WO2022181825A1 - 含フッ素共重合体 - Google Patents
含フッ素共重合体 Download PDFInfo
- Publication number
- WO2022181825A1 WO2022181825A1 PCT/JP2022/008441 JP2022008441W WO2022181825A1 WO 2022181825 A1 WO2022181825 A1 WO 2022181825A1 JP 2022008441 W JP2022008441 W JP 2022008441W WO 2022181825 A1 WO2022181825 A1 WO 2022181825A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- containing copolymer
- polymerization
- units
- mass
- Prior art date
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 138
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 130
- 239000011737 fluorine Substances 0.000 title claims abstract description 127
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 124
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical group FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims abstract description 71
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 40
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000178 monomer Substances 0.000 claims abstract description 36
- 239000000155 melt Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims description 29
- 239000011248 coating agent Substances 0.000 claims description 26
- 239000011247 coating layer Substances 0.000 claims description 23
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
- 238000002347 injection Methods 0.000 claims description 13
- 239000007924 injection Substances 0.000 claims description 13
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 105
- 238000006116 polymerization reaction Methods 0.000 description 105
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 68
- 239000008188 pellet Substances 0.000 description 67
- 238000000034 method Methods 0.000 description 54
- 239000007789 gas Substances 0.000 description 44
- 125000000524 functional group Chemical group 0.000 description 38
- 238000012360 testing method Methods 0.000 description 38
- 230000000977 initiatory effect Effects 0.000 description 37
- 238000000465 moulding Methods 0.000 description 34
- -1 polytetrafluoroethylene Polymers 0.000 description 34
- 229910052757 nitrogen Inorganic materials 0.000 description 33
- 239000010408 film Substances 0.000 description 30
- 230000035699 permeability Effects 0.000 description 29
- 239000002904 solvent Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 24
- 239000000126 substance Substances 0.000 description 23
- 150000002978 peroxides Chemical class 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 238000001125 extrusion Methods 0.000 description 20
- 238000001746 injection moulding Methods 0.000 description 18
- 239000011162 core material Substances 0.000 description 17
- 239000000843 powder Substances 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 16
- 239000007788 liquid Substances 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- 238000012546 transfer Methods 0.000 description 14
- 238000003682 fluorination reaction Methods 0.000 description 13
- 238000012856 packing Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000004020 conductor Substances 0.000 description 12
- 238000002844 melting Methods 0.000 description 12
- 230000008018 melting Effects 0.000 description 12
- 238000010521 absorption reaction Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000446 fuel Substances 0.000 description 11
- 238000005299 abrasion Methods 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000011255 nonaqueous electrolyte Substances 0.000 description 10
- 239000000523 sample Substances 0.000 description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 9
- 238000007789 sealing Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000003505 polymerization initiator Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 235000013305 food Nutrition 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000003381 stabilizer Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 125000002252 acyl group Chemical group 0.000 description 5
- 125000005587 carbonate group Chemical group 0.000 description 5
- 239000012986 chain transfer agent Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 229940079593 drug Drugs 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 230000008054 signal transmission Effects 0.000 description 5
- 229920001897 terpolymer Polymers 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 230000008033 biological extinction Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000012937 correction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920002313 fluoropolymer Polymers 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000007870 radical polymerization initiator Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000004811 fluoropolymer Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000012778 molding material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000010557 suspension polymerization reaction Methods 0.000 description 3
- 238000001721 transfer moulding Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 2
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000004927 clay Substances 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005796 dehydrofluorination reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012785 packaging film Substances 0.000 description 2
- 229920006280 packaging film Polymers 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical class OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 150000004978 peroxycarbonates Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 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 2
- 239000011253 protective coating Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UJZCJVSSNLSCSR-UHFFFAOYSA-N (15,16,16,17,17,18,18,19,19,20,20-undecachloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14,15,22,22,22-triacontafluorodocosanoyl) 15,16,16,17,17,18,18,19,19,20,20-undecachloro-2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,13,13,14,14 Chemical compound FC(F)(F)CC(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(F)(Cl)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(Cl)(Cl)CC(F)(F)F UJZCJVSSNLSCSR-UHFFFAOYSA-N 0.000 description 1
- HBGQVKNZGOFLRH-UHFFFAOYSA-N (3,3-dichloro-2,2,4,4,4-pentafluorobutanoyl) 3,3-dichloro-2,2,4,4,4-pentafluorobutaneperoxoate Chemical compound FC(F)(F)C(Cl)(Cl)C(F)(F)C(=O)OOC(=O)C(F)(F)C(Cl)(Cl)C(F)(F)F HBGQVKNZGOFLRH-UHFFFAOYSA-N 0.000 description 1
- QFKDUYDESCLRNT-UHFFFAOYSA-N (4,5,5-trichloro-2,2,3,3,4,6,6,6-octafluorohexanoyl) 4,5,5-trichloro-2,2,3,3,4,6,6,6-octafluorohexaneperoxoate Chemical compound FC(F)(F)C(Cl)(Cl)C(F)(Cl)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(Cl)C(Cl)(Cl)C(F)(F)F QFKDUYDESCLRNT-UHFFFAOYSA-N 0.000 description 1
- IDSJUBXWDMSMAR-UHFFFAOYSA-N (7,8,8,9,9-pentachloro-2,2,3,3,4,4,5,5,6,6,7,10,10,10-tetradecafluorodecanoyl) 7,8,8,9,9-pentachloro-2,2,3,3,4,4,5,5,6,6,7,10,10,10-tetradecafluorodecaneperoxoate Chemical compound FC(F)(F)C(Cl)(Cl)C(Cl)(Cl)C(F)(Cl)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(Cl)C(Cl)(Cl)C(Cl)(Cl)C(F)(F)F IDSJUBXWDMSMAR-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- SKYXLDSRLNRAPS-UHFFFAOYSA-N 1,2,4-trifluoro-5-methoxybenzene Chemical compound COC1=CC(F)=C(F)C=C1F SKYXLDSRLNRAPS-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-UHFFFAOYSA-N 0.000 description 1
- LNTDXONIQLFHFG-UHFFFAOYSA-N 1-ethenoxy-2-methylpropan-1-ol Chemical compound CC(C)C(O)OC=C LNTDXONIQLFHFG-UHFFFAOYSA-N 0.000 description 1
- OZCMOJQQLBXBKI-UHFFFAOYSA-N 1-ethenoxy-2-methylpropane Chemical compound CC(C)COC=C OZCMOJQQLBXBKI-UHFFFAOYSA-N 0.000 description 1
- FLFWDKGWSOCXQK-UHFFFAOYSA-N 1-ethenoxycyclohexan-1-ol Chemical compound C=COC1(O)CCCCC1 FLFWDKGWSOCXQK-UHFFFAOYSA-N 0.000 description 1
- GBOWGKOVMBDPJF-UHFFFAOYSA-N 1-fluoro-3-(trifluoromethyl)benzene Chemical compound FC1=CC=CC(C(F)(F)F)=C1 GBOWGKOVMBDPJF-UHFFFAOYSA-N 0.000 description 1
- IBTLFDCPAJLATQ-UHFFFAOYSA-N 1-prop-2-enoxybutane Chemical compound CCCCOCC=C IBTLFDCPAJLATQ-UHFFFAOYSA-N 0.000 description 1
- LWJHSQQHGRQCKO-UHFFFAOYSA-N 1-prop-2-enoxypropane Chemical compound CCCOCC=C LWJHSQQHGRQCKO-UHFFFAOYSA-N 0.000 description 1
- JUTIIYKOQPDNEV-UHFFFAOYSA-N 2,2,3,3,4,4,4-heptafluorobutanoyl 2,2,3,3,4,4,4-heptafluorobutaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)F JUTIIYKOQPDNEV-UHFFFAOYSA-N 0.000 description 1
- QLJQYPFKIVUSEF-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanoyl 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QLJQYPFKIVUSEF-UHFFFAOYSA-N 0.000 description 1
- LFCQGZXAGWRTAL-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptanoyl 2,2,3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LFCQGZXAGWRTAL-UHFFFAOYSA-N 0.000 description 1
- YQIZLPIUOAXZKA-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YQIZLPIUOAXZKA-UHFFFAOYSA-N 0.000 description 1
- BECCBTJLCWDIHG-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononanoyl 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluorononaneperoxoate Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(=O)OOC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BECCBTJLCWDIHG-UHFFFAOYSA-N 0.000 description 1
- RFJVDJWCXSPUBY-UHFFFAOYSA-N 2-(difluoromethylidene)-4,4,5-trifluoro-5-(trifluoromethyl)-1,3-dioxolane Chemical compound FC(F)=C1OC(F)(F)C(F)(C(F)(F)F)O1 RFJVDJWCXSPUBY-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
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- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—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
- C08F214/18—Monomers containing fluorine
- C08F214/28—Hexyfluoropropene
- C08F214/282—Hexyfluoropropene with fluorinated vinyl ethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
- C08F8/22—Halogenation by reaction with free halogens
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
- H01B3/445—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds from vinylfluorides or other fluoroethylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
Definitions
- the present disclosure relates to fluorine-containing copolymers.
- U.S. Pat. No. 5,301,003 discloses (a) tetrafluoroethylene, (b) hexafluoropropylene in an amount of from about 4 to about 12 weight percent based on the weight of the terpolymer, and (c) about 0.5 weight percent based on the weight of the terpolymer.
- Terpolymers containing from to about 3% by weight of perfluoro(ethyl vinyl ether) or perfluoro(n-propyl vinyl ether), in copolymerized form, are described.
- a beautiful injection molded body can be obtained by molding by an injection molding method, and has wear resistance at 95°C, solvent crack resistance, low nitrogen permeability, rigidity at high temperature of 75°C, and tensile creep resistance at 150°C.
- An object of the present invention is to provide a fluorine-containing copolymer from which a molded article having excellent durability against repeated loads can be obtained.
- a fluorine-containing copolymer containing tetrafluoroethylene units, hexafluoropropylene units and perfluoro(propyl vinyl ether) units, wherein the content of hexafluoropropylene units is 10.3 to 12.0% by mass, and the content of perfluoro (propyl vinyl ether) units is 1.6 to 2.9% by mass with respect to the total monomer units, and at 372 ° C.
- a fluorine-containing copolymer having a melt flow rate of 5.0 to 40.0 g/10 minutes is provided.
- the content of hexafluoropropylene units is preferably 10.4 to 12.0% by mass with respect to all monomer units.
- the content of perfluoro(propyl vinyl ether) units is preferably 1.7 to 2.6% by mass based on the total monomer units.
- the melt flow rate at 372° C. is preferably 6.0-37.0 g/10 minutes.
- an injection-molded article containing the fluorine-containing copolymer is provided.
- a covered electric wire that includes a covering layer containing the fluorine-containing copolymer.
- a molded article containing the fluorine-containing copolymer described above wherein the molded article is a flow meter, a fitting, a filter housing, a tube, a film or a wire coating. be.
- a beautiful injection molded body can be obtained by molding by an injection molding method, and has wear resistance at 95°C, solvent crack resistance, low nitrogen permeability, rigidity at high temperature of 75°C, and tensile resistance at 150°C. It is possible to provide a fluorine-containing copolymer from which molded articles having excellent creep properties and durability against repeated loads can be obtained.
- the fluorine-containing copolymer of the present disclosure contains tetrafluoroethylene (TFE) units, hexafluoropropylene (HFP) units and perfluoro(propyl vinyl ether) (PPVE) units.
- TFE tetrafluoroethylene
- HFP hexafluoropropylene
- PPVE perfluoro(propyl vinyl ether)
- Patent Document 1 proposes the above-described terpolymer as a fluorocarbon polymer that overcomes these drawbacks.
- Piping components for transporting chemicals and flow meter components for measuring the flow rate of chemicals need to be resistant to the stress that occurs during the flow of chemicals, such as starting, stopping, and changing flow rates. Durability against wear, chemical resistance, heat deformation resistance, etc. are required. Therefore, if such a molded product can be obtained, the performance of piping members and flow meter members can be significantly improved.
- the fluorine-containing copolymer Injection moldability is remarkably improved, and by using such a fluorine-containing copolymer, wear resistance at 95°C, solvent crack resistance, low nitrogen permeability, rigidity at high temperature of 75°C, and tensile creep resistance at 150°C are obtained. , it was found that a molded article having excellent durability against repeated loads can be obtained.
- a thin coating layer can be formed on a cord with a small diameter at a high speed, and a thin coating layer can be formed on a cord with a very large diameter.
