WO2022220180A1 - 含フッ素共重合体、含フッ素共重合体の製造方法、含フッ素共重合体組成物および架橋ゴム物品 - Google Patents
含フッ素共重合体、含フッ素共重合体の製造方法、含フッ素共重合体組成物および架橋ゴム物品 Download PDFInfo
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- WO2022220180A1 WO2022220180A1 PCT/JP2022/017143 JP2022017143W WO2022220180A1 WO 2022220180 A1 WO2022220180 A1 WO 2022220180A1 JP 2022017143 W JP2022017143 W JP 2022017143W WO 2022220180 A1 WO2022220180 A1 WO 2022220180A1
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- Prior art keywords
- fluorine
- containing copolymer
- monomer
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- fluorocopolymer
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- 239000005060 rubber Substances 0.000 title claims abstract description 111
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 184
- 239000000178 monomer Substances 0.000 claims abstract description 142
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 39
- -1 alkyl vinyl ether Chemical compound 0.000 claims abstract description 20
- 125000002560 nitrile group Chemical group 0.000 claims abstract description 20
- 238000003860 storage Methods 0.000 claims abstract description 18
- 238000005259 measurement Methods 0.000 claims abstract description 12
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001577 copolymer Polymers 0.000 claims description 162
- 239000011737 fluorine Substances 0.000 claims description 156
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 154
- 238000004132 cross linking Methods 0.000 claims description 36
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- 125000004430 oxygen atom Chemical group O* 0.000 claims description 24
- 239000003431 cross linking reagent Substances 0.000 claims description 19
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 18
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- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000007870 radical polymerization initiator Substances 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 6
- 238000007334 copolymerization reaction Methods 0.000 claims description 4
- 101000744947 Homo sapiens Zinc finger protein 213 Proteins 0.000 claims description 3
- 102100039942 Zinc finger protein 213 Human genes 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
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- 238000012360 testing method Methods 0.000 description 36
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 8
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- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
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- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 4
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- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
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- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 2
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- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- MKTOIPPVFPJEQO-UHFFFAOYSA-N 4-(3-carboxypropanoylperoxy)-4-oxobutanoic acid Chemical compound OC(=O)CCC(=O)OOC(=O)CCC(O)=O MKTOIPPVFPJEQO-UHFFFAOYSA-N 0.000 description 1
- CPFKVVLZVUUQGV-UHFFFAOYSA-N 4-[2-(3,4-diaminophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(N)C(N)=C1 CPFKVVLZVUUQGV-UHFFFAOYSA-N 0.000 description 1
- BCHSTYJVRPEVKP-UHFFFAOYSA-N 4-[2-(3,4-diaminophenyl)propan-2-yl]benzene-1,2-diamine Chemical compound C=1C=C(N)C(N)=CC=1C(C)(C)C1=CC=C(N)C(N)=C1 BCHSTYJVRPEVKP-UHFFFAOYSA-N 0.000 description 1
- GQILCMONWYJNFP-UHFFFAOYSA-N 4-[2-(3-amino-4-anilinophenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-1-n-phenylbenzene-1,2-diamine Chemical compound NC1=CC(C(C=2C=C(N)C(NC=3C=CC=CC=3)=CC=2)(C(F)(F)F)C(F)(F)F)=CC=C1NC1=CC=CC=C1 GQILCMONWYJNFP-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical compound C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- 239000000370 acceptor Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- OWCNWICUDXNCTI-UHFFFAOYSA-N azanium;2,2,3,3,4,4,5,5,6,6,6-undecafluorohexanoate Chemical compound N.OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F OWCNWICUDXNCTI-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229960003328 benzoyl peroxide Drugs 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 235000012241 calcium silicate Nutrition 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
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- 238000001125 extrusion Methods 0.000 description 1
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- 229940060037 fluorine Drugs 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- PZVZTKFRZJMHEM-UHFFFAOYSA-N iodotrifluoroethylene Chemical group FC(F)=C(F)I PZVZTKFRZJMHEM-UHFFFAOYSA-N 0.000 description 1
- 229910000464 lead oxide Inorganic materials 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- LWHQXUODFPPQTL-UHFFFAOYSA-M sodium;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoate Chemical compound [Na+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LWHQXUODFPPQTL-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical class [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- PNWOTXLVRDKNJA-UHFFFAOYSA-N tert-butylperoxybenzene Chemical compound CC(C)(C)OOC1=CC=CC=C1 PNWOTXLVRDKNJA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000011787 zinc oxide 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
-
- 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
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/20—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds unconjugated
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34924—Triazines containing cyanurate groups; Tautomers thereof
-
- 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
Definitions
- the present invention relates to a fluorocopolymer, a method for producing a fluorocopolymer, a fluorocopolymer composition, and a crosslinked rubber article.
- Crosslinked rubber articles obtained by crosslinking fluorine-containing copolymers are excellent in heat resistance, chemical resistance, oil resistance, weather resistance, etc., and are used in various environments.
- fluorine-containing copolymers used to obtain such crosslinked rubber articles Patent Document 1 discloses units based on tetrafluoroethylene, units based on perfluoro(alkyl vinyl ether), and nitrile groups (cyano groups ) is disclosed as a fluorine-containing copolymer having units based on a monomer having
- a crosslinked rubber article is produced, for example, by supplying a fluorine-containing copolymer to a mold and heat-molding it.
- a fluorine-containing copolymer to a mold and heat-molding it.
- the present invention has been made in view of the above problems, and provides a fluorocopolymer capable of producing a crosslinked rubber article having excellent releasability, a method for producing a fluorocopolymer, a fluorocopolymer composition, and a crosslinked rubber article.
- the challenge is to provide
- the present inventors have found that a monomer having a tetrafluoroethylene-based unit, a perfluoro(alkyl vinyl ether)-based unit, a fluorine atom and two or more polymerizable unsaturated bonds and a unit based on a monomer having a nitrile group and a fluorine atom, and G' 0.3 /G' 0.03 is within a specific range.
- the present inventors have found that a crosslinked rubber article having excellent mold releasability can be obtained by using the above method, and have completed the present invention.
- a fluorine-containing copolymer wherein G'0.3 / G'0.03 is from 1.00 to 1.45, where G'0.03 is the storage modulus of the polymer.
- CF 2 CF- OR f1 (1)
- R f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms.
- a plurality of R 21 s, a plurality of R 22 and a plurality of R 23 may be the same or different from each other.
- R 31 represents a divalent C 1-10 perfluorohydrocarbon group, or a group having an etheric oxygen atom at the end of the perfluorohydrocarbon group or between carbon-carbon bonds. .
- R 41 represents a divalent C 1-10 perfluorohydrocarbon group, or a group having an etheric oxygen atom at the end of the perfluorohydrocarbon group or between the carbon-carbon bonds.
- R 51 , R 52 and R 53 are fluorine atoms or all of them are hydrogen atoms, and R 54 has an etheric oxygen atom and the number of etheric oxygen atoms is 1 to
- a fluorine-containing copolymer composition comprising the fluorine-containing copolymer according to any one of [1] to [8] and a cross-linking agent.
- a crosslinked rubber article obtained by crosslinking the fluorocopolymer in the fluorocopolymer composition according to any one of [11] to [13].
- a fluorocopolymer capable of producing a crosslinked rubber article having excellent releasability
- a method for producing a fluorocopolymer, a fluorocopolymer composition, and a crosslinked rubber article a fluorocopolymer capable of producing a crosslinked rubber article having excellent releasability
- Unit is a general term for an atomic group derived from one molecule of the above-mentioned monomer directly formed by polymerization of the monomer, and an atomic group obtained by chemically converting a part of the above-mentioned atomic group.
- a "unit based on a monomer” is hereinafter simply referred to as a “unit”.
- Rubberer means rubber exhibiting properties defined by JIS K 6200 (2008), and is distinguished from “resin”.
- the fluorine-containing copolymer of the present invention comprises units based on tetrafluoroethylene (hereinafter also referred to as "TFE”), units based on perfluoro(alkyl vinyl ether) (hereinafter also referred to as "PAVE”), and fluorine A monomer having an atom and two or more polymerizable unsaturated bonds (hereinafter also referred to as "monomer A”)-based units and a monomer having a nitrile group and a fluorine atom (hereinafter, " Also referred to as R CN ”).
