WO2021054363A1 - 含フッ素共重合体 - Google Patents
含フッ素共重合体 Download PDFInfo
- Publication number
- WO2021054363A1 WO2021054363A1 PCT/JP2020/035088 JP2020035088W WO2021054363A1 WO 2021054363 A1 WO2021054363 A1 WO 2021054363A1 JP 2020035088 W JP2020035088 W JP 2020035088W WO 2021054363 A1 WO2021054363 A1 WO 2021054363A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- fluorine
- containing copolymer
- unit
- hexafluoropropylene
- tetrafluoroethylene
- Prior art date
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 89
- 239000011737 fluorine Substances 0.000 title claims abstract description 87
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229920001577 copolymer Polymers 0.000 title claims abstract description 83
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 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 37
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005977 Ethylene Substances 0.000 claims abstract description 30
- 239000000155 melt Substances 0.000 claims abstract description 11
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 description 24
- 239000000843 powder Substances 0.000 description 21
- 150000002978 peroxides Chemical class 0.000 description 18
- 239000000463 material Substances 0.000 description 17
- 239000008188 pellet Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 13
- 239000000126 substance Substances 0.000 description 13
- 238000012546 transfer Methods 0.000 description 13
- 238000011156 evaluation Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 239000000446 fuel Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000004040 coloring Methods 0.000 description 9
- -1 propyl peroxy Chemical group 0.000 description 9
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 8
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 235000013305 food Nutrition 0.000 description 7
- 238000000465 moulding Methods 0.000 description 7
- 238000012856 packing Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000007870 radical polymerization initiator Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 239000003205 fragrance Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000003566 sealing material Substances 0.000 description 4
- 238000010557 suspension polymerization reaction Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical class CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920006280 packaging film Polymers 0.000 description 3
- 239000012785 packaging film Substances 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009503 electrostatic coating Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000000565 sealant Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 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
- AYMDJPGTQFHDSA-UHFFFAOYSA-N 1-(2-ethenoxyethoxy)-2-ethoxyethane Chemical compound CCOCCOCCOC=C AYMDJPGTQFHDSA-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
- 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
- GENYBPRYOMJDAG-UHFFFAOYSA-N 3,4-dioctylphthalic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C(C(O)=O)=C1CCCCCCCC GENYBPRYOMJDAG-UHFFFAOYSA-N 0.000 description 1
- JGZVUTYDEVUNMK-UHFFFAOYSA-N 5-carboxy-2',7'-dichlorofluorescein Chemical compound C12=CC(Cl)=C(O)C=C2OC2=CC(O)=C(Cl)C=C2C21OC(=O)C1=CC(C(=O)O)=CC=C21 JGZVUTYDEVUNMK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910000576 Laminated steel Inorganic materials 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- BSJPKCJHTSQKHH-UHFFFAOYSA-N butan-2-yl butan-2-yloxycarbonyloxyperoxy carbonate Chemical compound CCC(C)OC(=O)OOOOC(=O)OC(C)CC BSJPKCJHTSQKHH-UHFFFAOYSA-N 0.000 description 1
- HXTLWOZJMYIANK-UHFFFAOYSA-N butyl acetate;methanol Chemical compound OC.CCCCOC(C)=O HXTLWOZJMYIANK-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KYKAJFCTULSVSH-UHFFFAOYSA-N chloro(fluoro)methane Chemical compound F[C]Cl KYKAJFCTULSVSH-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000003254 gasoline additive Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- PEYVWSJAZONVQK-UHFFFAOYSA-N hydroperoxy(oxo)borane Chemical compound OOB=O PEYVWSJAZONVQK-UHFFFAOYSA-N 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 150000004978 peroxycarbonates Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000009372 pisciculture Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MWNQXXOSWHCCOZ-UHFFFAOYSA-L sodium;oxido carbonate Chemical compound [Na+].[O-]OC([O-])=O MWNQXXOSWHCCOZ-UHFFFAOYSA-L 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 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
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000001721 transfer moulding Methods 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
- F16L11/00—Hoses, i.e. flexible pipes
- F16L11/04—Hoses, i.e. flexible pipes made of rubber or flexible plastics
- F16L11/06—Hoses, i.e. flexible pipes made of rubber or flexible plastics with homogeneous wall
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D34/00—Containers or accessories specially adapted for handling liquid toiletry or cosmetic substances, e.g. perfumes
- A45D34/02—Scent flasks, e.g. with evaporator
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L9/00—Disinfection, sterilisation or deodorisation of air
- A61L9/015—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone
- A61L9/04—Disinfection, sterilisation or deodorisation of air using gaseous or vaporous substances, e.g. ozone using substances evaporated in the air without heating
- A61L9/12—Apparatus, e.g. holders, therefor
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions 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; Compositions of derivatives of such polymers
- C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/20—Homopolymers or copolymers of hexafluoropropene
-
- 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
- C08F214/22—Vinylidene fluoride
-
- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/10—Copolymer characterised by the proportions of the comonomers expressed as molar percentages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/10—Applications used for bottles
Definitions
- the present disclosure relates to a fluorine-containing copolymer.
- Fluorine-containing copolymers are used in a wide range of applications including optical applications because they are excellent in heat resistance, chemical resistance, etc., and at the same time, they are excellent in transparency.
- Patent Document 1 describes tetrafluoroethylene copolymerization units of 60 mol% or less, ethylene copolymer units of 40 to 60 mol%, and tetrafluoroethylene and ⁇ -olefinic monomer 0 copolymerizable with ethylene.