- a thick coating layer can be formed with a uniform thickness, and a thin film with a uniform thickness can be formed at a high forming speed.
- the fluorocopolymer of the present disclosure can be used not only as a material for valves, but also for a wide range of applications such as wire coatings and films.
- the fluorocopolymer of the present disclosure is a melt-processable fluororesin.
- Melt processability means that the polymer can be melt processed using conventional processing equipment such as extruders and injection molding machines.
- the content of HFP units in the fluorine-containing copolymer is 10.3 to 12.0% by mass, preferably 10.4% by mass or more, more preferably 10.0% by mass, based on the total monomer units. 5% by mass or more, particularly preferably 10.6% by mass or more, preferably 11.8% by mass or less, more preferably 11.7% by mass or less, still more preferably 11.6% by mass or less, particularly preferably 11.5% by mass or less, and most preferably 11.1% by mass or less.
- the content of the HFP unit in the fluorine-containing copolymer is within the above range, it is possible to obtain a beautiful injection-molded article by molding by an injection molding method.
- a molded article having low permeability, high rigidity at 75° C., tensile creep resistance at 150° C., and durability against repeated loads can be obtained. If the content of the HFP units is too small, it is not possible to obtain a molded article having excellent 95° C. wear resistance and solvent crack resistance. If the content of HFP units is too high, it is not possible to obtain a molded article that is excellent in rigidity at high temperatures of 75°C, tensile creep resistance at 150°C, and durability against repeated loads.
- the content of PPVE units in the fluorine-containing copolymer is 1.6 to 2.9% by mass, preferably 1.7% by mass or more, more preferably 1.7% by mass or more, based on the total monomer units. 8% by mass or more, more preferably 1.9% by mass or more, particularly preferably 2.0% by mass or more, preferably 2.8% by mass or less, more preferably 2.7% by mass or less, more preferably 2.6% by mass or less, still more preferably 2.4% by mass or less, particularly preferably 2.2% by mass or less, and most preferably 2.0% by mass or less is.
- the PPVE unit content of the fluorine-containing copolymer is within the above range, it is possible to obtain a beautiful injection-molded article by injection molding, which exhibits 95°C abrasion resistance, solvent crack resistance, nitrogen A molded article having low permeability, high rigidity at 75° C., tensile creep resistance at 150° C., and durability against repeated loads can be obtained. If the PPVE unit content is too low, a molded article having excellent solvent crack resistance cannot be obtained. If the content of PPVE units is too high, it is not possible to obtain a molded article having excellent low nitrogen permeability, high rigidity at 75°C, and tensile creep resistance at 150°C.
- PEVE perfluoro(ethyl vinyl ether)
- the content of TFE units in the fluorine-containing copolymer is preferably 85.1 to 88.1% by mass, more preferably 85.3% by mass or more, and still more preferably, based on the total monomer units. is 85.4% by mass or more, particularly preferably 86.1% by mass or more, more preferably 88.1% by mass or less, still more preferably 87.9% by mass or less, particularly preferably 87 0.6% by mass or less, and most preferably 87.4% by mass or less.
- the content of TFE units may be selected so that the total content of HFP units, PPVE units, TFE units and other monomer units is 100% by mass.
- the fluorine-containing copolymer of the present disclosure contains the above three monomer units, even if it is a copolymer containing only the above three monomer units, the above three It may be a copolymer containing monomeric units and other monomeric units.
- Other monomers are not particularly limited as long as they are copolymerizable with TFE, HFP and PPVE, and may be fluoromonomers or fluorine-free monomers.
- Fluorine-free monomers include hydrocarbon-based monomers copolymerizable with TFE, HFP and PPVE.
- hydrocarbon-based monomers include alkenes such as ethylene, propylene, butylene, and isobutylene; alkyl vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, isobutyl vinyl ether, and cyclohexyl vinyl ether; vinyl acetate, vinyl propionate, n- Vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl versatate, vinyl laurate, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl benzoate , vinyl para-t-butylbenzoate, vinyl cyclohexanecarboxylate, vinyl monochloroacetate, vinyl adipate, vinyl acrylate, vinyl methacrylate, vinyl crotonate
- the non-fluorine-containing monomer may also be a functional group-containing hydrocarbon-based monomer copolymerizable with TFE, HFP and PPVE.
- functional group-containing hydrocarbon monomers include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether, hydroxybutyl vinyl ether, hydroxyisobutyl vinyl ether, and hydroxycyclohexyl vinyl ether; glycidyl group-containing monomers such as glycidyl vinyl ether and glycidyl allyl ether.
- fluorine-free monomers fluorine-free monomers having an amino group such as aminoalkyl vinyl ether and aminoalkyl allyl ether; fluorine-free monomers having an amide group such as (meth)acrylamide and methylolacrylamide; bromine-containing olefins, iodine-containing olefins, bromine-containing vinyl ethers, iodine-containing vinyl ethers; non-fluorine-containing monomers having a nitrile group;
- the content of other monomer units in the fluorine-containing copolymer of the present disclosure is preferably 0 to 3.0% by mass, more preferably 1.0% by mass, based on the total monomer units. or less, more preferably 0.5% by mass or less, and particularly preferably 0.1% by mass or less.
- the melt flow rate (MFR) of the fluorine-containing copolymer is 5.0 to 40.0 g/10 minutes, preferably 5.1 g/10 minutes or more, more preferably 5.5 g/10 minutes or more. more preferably 6.0 g/10 min or more, still more preferably 6.5 g/10 min or more, particularly preferably 7.0 g/10 min or more, most preferably 7.1 g/10 min or more 10 minutes or more, preferably 39.9 g/10 minutes or less, more preferably 39.0 g/10 minutes or less, still more preferably 38.0 g/10 minutes or less, and still more preferably 37.0 g/10 minutes or less.
- MFR of the fluorine-containing copolymer is within the above range, it is possible to obtain a beautiful injection-molded article by molding by an injection molding method. It is possible to obtain a molded article which is excellent in rigidity at a high temperature of 75°C, tensile creep resistance at 150°C, and durability against repeated loads. If the MFR is too low, a molded article having excellent low nitrogen permeability cannot be obtained, and a beautiful injection molded article cannot be obtained by molding by an injection molding method. If the MFR is too high, a molded article having excellent 95° C. wear resistance and solvent crack resistance cannot be obtained.
- the MFR is preferably 18.0 g/10 minutes or less, more preferably 16.0 g/10 minutes or less.
- the MFR is preferably 10.0 g. /10 minutes or less, more preferably 9.0 g/10 minutes or less.
- the MFR is preferably more than 10.0 g/10 minutes, more preferably 11.0 g/10 minutes. or more, more preferably 13.0 g/10 minutes or more, and particularly preferably 15.0 g/10 minutes or more.
- the MFR is preferably 13.0 g/10 minutes or less, more preferably 11.0 g/10 minutes or less.
- the melt flow rate is measured in accordance with ASTM D-1238 using a melt indexer G-01 (manufactured by Toyo Seiki Seisakusho) at 372°C under a load of 5 kg from a die with an inner diameter of 2 mm and a length of 8 mm. The value is given as the mass of polymer that flows out per 10 minutes (g/10 minutes).
- the MFR can be adjusted by adjusting the type and amount of the polymerization initiator and the type and amount of the chain transfer agent used when polymerizing the monomers.
- the fluorocopolymer of the present disclosure may or may not have a functional group.
- the functional group is a functional group present at the main chain end or side chain end of the fluorine-containing copolymer, and a functional group present in the main chain or side chain.
- the number of functional groups per 10 6 carbon atoms in the main chain of the fluorine-containing copolymer is preferably 90 or less, more preferably 70 or less, still more preferably 50 or less, and even more preferably 40. 1 or less, particularly preferably 30 or less, particularly preferably 20 or less, and most preferably less than 15.
- the number of functional groups of the fluorine-containing copolymer is within the above range, it is possible to obtain a molded article from which fluorine ions are less likely to be eluted in a chemical solution such as hydrogen peroxide solution.
- the number of —CF 2 H groups per 10 6 carbon atoms in the main chain of the fluorine-containing copolymer is preferably 50 or less, more preferably 40 or less, and still more preferably 30 or less. It is more preferably 20 or less, particularly preferably less than 15, and most preferably 10 or less.
- the number of carbonate groups in the fluorine-containing copolymer is within the above range, it is possible to obtain a molded article from which fluorine ions are less likely to be eluted in a chemical solution such as hydrogen peroxide solution.
- the solvent crack resistance can be further improved.
- Infrared spectroscopic analysis can be used to identify the types of functional groups and measure the number of functional groups.
- the number of functional groups is measured by the following method.
- the fluorine-containing copolymer is cold-pressed to form a film having a thickness of 0.25 to 0.30 mm.
- This film is analyzed by Fourier transform infrared spectroscopy to obtain the infrared absorption spectrum of the fluorine-containing copolymer, and the difference spectrum from the completely fluorinated base spectrum in which no functional groups are present. From the absorption peak of the specific functional group appearing in this difference spectrum, the number N of functional groups per 1 ⁇ 10 6 carbon atoms in the fluorine-containing copolymer is calculated according to the following formula (A).
- N I ⁇ K/t (A) I: Absorbance K: Correction coefficient t: Film thickness (mm)
- Table 1 shows absorption frequencies, molar extinction coefficients and correction factors for some functional groups. Also, the molar extinction coefficient was determined from the FT-IR measurement data of the low-molecular-weight model compound.
- the absorption frequencies of —CH 2 CF 2 H, —CH 2 COF, —CH 2 COOH, —CH 2 COOCH 3 and —CH 2 CONH 2 are shown in the table, respectively, —CF 2 H, —COF and —COOH free.
- the absorption frequency of -COOH bonded, -COOCH 3 and -CONH 2 is several tens of Kaiser (cm -1 ) lower than that of -CONH 2 .
- the number of functional groups of —COF is determined from the number of functional groups obtained from the absorption peak at an absorption frequency of 1883 cm ⁇ 1 due to —CF 2 COF and from the absorption peak at an absorption frequency of 1840 cm ⁇ 1 due to —CH 2 COF. It is the sum of the number of functional groups.
- the number of -CF 2 H groups can also be obtained from the peak integration value of -CF 2 H groups by performing 19 F-NMR measurement using a nuclear magnetic resonance apparatus at a measurement temperature of (the melting point of the polymer +20) °C. can be done.
- the functional group is a functional group present at the main chain end or side chain end of the fluorine-containing copolymer, and a functional group present in the main chain or side chain.
- the functional group is introduced into the fluorocopolymer by, for example, a chain transfer agent or a polymerization initiator used in producing the fluorocopolymer.
- a chain transfer agent for example, an alcohol is used as a chain transfer agent, or a peroxide having a structure of —CH 2 OH is used as a polymerization initiator, —CH 2 OH is introduced at the main chain end of the fluorine-containing copolymer. .
- the functional group is introduced into the side chain end of the fluorine-containing copolymer.
- a fluorine-containing copolymer having the number of functional groups within the above range can be obtained by subjecting the fluorine-containing copolymer having such functional groups to treatment such as wet heat treatment and fluorination treatment.
- the fluorocopolymer of the present disclosure is preferably subjected to wet heat treatment or fluorination treatment, more preferably fluorination treatment.
- the fluorine-containing copolymer of the present disclosure also preferably has a —CF 3 terminal group.
- the melting point of the fluorine-containing copolymer is preferably 225-270°C, more preferably 232-250°C.
- the moldability of the fluorine-containing copolymer is further improved, and a more beautiful injection-molded article can be obtained by injection molding.
- a molded article having excellent solvent crack resistance, low nitrogen permeability, high rigidity at 75° C., tensile creep resistance at 150° C., and durability against repeated loads can be obtained.
- the melting point can be measured using a differential scanning calorimeter [DSC].
- the nitrogen permeability coefficient of the copolymer is preferably 310 cm 3 ⁇ mm/(m 2 ⁇ 24 h ⁇ atm) or less, more preferably 300 cm 3 ⁇ mm/(m 2 ⁇ 24 h ⁇ atm) or less.
- the fluorine-containing copolymer of the present disclosure has excellent low nitrogen permeability because the content of HFP units and PPVE units and the melt flow rate are appropriately adjusted.
- the nitrogen permeability coefficient can be measured under the conditions of a test temperature of 70°C and a test humidity of 0% RH.
- a specific measurement of the nitrogen permeability coefficient can be performed by the method described in Examples.