- TFE tetrafluoroethylene
- PAVE perfluoro(alkyl vinyl ether)
- R CN fluorine A monomer having an atom and two or more polymerizable unsaturated bonds
- the fluorocopolymer of the present invention has a storage elastic modulus of G' 0.3 at an angular frequency of 0.3 rad/s, which is determined by dynamic viscoelasticity measurement at 140°C. Assuming that the storage elastic modulus of the fluorine-containing copolymer at an angular frequency of 0.03 rad/s is G'0.03, G'0.3 / G'0.03 is 1.00 to 1.45.
- the crosslinked rubber article obtained using the fluorine-containing copolymer of the present invention is excellent in releasability from molds. Although the details of this reason have not been clarified, it is presumed to be due to the following reason.
- the fluorine-containing copolymer of the present invention has monomer A units and RCN units.
- the monomer A unit in the fluorine-containing copolymer constitutes a branched structure in the crosslinked rubber article obtained using the fluorine-containing copolymer. Therefore, when the monomer A unit is sufficiently introduced into the fluorine-containing copolymer, the crosslinked rubber article obtained by using it becomes rigid.
- the nitrile group of the RCN unit is a crosslinkable group, and the crosslinked rubber article obtained by crosslinking the fluorine-containing copolymer having the monomer A unit and the RCN unit becomes more rigid.
- the rigid crosslinked rubber article became easier to detach because the crosslinked rubber hardly followed the mold when the crosslinked rubber article was detached from the mold.
- the branched structure and cross-linking sites are uniformly distributed throughout the fluorine-containing copolymer as compared with a fluorine-containing copolymer in which the monomer A or RCN is not used in combination. It is assumed that When a gaseous monomer and a liquid monomer are polymerized, it is considered that the movement of the liquid monomer to the reaction field is rate-limiting for the reaction.
- the present inventors have found that the storage modulus (specifically, G'0. 03 ) to the storage modulus (specifically, G' 0.3 ) measured under conditions where the angular frequency is large, that is, G' 0.3 /G' 0.03 . It can be said that the closer G' 0.3 /G' 0.03 is to 1.00, the more branched structures are present in the fluorine-containing copolymer.
- PAVE units are units based on perfluoro(alkyl vinyl ether).
- PAVE is preferably a monomer represented by formula (1) from the viewpoint of excellent polymerization reactivity and rubber physical properties.
- CF 2 CF- OR f1 (1)
- R f1 represents a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in R f1 is preferably 1 to 8, more preferably 1 to 6, even more preferably 1 to 5, and particularly preferably 1 to 3, from the viewpoint of better polymerization reactivity.
- a perfluoroalkyl group may be linear or branched.
- PAVE perfluoro(methyl vinyl ether)
- PEVE perfluoro(ethyl vinyl ether)
- PEVE perfluoro(propyl vinyl ether)
- PPVE perfluoro(propyl vinyl ether)
- PMVE and PPVE are preferred.
- a monomer A unit is a unit based on a monomer having a fluorine atom and two or more polymerizable unsaturated bonds.
- the number of polymerizable unsaturated bonds in the monomer A is preferably 2 to 6, more preferably 2 or 3, and particularly preferably 2, for better polymerization reactivity.
- the monomeric A units do not have nitrile groups.
- Monomer A is preferably a monomer represented by formula (2) from the viewpoint that the releasability of the crosslinked rubber article is more excellent.
- (CR 21 R 22 CR 23 -) a1 R 24 (2)
- R 21 , R 22 and R 23 each independently represent a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group
- a1 represents an integer of 2 to 6
- R 24 represents a1 It represents a perfluorohydrocarbon group having a valence of 1 to 10 carbon atoms, or a group having an etheric oxygen atom at the terminal or between the carbon-carbon bonds of the perfluorohydrocarbon group.
- a plurality of R 21 s, a plurality of R 22 and a plurality of R 23 may be the same or different, and are particularly preferably the same.
- a1 is preferably 2 or 3, and particularly preferably 2.
- R 21 , R 22 and R 23 are preferably fluorine atoms or hydrogen atoms from the viewpoint of better polymerization reactivity of the monomer A, and whether all of R 21 , R 22 and R 23 are fluorine atoms Alternatively, all of them are more preferably hydrogen atoms, and it is particularly preferable that all of R 21 , R 22 , and R 23 are fluorine atoms from the standpoint of better releasability of the crosslinked rubber article.
- R 24 may be linear, branched or cyclic, preferably linear or branched, and particularly preferably linear. The number of carbon atoms in R 24 is preferably 2-8, more preferably 3-7, even more preferably 3-6, and particularly preferably 3-5.
- R 24 may or may not have an etheric oxygen atom, but preferably has an etheric oxygen atom from the viewpoint of better cross-linking reactivity and rubber physical properties.
- the number of etheric oxygen atoms in R 24 is preferably 1-6, more preferably 1-3, and particularly preferably 1 or 2.
- the etheric oxygen atom in R 24 is preferably present at the terminal of R 24 .
- Suitable monomers include the monomers represented by the formula (3) and the monomers represented by the formula (4). be done.
- (CF 2 CF-) 2 R 31 (3)
- R 31 represents a divalent C 1-10 perfluorohydrocarbon group, or a group having an etheric oxygen atom at the end of the perfluorohydrocarbon group or between carbon-carbon bonds.
- (CH 2 CH-) 2 R 41 (4)
- R 41 represents a divalent C 1-10 perfluorohydrocarbon group, or a group having an etheric oxygen atom at the end of the perfluorohydrocarbon group or between the carbon-carbon bonds. .
- the polymerizable double bond at the terminal of the monomer A reacts during the polymerization to obtain a fluorine-containing copolymer having a branched chain.
- RCN unit is a unit based on a monomer having a nitrile group and a fluorine atom. Since the fluorine-containing copolymer has RCN units, the heat resistance of the crosslinked rubber article is excellent. From the viewpoint of polymerization reactivity, RCN preferably has a polymerizable unsaturated bond, and particularly preferably has one polymerizable unsaturated bond. Specific examples of the polymerizable unsaturated bond are as described above.
- RCN is preferably a monomer represented by the following formula (5) from the viewpoint that the releasability and heat resistance of the crosslinked rubber article are more excellent.
- CR51R52 CR53 - R54 - CN (5)
- R 51 , R 52 and R 53 each independently represent a hydrogen atom, a fluorine atom or a methyl group
- R 54 is a divalent C 1-10 perfluorohydrocarbon group, or A group having an etheric oxygen atom at the end of the perfluorohydrocarbon group or between carbon-carbon bonds.
- R 51 , R 52 and R 53 are preferably fluorine atoms or hydrogen atoms from the viewpoint of excellent polymerization reactivity of R CN , and all of R 51 , R 52 and R 53 are fluorine atoms or all of them is more preferably a hydrogen atom, and it is particularly preferable that all of R 51 , R 52 and R 53 are fluorine atoms from the viewpoint that the releasability and heat resistance of the crosslinked rubber article are more excellent.
- R 54 may be linear, branched or cyclic, preferably linear or branched. The number of carbon atoms in R 54 is preferably 2-8, more preferably 3-7, even more preferably 3-6, and particularly preferably 3-5.
- R 54 may or may not have an etheric oxygen atom, but preferably has an etheric oxygen atom from the viewpoint of better rubber physical properties.
- the number of etheric oxygen atoms in R 54 is preferably 1-3, particularly preferably 1 or 2.
- CF 2 CFOCF 2 CF(CF 3 )OCF 2 CF 2 CN (hereinafter also referred to as “8CNVE”)
- CF 2 CFO(CF 2 ) 5CN (hereinafter also referred to as “ MV5CN ”)
- CF2 CFOCF2CF2CF2OCF ( CF3 )CN
- CF2 CFO ( CF2)3CN
- 8CNVE and MV5CN are preferred from the viewpoint of better moldability and heat resistance.
- the fluorine-containing copolymer may have units derived from monomers other than TFE, PAVE , monomer A and RCN.
- monomers other than TFE, PAVE , monomer A and RCN may be collectively referred to as "other monomers”.
- Specific examples of other monomers include monomers represented by the following formula (6), vinylidene fluoride (hereinafter also referred to as "VdF”), and hexafluoropropylene (hereinafter also referred to as "HFP").
- CTFE chlorotrifluoroethylene
- ethylene ethylene
- TFE chlorotrifluoroethylene
- PAVE monomers A, R CN , monomers represented by formula (6), VdF, HFP and CTFE monomers having halogen atoms other than (hereinafter also referred to as monomers having other halogen atoms) (eg, bromotrifluoroethylene, iodotrifluoroethylene).