- Fluorine-containing copolymers containing up to 15 mol% and methods for producing such fluoropolymers are disclosed.
- An object of the present disclosure is to provide a fluorine-containing copolymer having a low refractive index, a small haze value, suppressed coloring, and excellent molding processability.
- it is a fluorine-containing copolymer containing a tetrafluoroethylene unit (a), an ethylene unit (b), and a hexafluoropropylene unit (c), and the hexagon in all the monomer units.
- the content ratio of the fluoropropylene unit (c) is 6 to 21 mol%
- the molar ratio of the tetrafluoroethylene unit (a) to the total of the tetrafluoroethylene unit (a) and the ethylene unit (b) ( (A) / ((a) + (b)) is 0.40 to 0.54, and the melt flow rate measured under the conditions of 230 ° C. and a load of 5 kg is 12 to 100 g / 10 minutes.
- Copolymers are provided.
- the fluorine-containing copolymer of the present disclosure preferably contains 0 to 10 mol% of a unit of a monomer copolymerizable with tetrafluoroethylene, ethylene, and hexafluoropropylene in the total monomer unit.
- the content ratio of the hexafluoropropylene unit (c) in all the monomer units is preferably 9 to 21 mol%.
- the content ratio of the hexafluoropropylene unit (c) in all the monomer units is preferably 10.5 to 18.5 mol%.
- the fluorine-containing copolymer of the present disclosure preferably has a melt flow rate of 25 to 50 g / 10 minutes measured under the conditions of 230 ° C. and a load of 5 kg.
- the fluorine-containing copolymer of the present disclosure preferably has a melting point of 155 to 170 ° C.
- the fluorine-containing copolymer of the present disclosure is a fluorine-containing copolymer containing a tetrafluoroethylene unit (a), an ethylene unit (b), and a hexafluoropropylene unit (c).
- the content ratio of the hexafluoropropylene unit (c) in all the monomer units is 6 to 21 mol%.
- the molar ratio ((a) / ((a) + (b)) of the tetrafluoroethylene unit (a) to the total of the tetrafluoroethylene unit (a) and the ethylene unit (b) is 0.40 to 0.54,
- the melt flow rate measured under the conditions of 230 ° C. and a load of 5 kg is 12 to 100 g / 10 minutes.
- the fluorine-containing copolymer of the present disclosure contains a hexafluoropropylene unit (c) in a content ratio of 6 to 21 mol% in all the monomer units, and the hexafluoropropylene unit (c)
- the content of the above is preferably 9 to 21 mol%, more preferably 10.5 to 18.5 mol%, still more preferably 12 to 17.5 mol%, and particularly preferably 13 to 16 mol%. If the content ratio of the hexafluoropropylene unit (c) is too small, the haze value becomes large and the transparency becomes inferior. On the other hand, if the content ratio of the hexafluoropropylene unit (c) is too large, coloring will occur.
- the molar ratio of the tetrafluoroethylene unit (a) to the total of the tetrafluoroethylene unit (a) and the ethylene unit (b) ((a) / ((a) +).
- B) that is, the content ratio of the tetrafluoroethylene unit (a) in terms of molars / (content ratio of tetrafluoroethylene units (a) in terms of molars + content ratio of ethylene units (b) in terms of molars).
- the content ratio of the tetrafluoroethylene unit (a) in all the monomer units constituting the fluorine-containing copolymer of the present disclosure is not particularly limited, but is preferably 36.0 to 45.0 mol%, more preferably. Is 38.0 to 43.0 mol%, more preferably 39.0 to 42.0 mol%.
- the content ratio of the ethylene unit (b) in all the monomer units constituting the fluorine-containing copolymer of the present disclosure is not particularly limited, but is preferably 41.0 to 50.0 mol%, more preferably 43. It is 0.0 to 48.0 mol%, more preferably 44.0 to 47.0 mol%. By setting the content ratio of the ethylene unit (b) in the above range, the effect of suppressing coloring can be further enhanced.
- the fluorine-containing copolymer of the present disclosure preferably contains a unit of a monomer copolymerizable with tetrafluoroethylene, ethylene, and hexafluoropropylene.
- the content of the unit of such a copolymerizable monomer is preferably 0 to 10 mol%, more preferably 0.05 to 3 mol%, still more preferably 0.3, based on the total polymerization units. ⁇ 1.0 mol%.
- the copolymerizable monomer that gives the unit of such a copolymerizable monomer is not particularly limited, but is an ethylenically unsaturated single amount represented by the following formulas (1) and (2). It is preferably at least one selected from the group consisting of polymers (excluding tetrafluoroethylene and hexafluoropropylene).
- CF 2 CFCl
- CH 2 CF- (CF 2 ) n X 4 (3) (. Wherein, X 4 and n are as defined above)
- the content ratio of each monomer unit in the fluorine-containing copolymer of the present disclosure is calculated by appropriately combining NMR and elemental analysis according to the type of the monomer unit constituting the fluorine-containing copolymer. be able to.
- the fluorine-containing copolymer of the present disclosure has a melt flow rate (MFR) of 12 to 100 g / 10 minutes, preferably 25 to 50 g / 10 minutes, measured under the conditions of 230 ° C. and a load of 5 kg. If the melt flow rate is too high, the strength will be lowered, chipping or cracking will occur during molding, or the strength will be insufficient when used as various molded products. On the other hand, if the melt flow rate is too low, the molding processability is lowered, and it becomes difficult to mold into a desired shape.