- the amount of eluted fluorine ions detected in an immersion test in hydrogen peroxide water is preferably 4.0 ppm or less, more preferably 3.0 ppm or less, on a mass basis. , more preferably 2.8 ppm or less.
- a molded body is obtained using the fluorocopolymer of the present disclosure, and a piping member used for transporting the chemical liquid, and a flow meter frame including a flow path for the chemical liquid in the flow meter.
- the immersion test in hydrogen peroxide water is performed by using a fluorine-containing copolymer to prepare a test piece having a weight equivalent to 10 molded articles (15 mm ⁇ 15 mm ⁇ 0.2 mm). and 15 g of a 3% by mass aqueous hydrogen peroxide solution are placed in a constant temperature bath at 95° C. and allowed to stand for 20 hours.
- the fluorine-containing copolymer of the present disclosure can be produced by any polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization.
- conditions such as temperature and pressure, polymerization initiator, chain transfer agent, solvent and other additives can be appropriately set according to the desired composition and amount of the fluorine-containing copolymer. .
- an oil-soluble radical polymerization initiator or a water-soluble radical initiator can be used as the polymerization initiator.
- Oil-soluble radical polymerization initiators may be known oil-soluble peroxides, for example, Dialkyl peroxycarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate; Peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate; Dialkyl peroxides such as di-t-butyl peroxide; Di[fluoro (or fluorochloro) acyl] peroxides; etc. are typical examples.
- Dialkyl peroxycarbonates such as di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di-sec-butyl peroxydicarbonate
- Peroxyesters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate
- Dialkyl peroxides such as di-
- Di[fluoro(or fluorochloro)acyl] peroxides include diacyl represented by [(RfCOO)-] 2 (Rf is a perfluoroalkyl group, ⁇ -hydroperfluoroalkyl group or fluorochloroalkyl group) peroxides.
- Di[fluoro(or fluorochloro)acyl] peroxides include, for example, di( ⁇ -hydro-dodecafluorohexanoyl) peroxide, di( ⁇ -hydro-tetradecafluoroheptanoyl) peroxide, di( ⁇ -hydro-hexadecafluorononanoyl)peroxide, di(perfluorobutyryl)peroxide, di(perfluoropareryl)peroxide, di(perfluorohexanoyl)peroxide, di(perfluoroheptanoyl)peroxide oxide, di(perfluorooctanoyl) peroxide, di(perfluorononanoyl) peroxide, di( ⁇ -chloro-hexafluorobutyryl) peroxide, di( ⁇ -chloro-decafluorohexanoyl) peroxide, Di( ⁇ -chloro-tetrade
- the water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts, potassium salts, sodium salts of persulfuric acid, perboric acid, perchloric acid, perphosphoric acid, percarbonate, etc. , t-butyl permaleate, t-butyl hydroperoxide and the like.
- a reducing agent such as sulfites may also be included, and the amount used may be 0.1 to 20 times that of the peroxide.
- chain transfer agents examples include hydrocarbons such as ethane, isopentane, n-hexane and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetic esters such as ethyl acetate and butyl acetate; , ethanol, 2,2,2-trifluoroethanol and other alcohols; methyl mercaptan and other mercaptans; carbon tetrachloride, chloroform, methylene chloride, methyl chloride and other halogenated hydrocarbons; 3-fluorobenzotrifluoride and the like mentioned.
- the amount to be added may vary depending on the magnitude of the chain transfer constant of the compound used, but it is usually used in the range of 0.01 to 20 parts by weight per 100 parts by weight of the solvent.
- the molecular weight of the resulting fluorine-containing copolymer becomes too high, resulting in a desired melt flow rate.
- chain transfer agents can be used to control the molecular weight.
- the solvent examples include water, a mixed solvent of water and alcohol, and the like.
- the monomer used for the polymerization of the fluorine-containing copolymer of the present disclosure can also be used as a solvent.
- a fluorinated solvent may be used in addition to water.
- Hydrochlorofluoroalkanes such as CH 3 CClF 2 , CH 3 CCl 2 F, CF 3 CF 2 CCl 2 H, CF 2 ClCF 2 CFHCl; CF 2 ClCFClCF 2 CF 3 , CF 3 CFClCFClCF 3 , etc. chlorofluoroalkanes ; perfluoroalkanes such as perfluorocyclobutane , CF3CF2CF2CF3 , CF3CF2CF2CF2CF3 , CF3CF2CF2CF2CF2CF3 , etc. _ Among them, perfluoroalkanes are preferred.
- the amount of fluorine-based solvent to be used is preferably 10 to 100 parts by mass per 100 parts by mass of the solvent, from the viewpoint of suspendability and economy.
- the polymerization temperature is not particularly limited, and may be 0 to 100°C.
- the polymerization initiator may be reduced from 0 to It is preferred to employ a relatively low polymerization temperature, such as in the range of 35°C.
- the polymerization pressure is appropriately determined according to other polymerization conditions such as the type of solvent used, the amount of solvent, the vapor pressure, and the polymerization temperature, but usually it may be 0 to 9.8 MPaG.
- the polymerization pressure is preferably 0.1 to 5 MPaG, more preferably 0.5 to 2 MPaG, still more preferably 0.5 to 1.5 MPaG. Moreover, when the polymerization pressure is 1.5 MPaG or more, the production efficiency can be improved.
- Additives in polymerization include, for example, suspension stabilizers.
- the suspension stabilizer is not particularly limited as long as it is a conventionally known one, and methyl cellulose, polyvinyl alcohol and the like can be used.
- a suspension stabilizer is used, the suspended particles generated by the polymerization reaction are stably dispersed in the aqueous medium. Suspended particles are less likely to adhere to Therefore, since a reactor that can withstand high pressure can be used, polymerization can be performed under high pressure, and production efficiency can be improved.
- suspension stabilizer when polymerization is carried out without using a suspension stabilizer, if a SUS reaction tank that has not been subjected to an anti-adhesion treatment is used, suspended particles may adhere, resulting in a decrease in production efficiency.
- concentration of the suspension stabilizer in the aqueous medium can be appropriately adjusted depending on the conditions.
- the dry fluoropolymer may be recovered by coagulating the fluorine-containing copolymer contained in the aqueous dispersion, washing, and drying. Moreover, when the fluorine-containing copolymer is obtained as a slurry by the polymerization reaction, the slurry may be taken out from the reaction vessel, washed and dried to recover the dried fluoropolymer. By drying, the fluorine-containing copolymer can be recovered in the form of powder.
- the fluorine-containing copolymer obtained by polymerization may be molded into pellets.
- a molding method for molding into pellets is not particularly limited, and conventionally known methods can be used. For example, a method of melt extruding a fluorine-containing copolymer using a single-screw extruder, twin-screw extruder, or tandem extruder, cutting it into a predetermined length, and molding it into a pellet can be used.
- the extrusion temperature for melt extrusion must be changed according to the melt viscosity of the fluorine-containing copolymer and the production method, and is preferably from the melting point of the fluorine-containing copolymer +20°C to the melting point of the fluorine-containing copolymer +140°C.
- the method for cutting the fluorine-containing copolymer is not particularly limited, and conventionally known methods such as a strand cut method, a hot cut method, an underwater cut method, and a sheet cut method can be employed.
- the obtained pellets may be heated to remove volatile matter in the pellets (deaeration treatment).
- the obtained pellets may be treated by contacting them with warm water of 30-200°C, steam of 100-200°C, or hot air of 40-200°C.
- a fluorine-containing copolymer obtained by polymerization may be heated to a temperature of 100° C. or higher in the presence of air and water (wet heat treatment).
- wet heat treatment methods include a method in which an extruder is used to melt and extrude the fluorine-containing copolymer obtained by polymerization while supplying air and water.
- the thermally unstable functional groups such as —COF and —COOH of the fluorocopolymer can be converted to relatively thermally stable —CF 2 H, and the fluorocopolymer
- the conversion reaction to —CF 2 H can be promoted.
- contamination with alkali metal salts should be avoided.
- a fluorine-containing copolymer obtained by polymerization may be subjected to a fluorination treatment.
- the fluorination treatment can be carried out by contacting the unfluorinated fluorocopolymer with a fluorine-containing compound.
- thermally Functional groups such as —CF 2 H, which are relatively stable to
- the fluorine-containing compound is not particularly limited, but includes fluorine radical sources that generate fluorine radicals under fluorination treatment conditions.
- fluorine radical source include F 2 gas, CoF 3 , AgF 2 , UF 6 , OF 2 , N 2 F 2 , CF 3 OF, halogen fluoride (eg IF 5 , ClF 3 ), and the like.
- the fluorine radical source such as F 2 gas may have a concentration of 100%, but from the viewpoint of safety, it is preferable to mix it with an inert gas and dilute it to 5 to 50% by mass before use. It is more preferable to dilute to 30% by mass before use.
- the inert gas include nitrogen gas, helium gas, argon gas, etc. Nitrogen gas is preferable from an economical point of view.
- Conditions for the fluorination treatment are not particularly limited, and the melted fluorine-containing copolymer may be brought into contact with the fluorine-containing compound. It can be carried out at a temperature of 220°C, more preferably from 100 to 200°C.
- the fluorination treatment is generally carried out for 1 to 30 hours, preferably 5 to 25 hours.
- the fluorination treatment is preferably carried out by contacting a fluorine-containing copolymer that has not been fluorinated with fluorine gas ( F2 gas).
- a composition may be obtained by mixing the fluorine-containing copolymer of the present disclosure with other components, if necessary.
- Other components include fillers, plasticizers, processing aids, release agents, pigments, flame retardants, lubricants, light stabilizers, weather stabilizers, conductive agents, antistatic agents, ultraviolet absorbers, antioxidants, Foaming agents, fragrances, oils, softening agents, dehydrofluorination agents and the like can be mentioned.
- fillers include silica, kaolin, clay, organic clay, talc, mica, alumina, calcium carbonate, calcium terephthalate, titanium oxide, calcium phosphate, calcium fluoride, lithium fluoride, crosslinked polystyrene, potassium titanate, Examples include carbon, boron nitride, carbon nanotubes, glass fibers, and the like.
- the conductive agent include carbon black and the like.
- plasticizers include dioctylphthalic acid and pentaerythritol.
- processing aids include carnauba wax, sulfone compounds, low-molecular-weight polyethylene, fluorine-based aids, and the like.
- dehydrofluorination agents include organic oniums and amidines.
- polymers other than the fluorine-containing copolymers described above may be used as the other components.
- Other polymers include fluororesins, fluororubbers, and non-fluorinated polymers other than the above fluorocopolymers.
- Examples of the method for producing the composition include a method of dry mixing the fluorocopolymer and other components, or a method of premixing the fluorocopolymer and other components in a mixer, followed by kneading and melting. A method of melt-kneading with an extruder or the like can be mentioned.
- the fluorine-containing copolymer of the present disclosure or the composition described above can be used as a processing aid, molding material, etc., but is preferably used as a molding material.
- Aqueous dispersions, solutions, suspensions, and copolymer/solvent systems of the fluorocopolymers of the present disclosure are also available, which can be applied as coatings, encapsulated, impregnated, flowed into films. It can be used for spreading.
- the fluorine-containing copolymer of the present disclosure has the properties described above, it is preferably used as the molding material.
- a molded article may be obtained by molding the fluorine-containing copolymer of the present disclosure or the above composition.
- the method for molding the fluorine-containing copolymer or composition is not particularly limited, and injection molding, extrusion molding, compression molding, blow molding, transfer molding, roto molding, roto lining molding, and the like can be used. mentioned.
- extrusion molding, compression molding, injection molding, or transfer molding is preferable, and injection molding, extrusion, or transfer molding is more preferable because it can produce molded articles with high productivity.
- the injection molding method is preferably an extrusion molded article, a compression molded article, an injection molded article or a transfer molded article. is more preferred, and an injection molded article is even more preferred.
- a beautiful molded article can be obtained by molding the fluorine-containing copolymer of the present disclosure by an injection molding method.
- Molded articles containing the fluorocopolymer of the present disclosure include, for example, nuts, bolts, joints, films, bottles, gaskets, wire coatings, tubes, hoses, pipes, valves, sheets, seals, packings, tanks, and rollers. , vessels, cocks, connectors, filter housings, filter cages, flow meters, pumps, wafer carriers, wafer boxes, and the like.
- the fluorine-containing copolymer of the present disclosure, the above composition, or the above molding can be used, for example, in the following applications.