- Equation (6) is as follows.
- CF 2 CF- OR f2 (6)
- R f2 represents a perfluoroalkyl group having 1 to 8 carbon atoms and containing 1 to 5 etheric oxygen atoms.
- the number of carbon atoms in R f2 is preferably 1-6, particularly preferably 1-5.
- monomer represented by formula (6) examples include perfluoro(3,6-dioxa-1-heptene), perfluoro(3,6-dioxa-1-octene), perfluoro(5- methyl-3,6-dioxa-1-nonene).
- the content of the TFE unit is preferably 60 to 79 mol%, more preferably 63 to 75 mol%, more preferably 66 to 75 mol%, based on the total units of the fluorine-containing copolymer, from the viewpoint of better heat resistance of the crosslinked rubber article. 72 mol % is particularly preferred.
- the content of PAVE units is preferably 20 to 39 mol%, more preferably 24 to 36 mol%, more preferably 27 to 33, based on the total units of the fluorine-containing copolymer, from the viewpoint of better elasticity of the crosslinked rubber article. Mole % is particularly preferred.
- the content of the monomer A unit is particularly easy to adjust G' 0.3 /G' 0.03 within the above range, and the releasability, physical properties, and appearance of the crosslinked rubber article are more excellent.
- 0.01 to 0.35 mol% is preferable, 0.03 to 0.20 mol% is more preferable, and 0.03 to 0.15 mol% is still more preferable with respect to the total units of the fluorine-containing copolymer, 0.06 to 0.13 mol % is particularly preferred.
- the content of R CN units is preferably 0.05 to 5 mol%, preferably 0.1 to 3 mol % is more preferred, 0.2 to 1.5 mol % is even more preferred, and 0.4 to 0.8 mol % is particularly preferred.
- G' 0.3 /G' 0.03 can be easily adjusted within the above range.
- the fluorine-containing copolymer contains other monomer units, the content of the other monomer units is 0 based on the total units of the fluorine-containing copolymer, from the viewpoint of the heat resistance of the crosslinked rubber article. 0.01 to 20 mol % is preferred, 0.5 to 10 mol % is more preferred, and 1 to 5 mol % is particularly preferred.
- the molar ratio of the content of the monomer A unit to the content of the R CN unit is preferably 0.002 to 7, more preferably 0.01 to 2, and 0 0.02 to 0.75 is more preferred, 0.075 to 0.43 is particularly preferred, and 0.09 to 0.30 is most preferred. If the molar ratio is within the above range, the release property and heat resistance of the crosslinked rubber article can both be achieved at high levels, and the appearance is also excellent.
- the monomer A unit with respect to all units in the fluorocopolymer is calculated based on the amount of monomer A used in the production of the fluorocopolymer (amount of monomer A used).
- the "amount of monomer A used” is the amount of monomer A added to the polymerization vessel (amount of monomer A charged) minus the amount of unpolymerized monomer A. value. It is believed that the unpolymerized monomer A aggregates the latex after polymerization and is contained in the filtrate after removing the fluorine-containing copolymer and the filtrate remaining after washing the latex.
- the amount can be measured by measuring fluoride ions with an ion chromatograph.
- the TFE units, PAVE units and R CN units for all units in the fluorocopolymer are calculated by 19 F-nuclear magnetic resonance (NMR) analysis. Specifically, by 19 F-nuclear magnetic resonance (NMR) analysis, TFE units:PAVE units: RCN units (molar ratio) in the fluorine-containing copolymer are obtained. Then, a value obtained by subtracting the content (mol%) of the monomer A unit from 100 mol% was obtained by 19 F-nuclear magnetic resonance (NMR) analysis. TFE units in the fluorine-containing copolymer: PAVE units: Apply R CN units (molar ratio) to determine the content of each unit.
- the fluorine-containing copolymer preferably contains substantially no iodine atoms. Since the fluorine-containing copolymer does not substantially contain iodine atoms, the cross-linking property of the fluorine-containing copolymer is excellent, and the cross-linked article obtained by using the same has little cracking and a low compression set at high temperatures. can. Since the iodine atoms in the fluorine-containing copolymer can serve as cross-linking points, inclusion of iodine atoms seems to provide excellent cross-linking properties.
- the cross-linking agent contained in the fluorine-containing copolymer composition preferentially reacts with the iodine atoms rather than with the nitrile groups. If the content of iodine atoms in the fluorine-containing copolymer is small, the nitrile groups and the cross-linking agent can react sufficiently.
- the crosslinked structure formed by the reaction between the nitrile groups of the fluorine-containing copolymer and the cross-linking agent has excellent heat resistance
- the sufficient reaction between the nitrile groups of the fluorine-containing copolymer and the cross-linking agent results in a heat resistant structure. improve sexuality. Therefore, by using a fluorine-containing copolymer composition containing a fluorine-containing copolymer containing substantially no iodine atoms, a crosslinked article having excellent crosslinkability, less cracking, and a small compression set at high temperatures can be formed. can.
- the resulting fluorocopolymer has a broader molecular weight distribution and a better balance between hardness and elongation. It also has excellent properties (eg, tensile strength).
- the widening of the molecular weight distribution of the fluorine-containing copolymer increases the number of relatively low-molecular fluorine-containing copolymers, making it easy to adjust G' 0.3 /G' 0.03 within the above range. .
- the fluorine-containing copolymer does not substantially contain iodine atoms
- the content of iodine atoms is 0.09% by mass or less with respect to the total mass of the fluorine-containing copolymer. is preferably 0.05% by mass or less, more preferably 0.02% by mass or less, and particularly preferably 0% by mass (that is, containing no iodine atoms).
- the iodine atom an iodine atom derived from an iodine compound that functions as a chain transfer agent, an iodine atom among monomers having other halogen atoms such as the above-mentioned iodotrifluoroethylene, etc.
- iodine atom is mentioned.
- iodine compounds that function as chain transfer agents include 1,3-diiodopropane, 1,4-diiodobutane (hereinafter also referred to as "DIB"), 1,6-diiodohexane, 1,8- diiodooctane, 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,6-diiodoperfluorohexane, and 1,8-diiodoperfluorooctane.
- DIB 1,3-diiodopropane
- 1,4-diiodobutane 1,6-diiodoperfluorohexane
- 1,8-diiodoperfluorooctane 1,3-diiodoperfluoropropane, 1,4-di
- G' 0.3 /G' 0.03 of the fluorine-containing copolymer is 1.00 to 1.45, and 1.00 to 1.43 is preferable from the viewpoint that the releasability of the crosslinked rubber article is more excellent. It is preferably 1.20 to 1.43, more preferably 1.30 to 1.43, and most preferably 1.40 to 1.43. Since the value of the storage modulus increases as the angular frequency at the time of measurement increases, the value of G'0.3 / G'0.03 does not fall below 1.00.
- G′ 0.3 of the fluorine-containing copolymer is preferably 600 to 800 kPa, more preferably 650 to 750 kPa, particularly preferably 670 to 700 kPa, from the viewpoint of molding workability.
- G′ 0.03 of the fluorine-containing copolymer is preferably 400 to 600 kPa, more preferably 430 to 550 kPa, particularly preferably 470 to 500 kPa, from the viewpoint of molding workability.
- G' 0.3 means the storage elastic modulus of the fluorine-containing copolymer at an angular frequency of 0.3 rad/s, determined by dynamic viscoelasticity measurement at 140°C.
- G' 0.03 means the storage modulus measured at each frequency of 0.03 rad/s, which is obtained by dynamic viscoelasticity measurement at 140°C. Note that "rad/s" means radians per second.
- G' 0.3 and G' 0.03 of the fluorine-containing copolymer in the present invention are values measured according to ASTM D6204 using a rubber processing analyzer, and detailed measurement conditions are described in Examples. as shown in
- G' 0.3 /G' 0.03 of the fluorine-containing copolymer can be converted to the value of G' 1 /G' 0.1 of the fluorine-containing copolymer by multiplying it by 0.92.
- G' 0.1 means the storage modulus measured at an angular frequency of 0.1 rad/s, determined by dynamic viscoelasticity measurement at 140°C.
- G'1 means the storage modulus measured at an angular frequency of 1 rad/s, which is determined by dynamic viscoelasticity measurement at 140°C.
- the present invention is also a method for producing the fluorine-containing copolymer. That is, the method for producing a fluorine-containing copolymer of the present invention is a method of copolymerizing TFE, PAVE , monomer A and RCN in the presence of a radical polymerization initiator.