- MFR melt flow rate
- the melt flow rate (MFR) conforms to ASTM D1238 and can be measured using a melt indexer. Specifically, it can be determined as the mass (g / 10 minutes) of the polymer flowing out from a nozzle having an inner diameter of 2.1 mm and a length of 8 mm per 10 minutes under a load of 230 ° C. and 5 kg.
- the fluorine-containing copolymer of the present disclosure preferably has a melting point of 140 to 185 ° C, more preferably 150 to 175 ° C, and even more preferably 155 to 170 ° C.
- the melting point can be measured according to ASTM D4591 using a differential scanning calorimeter. Specifically, heat measurement can be performed at a heating rate of 10 ° C./min using a differential scanning calorimeter, and the temperature corresponding to the peak of the obtained endothermic curve can be set as the melting point.
- the fluoropolymers of the present disclosure are copolymerized with tetrafluoroethylene, ethylene, and hexafluoropropylene, and optionally copolymerizable monomers thereof, in the presence of a polymerization initiator.
- a polymerization initiator can be manufactured by
- the copolymerization may be solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, etc., but emulsion polymerization or suspension polymerization is preferable, and suspension polymerization is more preferable, because it is industrially easy to carry out.
- an oil-soluble radical polymerization initiator or a water-soluble radical polymerization initiator can be used, but an oil-soluble radical polymerization initiator is preferable.
- the oil-soluble radical polymerization initiator may be a known oil-soluble peroxide, for example.
- Dialkyl peroxy carbonates such as dinormal propyl peroxy dicarbonate, diisopropyl peroxy dicarbonate, disec-butyl peroxy dicarbonate; Peroxy esters such as t-butyl peroxyisobutyrate and t-butyl peroxypivalate; Dialkyl peroxides such as dit-butyl peroxide; Di [fluoro (or fluorochloro) acyl] peroxides; Etc. are typical examples.
- Di [fluoro (or fluorochloro) acyl] peroxides include diacyls represented by [(RfCOO)-] 2 (Rf is a perfluoroalkyl group, ⁇ -hydroperfluoroalkyl group or fluorochloroalkyl group). Peroxide can be mentioned.
- di [fluoro (or fluorochloro) acyl] peroxides examples include di ( ⁇ -hydro-dodecafluorohexanoyl) peroxide, di ( ⁇ -hydro-tetradecafluoroheptanoid) peroxide, and di ( ⁇ ).
- the water-soluble radical polymerization initiator may be a known water-soluble peroxide, for example, ammonium salts such as persulfate, perboric acid, perchloric acid, perphosphoric acid, and percarbonate, potassium salts, and sodium salts. , T-butyl permalate, t-butyl hydroperoxide and the like. Reducing agents such as sulfites and sulfites may be used in combination with the peroxide, and the amount used may be 0.1 to 20 times that of the peroxide.
- a surfactant a chain transfer agent, and a solvent can be used, and conventionally known ones can be used for each.
- a known surfactant can be used, for example, a nonionic surfactant, an anionic surfactant, a cationic surfactant and the like can be used.
- a fluorine-containing anionic surfactant is preferable, and an ether-bonding oxygen may be contained (that is, an oxygen atom may be inserted between carbon atoms), and a linear or branched surfactant having 4 to 20 carbon atoms is used. Fluorine-containing anionic surfactants are more preferred.
- the amount of the surfactant added is preferably 50 to 5000 ppm.
- chain transfer agent examples include hydrocarbons such as ethane, isopentan, n-hexane and cyclohexane; aromatics such as toluene and xylene; ketones such as acetone; acetates such as ethyl acetate and butyl acetate; methanol. , Ethanols and the like; mercaptans such as methyl mercaptan; halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, methyl chloride and the like.
- the amount of the chain transfer agent added may vary depending on the magnitude of the chain transfer constant of the compound used, but is usually used in the range of 0.01 to 20% by mass with respect to the polymerization solvent.
- Examples of the solvent include water, a mixed solvent of water and alcohol, and the like.
- a fluorine-based solvent may be used in addition to water.
- Fluorine-based solvents include hydrochlorofluoroalkanes such as CH 3 CClF 2 , CH 3 CCl 2 F, CF 3 CF 2 CCl 2 H, CF 2 ClCF 2 CF HCl ; CF 2 ClCFClCF 2 CF 3 , CF 3 CFClCFClCF 3, etc. Chlorofluoroalkanes; perfluorocyclobutane, CF 3 CF 2 CF 2 CF 3 , CF 3 CF 2 CF 2 CF 2 CF 3 , CF 3 CF 2 CF 2 CF 2 CF 3 , etc. Among them, perfluoroalkanes are preferable.
- the amount of the fluorine-based solvent used is preferably 10 to 100% by mass with respect to the aqueous medium from the viewpoint of suspension and economy.
- the polymerization temperature is not particularly limited and may be 0 to 100 ° C.
- the polymerization pressure is appropriately determined depending on the type and amount of the solvent used and other polymerization conditions such as vapor pressure and polymerization temperature, but is usually 0 to 9.8 MPaG.
- the fluorine-containing copolymer of the present disclosure may be in any form, and may be an aqueous dispersion, powder, pellets or the like.
- the fluorine-containing copolymer of the present disclosure has a low refractive index and a small haze value, is excellent in transparency, and is further suppressed in coloring.