- Films for food packaging, lining materials for fluid transfer lines used in food manufacturing processes, packings, sealing materials, and fluid transfer members for food manufacturing equipment such as sheets
- Drug stoppers for drugs, packaging films, lining materials for fluid transfer lines used in the process of manufacturing drugs, packings, sealing materials, and chemical liquid transfer members such as sheets
- Inner lining members for chemical tanks and piping in chemical plants and semiconductor factories O (square) rings, tubes, packings, valve core materials, hoses, sealing materials, etc. used in automobile fuel systems and peripheral devices; fuel transfer members such as hoses, sealing materials, etc.
- Coating and ink components such as coating rolls, hoses, tubes, and ink containers for coating equipment; Tubes for food and drink or tubes such as food and drink hoses, hoses, belts, packings, food and drink transfer members such as joints, food packaging materials, glass cooking equipment; Parts for transporting waste liquid such as tubes and hoses for transporting waste liquid; Parts for transporting high-temperature liquids, such as tubes and hoses for transporting high-temperature liquids; Steam piping members such as steam piping tubes and hoses; Anti-corrosion tape for piping such as tape to be wrapped around piping on ship decks; Various coating materials such as wire coating materials, optical fiber coating materials, transparent surface coating materials and back coating materials provided on the light incident side surface of photovoltaic elements of solar cells; Sliding members such as diaphragms of diaphragm pumps and various packings; Agricultural films, weather-resistant covers for various roofing materials and side walls; Interior materials used in the construction field, coating materials for glasses such
- fuel transfer members used in the fuel system of automobiles include fuel hoses, filler hoses, and evaporation hoses.
- the above-mentioned fuel transfer member can also be used as a fuel transfer member for sour gasoline-resistant fuel, alcohol-resistant fuel, and fuel containing gasoline additives such as methyl tert-butyl ether and amine-resistant fuel.
- the above drug stoppers and packaging films for drugs have excellent chemical resistance against acids and the like.
- an anticorrosive tape to be wound around chemical plant pipes can also be mentioned.
- Examples of the above molded bodies also include automobile radiator tanks, chemical liquid tanks, bellows, spacers, rollers, gasoline tanks, containers for transporting waste liquids, containers for transporting high-temperature liquids, fisheries and fish farming tanks, and the like.
- Examples of the molded article include automobile bumpers, door trims, instrument panels, food processing equipment, cooking equipment, water- and oil-repellent glass, lighting-related equipment, display panels and housings for OA equipment, illuminated signboards, displays, and liquid crystals.
- Members used for displays, mobile phones, printed circuit boards, electrical and electronic parts, miscellaneous goods, trash cans, bathtubs, unit baths, ventilation fans, lighting frames and the like are also included.
- Molded articles containing the fluorocopolymer of the present disclosure have excellent wear resistance at 95°C, solvent crack resistance, low nitrogen permeability, rigidity at high temperatures of 75°C, tensile creep resistance at 150°C, and durability against repeated loads. Since it is excellent, it can be suitably used for nuts, bolts, joints, packings, valves, cocks, connectors, filter housings, filter cages, flowmeters, pumps, and the like. Among others, it can be suitably used as a piping member (especially valves and joints) used for transporting chemical liquids, and as a flowmeter frame provided with a chemical liquid flow path in a flowmeter.
- the piping member and flowmeter frame of the present disclosure are excellent in wear resistance at 95°C, solvent crack resistance, low nitrogen permeability, rigidity at high temperature of 75°C, tensile creep resistance at 150°C, and durability against repeated loads. Therefore, the piping member and the flow meter body of the present disclosure are not easily damaged even if stress is repeatedly applied according to the start, stop, and change of the flow rate of the chemical solution, and the durability against abrasion that occurs during the flow of the chemical solution, and the chemical solution resistance. , excellent heat deformation resistance.
- a molded article containing the fluorine-containing copolymer of the present disclosure can be molded by an injection molding method to obtain a beautiful injection molded article. Since it is excellent in rigidity at high temperatures at 150° C., tensile creep resistance at 150° C., and durability against repeated loads, it can be suitably used as members to be compressed such as gaskets and packings.
- the compressible member of the present disclosure may be a gasket or packing. Gaskets or packings of the present disclosure can be manufactured at low cost by injection molding methods, and have 95° C. abrasion resistance, solvent crack resistance, low nitrogen permeability, 75° C. high temperature stiffness, 150° C. tensile creep resistance, Excellent durability against repeated loads.
- the size and shape of the member to be compressed of the present disclosure may be appropriately set according to the application, and are not particularly limited.
- the shape of the compressible member of the present disclosure may be annular, for example.
- the member to be compressed of the present disclosure may have a shape such as a circle, an oval, or a rectangle with rounded corners in a plan view, and may have a through hole in the center thereof.
- the member to be compressed of the present disclosure is preferably used as a member for configuring a non-aqueous electrolyte battery.
- the member to be compressed of the present disclosure is excellent in wear resistance at 95° C., solvent crack resistance, low nitrogen permeability, rigidity at high temperature of 75° C., tensile creep resistance at 150° C., and durability against repeated loads. It is particularly suitable as a member used in contact with a non-aqueous electrolyte in an aqueous electrolyte battery. That is, the member to be compressed of the present disclosure may have a liquid contact surface with the non-aqueous electrolyte in the non-aqueous electrolyte battery.
- the non-aqueous electrolyte battery is not particularly limited as long as it is a battery with a non-aqueous electrolyte, and examples thereof include lithium ion secondary batteries and lithium ion capacitors. Further, examples of members constituting the non-aqueous electrolyte battery include a sealing member and an insulating member.
- the non-aqueous electrolyte is not particularly limited, but includes propylene carbonate, ethylene carbonate, butylene carbonate, ⁇ -butyl lactone, 1,2-dimethoxyethane, 1,2-diethoxyethane, dimethyl carbonate, and diethyl carbonate. , ethyl methyl carbonate and the like can be used.
- the nonaqueous electrolyte battery may further include an electrolyte.
- the electrolyte is not particularly limited, but LiClO 4 , LiAsF 6 , LiPF 6 , LiBF 4 , LiCl, LiBr, CH 3 SO 3 Li, CF 3 SO 3 Li, cesium carbonate, or the like can be used.
- the member to be compressed of the present disclosure can be suitably used as, for example, a sealing member such as a sealing gasket and sealing packing, and an insulating member such as an insulating gasket and insulating packing.
- a sealing member is a member used to prevent leakage of liquid or gas or intrusion of liquid or gas from the outside.
- An insulating member is a member used to insulate electricity.
- Compressed members of the present disclosure may be members used for both sealing and insulating purposes.
- the member to be compressed of the present disclosure is excellent in wear resistance at 95° C., solvent crack resistance, low nitrogen permeability, rigidity at high temperature of 75° C., tensile creep resistance at 150° C., and durability against repeated loads. It can be suitably used as a sealing member for aqueous electrolyte batteries or an insulating member for non-aqueous electrolyte batteries.
- the member to be compressed of the present disclosure contains the fluorine-containing copolymer, it has excellent insulating properties. Therefore, when the compressible member of the present disclosure is used as an insulating member, it adheres tightly to two or more conductive members to prevent short circuits over time.
- the fluorocopolymer of the present disclosure can form a thin coating layer on a small-diameter core wire at a high speed by an extrusion molding method, so it is suitably used as a material for forming an electric wire coating. be able to.
- a coated wire provided with a coating layer containing the fluorocopolymer of the present disclosure has excellent electrical properties because it has almost no defects that cause sparks.
- the fluorocopolymer of the present disclosure can form a very thick coating layer with a uniform thickness on a core wire with a very large diameter, it is suitably used as a material for forming an electric wire coating. be able to.
- a covered electric wire provided with a covering layer containing the fluorine-containing copolymer of the present disclosure has excellent electrical properties because there is almost no variation in outer diameter.
- a covered electric wire includes a core wire and a coating layer provided around the core wire and containing the fluorine-containing copolymer of the present disclosure.
- the coating layer can be an extruded product obtained by melt extruding the fluorine-containing copolymer of the present disclosure on the core wire.
- the coated electric wire is suitable for LAN cables (Ethernet Cable), high frequency transmission cables, flat cables, heat resistant cables, etc., and particularly suitable for transmission cables such as LAN cables (Eathnet Cable) and high frequency transmission cables.
- the core wire for example, a metal conductor material such as copper or aluminum can be used.
- the core wire preferably has a diameter of 0.02 to 3 mm.
- the diameter of the cord is more preferably 0.04 mm or more, still more preferably 0.05 mm or more, and particularly preferably 0.1 mm or more.
- the diameter of the cord is more preferably 2 mm or less.
- core wires include AWG (American Wire Gauge)-46 (solid copper wire with a diameter of 40 micrometers), AWG-26 (solid copper wire with a diameter of 404 micrometers), AWG-24 (diameter 510 micrometer solid copper wire), AWG-22 (635 micrometer diameter solid copper wire), etc. may be used.
- AWG American Wire Gauge
- AWG-46 solid copper wire with a diameter of 40 micrometers
- AWG-26 solid copper wire with a diameter of 404 micrometers
- AWG-24 diameter 510 micrometer solid copper wire
- AWG-22 (635 micrometer diameter solid copper wire), etc.
- the thickness of the coating layer is preferably 0.1 to 3.0 mm. It is also preferable that the thickness of the coating layer is 2.0 mm or less.
- a coaxial cable is an example of a high-frequency transmission cable.
- a coaxial cable generally has a structure in which an inner conductor, an insulating coating layer, an outer conductor layer and a protective coating layer are laminated in order from the core to the outer periphery.
- a molded article containing the fluorocopolymer of the present disclosure can be suitably used as an insulating coating layer containing the fluorocopolymer.
- the thickness of each layer in the above structure is not particularly limited, but usually the inner conductor has a diameter of about 0.1 to 3 mm, the insulating coating layer has a thickness of about 0.3 to 3 mm, and the outer conductor layer has a thickness of about 0.5-10 mm, the protective coating layer is about 0.5-2 mm thick.
- the coating layer may contain air bubbles, and it is preferable that the air bubbles are uniformly distributed in the coating layer.
- the average bubble diameter of the bubbles is not limited, for example, it is preferably 60 ⁇ m or less, more preferably 45 ⁇ m or less, even more preferably 35 ⁇ m or less, and even more preferably 30 ⁇ m or less. It is preferably 25 ⁇ m or less, particularly preferably 23 ⁇ m or less, and most preferably 23 ⁇ m or less. Also, the average bubble diameter is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more. The average bubble diameter can be obtained by taking an electron microscope image of the cross section of the electric wire, calculating the diameter of each bubble by image processing, and averaging the diameters.
- the coating layer may have an expansion rate of 20% or more. It is more preferably 30% or more, still more preferably 33% or more, and even more preferably 35% or more.
- the upper limit is not particularly limited, it is, for example, 80%.
- the upper limit of the expansion rate may be 60%.
- the foaming rate is a value obtained by ((specific gravity of wire coating material ⁇ specific gravity of coating layer)/specific gravity of wire coating material) ⁇ 100. The foaming rate can be appropriately adjusted depending on the application, for example, by adjusting the amount of gas inserted into the extruder, which will be described later, or by selecting the type of gas to be dissolved.
- the covered electric wire may have another layer between the core wire and the covering layer, and may have another layer (outer layer) around the covering layer.
- the electric wire of the present disclosure has a two-layer structure (skin-foam) in which a non-foaming layer is inserted between the core wire and the covering layer, or a two-layer structure in which the outer layer is covered with a non-foaming layer. (foam-skin), or a three-layer structure (skin-foam-skin) in which the outer layer of skin-foam is covered with a non-foamed layer.
- the non-foamed layer is not particularly limited, and includes TFE/HFP copolymers, TFE/PAVE copolymers, TFE/ethylene copolymers, vinylidene fluoride polymers, polyolefin resins such as polyethylene [PE], polychlorinated It may be a resin layer made of a resin such as vinyl [PVC].
- a covered electric wire can be produced, for example, by heating a fluorine-containing copolymer using an extruder and extruding the melted fluorine-containing copolymer onto a core wire to form a coating layer.
- the fluorocopolymer is heated and a gas is introduced into the fluorocopolymer in a molten state to form the coating layer containing air bubbles.
- a gas such as chlorodifluoromethane, nitrogen, carbon dioxide, or a mixture of the above gases can be used.