- the method for producing the fluorine-containing copolymer of the present invention is a method of copolymerizing the above-mentioned monomers in the presence of a radical polymerization initiator and in the absence of a chain transfer agent containing an iodine atom. is preferred.
- the effect of polymerizing in the absence of a chain transfer agent containing iodine atoms is as described above.
- the polymerization method include emulsion polymerization, solution polymerization, and suspension polymerization.
- Emulsion polymerization is preferable from the viewpoint of excellent productivity and adjustment of the molecular weight and copolymerization composition.
- the fluorine-containing copolymer is produced by emulsion polymerization, it can be carried out, for example, by heating the above monomers in the presence of an aqueous medium, an emulsifier and a radical polymerization initiator.
- the aqueous medium is preferably water or a mixed solvent of water and a water-soluble organic solvent.
- Water-soluble organic solvents include tert-butanol, propylene glycol, dipropylene glycol, dipropylene glycol monomethyl ether, tripropylene glycol and the like. Especially preferred are tert-butanol and dipropylene glycol monomethyl ether.
- the aqueous medium contains a water-soluble organic solvent, the content of the water-soluble organic solvent is based on 100 parts by mass of water. 1 to 40 parts by mass is preferable, and 3 to 30 parts by mass is more preferable.
- the amount of the aqueous medium used is preferably 150 to 400 parts by mass, particularly preferably 250 to 350 parts by mass, relative to 100 parts by mass of the monomer.
- an emulsifier conventionally used in emulsion polymerization can be used, and an ionic emulsifier is preferred, and an anionic emulsifier is particularly preferred, from the viewpoint that the obtained latex has excellent mechanical and chemical stability.
- anionic emulsifiers include hydrocarbon emulsifiers such as sodium lauryl sulfate and sodium dodecylbenzenesulfonate, and fluorine-containing fatty acid salts such as ammonium perfluorooctanoate, sodium perfluorooctanoate, and ammonium perfluorohexanoate.
- F(CF 2 ) p O(CF(X 3 )CF 2 O) q CF(Y)COOA (wherein X 3 and Y are each independently a fluorine atom or a perfluoroalkyl group having 1 to 3 carbon atoms A is a hydrogen atom, an alkali metal atom or NH 4 , p is an integer of 1 to 10, and q is an integer of 0 to 3.). Specific examples of the alkali metal atom for A include sodium and potassium.
- fluorine-containing emulsifier represented by F(CF 2 ) p O(CF(X 3 )CF 2 O) q CF(Y)COOA include F(CF 2 ) 3 O(CF(CF 3 )CF 2O ) 2CF ( CF3 ) COONH4 , F(CF2) 3OCF ( CF3 ) CF2OCF ( CF3 ) COONH4 , F ( CF2 ) 3OCF2CF2OCF2COONH4 , F( CF2 ) 3O ( CF2CF2O ) 2CF2COONH4 , F ( CF2 ) 4OCF2CF2OCF2COONH4 , F ( CF2 ) 4O ( CF2CF2O ) 2CF2 COONH4 , F ( CF2 ) 3OCF2CF2OCF2COONa , F ( CF2 ) 3O ( CF2CF2OCF2COONa , F ( CF2
- emulsifiers include ammonium perfluorooctanoate , F ( CF2 ) 4OCF2CF2OCF2COONH4 , F ( CF2 ) 3OCF2CF2OCF2COONH4 , F ( CF2 ) 2OCF2CF 2OCF2COONH4 and CF3OCF2CF2CF2OCF2COONH4 are preferred .
- F ( CF2 ) 4OCF2CF2OCF2COONH4 F ( CF2 ) 3OCF2CF2OCF2COONH4
- F ( CF2 ) 2OCF2CF 2OCF2COONH4 and CF3OCF2CF2CF2OCF2COONH4 are preferred .
- the molecular weight of the emulsifier is preferably 100 to 1000, particularly preferably 100 to 500, because the emulsifier can be easily removed when the obtained latex is aggregated to isolate the fluorine-containing copolymer.
- the amount of emulsifier used is preferably 1 to 10 parts by mass, more preferably 3 to 5 parts by mass, relative to 100 parts by mass of the aqueous medium.
- a water-soluble polymerization initiator and a redox polymerization initiator are preferred.
- water-soluble polymerization initiators include persulfates such as ammonium persulfate, sodium persulfate and potassium persulfate, and organic polymerization initiators such as disuccinic acid peroxide and azobisisobutylamidine dihydrochloride. Among these, persulfates are preferred, and ammonium persulfate is more preferred.
- redox polymerization initiators include polymerization initiators in which persulfates and reducing agents are combined.
- a polymerization initiator capable of polymerizing each monomer at a polymerization temperature in the range of 0 to 80° C. is preferred.
- the persulfate constituting the redox polymerization initiator include alkali metal salts of persulfate such as ammonium persulfate, sodium persulfate and potassium persulfate, with ammonium persulfate being preferred.
- Specific examples of reducing agents combined with persulfates include thiosulfates, sulfites, hydrogen sulfites, pyrosulfites, and hydroxymethanesulfinates, with hydroxymethanesulfinates being preferred, and sodium hydroxymethanesulfinate. Salt is particularly preferred.
- the monomers in multiple batches.
- TFE, PAVE and RCN are preferably added in multiple batches.
- Each monomer unit can be uniformly distributed in the fluorine-containing copolymer by being added in multiple times.
- the amount of the radical polymerization initiator used is preferably 0.03 to 0.50 parts by mass, particularly preferably 0.05 to 0.10 parts by mass, per 100 parts by mass of the monomer.
- the latex obtained by the emulsion polymerization may be aggregated to isolate the fluorocopolymer.
- Aggregation methods include the addition of metal salts and the addition of inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid. ), it is preferable to add an inorganic acid.
- the fluorocopolymer composition of the present invention contains the fluorocopolymer described above and a cross-linking agent.
- cross-linking agent examples include organic peroxides and compounds having two or more amino groups (hereinafter also referred to as "polyamine compounds").
- a polyamine compound is preferred because it provides a crosslinked rubber article having a smaller compression set at 100 rpm.
- organic peroxides include dialkyl peroxides, ⁇ , ⁇ '-bis(tert-butylperoxy)-p-diisopropylbenzene, ⁇ , ⁇ '-bis(tert-butylperoxy)-m- Diisopropylbenzene, benzoylperoxide, tert-butylperoxybenzene, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane.
- dialkyl peroxides include 1,1-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroxyperoxide, tert-butyl Cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-di(tert-butylperoxy)-3- Hexyne, tert-butylperoxymaleate, tert-butylperoxyisopropyl carbonate.
- polyamine compounds include hexamethylenediamine, hexamethylenediamine carbamate, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis(3-amino-4-hydroxyphenyl) Propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter also referred to as “BOAP”, also known as bisaminophenol AF.), 2,2-bis(3,4-diaminophenyl ) propane, 2,2-bis(3,4-diaminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-(N-phenylamino)phenyl)hexafluoropropane, 4,4′-methylene dianiline, m-phenylenediamine, adipic acid dihydrazide, and compounds represented by formula (XII) of Japanese Patent No. 5,833,657.
- the content of the cross-linking agent is preferably less than 1.0 parts by mass, more preferably 0.9 parts by mass or less, still more preferably 0.8 parts by mass or less, with respect to 100 parts by mass of the fluorine-containing copolymer. .6 parts by mass or less is particularly preferred. If the content of the cross-linking agent is within the above range, a cross-linked rubber article having a smaller compression set at high temperatures can be obtained.
- the lower limit of the content of the cross-linking agent is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, and further preferably 0.2 parts by mass or more with respect to 100 parts by mass of the fluorine-containing copolymer. Preferably, 0.4 parts by mass or more is most preferable. When the content of the cross-linking agent is within the above range, the releasability of the cross-linked article is more excellent.
- the fluorine-containing copolymer composition may contain components other than the above as long as the effects of the present invention are not impaired.
- Other components include cross-linking aids (e.g., triallyl cyanurate, triallyl isocyanurate, trimethallyl isocyanurate), acid acceptors (e.g., fatty acid esters, fatty acid metal salts, divalent metal oxides (magnesium oxide , calcium oxide, zinc oxide, lead oxide, etc.)), fillers and reinforcing agents (e.g. carbon black, barium sulfate, calcium metasilicate, calcium carbonate, titanium oxide, silicon dioxide, clay, talc), scorch retarders (e.g.