- the refractive index of the fluorine-containing copolymer of the present disclosure is preferably 1.340 to 1.375, more preferably 1.345 to 1.370, and further preferably 1.347 to 1.360.
- the refractive index of the fluorine-containing copolymer can be measured using an Abbe refractive index meter at 25 ° C. using a sodium D line as a light source.
- the haze value of the fluorine-containing copolymer of the present disclosure is preferably 50 or less, more preferably 35 or less, still more preferably 20 or less, and the lower limit thereof is preferably 10 or more.
- the haze value of the fluorine-containing copolymer can be measured according to ASTM D1003 using a haze meter for a sheet of the fluorine-containing copolymer having a thickness of 2.0 mm.
- the fluorine-containing copolymer of the present disclosure has a yellow index value (YI value) of preferably 0 or less, more preferably -2 or less, still more preferably -5 or less.
- the yellow index value can be measured using a colorimetric color difference meter according to ASTM D1925.
- the fluorine-containing copolymer of the present disclosure can be molded into various molded products, and the obtained molded product has a low refractive index, a small haze value, and suppressed coloring. Further, since the fluorine-containing copolymer of the present disclosure is excellent in molding processability, it can be molded satisfactorily when it is molded into various molded bodies, and a molded body having a desired shape is preferably used. Obtainable.
- the shape of the molded product is not particularly limited, and may be, for example, a hose, a pipe, a tube, a sheet, a seal, a gasket, a packing, a film, a tank, a roller, a bottle, a container, or the like.
- the molding method of the fluorine-containing copolymer is not particularly limited, and examples thereof include compression molding, extrusion molding, transfer molding, injection molding, roto molding, rotolining molding, and electrostatic coating.
- extrusion molding is preferable.
- Fluorine-containing copolymers of the present disclosure include fillers, plasticizers, processing aids, mold release agents, pigments, flame retardants, lubricants, light stabilizers, weather stabilizers, conductive agents, antistatic agents, ultraviolet absorbers, etc. It may be molded after mixing an antioxidant, a foaming agent, a fragrance, an oil, a softening agent, a defluorinated hydrogen agent and the like.
- the filler include polytetrafluoroethylene, mica, silica, talc, celite, clay, titanium oxide, barium sulfate and the like.
- the conductive agent include carbon black and the like.
- the plasticizer include dioctylphthalic acid and pentaerythritol.
- the processing aid include carnauba wax, sulfone compounds, low molecular weight polyethylene, and fluorine-based auxiliary agents.
- the defluorinated hydrogenating agent include organic onium and amidines.
- the fluorine-containing copolymer of the present disclosure has a low refractive index, a small haze value, excellent transparency, and further, since coloring is suppressed, it can be suitably used as a transparent tube.
- the transparent tube is not particularly limited, but may be a transparent tube for circulating various liquids, and for example, includes a liquid product, for example, a liquid fragrance, which is required to have excellent aesthetic appearance. In fragrance products, it can be suitably used as a transparent tube or the like for distributing a liquid fragrance.
- the fluorine-containing copolymer of the present disclosure can be suitably used as a molding material for the following molded products. That is, as such a molded product, for example, Fluid transfer members for food manufacturing equipment such as food packaging films, lining materials for fluid transfer lines used in food manufacturing processes, packings, sealing materials, and sheets; Chemical transfer members such as chemical plugs, packaging films, fluid transfer line linings, packings, sealants, and sheets used in the chemical manufacturing process; Inner lining members for chemical tanks and pipes in chemical plants and semiconductor factories; O (corner) ring tube packing used for automobile fuel system and peripheral devices, valve core material, hose, sealing material, etc.
- Fluid transfer members for food manufacturing equipment such as food packaging films, lining materials for fluid transfer lines used in food manufacturing processes, packings, sealing materials, and sheets
- Chemical transfer members such as chemical plugs, packaging films, fluid transfer line linings, packings, sealants, and sheets used in the chemical manufacturing process
- Inner lining members for chemical tanks and pipes in chemical plants and semiconductor factories
- Fuel transfer member such as hose, sealing material used for automobile AT device; Carburetor flange gaskets, shaft seals, valve stem seals, sealants, hoses, etc. used for automobile engines and peripheral devices, other automobile parts such as automobile brake hoses, air conditioner hoses, radiator hoses, wire coating materials; Chemical transfer members for semiconductor devices such as O (corner) rings, tubes, packings, valve cores, hoses, sealing materials, rolls, gaskets, diaphragms, fittings, etc.
- O corner
- examples of the fuel transfer member used in the fuel system of the automobile include a fuel hose, a filler hose, an evacuation hose, and the like.
- the 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 tertiary butyl ether and amine resistant.
- the chemical stopper / packaging film for the above chemicals has excellent chemical resistance to acids and the like. Further, as the chemical liquid transfer member, an anticorrosion tape wrapped around a chemical plant pipe can also be mentioned.
- Examples of the molded body include automobile radiator tanks, chemical tanks, bellows, spacers, rollers, gasoline tanks, waste liquid transport containers, high temperature liquid transport containers, fishery / fish farming tanks, and the like.
- the molded body further includes automobile bumpers, door trims, instrument panels, food processing equipment, cooking equipment, water- and oil-repellent glass, lighting-related equipment, display boards / housings for OA equipment, illuminated signboards, displays, and liquid crystals.