- the gas may be introduced as a pressurized gas into the heated fluorocopolymer, or may be generated by incorporating a chemical blowing agent into the fluorocopolymer. The gas dissolves in the molten fluorine-containing copolymer.
- the fluorine-containing copolymer of the present disclosure can be suitably used as a material for high-frequency signal transmission products.
- the product for high-frequency signal transmission is not particularly limited as long as it is a product used for high-frequency signal transmission. Molded bodies such as high-frequency vacuum tube bases and antenna covers, (3) coated electric wires such as coaxial cables and LAN cables, and the like.
- the above products for high-frequency signal transmission can be suitably used in equipment that uses microwaves, particularly microwaves of 3 to 30 GHz, such as satellite communication equipment and mobile phone base stations.
- the fluorine-containing copolymer of the present disclosure can be suitably used as an insulator because of its low dielectric loss tangent.
- a printed wiring board is preferable in terms of obtaining good electrical characteristics.
- the printed wiring board include, but are not particularly limited to, printed wiring boards for electronic circuits such as mobile phones, various computers, and communication devices.
- an antenna cover is preferable in terms of low dielectric loss.
- the fluorine-containing copolymer of the present disclosure can be molded into a thin film having a uniform thickness at a high molding speed by an extrusion molding method, and the obtained molded article has 95° C. abrasion resistance and solvent crack resistance. , low nitrogen permeability, rigidity at high temperature of 75°C, tensile creep resistance at 150°C, and durability against repeated loads, and can be suitably used for films.
- the film of the present disclosure is useful as a release film.
- the release film can be produced by molding the fluorine-containing copolymer of the present disclosure by melt extrusion molding, calendar molding, press molding, casting molding, or the like. From the viewpoint of obtaining a uniform thin film, the release film can be produced by melt extrusion molding.
- the film of the present disclosure can be applied to the surface of rolls used in OA equipment.
- the fluorine-containing copolymer of the present disclosure is molded into a required shape by extrusion molding, compression molding, press molding, etc., and is molded into a sheet, film, or tube, and is used for OA equipment rolls, OA equipment belts, and the like.
- thin-walled tubes and films can be produced by melt extrusion.
- the fluorine-containing copolymer of the present disclosure can be molded by an injection molding method to obtain a beautiful injection-molded article, and has abrasion resistance at 95°C, solvent crack resistance, low nitrogen permeability, rigidity at a high temperature of 75°C, Since it has excellent tensile creep resistance at 150° C. and durability against repeated loads, it can be suitably used for valves. Therefore, the valve containing the fluorocopolymer of the present disclosure can be manufactured at low cost and with high productivity, is less likely to be damaged even when repeatedly opened and closed at high frequency, and has excellent sealing properties.
- at least the liquid-contacting portion can be made of the above fluorocopolymer.
- the valve of the present disclosure may be a valve provided with a housing containing the fluorocopolymer described above.
- each monomer unit of the fluorine-containing copolymer is measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured by Bruker Biospin) or an infrared absorption measuring device (Spectrum One, manufactured by PerkinElmer). was measured using an NMR spectrometer (for example, AVANCE300 high temperature probe, manufactured
- the number of —CF 2 H groups in the fluorine-containing copolymer is measured by 19 F-NMR using a nuclear magnetic resonance apparatus AVANCE-300 (manufactured by Bruker Biospin) at a temperature of (the melting point of the polymer +20)°C. , was obtained from the peak integration value of the —CF 2 H group.
- N I ⁇ K/t (A) I: Absorbance K: Correction coefficient t: Film thickness (mm)
- Table 2 shows the absorption frequencies, molar extinction coefficients, and correction coefficients for the functional groups in the examples. Also, the molar extinction coefficient was determined from the FT-IR measurement data of the low-molecular-weight model compound.
- MFR Melt flow rate
- melting point The melting point of the fluorine-containing copolymer was measured using a differential scanning calorimeter (trade name: X-DSC7000, manufactured by Hitachi High-Tech Science Co., Ltd.) at a heating rate of 10°C/min from 200°C to 350°C for the first time. followed by cooling from 350°C to 200°C at a cooling rate of 10°C/min; The melting point was determined from the peak of the melting curve that occurred during the second heating process.
- Example 1 40.25 kg of deionized water and 0.104 kg of methanol were put into an autoclave with a volume of 174 L and equipped with a stirrer, and the inside of the autoclave was sufficiently replaced with vacuum nitrogen. After that, the inside of the autoclave was evacuated, and 40.25 kg of HFP and 0.99 kg of PPVE were put into the vacuumed autoclave, and the autoclave was heated to 30.0°C. Subsequently, TFE was added until the internal pressure of the autoclave reached 0.918 MPa, and then 0.63 kg of 8 mass% di( ⁇ -hydroperfluorohexanoyl) peroxide solution (hereinafter abbreviated as DHP) was added to the autoclave.
- DHP di( ⁇ -hydroperfluorohexanoyl) peroxide solution
- the internal pressure of the autoclave at the start of polymerization was set to 0.918 MPa, and the set pressure was maintained by continuously adding TFE. After 1.5 hours from the initiation of polymerization, 0.104 kg of methanol was added. After 2 hours and 4 hours from the start of polymerization, 0.63 kg of DHP was added and the internal pressure was lowered by 0.001 MPa. After 6 hours, 0.48 kg was added and the internal pressure was lowered by 0.001 MPa. Thereafter, 0.13 kg of DHP was added every 2 hours until the reaction was completed, and the internal pressure was lowered by 0.001 MPa each time.
- the resulting powder was melt extruded at 370°C with a screw extruder (trade name: PCM46, manufactured by Ikegai Co., Ltd.) to obtain copolymer pellets.
- a screw extruder (trade name: PCM46, manufactured by Ikegai Co., Ltd.) to obtain copolymer pellets.
- various physical properties were measured by the methods described above. Table 3 shows the results.
- Example 2 The amount of methanol charged before the initiation of polymerization was changed to 0.122 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.122 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.122 kg.
- Example 3 The amount of methanol charged before the initiation of polymerization was changed to 0.140 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.140 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.140 kg.
- Example 4 The amount of methanol charged before the start of polymerization was changed to 0.155 kg, the amount of methanol charged separately after the start of polymerization was changed to 0.155 kg, and the amount of PPVE charged before the start of polymerization was changed to 0.155 kg.
- Example 5 The amount of methanol charged before the initiation of polymerization was changed to 0.158 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.158 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.158 kg.
- the obtained pellets were degassed in an electric furnace at 200°C for 72 hours, then placed in a vacuum vibration reactor VVD-30 (manufactured by Okawara Seisakusho) and heated to 110°C. After evacuation, F2 gas diluted to 20 % by volume with N2 gas was introduced to atmospheric pressure. After 0.5 hours from the introduction of the F2 gas, the chamber was once evacuated, and the F2 gas was introduced again. Further, after 0.5 hours, the chamber was evacuated again and F 2 gas was introduced again. Thereafter, the F 2 gas introduction and evacuation operations were continued once an hour, and the reaction was carried out at a temperature of 110° C. for 8 hours. After completion of the reaction, the interior of the reactor was sufficiently replaced with N 2 gas to complete the fluorination reaction and obtain pellets. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Example 6 The amount of methanol charged before the initiation of polymerization was changed to 0.186 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.186 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.186 kg.
- Example 7 The amount of methanol charged before the initiation of polymerization was changed to 0.209 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.209 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.209 kg.
- the obtained pellets were degassed in an electric furnace at 200°C for 8 hours, then placed in a vacuum vibration reactor VVD-30 (manufactured by Okawara Seisakusho Co., Ltd.) and heated to 200°C. After evacuation, F2 gas diluted to 20 % by volume with N2 gas was introduced to atmospheric pressure. After 0.5 hours from the introduction of the F2 gas, the chamber was once evacuated, and the F2 gas was introduced again. Further, after 0.5 hours, the chamber was evacuated again and F 2 gas was introduced again. Thereafter, the F 2 gas introduction and evacuation operations were continued once an hour, and the reaction was carried out at a temperature of 200° C. for 8 hours. After completion of the reaction, the interior of the reactor was sufficiently replaced with N 2 gas to complete the fluorination reaction and obtain pellets. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Example 8 The amount of methanol charged before the initiation of polymerization was changed to 0.215 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.215 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.215 kg.
- the obtained pellets were fluorinated in the same manner as in Example 7. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Example 9 The amount of methanol charged before the initiation of polymerization was changed to 0.218 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.218 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.218 kg. 80 kg, the amount of PPVE to be separately added after the start of polymerization was changed to 0.27 kg, and the set pressure inside the autoclave before and after the start of polymerization was changed to 0.887 MPa. to obtain copolymer pellets. Using the obtained pellets, the HFP content and PPVE content were measured by the methods described above. Table 3 shows the results.
- the obtained pellets were fluorinated in the same manner as in Example 7. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Comparative example 1 The amount of methanol charged before the start of polymerization was changed to 0.363 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.363 kg, and the amount of PPVE charged before the start of polymerization was changed to 0.363 kg.
- Comparative example 2 40.25 kg of deionized water and 0.152 kg of methanol were put into an autoclave with a volume of 174 L and equipped with a stirrer, and the inside of the autoclave was sufficiently replaced with vacuum nitrogen. After that, the inside of the autoclave was evacuated, and 40.25 kg of HFP and 0.78 kg of PPVE were put into the vacuumed autoclave, and the autoclave was heated to 32.0°C. Subsequently, TFE was added until the internal pressure of the autoclave reached 0.926 MPa, and then 0.31 kg of 8 mass% di( ⁇ -hydroperfluorohexanoyl) peroxide solution (hereinafter abbreviated as DHP) was added to the autoclave.
- DHP di( ⁇ -hydroperfluorohexanoyl) peroxide solution
- the internal pressure of the autoclave at the start of polymerization was set to 0.926 MPa, and the set pressure was maintained by continuously adding TFE. After 1.5 hours from the initiation of polymerization, 0.152 kg of methanol was added. After 2 hours and 4 hours from the start of polymerization, 0.31 kg of DHP was added and the internal pressure was lowered by 0.001 MPa. After 6 hours, 0.24 kg was added and the internal pressure was lowered by 0.001 MPa. Thereafter, 0.07 kg of DHP was added every 2 hours until the reaction was completed.
- the resulting powder was melt extruded at 370°C with a screw extruder (trade name: PCM46, manufactured by Ikegai Co., Ltd.) to obtain copolymer pellets.
- a screw extruder (trade name: PCM46, manufactured by Ikegai Co., Ltd.) to obtain copolymer pellets.
- various physical properties were measured by the methods described above. Table 3 shows the results.
- Comparative example 3 A copolymer was prepared in the same manner as in Comparative Example 2, except that the amount of methanol charged before the initiation of polymerization was changed to 0.282 kg, and the amount of methanol added separately after the initiation of polymerization was changed to 0.282 kg. A pellet was obtained. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Comparative example 4 The amount of methanol charged before the start of polymerization was changed to 0.290 kg, the amount of methanol charged separately after the start of polymerization was changed to 0.290 kg, and the amount of PPVE charged before the start of polymerization was changed to 1.0 kg.
- the HFP content and PPVE content were measured by the methods described above.
- Table 3 shows the results.
- the obtained pellets were fluorinated in the same manner as in Example 5. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Comparative example 5 1.10 kg of deionized water was charged into an autoclave with a volume of 4 L and equipped with a stirrer, and the inside of the autoclave was sufficiently replaced with vacuum nitrogen. After that, the inside of the autoclave was evacuated, and 1.10 kg of HFP and 16.2 g of PPVE were charged into the evacuated autoclave, and the autoclave was heated to 40.0°C. Subsequently, a gas obtained by mixing TFE and HFP at a molar ratio of 91:9 was introduced until the internal pressure of the autoclave reached 1.290 MPa, and then 7.0 g of a 40% by mass diisopropyl peroxydicarbonate solution was introduced into the autoclave. to initiate polymerization. The internal pressure of the autoclave at the start of polymerization was set to 1.290 MPa, and the set pressure was maintained by continuously adding gas obtained by mixing TFE and HFP at a molar ratio of 91:9.
- Comparative example 6 945 g of deionized water and 4.3 g of methanol were put into an autoclave having a volume of 4 L and equipped with a stirrer, and the inside of the autoclave was sufficiently replaced with vacuum nitrogen. After that, the inside of the autoclave was evacuated, and 945 g of HFP and 18.8 g of PEVE were put into the vacuumed autoclave, and the autoclave was heated to 30.0°C. Subsequently, TFE was added until the internal pressure of the autoclave reached 0.890 MPa, and then 14.7 g of 8 mass% di( ⁇ -hydroperfluorohexanoyl) peroxide solution (hereinafter abbreviated as DHP) was added to the autoclave.