- phenolic hydroxyl group-containing compounds such as bisphenol A, quinones such as hydroquinone, ⁇ -methylstyrene dimers such as 2,4-di(3-isopropylphenyl)-4-methyl-1-pentene), crown ethers ( Examples include 18-crown-6), release agents (eg sodium stearate).
- the fluorine-containing copolymer composition may contain a release agent, but the release agent may bleed out from the surface of the crosslinked rubber article obtained using the composition, causing contamination. . Therefore, it is preferable that the fluorine-containing copolymer composition does not substantially contain a release agent from the viewpoint of suitable use as a member (for example, an O-ring) of a semiconductor manufacturing apparatus.
- the fluorocopolymer composition does not substantially contain a release agent means that the content of the release agent is 0.1 mass parts per 100 mass parts of the fluorocopolymer. 0.01 part by mass or less is preferred, and 0 part by mass is particularly preferred.
- the total content of the other components is more than 0.1 parts by mass and 30 parts by mass or less with respect to 100 parts by mass of the fluorocopolymer. It is preferably 1 to 25 parts by mass, and particularly preferably 5 to 15 parts by mass.
- a method for preparing the fluorine-containing copolymer composition includes a method of mixing the above components. Mixing of the components can be carried out using rubber mixing equipment such as rolls, kneaders, Banbury mixers or extruders. Moreover, after obtaining the mixture which mixed each said component, you may shape
- the crosslinked rubber article of the present invention is a rubber article obtained by crosslinking the fluorocopolymer in the fluorocopolymer composition described above.
- a method for crosslinking the fluorocopolymer in the fluorocopolymer composition a method of crosslinking by heating the fluorocopolymer composition is preferred.
- Specific examples of the crosslinking method by heating include heat press crosslinking, steam crosslinking, and hot air crosslinking.
- a suitable method may be selected from these methods in consideration of the shape and application of the fluorocopolymer or fluorocopolymer composition. Heating conditions are preferably 100 to 400° C. for 1 second to 24 hours.
- the crosslinked rubber obtained by heating (primary crosslinking) the fluorine-containing copolymer composition may be further heated for secondary crosslinking.
- Secondary cross-linking can stabilize or improve the mechanical properties, compression set and other properties of the cross-linked rubber.
- the heating conditions for the secondary cross-linking are preferably 80 to 350° C. for 30 minutes to 48 hours.
- Examples of cross-linking methods other than cross-linking the fluorine-containing copolymer by heating include a method in which the fluorine-containing copolymer composition is irradiated with radiation to cross-link the fluorine-containing copolymer.
- Specific examples of radiation to be applied include electron beams and ultraviolet rays.
- the tensile strength (tensile breaking strength) of the crosslinked rubber article is preferably 15 to 40 MPa, particularly preferably 21 to 35 MPa, from the viewpoint of excellent rubber properties.
- the 100% modulus (tensile stress at 100% elongation) of the crosslinked rubber article is preferably 3.0 to 5.0 MPa, particularly preferably 3.5 to 4.4 MPa, from the viewpoint of excellent rubber properties.
- the tensile elongation (elongation at break) of the crosslinked rubber article is preferably 100 to 250%, particularly preferably 180 to 215%, from the viewpoint of excellent rubber properties.
- the tensile strength, 100% modulus and elongation at break of the crosslinked rubber article are values measured by a method based on JIS K 6251:2010 (corresponding international standard ISO 37:2005).
- the hardness (Shore-A) of the crosslinked rubber article is preferably 50 to 90, more preferably 6080, and particularly preferably 65 to 75, from the viewpoint of excellent rubber properties.
- the hardness (Shore-A) of the crosslinked rubber article is measured using a type A durometer in accordance with JIS K6253-1: 2012 using a plate-shaped molding (thickness 1 mm) of the crosslinked rubber article. is.
- the compression set at 300° C. of the crosslinked rubber article is preferably 20% or less, and since the fluorocopolymer is well crosslinked and the shape recovery of the crosslinked rubber article after pressurization is excellent, it is 15% or less. More preferably, 13% or less is even more preferable, and 11% or less is particularly preferable.
- the lower limit of the compression set at 300° C. of the crosslinked rubber article is preferably 0%.
- the compression set at 320°C of the crosslinked rubber article is preferably 35% or less, and the fluorine-containing copolymer is well crosslinked, and the crosslinked rubber article has excellent shape recovery after pressurization, so it is 30% or less. More preferably, 29% or less is even more preferable, and 24% or less is particularly preferable.
- the lower limit of the compression set at 320°C of the crosslinked rubber article is preferably 0%.
- the compression set at 325° C. of the crosslinked rubber article is preferably 35% or less, and since the fluorocopolymer is well crosslinked and the shape recovery of the crosslinked rubber article after pressurization is excellent, it is preferably 30% or less. More preferably, 29% or less is even more preferable, and 27% or less is particularly preferable.
- the lower limit of the compression set at 325°C of the crosslinked rubber article is preferably 0%.
- the compression set at 300° C., 320° C. and 325° C. of the crosslinked rubber article is a value measured according to JIS K6301 using a plate-shaped molding (thickness 1 mm) of the crosslinked rubber article.
- the physical properties of the crosslinked rubber article are determined, for example, by the production conditions of the above-mentioned fluorine-containing copolymer (for example, the order of addition, the number of times of addition, and the amount of addition of each monomer), and the above-mentioned fluorine-containing copolymer composition. It can be adjusted by the type and content of each component contained, the production conditions of the crosslinked rubber article (for example, the crosslinking conditions), and the like.
- Crosslinked rubber articles are suitable materials for O-rings, sheets, gaskets, oil seals, diaphragms, V-rings and the like.
- Example 2-1 to Example 2-4, Example 2-8, Example 2-9, Example 2-11, and Example 2-12 are examples, and examples 1-3, 1-4, 2-5, 2-6, 2-7, and 2-10 are comparative examples.
- the present invention is not limited to these examples.
- the content of each component in the tables to be described later indicates a mass standard unless otherwise specified.
- the content (mol%) of the monomer A unit with respect to the total units of the fluorine-containing copolymer is the amount of the monomer A used in the production of the fluorine-containing copolymer (amount of monomer A used). calculated based on The contents (mol %) of TFE units, PAVE units and RCN units with respect to all units of the fluorine-containing copolymer were calculated based on 19 F-nuclear magnetic resonance (NMR) analysis.
- NMR 19 F-nuclear magnetic resonance
- the amount of monomer A used includes the amount of monomer A added to the reactor (monomer A charged amount) minus the amount of monomer A in the liquid calculated based on the measurement results of the ion chromatography was used.
- the amount of monomer A used is determined assuming that all the monomers A used for charging are polymerized. , the charged amount of the monomer A was used. Based on the usage amount of the monomer A unit thus obtained, the content (mol %) of the monomer A unit relative to the total units of the fluorine-containing copolymer was calculated.
- G' 0.3 /G' 0.03 of fluorine-containing copolymer Using a rubber processing analyzer (RPA2000, manufactured by Alpha Technologies), the value measured according to ASTM D6204 at a temperature of 140° C. and an angular frequency of 0.3 rad/s was determined as the G′ of the fluorine-containing copolymer . 3 .
- G' 0.03 of the fluorine-containing copolymer was measured in the same manner as the measurement method for G' 0.3 , except that the angular frequency was changed to 0.03 rad/s. Based on the obtained values, G' 0.3 /G' 0.03 of the fluorine-containing copolymer was calculated.
- MH and ML were measured using a rubber processing analyzer (RPA2000, manufactured by Alpha Technologies) at 177°C for 12 minutes under conditions of an amplitude of 3 degrees and a frequency of 100 times per minute. It was measured.
- the measured MH indicates the maximum value of torque
- ML indicates the minimum value of torque
- MH - ML value obtained by subtracting ML from MH
- the degree of cross-linking serves as an index of the cross-linking reactivity of the fluorine-containing copolymer, and the larger the value of M H -M L , the better the cross-linking reactivity.
- Specific gravity of crosslinked rubber article The specific gravity of the crosslinked rubber article was measured according to JIS K 6220-1:2015 using a specific gravity meter (manufactured by Shinko Denshi Co., Ltd.).