- Displays mobile phones, printed boards, electrical and electronic parts, miscellaneous goods, trash cans, bathtubs, unit baths, ventilation fans, lighting frames and the like can also be mentioned.
- the fluorine-containing copolymer of the present disclosure can also be a powder coating material made of the fluorine-containing copolymer.
- a powder coating material may have an average particle size of 10 to 500 ⁇ m. The average particle size can be measured using a laser diffraction type particle size distribution measuring machine. By spraying such a powder coating film on a base material by electrostatic coating and then firing it, a coating film having no foaming marks can be obtained.
- MFR Melt flow rate
- ⁇ Melting point> The powder of the fluorine-containing copolymer was heat-measured at a heating rate of 10 ° C./min using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments Inc.) in accordance with ASTM D4591, and the obtained endothermic curve was obtained. The melting point was determined from the peak.
- ⁇ Refractive index> Pellets of a fluorine-containing copolymer were compression-molded into a film having a thickness of 200 ⁇ m, and the obtained sheet-shaped molded body was subjected to an Abbe refractive index meter (manufactured by Atago Optical Instruments Mfg. Co., Ltd.) at 25 ° C. using a sodium D line as a light source. ) was used to measure the refractive index.
- ⁇ Haze value> The pellets of the fluorine-containing copolymer were compression-molded into a sheet having a thickness of 2.0 mm, and the obtained sheet-shaped molded product was subjected to a haze meter (Haze Guard II manufactured by Toyo Seiki Co., Ltd.) according to ASTM D1003. The haze value was measured.
- ⁇ Yellow index value (YI value)> Fluorine-containing copolymer pellets were placed in a case for reflection measurement, and the yellow index value (YI value) was measured using a color difference meter ZE6000 (manufactured by Nippon Denshoku Industries Co., Ltd.) according to ASTM D1925. ..
- the TFE unit is tetrafluoroethylene unit
- the Et unit is ethylene unit
- the HFP unit is hexafluoropropylene unit
- the H2P unit is 2,3,3,4,5,5-heptafluoro-1-pentene unit.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Engineering & Computer Science (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Packaging Of Annular Or Rod-Shaped Articles, Wearing Apparel, Cassettes, Or The Like (AREA)
- Wrappers (AREA)
Abstract
Description
本開示の含フッ素共重合体において、全単量体単位中における、前記ヘキサフルオロプロピレン単位(c)の含有割合が9~21モル%であることが好ましい。
本開示の含フッ素共重合体において、全単量体単位中における、前記ヘキサフルオロプロピレン単位(c)の含有割合が10.5~18.5モル%であることが好ましい。
本開示の含フッ素共重合体は、230℃、荷重5kgの条件下で測定したメルトフローレートが25~50g/10分であることが好ましい。
本開示の含フッ素共重合体は、融点が155~170℃であることが好ましい。
全単量体単位中における、前記ヘキサフルオロプロピレン単位(c)の含有割合が6~21モル%であり、
前記テトラフルオロエチレン単位(a)と前記エチレン単位(b)との合計に対する、前記テトラフルオロエチレン単位(a)のモル比率((a)/((a)+(b))が0.40~0.54であり、
230℃、荷重5kgの条件下で測定したメルトフローレートが12~100g/10分である。
(式中、X1、X2、X3およびX4は、同一または異なって、H、FまたはClを表し、nは0~8の整数を表す。但し、テトラフルオロエチレンおよびヘキサフルオロプロピレンを除く。)
(式中、Rf1は炭素数1~3のアルキル基または炭素数1~3のフルオロアルキル基を表す。)
CH2=CF-(CF2)nX4 (3)
(式中、X4およびnは上記と同じ。)、および、下記式(4):
CH2=CH-(CF2)nX4 (4)
(式中、X4およびnは上記と同じ。)
からなる群より選択される少なくとも1種であることが好ましく、CF2=CFCl、CH2=CFCF3、CH2=CH-C4F9、CH2=CH-C6F13、およびCH2=CF-C3F6Hからなる群より選択される少なくとも1種であることがより好ましく、CF2=CFCl、CH2=CH-C6F13、CH2=CFCF3、およびCH2=CF-C3F6Hからなる群より選択される少なくとも1種であることがさらに好ましく、CH2=CF-C3F6H(すなわち、2,3,3,4,4,5,5-ヘプタフルオロ-1-ペンテン(CH2=CFCF2CF2CF2H)が特に好ましい。
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。
本開示の含フッ素共重合体の屈折率は、好ましくは1.340~1.375であり、より好ましくは1.345~1.370、さらに好ましくは1.347~1.360である。含フッ素共重合体の屈折率は、ナトリウムD線を光源として25℃において、アッベ屈折率計を用いて測定することができる。
すなわち、このような成形体としては、たとえば、
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;
自動車のエンジンなら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また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;