- DHP di( ⁇ -hydroperfluorohexanoyl) peroxide solution
- the internal pressure of the autoclave at the start of polymerization was set to 0.890 MPa, and the set pressure was maintained by continuously adding TFE. After 1.5 hours from the initiation of polymerization, 4.3 g of methanol was added. After 2 hours and 4 hours from the start of polymerization, 14.7 g of DHP was added and the internal pressure was lowered by 0.001 MPa, and after 6 hours, 11.3 g was added and the internal pressure was lowered by 0.001 MPa. Thereafter, 3.0 g of DHP was added every 2 hours until the reaction was completed, and the internal pressure was lowered by 0.001 MPa each time.
- the obtained powder was melt-extruded at 370°C with a 14 ⁇ screw extruder (manufactured by Imoto Seisakusho) to obtain copolymer pellets.
- the HFP content and the PEVE content were measured by the methods described above. Table 3 shows the results.
- the obtained pellets were degassed in an electric furnace at 200°C for 8 hours, then placed in a portable reactor TVS1 (manufactured by Pressure Glass Industry Co., Ltd.) and heated to 200°C. After evacuation, F2 gas diluted to 20 % by volume with N2 gas was introduced to atmospheric pressure. After 0.5 hours from the introduction of the F2 gas, the chamber was once evacuated, and the F2 gas was introduced again. Further, after 0.5 hours, the chamber was evacuated again and F 2 gas was introduced again. Thereafter, the F 2 gas introduction and evacuation operations were continued once an hour, and the reaction was carried out at a temperature of 200° C. for 8 hours. After completion of the reaction, the interior of the reactor was sufficiently replaced with N 2 gas to complete the fluorination reaction and obtain pellets. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Comparative example 7 The amount of methanol charged before the initiation of polymerization was changed to 0.061 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.061 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.061 kg.
- the obtained pellets were fluorinated in the same manner as in Example 5. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- Comparative example 8 The amount of methanol charged before the initiation of polymerization was changed to 0.384 kg, the amount of methanol charged separately after the initiation of polymerization was changed to 0.384 kg, and the amount of PPVE charged before initiation of polymerization was changed to 0.384 kg.
- the obtained pellets were fluorinated in the same manner as in Example 7. Using the obtained pellets, various physical properties were measured by the methods described above. Table 3 shows the results.
- the description “ ⁇ 9” in Table 3 means that the number of —CF 2 H groups is less than nine.
- the description “ ⁇ 6” in Table 3 means that the number of corresponding functional groups is less than 6.
- the entry “ND” in Table 3 means that the functional group of interest was not detected.
- Wear amount (mg) M1-M2 M1: Specimen weight after 1000 rotations (mg) M2: Specimen weight after 3500 rotations (mg)
- notch test pieces and 25 g of an 85% by mass phosphoric acid aqueous solution were placed in a 100 mL polypropylene bottle, heated in an electric furnace at 120° C. for 20 hours, and then the notch test pieces were taken out.
- the three notch test pieces obtained were attached to a stress crack test jig according to ASTM D1693, heated at 180 ° C. for 2 hours in an electric furnace, and then the notch and its surroundings were visually observed and the number of cracks was counted.
- a crack-free sheet has excellent solvent crack resistance.
- ⁇ The number of cracks is 0
- the number of cracks is 1 or more
- GTR Nitrogen permeability (cm 3 /(m 2 ⁇ 24 h ⁇ atm))
- d test piece thickness (mm)
- a sheet having a small load deflection rate at 75°C has excellent rigidity at a high temperature of 75°C.
- Load deflection rate (%) a2/a1 x 100
- a1 Specimen thickness before test (mm)
- a2 Amount of deflection at 75°C (mm)
- Tensile creep strain was measured using TMA-7100 manufactured by Hitachi High-Tech Science. Using a pellet and heat press molding machine, a sheet having a thickness of about 0.1 mm was produced, and a sample having a width of 2 mm and a length of 22 mm was produced from the sheet. The sample was attached to the measurement jig with a distance between the jigs of 10 mm. A load is applied to the sample so that the cross-sectional load is 2.93 N / mm 2 , left at 150 ° C., and the length of the sample from 90 minutes after the start of the test to 300 minutes after the start of the test.
- the displacement (mm) was measured, and the ratio of the length displacement (mm) to the initial sample length (10 mm) (tensile creep strain (%)) was calculated.
- a sheet with a small tensile creep strain (%) measured under conditions of 150°C for 300 minutes does not stretch easily even when a tensile load is applied for a long time in a high-temperature environment, and has excellent high-temperature tensile creep resistance (150°C).
- the tensile strength was measured after 100,000 cycles using a fatigue tester MMT-250NV-10 manufactured by Shimadzu Corporation.
- a sheet with a thickness of about 2.4 mm was produced using a pellet and heat press molding machine, and a dumbbell-shaped sample (thickness 2.4 mm, width 5.0 mm, measurement length 22 mm) was prepared using ASTM D1708 micro dumbbells. made.
- a sample was attached to a measuring jig, and the measuring jig with the sample attached was placed in a constant temperature bath at 110°C. With a stroke of 0.2 mm and a frequency of 100 Hz, uniaxial tension was repeatedly applied, and the tensile strength (tensile strength when the stroke was +0.2 mm, unit: N) was measured.
- a sheet with high tensile strength after 100,000 cycles maintains high tensile strength even after loading 100,000 times, and has excellent durability (110°C) against repeated loads.
- Electrode coating molding conditions (1) A copper conductor having a conductor diameter of 0.50 mm was extruded and coated with a fluorine-containing copolymer with the following coating thickness using a 30 mm diameter wire coating molding machine (manufactured by Tanabe Plastic Machine Co., Ltd.) to obtain a coated wire.
- the wire covering extrusion molding conditions are as follows.
- spark A spark tester (DENSOK HIGH FREQ SPARK TESTER) was installed online in the wire coating line, and the presence or absence of defects in the wire coating was evaluated at a voltage of 1500V. After continuous molding for 1 hour, the number of sparks was counted.
- Electrode coating molding conditions (2) A copper conductor having a diameter of 1.00 mm was extruded and coated with a fluorine-containing copolymer with the following coating thickness using a 30 mm diameter wire coating molding machine (manufactured by Tanabe Plastic Machinery Co., Ltd.) to obtain a coated wire.
- the wire covering extrusion molding conditions are as follows.
- outer diameter of the obtained coated electric wire was continuously measured for 1 hour using an outer diameter measuring device (ODAC18XY manufactured by Zumbach).
- Outer diameter fluctuation values were obtained by rounding off to the third decimal place the outer diameter value that deviated most from the predetermined outer diameter value (2.40 mm) among the measured outer diameter values.
- the ratio of the absolute value of the difference between the predetermined outer diameter (2.40 mm) and the outer diameter variation value (outer diameter variation rate) was calculated and evaluated according to the following criteria.
- Outer diameter variation rate (%))
- the extrusion molding of the fluorine-containing copolymer was continued until the fluorine-containing copolymer could be stably extruded from the molding machine. Subsequently, by extruding the fluorine-containing copolymer, a film having a length of 11 m or more and a thickness of 0.10 mm (width of 70 mm) was produced. A portion of 10 to 11 m from the edge of the obtained film was cut to prepare a test piece (length 1 m, width 70 mm) for measuring variation in thickness. The thickness was measured at a total of three points, namely, the central point in the width direction of the edge of the produced film and two points separated from the central point in the width direction by 25 mm.
