic monomer aqueous dispersion amount <Table 2>. Using this, a coating film was prepared in the same manner as in Example 1 to evaluate weather resistance and moisture resistance. The results are shown in Table 2 below.
<표 2><Table 2>
* FA : CnF2n+1CH2CH2COOCH=CH2, n=4,6,8,10,12,14(평균 n=8);FA: C n F 2n + 1 CH 2 CH 2 COOCH = CH 2 , n = 4,6,8,10,12,14 (average n = 8);
FMA: CnF2n+1CH2CH2COOC(CH3)=CH2, n=4,6,8,10,12,14(평균n=8)FMA: C n F 2n + 1 CH 2 CH 2 COOC (CH 3 ) = CH 2 , n = 4,6,8,10,12,14 (average n = 8)
Claims (9)
b) 상기 씨드 입자 100중량부에 대하여, 20~100 중량부의 탄소수 4~20인 퍼플루오로알킬기 함유 (메타)아크릴산 에스테르 2 내지 70 중량%, 비불소계 (메타)아크릴산 에스테르 25 내지 97 중량% 및 아크릴 아미드계 단량체 0.1 내지 5 중량% 를 중합하는 단계;
를 포함하여 제조하는 불소고분자-퍼플루오로알킬기 함유 아크릴 입자.a) vinylidene fluoride (VDF) homopolymerization or copolymerization of vinylidene fluoride (VDF) with a comonomer to produce seed particles; And
b) 2 to 70% by weight of 20 to 100 parts by weight of a perfluoroalkyl group-containing (meth) acrylic acid ester having 4 to 20 carbon atoms, 25 to 97% by weight of a non-fluorine-based (meth) acrylic acid ester, relative to 100 parts by weight of the seed particles; Polymerizing 0.1 to 5% by weight of acrylamide monomers;
Fluoropolymer-perfluoroalkyl group containing acrylic particle manufactured including.
상기 a) 단계의 상기 공단량체는 비닐 플루오라이드(VF), 트리플루오로에틸렌(TrFE), 클로로트리플루오로에틸렌(CTFE), 테트라플루오로에틸렌(TFE) 및 헥사플루오로프로필렌(HFP) 중에서 선택된 하나 또는 둘 이상인 불소고분자-퍼플루오로알킬기 함유 아크릴 입자.The method of claim 1,
The comonomer of step a) is selected from vinyl fluoride (VF), trifluoroethylene (TrFE), chlorotrifluoroethylene (CTFE), tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) One or two or more fluoropolymer-perfluoroalkyl group-containing acrylic particles.
상기 b) 단계의 불소함유 (메타)아크릴산 에스테르는 하기 화학식 1 내지 6 에서 선택된 하나 또는 둘 이상의 화합물인 불소고분자-퍼플루오로알킬기 함유 아크릴 입자.
[화학식 1]
Rf(CH2)jOCOCR1=CH2
[화학식 2]
Rf(CH2)kOCOOCR1=CH2
[화학식 3]
RfCH2C(OH)HCH2OCOR1=CH2
[화학식 4]
RfCON(R2)R3OCOR1=CH2
[화학식 5]
RfSO2N(R2)R3OCOR1=CH2
[화학식 6]
RfCH2C(OCOR4)HCH2OCOR1=CH2
(화학식 1 ~ 6 에서 Rf는 각각 탄소원자 4-20개의 퍼플루오로알킬기(CnF2n+1: n=4-20); R1은 각각 H 또는 CH3; R2은 탄소원자 1-10개의 알킬렌기 ; R3은 각각 H 또는 탄소원자 1-10개의 알킬기 ; R4은 각각 탄소원자 1-17개의 알킬기 ; j=1-10 ,j는 정수; k=0-10, k는 정수)The method of claim 1,
The fluorine-containing (meth) acrylic acid ester of step b) is one or two or more compounds selected from Chemical Formulas 1 to 6 below.
[Formula 1]
R f (CH 2 ) j OCOCR 1 = CH 2
(2)
R f (CH 2 ) kOCOOCR 1 = CH 2
(3)
R f CH 2 C (OH) HCH 2 OCOR 1 = CH 2
[Chemical Formula 4]
R f CON (R 2 ) R 3 OCOR 1 = CH 2
[Chemical Formula 5]
R f SO 2 N (R 2 ) R 3 OCOR 1 = CH 2
[Chemical Formula 6]
R f CH 2 C (OCOR 4 ) HCH 2 OCOR 1 = CH 2
In Formulas 1 to 6, R f is a perfluoroalkyl group having 4 to 20 carbon atoms (C n F 2n + 1: n = 4-20); and R 1 is each H or CH 3 ; R 2 is an alkylene group of 1-10 carbon atoms; R 3 is each H or an alkyl group of 1-10 carbon atoms; Each R 4 is an alkyl group of 1-17 carbon atoms; j = 1-10, j is an integer; k = 0-10, k is an integer)
상기 a) 단계에서 상기 공단량체는 상기 씨드 입자의 1 내지 30 중량%인 불소고분자-퍼플루오로알킬기 함유 아크릴 입자.The method of claim 1,
In the a) step, the comonomer is 1 to 30% by weight of the seed particles fluorine polymer-perfluoroalkyl group-containing acrylic particles.
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