海底油田またはガス田において海底から海面上に物資を輸送するライザー管;
原油や天然ガスの流体移送金属配管の最内面および最外面のコーティング材料、ライニング材料;
等が挙げられる。
含フッ素共重合体の粉末、および、核磁気共鳴装置AC300(Bruker-Biospin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、各ピークの積分値から求めた。また、この際に、単量体の種類によっては元素分析を適宜組み合わせて求めた。
ASTM D1238に従って、含フッ素共重合体のペレット、および、メルトインデクサー(安田精機製作所社製)を用いて、230℃、5kg荷重下で、内径2.1mm、長さ8mmのノズルから10分間あたりに流出する共重合体の質量(g/10分)を求めた。
含フッ素共重合体の粉末について、示差走査熱量計RDC220(Seiko Instruments社製)を用い、ASTM D4591に準拠して、昇温速度10℃/分にて熱測定を行い、得られた吸熱曲線のピークから融点を求めた。
含フッ素共重合体のペレットを厚み200μmのフイルム状に圧縮成形し、得られたシート状の成形体に対し、ナトリウムD線を光源として25℃において、アッベ屈折率計(アタゴ光学機器製作所社製)を用いて、屈折率を測定した。
含フッ素共重合体のペレットを厚み2.0mmのシート状に圧縮成形し、得られたシート状の成形体に対し、ヘイズメーター(東洋精機社製 ヘイズガードII)を用いて、ASTM D1003に従い、ヘイズ値を測定した。
含フッ素共重合体のペレットを反射測定用のケースに入れ、測色色差計ZE6000(日本電色工業株式会社製)を用いて、ASTM D1925に準じて、イエローインデックス値(YI値)を測定した。
オートクレーブに蒸留水52Lを投入し、充分に窒素置換を行った後、パーフルオロシクロブタン13kg、ヘキサフルオロプロピレン26kg、2,3,3,4,4,5,5-ヘプタフルオロ-1-ペンテン(CH2=CFCF2CF2CF2H)0.1kgを仕込み、系内を35℃に加温し、攪拌することで、系内温度35℃、攪拌速度200rpmに保った。次いで、テトラフルオロエチレン5.4kgと、さらに引き続いてエチレン0.2kgとを圧入し、その後に、ジ-n-プロピルパーオキシジカーボネート0.5kgを投入して重合を開始した。重合の進行とともに系内圧力が低下するので、テトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=41/44.5/14.5モル%の混合ガスを連続して供給し、系内圧力を1.15MPaに保って、30時間攪拌を継続した。次いで、放圧して大気圧に戻した後、反応生成物を水洗、乾燥することで40kgの含フッ素共重合体の粉末を得た。得られた含フッ素共重合体の単量体組成を表1に示す。そして、得られた含フッ素共重合体の粉末を単軸押出し機VS50-24(田辺プラクティス機械社製)を用いてシリンダー温度255℃で押出して、含フッ素共重合体のペレットを得て、上記方法にしたがって、各評価を行った。評価結果を表1に示す。
重合開始時における、パーフルオロシクロブタンの仕込み量を25kg、ヘキサフルオロプロピレンの仕込み量を14kgに変更し、かつ、重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=44/48/8モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合開始時における、パーフルオロシクロブタンの仕込み量を22kg、ヘキサフルオロプロピレンの仕込み量を17kgに変更し、かつ、重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=43/47.5/9.5モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合開始時における、パーフルオロシクロブタンの仕込み量を17kg、ヘキサフルオロプロピレンの仕込み量を22kgに変更し、かつ、重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=42/46/12モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合開始時における、パーフルオロシクロブタンの仕込み量を7kg、ヘキサフルオロプロピレンの仕込み量を32kgに変更し、かつ、重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=39/43/18モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=37/48/15モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=43/42/15モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合開始時における、パーフルオロシクロブタンを使用せず、ヘキサフルオロプロピレンの仕込み量を39kgに変更し、かつ、重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=37/41/22モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合開始時における、パーフルオロシクロブタンの仕込み量を39kgに変更し、ヘキサフルオロプロピレンおよび2,3,3,4,4,5,5-ヘプタフルオロ-1-ペンテンを使用せず、かつ、重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン=48/52モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=32/53/15モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
重合反応進行時に供給する混合ガスの比率をテトラフルオロエチレン/エチレン/ヘキサフルオロプロピレン=48/37.5/14.5モル%に変更した以外は、実施例1と同様にして、含フッ素共重合体の粉末およびペレットを得て同様に評価を行った。得られた含フッ素共重合体の単量体組成および評価結果を表1に示す。
Claims (6)
- テトラフルオロエチレン単位(a)、エチレン単位(b)、およびヘキサフルオロプロピレン単位(c)を含有する含フッ素共重合体であって、
全単量体単位中における、前記ヘキサフルオロプロピレン単位(c)の含有割合が6~21モル%であり、
前記テトラフルオロエチレン単位(a)と前記エチレン単位(b)との合計に対する、前記テトラフルオロエチレン単位(a)のモル比率((a)/((a)+(b))が0.40~0.54であり、
230℃、荷重5kgの条件下で測定したメルトフローレートが12~100g/10分である含フッ素共重合体。 - テトラフルオロエチレン、エチレン、およびヘキサフルオロプロピレンと共重合可能な単量体の単位を、全単量体単位中、0~10モル%含有する請求項1に記載の含フッ素共重合体。
- 全単量体単位中における、前記ヘキサフルオロプロピレン単位(c)の含有割合が9~21モル%である請求項1または2に記載の含フッ素共重合体。
- 全単量体単位中における、前記ヘキサフルオロプロピレン単位(c)の含有割合が10.5~18.5モル%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。
- 230℃、荷重5kgの条件下で測定したメルトフローレートが25~50g/10分である請求項1~4のいずれかに記載の含フッ素共重合体。
- 融点が155~170℃である請求項1~5のいずれかに記載の含フッ素共重合体。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2021546932A JP7236012B2 (ja) | 2019-09-20 | 2020-09-16 | 含フッ素共重合体 |
CN202080062145.8A CN114341207B (zh) | 2019-09-20 | 2020-09-16 | 含氟共聚物 |
EP20865350.1A EP4032430A4 (en) | 2019-09-20 | 2020-09-16 | FLUORINE-CONTAINING COPOLYMER |
BR112022004448A BR112022004448A2 (pt) | 2019-09-20 | 2020-09-16 | Copolímero contendo flúor |