- Tensile strength, 100% modulus, tensile elongation of crosslinked rubber article Tensile strength, 100% modulus and tensile elongation were measured according to JIS K6251: 2010 (corresponding international standard ISO 37: 2005) using a test piece punched out from a plate-shaped crosslinked rubber article (thickness 1 mm) with a No. 4 dumbbell. degree was measured. As a measuring device, a tensile tester with data processing (Quick Reader TS-2530, manufactured by Ueshima Seisakusho Co., Ltd.) was used. Also, each test was performed using three test pieces, and the arithmetic average of the measured values of the three test pieces was recorded.
- compression set Using a test piece of a crosslinked rubber article, compression set (%) when the test piece is held at 300 ° C. for 70 hours and compression set (%) when held at 320 ° C. for 70 hours in accordance with JIS K 6301 And the compression set (%) when held at 325° C. for 70 hours was measured. A smaller compression set value indicates better recovery of the crosslinked rubber article, that is, better crosslinking. Also, the test was carried out using three test pieces, and the arithmetic average of the measured values of the three test pieces was recorded.
- Thermal aging test After measuring the thickness of the test piece of the crosslinked rubber article with a thickness gauge, the test piece was heated at 300° C. for 70 hours in an air atmosphere (heat aging). After cooling the test piece after heat aging to room temperature, the tensile strength and tensile elongation after heat aging were measured using the test piece after cooling under the same conditions as the test method described above. The test was performed using 3 test pieces, and the arithmetic average of the measured values of the 3 test pieces was recorded.
- Example 1-1 ⁇ Production of fluorine-containing copolymer> After degassing a stainless steel pressure-resistant reactor with an internal volume of 20 L equipped with anchor wings, 7.2 L of ultrapure water and 880 g of a 30% by mass aqueous solution of C 2 F 5 OCF 2 CF 2 OCF 2 COONH 4 as an emulsifier. , 7.3 g of 8CNVE, 6.8 g of C3DVE, and 15.9 g of a 5 mass % aqueous solution of disodium hydrogen phosphate dodecahydrate were charged. After charging 137 g of TFE and 635 g of PMVE into a container while stirring using an anchor blade, the internal temperature was raised to 80°C.
- the internal pressure of the reactor was 0.90 MPa [gauge]. 40 mL of a 3% by weight aqueous solution of ammonium persulfate (APS) was added to initiate polymerization.
- APS ammonium persulfate
- the monomer injected before the initiation of polymerization is hereinafter also referred to as "initial addition monomer”.
- the monomer was injected as follows.
- injection of a monomer after initiation of polymerization is also referred to as "post-addition”
- a monomer injected after initiation of polymerization is also referred to as “post-addition monomer”.
- TFE, 8CNVE and PMVE were pressurized to raise the internal pressure of the reactor to 0.90 MPa [gauge]. This was repeated each time the reactor internal pressure dropped to 0.89 MPa [gauge].
- the polymerization rate slowed down, a 3% by mass aqueous solution of APS was appropriately added.
- the total amount of 3% by mass aqueous solution of APS added after initiation of polymerization was 40 mL.
- the total mass of TFE added reached 1,193 g, the addition of the post-addition monomers was stopped, the internal temperature of the reactor was cooled, and the polymerization reaction was terminated to obtain a latex containing a fluorine-containing copolymer.
- the polymerization time was 429 minutes. Further, the total mass of each post-addition monomer was 1193 g for TFE, 668 g for PMVE, and 66.7 g for 8CNVE.
- the obtained latex was added to a 3% by mass aqueous solution of nitric acid (manufactured by Kanto Kagaku Co., Ltd., special grade) to coagulate the fluorine-containing copolymer.
- the fluorine-containing copolymer was filtered, washed with water, and vacuum-dried to obtain a white fluorine-containing copolymer.
- Example 1-2 to Example 1-3, Example 1-5, Example 1-6 Example 1-1 except that the types of monomers used, the amount of initially added monomers, the amount of post-added monomers, and the amount of polymerization initiator added were changed as shown in Table 1.
- a fluorine-containing copolymer was obtained in the same manner as above.
- the fluorine-containing copolymer obtained in Example 1-2 is referred to as "Copolymer 2”
- the fluorine-containing copolymer obtained in Example 1-3 as “Copolymer 3”
- the fluorine-containing copolymer obtained in Example 1-5 The fluorine-containing copolymer thus obtained is referred to as "copolymer 5"
- the fluorine-containing copolymer obtained in Example 1-6 is referred to as "copolymer 6".
- Example 1-4 The types of monomers used, the amount of initially added monomers, the amount of post-added monomers, and the amount of polymerization initiator added were changed as shown in Table 1, and ultrapure water, emulsifier, Fluorine-containing copolymerization was carried out in the same manner as in Example 1-1, except that 8CNVE, C3DVE, disodium hydrogen phosphate dodecahydrate and 3.8 g of DIB as a chain transfer agent were charged into the polymerization tank before the initiation of polymerization. got a union.
- the fluorine-containing copolymer obtained in Example 1-4 is hereinafter referred to as "copolymer 4".
- fluorine-containing copolymer composition 100 parts by mass of copolymer 1, 5 parts by mass of MT-C (manufactured by Cancarb, MT carbon), and BOAP (2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, cross-linking agent ) and kneaded with a double roll to obtain a fluorine-containing copolymer composition.
- the resulting fluorocopolymer composition is hereinafter referred to as "fluorocopolymer composition 1".
- crosslinked rubber article 1 The fluorine-containing copolymer composition 1 was crosslinked and molded at 180° C. for 20 minutes to obtain a crosslinked rubber sheet of 100 mm long ⁇ 60 mm wide ⁇ 1 mm thick (primary cross-linking). Then, in a nitrogen atmosphere, the crosslinked rubber sheet was heated at 90° C. for 3 hours, then heated to 305° C. over 5 hours, and further heated for 13 hours while maintaining the temperature at 305° C. (secondary crosslinking). After cooling the obtained crosslinked rubber sheet after secondary crosslinking to room temperature, it was punched into a No. 4 dumbbell shape defined in JIS K 6251 to obtain three crosslinked rubber article test pieces. The resulting crosslinked rubber article is hereinafter referred to as "crosslinked rubber article 1".
- Examples 2-2 to 2-12 A fluorine-containing copolymer composition was prepared in the same manner as in the production of fluorine-containing copolymer composition 1, except that the fluorine-containing copolymer, cross-linking agent, and carbon black shown in Tables 3-1 and 3-2 were used. Products 2-12 were obtained. Further, test pieces of crosslinked rubber articles 2 to 12 were obtained in the same manner as in the production of crosslinked rubber article 1, except that fluorine-containing copolymer compositions 2 to 12 were used.