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Abstract
Description
パーフルオロ(プロピルビニルエーテル)単位の含有量が、全単量体単位に対して、1.7~2.6質量%であることが好ましい。
372℃におけるメルトフローレートが、6.0~37.0g/10分であることが好ましい。
-CF=CF2、-CF2H、-COF、-COOH、-COOCH3、-CONH2および-CH2OHの合計数が、主鎖炭素数106個あたり、90個以下であることが好ましい。
I:吸光度
K:補正係数
t:フィルムの厚さ(mm)
ジノルマルプロピルパーオキシジカーボネート、ジイソプロピルパーオキシジカーボネート、ジsec-ブチルパーオキシジカーボネートなどのジアルキルパーオキシカーボネート類;
t-ブチルパーオキシイソブチレート、t-ブチルパーオキシピバレートなどのパーオキシエステル類;
ジt-ブチルパーオキサイドなどのジアルキルパーオキサイド類;
ジ[フルオロ(またはフルオロクロロ)アシル]パーオキサイド類;
などが代表的なものとしてあげられる。
食品包装用フィルム、食品製造工程で使用する流体移送ラインのライニング材、パッキン、シール材、シート等の食品製造装置用流体移送部材;
薬品用の薬栓、包装フィルム、薬品製造工程で使用される流体移送ラインのライニング材、パッキン、シール材、シート等の薬液移送部材;
化学プラントや半導体工場の薬液タンクや配管の内面ライニング部材;
自動車の燃料系統並びに周辺装置に用いられるO(角)リング・チューブ・パッキン、バルブ芯材、ホース、シール材等、自動車のAT装置に用いられるホース、シール材等の燃料移送部材;
自動車のエンジン並びに周辺装置に用いられるキャブレターのフランジガスケット、シャフトシール、バルブステムシール、シール材、ホース等、自動車のブレーキホース、エアコンホース、ラジエーターホース、電線被覆材等のその他の自動車部材;
半導体製造装置のO(角)リング、チューブ、パッキン、バルブ芯材、ホース、シール材、ロール、ガスケット、ダイヤフラム、継手等の半導体装置用薬液移送部材;
塗装設備用の塗装ロール、ホース、チューブ、インク用容器等の塗装・インク用部材;
飲食物用のチューブ又は飲食物用ホース等のチューブ、ホース、ベルト、パッキン、継手等の飲食物移送部材、食品包装材、ガラス調理機器;
廃液輸送用のチューブ、ホース等の廃液輸送用部材;
高温液体輸送用のチューブ、ホース等の高温液体輸送用部材;
スチーム配管用のチューブ、ホース等のスチーム配管用部材;
船舶のデッキ等の配管に巻き付けるテープ等の配管用防食テープ;
電線被覆材、光ファイバー被覆材、太陽電池の光起電素子の光入射側表面に設ける透明な表面被覆材および裏面剤等の各種被覆材;
ダイヤフラムポンプのダイヤフラムや各種パッキン類等の摺動部材;
農業用フィルム、各種屋根材・側壁等の耐侯性カバー;
建築分野で使用される内装材、不燃性防火安全ガラス等のガラス類の被覆材;
家電分野等で使用されるラミネート鋼板等のライニング材;
含フッ素共重合体の各単量体単位の含有量は、NMR分析装置(たとえば、ブルカーバイオスピン社製、AVANCE300 高温プローブ)、または、赤外吸収測定装置(パーキンエルマー社製、Spectrum One)を用いて測定した。
含フッ素共重合体の-CF2H基の数は、核磁気共鳴装置AVANCE-300(ブルカーバイオスピン社製)を用い、測定温度を(ポリマーの融点+20)℃として19F-NMR測定を行い、-CF2H基のピーク積分値から求めた。
実施例および比較例で得られた乾燥粉体もしくはペレットを、コールドプレスにより成形して、厚さ0.25~0.3mmのフィルムを作製した。このフィルムをフーリエ変換赤外分光分析装置〔FT-IR(Spectrum One、パーキンエルマー社製)〕により40回スキャンし、分析して赤外吸収スペクトルを得た。得られた赤外吸収スペクトルを、既知のフィルムの赤外吸収スペクトルと比較して末端基の種類を決定した。また、得られた赤外吸収スペクトルと、既知のフィルムの赤外吸収スペクトルとの差スペクトルに現れる特定の官能基の吸収ピークから、下記式(A)に従って試料における炭素原子1×106個あたりの官能基数Nを算出した。
I:吸光度
K:補正係数
t:フィルムの厚さ(mm)
国際公開第2019/220850号に記載の方法にて分析を行った。吸収周波数を1817cm-1、モル吸光度係数を170(l/cm/mol)、補正係数を1426とした以外は、官能基数Nの算出方法と同様にして、カーボネート基(-OC(=O)O-)の数を算出した。
含フッ素共重合体のMFRは、ASTM D-1238に準拠して、メルトインデクサーG-01(東洋精機製作所製)を用い、372℃、5kg荷重下で、内径2mm、長さ8mmのダイから10分間あたりに流出するポリマーの質量(g/10分)を測定することにより、求めた。
含フッ素共重合体の融点は、示差走査熱量計(商品名:X-DSC7000、日立ハイテクサイエンス社製)を用いて、昇温速度10℃/分で200℃から350℃までの1度目の昇温を行い、続けて、冷却速度10℃/分で350℃から200℃まで冷却し、再度、昇温速度10℃/分で200℃から350℃までの2度目の昇温を行 い、2度目の昇温過程で生ずる溶融曲線ピークから融点を求めた。
容積174Lの攪拌機付きオートクレーブに脱イオン水40.25kgとメタノール0.104kgを投入し、オートクレーブ内を十分に真空窒素置換した。その後、オートクレーブ内を真空脱気し、真空状態となったオートクレーブ内にHFP40.25kgとPPVE0.99kg投入し、オートクレーブを30.0℃に加温した。続けて、オートクレーブの内部圧力が0.918MPaになるまでTFEを投入し、次に8質量%のジ(ω-ヒドロパーフルオロヘキサノイル)パーオキサイド溶液(以下DHPと略す)0.63kgをオートクレーブ内に投入して重合を開始した。重合開始時点のオートクレーブの内部圧力を0.918MPaに設定し、TFEを連続追加することで設定圧力を保つようにした。重合開始から1.5時間後にメタノール0.104kgを追加投入した。重合開始から2時間後、4時間後、にDHP0.63kgを追加投入するとともに内部圧力を0.001MPa下げ、6時間後に0.48kgを投入するとともに内部圧力を0.001MPa下げた。以降、反応が終了するまで2時間ごとにDHP0.13kgを追加投入し、その都度内部圧力を0.001MPa下げた。
重合開始前に投入するメタノールの量を0.122kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.122kgに変更し、重合開始前に投入するPPVEの量を0.82kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.24kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.911MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.140kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.140kgに変更し、重合開始前に投入するPPVEの量を0.89kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.27kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.911MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.155kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.155kgに変更し、重合開始前に投入するPPVEの量を0.59kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.19kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.897MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.158kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.158kgに変更し、重合開始前に投入するPPVEの量を0.70kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.22kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.897MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.186kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.186kgに変更し、重合開始前に投入するPPVEの量を0.83kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.27kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.897MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.209kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.209kgに変更し、重合開始前に投入するPPVEの量を0.57kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.19kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.887MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.215kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.215kgに変更し、重合開始前に投入するPPVEの量を0.67kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.22kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.887MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.218kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.218kgに変更し、重合開始前に投入するPPVEの量を0.80kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.27kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.887MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.363kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.363kgに変更し、重合開始前に投入するPPVEの量を0.89kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.24kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.933MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
容積174Lの攪拌機付きオートクレーブに脱イオン水40.25kgとメタノール0.152kgを投入し、オートクレーブ内を十分に真空窒素置換した。その後、オートクレーブ内を真空脱気し、真空状態となったオートクレーブ内にHFP40.25kgとPPVE0.78kg投入し、オートクレーブを32.0℃に加温した。続けて、オートクレーブの内部圧力が0.926MPaになるまでTFEを投入し、次に8質量%のジ(ω-ヒドロパーフルオロヘキサノイル)パーオキサイド溶液(以下DHPと略す)0.31kgをオートクレーブ内に投入して重合を開始した。重合開始時点のオートクレーブの内部圧力を0.926MPaに設定し、TFEを連続追加することで設定圧力を保つようにした。重合開始から1.5時間後にメタノール0.152kgを追加投入した。重合開始から2時間後、4時間後、にDHP0.31kgを追加投入するとともに内部圧力を0.001MPa下げ、6時間後に0.24kgを投入するとともに内部圧力を0.001MPa下げた。以降、反応が終了するまで2時間ごとにDHP0.07kgを追加投入した。
重合開始前に投入するメタノールの量を0.282kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.282kgに変更した以外は、比較例2と同様にして共重合体ペレットを得た。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.290kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.290kgに変更し、重合開始前に投入するPPVEの量を1.16kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.39kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.938MPaに変更した以外は、比較例2と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
得られたペレットを、実施例5と同様にしてフッ素化をした。得られたペレットを用いて、上記した方法により各種物性を測定した。結果を表3に示す。
容積4Lの攪拌機付きオートクレーブに脱イオン水1.10kgを投入し、オートクレーブ内を十分に真空窒素置換した。その後、オートクレーブ内を真空脱気し、真空状態となったオートクレーブ内にHFP1.10kgとPPVE16.2g投入し、オートクレーブを40.0℃に加温した。続けて、オートクレーブの内部圧力が1.290MPaになるまで、TFEとHFPを91:9モル比で混合したガスを投入し、次に40質量%のジイソプロピルパーオキシジカーボネート溶液7.0gをオートクレーブ内に投入して重合を開始した。重合開始時点のオートクレーブの内部圧力を1.290MPaに設定し、TFEとHFPを91:9モル比で混合したガスを連続追加することで設定圧力を保つようにした。
容積4Lの攪拌機付きオートクレーブに脱イオン水945gとメタノール4.3gを投入し、オートクレーブ内を十分に真空窒素置換した。その後、オートクレーブ内を真空脱気し、真空状態となったオートクレーブ内にHFP945gとPEVE18.8g投入し、オートクレーブを30.0℃に加温した。続けて、オートクレーブの内部圧力が0.890MPaになるまでTFEを投入し、次に8質量%のジ(ω-ヒドロパーフルオロヘキサノイル)パーオキサイド溶液(以下DHPと略す)14.7gをオートクレーブ内に投入して重合を開始した。重合開始時点のオートクレーブの内部圧力を0.890MPaに設定し、TFEを連続追加することで設定圧力を保つようにした。重合開始から1.5時間後にメタノール4.3gを追加投入した。重合開始から2時間後、4時間後、にDHP14.7gを追加投入するとともに内部圧力を0.001MPa下げ、6時間後に11.3gを投入するとともに内部圧力を0.001MPa下げた。以降、反応が終了するまで2時間ごとにDHP3.0gを追加投入し、その都度内部圧力を0.001MPa下げた。
重合開始前に投入するメタノールの量を0.061kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.061kgに変更し、重合開始前に投入するPPVEの量を0.89kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.27kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.962MPaに変更した以外は、比較例2と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
重合開始前に投入するメタノールの量を0.384kgに変更し、重合開始後に分割して追加投入するメタノールの量をそれぞれ0.384kgに変更し、重合開始前に投入するPPVEの量を0.63kgに変更し、重合開始後に分割して追加投入するPPVEの量をそれぞれ0.19kgに変更し、重合開始前後のオートクレーブ内部の設定圧力を0.911MPaに変更した以外は、実施例1と同様にして共重合体ペレットを得た。得られたペレットを用いて上記した方法によりHFP含有量とPPVE含有量を測定した。結果を表3に示す。
ペレットおよびヒートプレス成形機を用いて、厚さ約0.2mmのシート状試験片を作製し、これから10cm×10cmの試験片を切り出した。テーバー摩耗試験機(No.101 特型テーバー式アブレーションテスター、安田精機製作所社製)の試験台に作製した試験片を固定し、試験片表面温度95℃、荷重500g、摩耗輪CS-10(研磨紙#240で20回転研磨したもの)、回転速度60rpmの条件で、テーバー摩耗試験機を用いて摩耗試験を行った。1000回転後の試験片重量を計量し、同じ試験片でさらに3500回転試験後に試験片重量を計量した。次式により、摩耗量を求めた。
摩耗量(mg)=M1-M2
M1:1000回転後の試験片重量(mg)
M2:3500回転後の試験片重量(mg)
金型(内径120mm、高さ38mm)に、上記ペレットを約50g投入した状態で、熱板プレスにて360℃で20分間加熱後、圧力1MPaで加圧しながら水冷して、厚み約2mmの成形体を作製した。13.5mm×38mmの長方形ダンベルを用いて、得られたシートを打ち抜くことにより、3個の試験片を得た。得られた各試験片の長辺の中心に、ASTM D1693に準じて、19mm×0.45mmの刃でノッチを入れた。100mLポリプロピレン製ボトルに、ノッチ試験片3個と85質量%リン酸水溶液25gを入れ、電気炉にて120℃で20時間加熱後、ノッチ試験片を取り出した。得られたノッチ試験片3個をASTM D1693に準じた応力亀裂試験治具に取り付け、電気炉にて180℃で2時間加熱した後、ノッチおよびその周辺を目視で観察し、亀裂の数を数えた。亀裂が生じないシートは、耐ソルベントクラック性が優れている。
○:亀裂の数が0個である