US17/692,349 US20220195087A1 (en) | 2019-09-20 | 2022-03-11 | Fluorine-containing copolymer |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2019-171294 | 2019-09-20 | ||
JP2019171294 | 2019-09-20 | ||
JP2019189130 | 2019-10-16 | ||
JP2019-189130 | 2019-10-16 | ||
JP2020-008109 | 2020-01-22 | ||
JP2020008109 | 2020-01-22 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US17/692,349 Continuation US20220195087A1 (en) | 2019-09-20 | 2022-03-11 | Fluorine-containing copolymer |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2021054363A1 true WO2021054363A1 (ja) | 2021-03-25 |
Family
ID=74884255
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/035088 WO2021054363A1 (ja) | 2019-09-20 | 2020-09-16 | 含フッ素共重合体 |
PCT/JP2020/035090 WO2021054364A1 (ja) | 2019-09-20 | 2020-09-16 | チューブおよびフレグランス製品 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2020/035090 WO2021054364A1 (ja) | 2019-09-20 | 2020-09-16 | チューブおよびフレグランス製品 |
Country Status (6)
Country | Link |
---|---|
US (2) | US20220195087A1 (ja) |
EP (2) | EP4032429A4 (ja) |
JP (2) | JP7236012B2 (ja) |
CN (2) | CN114402156A (ja) |
BR (2) | BR112022004448A2 (ja) |
WO (2) | WO2021054363A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023190928A1 (ja) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | 共重合体、成形体および射出成形体 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP4101871A4 (en) * | 2020-02-07 | 2024-03-13 | Daikin Ind Ltd | COPOLYMER |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4338237A (en) | 1980-06-28 | 1982-07-06 | Hoechst Aktiengesellschaft | Process for the preparation of aqueous, colloidal dispersions of copolymers of the tetrafluoroethylene/ethylene type |
JPH0841131A (ja) * | 1994-04-14 | 1996-02-13 | Hoechst Ag | テトラフルオルエチレン、ヘキサフルオルプロピレン及びエチレンのコポリマー |
JPH11315121A (ja) * | 1998-05-01 | 1999-11-16 | Daikin Ind Ltd | 官能基含有含フッ素共重合体 |
WO2001060606A1 (fr) * | 2000-02-18 | 2001-08-23 | Daikin Industries, Ltd. | Moulage de resine en couches et article moule multicouche |
Family Cites Families (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3439478B2 (ja) | 1993-05-21 | 2003-08-25 | ダイキン工業株式会社 | 含フッ素ポリマー中の微量金属不純物の測定方法およびそれを用いる含フッ素ポリマーの製法 |
EP0992518B1 (en) * | 1997-06-23 | 2004-09-01 | Daikin Industries, Limited | Tetrafluoroethylene copolymer and use thereof |
DE19844153A1 (de) * | 1998-09-25 | 2000-03-30 | Guenther Nath | Lichtleiter mit flüssigem Kern |
US20060088680A1 (en) * | 2002-12-25 | 2006-04-27 | Takahiro Kitahara | Fluoropolymer and composition thereof |
WO2004065504A1 (ja) * | 2003-01-10 | 2004-08-05 | Daikin Industries, Ltd. | 粉体塗料、塗膜形成方法及び積層体 |
JP3892400B2 (ja) * | 2003-01-10 | 2007-03-14 | ユニマテック株式会社 | 含フッ素共重合体、含フッ素共重合体を含む溶液および含フッ素共重合体からなる成形体 |
WO2004069534A1 (ja) * | 2003-02-10 | 2004-08-19 | Daikin Industries, Ltd. | 積層樹脂成形体及びその製造方法 |
JP2005022403A (ja) * | 2003-06-12 | 2005-01-27 | Daikin Ind Ltd | 積層体の製造方法 |
WO2004110756A1 (ja) * | 2003-06-17 | 2004-12-23 | Daikin Industries, Ltd. | 積層樹脂成形体、積層樹脂成形体製造方法及び多層成形品 |
US7538171B2 (en) * | 2004-11-25 | 2009-05-26 | Unimatec Co., Ltd. | Fluorine-containing copolymer |
JP2009511580A (ja) | 2005-10-11 | 2009-03-19 | ジュリア, ディコーレト ギブソン, | フレグランス製品、ディスペンサ及びディスペンサアセンブリ |
FR2917650B1 (fr) * | 2007-06-20 | 2011-03-18 | Valois Sas | Procede et dispositif de conditionnement de distributeur de produit fluide. |
JP2009035272A (ja) * | 2007-07-31 | 2009-02-19 | Yoshino Kogyosho Co Ltd | 放散容器 |
JP5191469B2 (ja) * | 2008-10-24 | 2013-05-08 | 日本ポリプロ株式会社 | 医療用プロピレン系樹脂組成物およびその成形品 |
JP5495932B2 (ja) * | 2009-05-15 | 2014-05-21 | 旭化成イーマテリアルズ株式会社 | プラスチック光ファイバ素線及びケーブル |
JP2011033643A (ja) * | 2009-07-29 | 2011-02-17 | Toppan Printing Co Ltd | 光路変更シート、バックライトユニット及びディスプレイ装置 |
FR2970474B1 (fr) * | 2011-01-18 | 2013-02-15 | Rexam Dispensing Sys | Systeme et flacon de distribution d'un produit fluide |