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Abstract
Description
このような架橋ゴム物品を得るために使用される含フッ素共重合体として、特許文献1には、テトラフルオロエチレンに基づく単位、パーフルオロ(アルキルビニルエーテル)に基づく単位、および、ニトリル基(シアノ基)を有する単量体に基づく単位を有する含フッ素共重合体が開示されている。
[1] テトラフルオロエチレンに基づく単位と、パーフルオロ(アルキルビニルエーテル)に基づく単位と、フッ素原子と2個以上の重合性不飽和結合とを有する単量体に基づく単位と、ニトリル基とフッ素原子とを有する単量体に基づく単位と、を有する、含フッ素共重合体であって、
140℃での動的粘弾性測定によって求められる、角周波数0.3rad/sにおける前記含フッ素共重合体の貯蔵弾性率をG’0.3、角周波数0.03rad/sにおける前記含フッ素共重合体の貯蔵弾性率をG’0.03とした場合、G’0.3/G’0.03が1.00~1.45である、含フッ素共重合体。
[2] 前記ニトリル基とフッ素原子とを有する単量体に基づく単位の含有量に対する、前記フッ素原子と2個以上の重合性不飽和結合とを有する単量体に基づく単位の含有量のモル比が、0.002~7である、[1]に記載の含フッ素共重合体。
[3] 前記パーフルオロ(アルキルビニルエーテル)が、下式(1)で表される単量体である、[1]または[2]に記載の含フッ素共重合体。
CF2=CF-O-Rf1 (1)
式(1)中、Rf1は、炭素数1~10のパーフルオロアルキル基を示す。
(CR21R22=CR23-)a1R24 (2)
式(2)中、R21、R22およびR23はそれぞれ独立に、水素原子、フッ素原子、メチル基またはトリフルオロメチル基を示し、a1は2~6の整数を示し、R24は、a1価の炭素数1~10のパーフルオロ炭化水素基または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。複数のR21、複数のR22および複数のR23はそれぞれ、互いに同一であっても異なっていてもよい。
[5] 前記式(2)で表される単量体が、下式(3)で表される単量体または下式(4)で表される単量体である、[4]に記載の含フッ素共重合体。
(CF2=CF-)2R31 (3)
式(3)中、R31は、2価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。
(CH2=CH-)2R41 (4)
式(4)中、R41は、2価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。
CR51R52=CR53-R54-CN (5)
式(5)中、R51、R52およびR53はそれぞれ独立に、水素原子、フッ素原子またはメチル基を示し、R54は、2価の炭素数1~10のパーフルオロ炭化水素基または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。
[7] 前記R51、R52およびR53の全てがフッ素原子であるかまたはそれら全てが水素原子であり、前記R54がエーテル性酸素原子を有しかつエーテル性酸素原子の数が1~3個である、[6]に記載の含フッ素共重合体。
[8] ヨウ素原子を実質的に含まない、[1]~[7]のいずれかに記載の含フッ素共重合体。
[10] ヨウ素原子を含む連鎖移動剤の非存在下で共重合する、[9]に記載の含フッ素共重合体の製造方法。
[11] [1]~[8]のいずれかに記載の含フッ素共重合体と、架橋剤と、を含む、含フッ素共重合体組成物。
[12] 前記架橋剤が2個以上のアミノ基を有する化合物である、[11]に記載の含フッ素共重合体組成物。
[13] 前記架橋剤の含有量が、前記含フッ素共重合体の100質量部に対して、1.0質量部未満である、[11]または[12]に記載の含フッ素共重合体組成物。
[14] [11]~[13]のいずれかに記載の含フッ素共重合体組成物中の含フッ素共重合体を架橋してなる、架橋ゴム物品。
「単位」とは、単量体が重合して直接形成された、上記単量体1分子に由来する原子団と、上記原子団の一部を化学変換して得られる原子団との総称である。「単量体に基づく単位」は、以下、単に「単位」ともいう。
「ゴム」とは、JIS K 6200(2008)により定義される性質を示すゴムを意味し、「樹脂」とは区別される。
本発明の含フッ素共重合体は、テトラフルオロエチレン(以下、「TFE」ともいう。)に基づく単位と、パーフルオロ(アルキルビニルエーテル)(以下、「PAVE」ともいう。)に基づく単位と、フッ素原子と2個以上の重合性不飽和結合とを有する単量体(以下、「単量体A」ともいう。)に基づく単位と、ニトリル基とフッ素原子とを有する単量体(以下、「RCN」ともいう。)に基づく単位と、を有する。
また、本発明の含フッ素共重合体は、140℃での動的粘弾性測定によって求められる、角周波数0.3rad/sにおける上記含フッ素共重合体の貯蔵弾性率をG’0.3、角周波数0.03rad/sにおける上記含フッ素共重合体の貯蔵弾性率をG’0.03とした場合、G’0.3/G’0.03が1.00~1.45である。
本発明の含フッ素共重合体を用いて得られた架橋ゴム物品は、金型からの離型性に優れる。この理由の詳細は明らかになっていないが、以下の理由によると推測される。
特に、本発明の含フッ素共重合体は、単量体AまたはRCNが併用されていない含フッ素共重合体と比較して、分岐構造と架橋部位が含フッ素共重合体全体に均一に分布すると推測される。気体の単量体と液体の単量体を重合させる場合には、液状の単量体の反応場への移動が反応の律速になると考えられる。詳細なメカニズムは不明だが、単量体AとRCNを併用すると、単量体Aを単独で使用する場合や、RCNを単独で使用する場合に比べて、単量体AおよびRCNの反応場への移動が促進されると考えられる。そのため、一般的なゴム硬度等の物性値からは差異が見出せないような、架橋ゴム物品のミクロな部分における硬度の向上によって、離型性が向上したと考えられる。
この問題に対して、本発明者らは、含フッ素共重合体中の分岐構造の存在の程度を示す指標として、角周波数が小さい条件で測定した貯蔵弾性率(具体的にはG’0.03)に対する、角周波数が大きい条件で測定した貯蔵弾性率(具体的にはG’0.3)の比、すなわち、G’0.3/G’0.03に着目した。G’0.3/G’0.03が1.00に近いほど、含フッ素共重合体中に分岐構造が多く存在しているといえる。この理由としては、分岐構造が多く含まれる程、貯蔵弾性率測定時の緩和時間が短く、せん断速度による貯蔵弾性率の違いは小さくなり、G’0.3/G’0.03が1.00に近い数値となるためである。
このような理由により、G’0.3/G’0.03が上記範囲内にある含フッ素共重合体を用いると、架橋ゴム物品の離型性が向上したと考えられる。
このように、単量体A単位とRCN単位とを有することによる効果と、G’0.3/G’0.03を上記範囲内にしたことによる効果と、が相乗的に作用して、離型性に優れた架橋ゴム物品が得られたと推測される。
PAVEは、重合反応性およびゴム物性に優れる点から、式(1)で表される単量体が好ましい。
CF2=CF-O-Rf1 (1)
式(1)中、Rf1は、炭素数1~10のパーフルオロアルキル基を示す。Rf1の炭素数は、重合反応性がより優れる点から、1~8が好ましく、1~6がより好ましく、1~5がさらに好ましく、1~3が特に好ましい。
パーフルオロアルキル基は、直鎖状であっても分岐鎖状であってもよい。
重合性不飽和結合の具体例としては、炭素原子-炭素原子の二重結合(C=C)、炭素原子-炭素原子の三重結合(C≡C)が挙げられる。
単量体Aにおける重合性不飽和結合の数は、重合反応性がより優れる、2~6個が好ましく、2または3個がより好ましく、2個が特に好ましい。
単量体A単位はニトリル基を有しないことが好ましい。
(CR21R22=CR23-)a1R24 (2)
式(2)中、R21、R22およびR23はそれぞれ独立に、水素原子、フッ素原子、メチル基またはトリフルオロメチル基を示し、a1は2~6の整数を示し、R24は、a1価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。複数のR21、複数のR22および複数のR23はそれぞれ、互いに同一であっても異なっていてもよく、互いに同一であるのが特に好ましい。
a1は2または3が好ましく、2が特に好ましい。
R24は、直鎖状、分岐鎖状、環状のいずれであってもよく、直鎖状または分岐鎖状が好ましく、直鎖状が特に好ましい。R24の炭素数は、2~8が好ましく、3~7がより好ましく、3~6がさらに好ましく、3~5が特に好ましい。
R24は、エーテル性酸素原子を有していても、有していなくてもよいが、架橋反応性やゴム物性がより優れる点から、エーテル性酸素原子を有しているのが好ましい。
R24におけるエーテル性酸素原子の数は1~6が好ましく、1~3がより好ましく、1または2が特に好ましい。R24におけるエーテル性酸素原子は、R24の末端に存在していることが好ましい。
(CF2=CF-)2R31 (3)
式(3)中、R31は、2価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。
(CH2=CH-)2R41 (4)