×:亀裂の数が1個以上である
ペレットおよびヒートプレス成形機を用いて、厚さ約0.1mmのシート状試験片を作製した。得られた試験片を用い、JIS K7126-1:2006に記載の方法に従って、差圧式ガス透過度計(L100-5000型ガス透過度計、Systech illinois社製)を用いて、窒素透過度の測定を行った。透過面積50.24cm2、試験温度70℃、試験湿度0%RHでの窒素透過度の数値を得た。得られた窒素透過度と試験片厚みを用いて、次式より窒素透過係数を算出した。
窒素透過係数(cm3・mm/(m2・24h・atm))=GTR×d
GTR:窒素透過度(cm3/(m2・24h・atm))
d:試験片厚み(mm)
ペレットおよびヒートプレス成形機を用いて、厚さ約3.2mmのシート状試験片を作製し、これから80×10mmの試験片を切り出し、電気炉にて100℃で20時間加熱した。得られた試験片を用いた以外は、JIS K-K 7191-1に記載の方法に準じて、ヒートディストーションテスター(安田精機製作所社製)にて、試験温度30~150℃、昇温速度120℃/時間、曲げ応力1.8MPa、フラットワイズ法の条件にて試験を行った。次式により荷重たわみ率を求めた。75℃での荷重たわみ率が小さいシートは、75℃高温時剛性に優れている。
荷重たわみ率(%)=a2/a1×100
a1:試験前の試験片厚み(mm)
a2:75℃でのたわみ量(mm)
日立ハイテクサイエンス社製TMA-7100を用いて引張クリープ歪を測定した。ペレットおよびヒートプレス成形機を用いて、厚さ約0.1mmのシートを作製し、シートから幅2mm、長さ22mmのサンプルを作製した。サンプルを治具間距離10mmで測定治具に装着した。サンプルに対して、断面荷重が2.93N/mm2になるように荷重を負荷し、150℃に放置し、試験開始後90分の時点から試験開始後300分の時点までのサンプルの長さの変位(mm)を測定し、初期のサンプル長(10mm)に対する長さの変位(mm)の割合(引張クリープ歪(%))を算出した。150℃、300分間の条件で測定する引張クリープ歪(%)が小さいシートは、高温の環境中で引張荷重が長時間負荷されても伸びにくく、高温耐引張クリープ特性(150℃)に優れている。
島津製作所社製疲労試験機MMT-250NV-10を用いて10万回サイクル後引張強度を測定した。ペレットおよびヒートプレス成形機を用いて、厚さ約2.4mmのシートを作製し、ASTM D1708マイクロダンベル用いて、ダンベル形状(厚み2.4mm、幅5.0mm、測定部長さ22mm)のサンプルを作製した。サンプルを測定治具に装着し、サンプルを装着した状態で測定治具を110℃の恒温槽中に設置した。ストローク0.2mm、周波数100Hzで、一軸方向への引張りを繰り返し、引張り毎の引張強度(ストロークが+0.2mmの時の引張強度、単位:N)を測定した。
・条件
射出成形機(住友重機械工業社製、SE50EV-A)を使用し、シリンダ温度を385℃、金型温度を180℃、射出速度3mm/sとして、含フッ素共重合体を射出成形した。金型として、HPM38にCrめっきを施した金型(100mm×100mm×3mmt、フィルムゲート、ゲートからの流動長100mm)を用いた。得られた射出成形体を観察し、以下の基準により評価した。白濁の有無は、目視により確認した。表面の荒れの有無は、射出成形体の表面を触ることにより、確認した。
3:射出成形体全体が透明であり、かつ、表面全体が平滑である
2:金型のゲートが位置していた箇所から1cmの範囲内に白濁が観察され、かつ、表面全体が平滑である
1:金型のゲートが位置していた箇所から1cmの範囲内に白濁が観察され、かつ、金型のゲートが位置していた箇所から1cmの範囲内の表面に荒れが確認される
0:金型全体に共重合体が充填されず、所望の形状の成形体が得られない
30mmφ電線被覆成形機(田辺プラスチック機械社製)を用いて、導体径0.50mmの銅導体上に、下記被覆厚みで含フッ素共重合体を押出被覆し、被覆電線を得た。電線被覆押出成形条件は以下の通りである。
a)心導体:導体径0.50mm
b)被覆厚み:0.20mm
c)被覆電線径:0.90mm
d)電線引取速度:70m/分
e)押出条件:
・シリンダー軸径=30mm,L/D=22の単軸押出成形機
・ダイ(内径)/チップ(外形)=9.0mm/5.0mm
押出機の設定温度:バレル部C-1(320℃)、バレル部C-2(350℃)、バレル部C-3(370℃)、ヘッド部H(380℃)、ダイ部D-1(380℃)、ダイ部D-2(380℃)。心線予備加熱は80℃に設定した。
電線被覆ラインにオンラインでスパークテスタ(DENSOK HIGH FREQ SPARK TESTER)を設置し、電圧1500Vで、電線被覆の欠損の有無を評価した。1時間連続成形してスパーク回数を数えた。
30mmφ電線被覆成形機(田辺プラスチック機械社製)を用いて、導体径1.00mmの銅導体上に、下記被覆厚みで含フッ素共重合体を押出被覆し、被覆電線を得た。電線被覆押出成形条件は以下の通りである。
a)心導体:導体径1.00mm
b)被覆厚み:0.70mm
c)被覆電線径:2.40mm
d)電線引取速度:3m/分
e)押出条件:
・シリンダー軸径=30mm,L/D=22の単軸押出成形機
・ダイ(内径)/チップ(外形)=24.0mm/10.0mm
押出機の設定温度:バレル部C-1(340℃)、バレル部C-2(375℃)、バレル部C-3(390℃)、ヘッド部H(400℃)、ダイ部D-1(400℃)、ダイ部D-2(400℃)心線予備加熱は80℃に設定した。
外径測定器(Zumbach社製ODAC18XY)を用いて、得られた被覆電線の外径を1時間連続で測定した。測定された外径値のうち、所定の外径値(2.40mm)よりも最も大きく乖離した外径値の小数点3桁目を四捨五入することにより、外径の変動値を求めた。所定の外径(2.40mm)に対する、所定の外径と、外径の変動値との差の絶対値の割合(外径の変動率)を算出し、以下の基準により評価した。
(外径の変動率(%))=|(外径の変動値)-(所定の外径)|/(所定の外径)×100
±1%:外径の変動率が1%以下である
±2%:外径の変動率が1%超2%以下である
×:外径の変動率が2%超である
φ14mm押出機(井元製作所製)およびTダイを用いて、ペレットを成形し、フィルムを作製した。押出成形条件は以下の通りである。
a)巻き取り速度:1m/分
b)ロール温度:120℃
c)フィルム幅:70mm
d)厚み:0.10mm
e)押出条件:
・シリンダー軸径=14mm,L/D=20の単軸押出成形機
押出機の設定温度:バレル部C-1(330℃)、バレル部C-2(350℃)、バレル部C-3(365℃)、Tダイ部(370℃)
ペレットおよびヒートプレス成形機を用いて、厚さ約0.2mmのシートを作製し、15mm四方の試験片を作製した。50mLポリプロピレン製ボトルに、試験片10枚と3質量%過酸化水素水溶液15gを入れ、電気炉にて95℃で20時間加熱後、室温まで冷却した。過酸化水素水溶液から試験片を取り出し、残った過酸化水素水溶液にTISAB溶液(10)(関東化学社製)を添加し、得られた過酸化水素水溶液中のフッ素イオン濃度を、フッ素イオンメーターにて測定した。得られた測定値から、下記式にしたがって、シート重量当たりのフッ素イオン濃度(溶出フッ素イオン濃度)を算出した。
溶出フッ素イオン濃度(質量ppm)=測定値(ppm)×過酸化水素水溶液量(g)/試験片重量(g)
Claims (8)
- テトラフルオロエチレン単位、ヘキサフルオロプロピレン単位およびパーフルオロ(プロピルビニルエーテル)単位を含有する含フッ素共重合体であって、
ヘキサフルオロプロピレン単位の含有量が、全単量体単位に対して、10.3~12.0質量%であり、
パーフルオロ(プロピルビニルエーテル)単位の含有量が、全単量体単位に対して、1.6~2.9質量%であり、
372℃におけるメルトフローレートが、5.0~40.0g/10分である
含フッ素共重合体。 - ヘキサフルオロプロピレン単位の含有量が、全単量体単位に対して、10.4~12.0質量%である請求項1に記載の含フッ素共重合体。
- パーフルオロ(プロピルビニルエーテル)単位の含有量が、全単量体単位に対して、1.7~2.6質量%である請求項1または2に記載の含フッ素共重合体。
- 372℃におけるメルトフローレートが、6.0~37.0g/10分である請求項1~3のいずれかに記載の含フッ素共重合体。
- -CF=CF2、-CF2H、-COF、-COOH、-COOCH3、-CONH2および-CH2OHの合計数が、主鎖炭素数106個あたり、90個以下である請求項1~4のいずれかに記載の含フッ素共重合体。
- 請求項1~5のいずれかに記載の含フッ素共重合体を含有する射出成形体。
- 請求項1~5のいずれかに記載の含フッ素共重合体を含有する被覆層を備える被覆電線。
- 請求項1~5のいずれかに記載の含フッ素共重合体を含有する成形体であって、前記成形体が、流量計、継手、フィルターハウジング、チューブ、フィルムまたは電線被覆である成形体。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52109588A (en) | 1976-03-10 | 1977-09-13 | Du Pont | Fluorinated terpolymers |
WO2003006566A1 (fr) * | 2001-06-18 | 2003-01-23 | Daikin Industries, Ltd. | Matiere de revetement en poudre |
JP2015054431A (ja) * | 2013-09-11 | 2015-03-23 | 宇部興産株式会社 | 積層チューブ |
JP2015147924A (ja) * | 2014-01-08 | 2015-08-20 | ダイキン工業株式会社 | 改質含フッ素共重合体及びフッ素樹脂成形品 |
WO2019220850A1 (ja) | 2018-05-14 | 2019-11-21 | ダイキン工業株式会社 | 積層体およびチューブ |
Family Cites Families (29)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2639109A1 (de) * | 1976-08-31 | 1978-03-09 | Hoechst Ag | Copolymerisate des tetrafluoraethylens und verfahren zu deren herstellung |
JPS5869213A (ja) | 1981-09-21 | 1983-04-25 | Daikin Ind Ltd | 含フツ素共重合体 |
TW231258B (ja) | 1992-05-27 | 1994-10-01 | Shell Internat Res Schappej B V | |
JP4449111B2 (ja) * | 1999-08-25 | 2010-04-14 | ダイキン工業株式会社 | 含フッ素共重合体の安定化方法 |
JP5044801B2 (ja) * | 2000-12-21 | 2012-10-10 | ダイキン工業株式会社 | 含フッ素重合体の改質法およびその制御方法 |
KR100726318B1 (ko) * | 2001-12-04 | 2007-06-11 | 다이킨 고교 가부시키가이샤 | 내오존성 물품용 성형 재료 및 내오존성 사출 성형품 |
US6849314B2 (en) * | 2002-04-18 | 2005-02-01 | 3M Innovative Properties Company | Fluoropolymer blends and multilayer articles |
CN1882614B (zh) * | 2003-11-20 | 2011-01-19 | 大金工业株式会社 | 含氟聚合物制造方法及含氟聚合物的物质 |
US8058556B2 (en) * | 2006-10-20 | 2011-11-15 | Daikin Industries, Ltd. | Fluorinated copolymer, electric wire, and method for production of the electric wire |
JP2013082888A (ja) * | 2011-09-30 | 2013-05-09 | Daikin Industries Ltd | 架橋性フッ素ゴム組成物、フッ素ゴム成形品及びその製造方法 |
JP5598579B2 (ja) * | 2012-07-05 | 2014-10-01 | ダイキン工業株式会社 | 改質フッ素樹脂混合物、フッ素樹脂成形品、及び、フッ素樹脂成形品の製造方法 |
KR101777930B1 (ko) * | 2012-08-31 | 2017-09-12 | 다이셀에보닉 주식회사 | 난연성 열가소성 수지 조성물 |
EP3076405B1 (en) * | 2014-01-08 | 2021-01-20 | Daikin Industries, Ltd. | Heat-resistant electric wire |
WO2015119053A1 (ja) | 2014-02-05 | 2015-08-13 | ダイキン工業株式会社 | テトラフルオロエチレン/ヘキサフルオロプロピレン系共重合体及び電線 |
JP6376304B1 (ja) * | 2017-05-22 | 2018-08-22 | ダイキン工業株式会社 | 極低温シール材 |
CN112189034B (zh) * | 2018-05-25 | 2023-08-25 | 大金工业株式会社 | 树脂组合物 |
JP7470596B2 (ja) * | 2020-08-05 | 2024-04-18 | 日本航空電子工業株式会社 | コネクタ組立体 |
JP2022029707A (ja) * | 2020-08-05 | 2022-02-18 | 凸版印刷株式会社 | 包装体 |
JP7409254B2 (ja) * | 2020-08-05 | 2024-01-09 | 横河電機株式会社 | 梱包体及びエンジニアリング方法 |
JP2022029717A (ja) * | 2020-08-05 | 2022-02-18 | 株式会社SEtech | 撮像装置 |
JP2022029705A (ja) * | 2020-08-05 | 2022-02-18 | 株式会社Adeka | 乳化化粧料組成物 |
JP7268660B2 (ja) * | 2020-08-05 | 2023-05-08 | 日新電機株式会社 | ガス遮断器 |
JP2022029708A (ja) * | 2020-08-05 | 2022-02-18 | Ihi運搬機械株式会社 | 機械式駐車装置の操作方法及び操作装置 |
JP2022029710A (ja) * | 2020-08-05 | 2022-02-18 | パナソニックIpマネジメント株式会社 | 部品搭載装置 |
JP2022029715A (ja) * | 2020-08-05 | 2022-02-18 | シャープ株式会社 | 家庭用電気機器 |
JP2022029694A (ja) * | 2020-08-05 | 2022-02-18 | キヤノン株式会社 | 定着装置、及び画像形成装置 |
JP2022029713A (ja) * | 2020-08-05 | 2022-02-18 | 京セラドキュメントソリューションズ株式会社 | 飛行装置及び印刷物運搬システム |
JP2022029716A (ja) * | 2020-08-05 | 2022-02-18 | シャープ株式会社 | 液晶表示装置 |
JP2022029709A (ja) * | 2020-08-05 | 2022-02-18 | 三浦工業株式会社 | 水処理システムの管理装置 |
-
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- 2023-08-18 US US18/452,015 patent/US20230391926A1/en active Pending
- 2023-08-22 US US18/453,487 patent/US20230399442A1/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52109588A (en) | 1976-03-10 | 1977-09-13 | Du Pont | Fluorinated terpolymers |
WO2003006566A1 (fr) * | 2001-06-18 | 2003-01-23 | Daikin Industries, Ltd. | Matiere de revetement en poudre |
JP2015054431A (ja) * | 2013-09-11 | 2015-03-23 | 宇部興産株式会社 | 積層チューブ |
JP2015147924A (ja) * | 2014-01-08 | 2015-08-20 | ダイキン工業株式会社 | 改質含フッ素共重合体及びフッ素樹脂成形品 |
WO2019220850A1 (ja) | 2018-05-14 | 2019-11-21 | ダイキン工業株式会社 | 積層体およびチューブ |
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JP7121328B1 (ja) | 2022-08-18 |
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US20230391916A1 (en) | 2023-12-07 |
US20230399437A1 (en) | 2023-12-14 |
JP7177377B2 (ja) | 2022-11-24 |
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US20230399442A1 (en) | 2023-12-14 |
CN116867824A (zh) | 2023-10-10 |
CN116888176A (zh) | 2023-10-13 |
EP4299636A1 (en) | 2024-01-03 |
US20230391926A1 (en) | 2023-12-07 |
CN116848151A (zh) | 2023-10-03 |
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JP7280540B2 (ja) | 2023-05-24 |
JP7112013B1 (ja) | 2022-08-03 |
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