JP2014014975A (ja) * | 2012-07-09 | 2014-01-30 | Daikin Ind Ltd | 積層体 |
JP6528552B2 (ja) * | 2015-06-16 | 2019-06-12 | ダイキン工業株式会社 | ポリオレフィン用加工助剤及びポリオレフィン組成物 |
US20170217793A1 (en) * | 2016-01-28 | 2017-08-03 | Saint-Gobain Performance Plastics Corporation | Article and method for making same |
-
2020
- 2020-09-16 WO PCT/JP2020/035088 patent/WO2021054363A1/ja unknown
- 2020-09-16 JP JP2021546932A patent/JP7236012B2/ja active Active
- 2020-09-16 BR BR112022004448A patent/BR112022004448A2/pt unknown
- 2020-09-16 EP EP20864621.6A patent/EP4032429A4/en active Pending
- 2020-09-16 EP EP20865350.1A patent/EP4032430A4/en active Pending
- 2020-09-16 BR BR112022003662A patent/BR112022003662A2/pt unknown
- 2020-09-16 WO PCT/JP2020/035090 patent/WO2021054364A1/ja unknown
- 2020-09-16 CN CN202080063142.6A patent/CN114402156A/zh active Pending
- 2020-09-16 CN CN202080062145.8A patent/CN114341207B/zh active Active
- 2020-09-16 JP JP2020155346A patent/JP6923057B2/ja active Active
-
2022
- 2022-03-11 US US17/692,349 patent/US20220195087A1/en active Pending
- 2022-03-11 US US17/692,424 patent/US20220195169A1/en not_active Abandoned
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4338237A (en) | 1980-06-28 | 1982-07-06 | Hoechst Aktiengesellschaft | Process for the preparation of aqueous, colloidal dispersions of copolymers of the tetrafluoroethylene/ethylene type |
JPH0841131A (ja) * | 1994-04-14 | 1996-02-13 | Hoechst Ag | テトラフルオルエチレン、ヘキサフルオルプロピレン及びエチレンのコポリマー |
JPH11315121A (ja) * | 1998-05-01 | 1999-11-16 | Daikin Ind Ltd | 官能基含有含フッ素共重合体 |
WO2001060606A1 (fr) * | 2000-02-18 | 2001-08-23 | Daikin Industries, Ltd. | Moulage de resine en couches et article moule multicouche |
Non-Patent Citations (1)
Title |
---|
See also references of EP4032430A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2023190928A1 (ja) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | 共重合体、成形体および射出成形体 |
JP7364986B1 (ja) | 2022-03-30 | 2023-10-19 | ダイキン工業株式会社 | 共重合体、成形体および射出成形体 |
Also Published As
Publication number | Publication date |
---|---|
US20220195169A1 (en) | 2022-06-23 |
CN114341207A (zh) | 2022-04-12 |
JP2021107740A (ja) | 2021-07-29 |
CN114341207B (zh) | 2023-05-02 |
EP4032429A1 (en) | 2022-07-27 |
WO2021054364A1 (ja) | 2021-03-25 |
EP4032430A4 (en) | 2023-11-01 |
BR112022004448A2 (pt) | 2022-06-21 |
US20220195087A1 (en) | 2022-06-23 |
BR112022003662A2 (pt) | 2022-05-24 |
JP7236012B2 (ja) | 2023-03-09 |
JP6923057B2 (ja) | 2021-08-18 |
CN114402156A (zh) | 2022-04-26 |
EP4032429A4 (en) | 2023-11-29 |
JPWO2021054363A1 (ja) | 2021-03-25 |
EP4032430A1 (en) | 2022-07-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5696794B2 (ja) | ポリビニリデンフルオライド水性分散液の製造方法及びポリビニリデンフルオライド水性分散液 | |
US20220195087A1 (en) | Fluorine-containing copolymer | |
JP6705512B2 (ja) | フッ素樹脂及び成形体 | |
JP6870794B1 (ja) | 共重合体 | |
JP2017020013A (ja) | フルオロポリマーの製造方法 | |
RU2789215C1 (ru) | Фторсодержащий сополимер | |
JP6717303B2 (ja) | フッ素樹脂及び成形体 | |
JP2017020014A (ja) | フッ素樹脂 | |
JP7401833B2 (ja) | 含フッ素共重合体 | |
JP7397386B2 (ja) | 含フッ素共重合体 | |
JP7401835B2 (ja) | 含フッ素共重合体 | |
JP7381981B1 (ja) | 含フッ素共重合体 | |
JP7381982B1 (ja) | 含フッ素共重合体 | |
JP7364977B1 (ja) | 含フッ素共重合体 | |
JP7397384B2 (ja) | 含フッ素共重合体 | |
WO2023190960A1 (ja) | 含フッ素共重合体 | |
WO2023190917A1 (ja) | 含フッ素共重合体 | |
WO2023190962A1 (ja) | 含フッ素共重合体 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 20865350 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2021546932 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112022004448 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 2020865350 Country of ref document: EP Effective date: 20220420 |
|
ENP | Entry into the national phase |
Ref document number: 112022004448 Country of ref document: BR Kind code of ref document: A2 Effective date: 20220310 |