式(4)中、R41は、2価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。
式(3)で表される単量体の具体例としては、CF2=CFO(CF2)2OCF=CF2、CF2=CFO(CF2)3OCF=CF2、CF2=CFO(CF2)4OCF=CF2、CF2=CFO(CF2)6OCF=CF2、CF2=CFO(CF2)8OCF=CF2、CF2=CFO(CF2)2OCF(CF3)CF2OCF=CF2、CF2=CFO(CF2)2O(CF(CF3)CF2O)2CF=CF2、CF2=CFOCF2O(CF2CF2O)2CF=CF2、CF2=CFO(CF2O)3O(CF(CF3)CF2O)2CF=CF2、CF2=CFOCF2CF(CF3)O(CF2)2OCF(CF3)CF2OCF=CF2、CF2=CFOCF2CF2O(CF2O)2CF2CF2OCF=CF2が挙げられる。
式(3)で表される単量体のうち、より好適な単量体の具体例としては、CF2=CFO(CF2)3OCF=CF2(以下、「C3DVE」ともいう。)、CF2=CFO(CF2)4OCF=CF2(以下、「C4DVE」ともいう。)が挙げられる。
式(4)で表される単量体の具体例としては、CH2=CH(CF2)2CH=CH2、CH2=CH(CF2)4CH=CH2、CH2=CH(CF2)6CH=CH2が挙げられる。
式(4)で表される単量体のうち、より好適な単量体の具体例としては、CH2=CH(CF2)6CH=CH2(以下、「C6DV」ともいう。)が挙げられる。
RCNは、重合反応性の点から、重合性不飽和結合を有するのが好ましく、重合性不飽和結合を1個有するのが特に好ましい。重合性不飽和結合の具体例は、上述の通りである。
CR51R52=CR53-R54-CN (5)
式(5)中、R51、R52およびR53はそれぞれ独立に、水素原子、フッ素原子またはメチル基を示し、R54は、2価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。
R54は、直鎖状、分岐鎖状、環状のいずれであってもよく、直鎖状または分岐鎖状が好ましい。R54の炭素数は、2~8が好ましく、3~7がより好ましく、3~6がさらに好ましく、3~5が特に好ましい。
R54は、エーテル性酸素原子を有していても、有していなくてもよいが、ゴム物性がより優れる点から、エーテル性酸素原子を有しているのが好ましい。
R54におけるエーテル性酸素原子の数は1~3が好ましく、1または2が特に好ましい。
他の単量体の具体例としては、下式(6)で表される単量体、フッ化ビニリデン(以下、「VdF」ともいう。)、ヘキサフルオロプロピレン(以下、「HFP」ともいう。)、クロロトリフルオロエチレン(以下、「CTFE」ともいう。)、エチレン、ならびに、TFE、PAVE、単量体A、RCN、式(6)で表される単量体、VdF、HFPおよびCTFE以外のハロゲン原子を有する単量体(以下、他のハロゲン原子を有する単量体ともいう。)(例えば、ブロモトリフルオロエチレン、ヨードトリフルオロエチレン)が挙げられる。
CF2=CF-O-Rf2 (6)
式(6)中、Rf2は、炭素数1~8のエーテル性酸素原子を1~5個含むパーフルオロアルキル基を示す。Rf2の炭素数は、1~6が好ましく、1~5が特に好ましい。
PAVE単位の含有量は、架橋ゴム物品の弾性がより優れる点から、含フッ素共重合体の全単位に対して、20~39モル%が好ましく、24~36モル%がより好ましく、27~33モル%が特に好ましい。
単量体A単位の含有量は、G’0.3/G’0.03を上述の範囲内に特に調節しやすい点、架橋ゴム物品の離型性、物性、外観がより優れる点から、含フッ素共重合体の全単位に対して、0.01~0.35モル%が好ましく、0.03~0.20モル%がより好ましく、0.03~0.15モル%がさらに好ましく、0.06~0.13モル%が特に好ましい。
RCN単位の含有量は、架橋ゴム物品の離型性および耐熱性がより優れる点から、含フッ素共重合体の全単位に対して、0.05~5モル%が好ましく、0.1~3モル%がより好ましく、0.2~1.5モル%がさらに好ましく、0.4~0.8モル%が特に好ましい。
TFE単位、PAVE単位、単量体A単位およびRCN単位が上記範囲内であると、G’0.3/G’0.03を上述の範囲内に調節しやすい。
含フッ素共重合体が他の単量体単位を含む場合、他の単量体単位の含有量は、架橋ゴム物品の耐熱性の点から、含フッ素共重合体の全単位に対して、0.01~20モル%が好ましく、0.5~10モル%がより好ましく、1~5モル%が特に好ましい。
また、含フッ素共重合体中の全単位に対するTFE単位、PAVE単位およびRCN単位は、19F-核磁気共鳴(NMR)分析によって算出する。具体的には、19F-核磁気共鳴(NMR)分析によって、含フッ素共重合体中のTFE単位:PAVE単位:RCN単位(モル比)を求める。そして、100モル%から単量体A単位の含有量(モル%)を引いた値に、19F-核磁気共鳴(NMR)分析によって求めた含フッ素共重合体中のTFE単位:PAVE単位:RCN単位(モル比)を当てはめ、各単位の含有量を求める。
含フッ素共重合体がヨウ素原子を実質的に含まないことで、含フッ素共重合体の架橋特性が優れ、これを用いて得られる架橋物品の割れが少なく、高温時の圧縮永久歪率を小さくできる。含フッ素共重合体中のヨウ素原子は架橋点になりうるため、ヨウ素原子を含むほうが架橋特性に優れるように思われる。しかし、ニトリル基を架橋点として有する含フッ素共重合体が、仮にヨウ素原子を含む場合、含フッ素共重合体組成物に含まれる架橋剤がニトリル基よりもヨウ素原子と優先的に反応する。含フッ素共重合体中のヨウ素原子の含有量が少なければ、ニトリル基と架橋剤とが十分に反応できる。また、含フッ素共重合体のニトリル基と架橋剤とが反応してできた架橋構造は耐熱性に優れるので、含フッ素共重合体のニトリル基と架橋剤とが十分に反応することで、耐熱性が向上する。そのため、ヨウ素原子を実質的に含まない含フッ素共重合体を含む含フッ素共重合体組成物を用いれば、架橋特性に優れ、割れが少なく、高温時の圧縮永久歪率の小さい架橋物品を形成できる。特に、含フッ素共重合体の製造時にヨウ素原子を含む連鎖移動剤(後述)を用いない場合、得られる含フッ素共重合体の分子量分布が広くなり、硬度と伸度のバランスがよくなるので、機械特性(例えば、引張り強度)にも優れる。また、含フッ素共重合体の分子量分布が広くなることで、比較的低分子の含フッ素共重合体が増えるので、G’0.3/G’0.03を上述の範囲内に調節しやすい。
ここで、「含フッ素共重合体がヨウ素原子を実質的に含まない」とは、ヨウ素原子の含有量が、含フッ素共重合体の全質量に対して、0.09質量%以下であるのを意味し、0.05質量%以下であることが好ましく、0.02質量%以下であることがより好ましく、0質量%であること(すなわち、ヨウ素原子を含まないこと)が特に好ましい。
ヨウ素原子としては、連鎖移動剤として機能するヨード化合物に由来するヨウ素原子、上述のヨードトリフルオロエチレン等の他のハロゲン原子を有する単量体のうちヨウ素原子を有する単量体に基づく単位中のヨウ素原子が挙げられる。
連鎖移動剤として機能するヨード化合物の具体例としては、1,3-ジヨードプロパン、1,4-ジヨードブタン(以下、「DIB」ともいう。)、1,6-ジヨードヘキサン、1,8-ジヨードオクタン、1,3-ジヨードパーフルオロプロパン、1,4-ジヨードパーフルオロブタン、1,6-ジヨードパーフルオロヘキサン、1,8-ジヨードパーフルオロオクタンが挙げられる。
含フッ素共重合体のG’0.3/G’0.03は、1.00~1.45であり、架橋ゴム物品の離型性がより優れる点から、1.00~1.43が好ましく、1.20~1.43がより好ましく、1.30~1.43がさらに好ましく、1.40~1.43が最も好ましい。
測定時の角周波数が大きいほど、貯蔵弾性率の値は大きくなるので、G’0.3/G’0.03の値は1.00を下回ることはない。
含フッ素共重合体のG’0.3は、成型作業性の点から、600~800kPaが好ましく、650~750kPaがより好ましく、670~700kPaが特に好ましい。
含フッ素共重合体のG’0.03は、成型作業性の点から、400~600kPaが好ましく、430~550kPaがより好ましく、470~500kPaが特に好ましい。
ここで、G’0.3は、140℃での動的粘弾性測定によって求められる、角周波数0.3rad/sにおける含フッ素共重合体の貯蔵弾性率を意味する。また、G’0.03は、140℃での動的粘弾性測定によって求められる、各周波数0.03rad/sの条件で測定される貯蔵弾性率を意味する。なお、「rad/s」は、ラジアン毎秒を意味する。
本発明における含フッ素共重合体のG’0.3およびG’0.03は、ゴム加工解析装置を用いて、ASTM D6204に準拠して測定される値であり、詳細な測定条件は実施例に示す通りである。
ここで、G’0.1は、140℃での動的粘弾性測定によって求められる、角周波数0.1rad/sの条件で測定される貯蔵弾性率を意味する。また、G’1は、140℃での動的粘弾性測定によって求められる、角周波数1rad/sの条件で測定される貯蔵弾性率を意味する。
本発明は、また、前記含フッ素共重合体を製造する方法である。
すなわち、本発明の含フッ素共重合体の製造方法は、TFEと、PAVEと、単量体Aと、RCNを、ラジカル重合開始剤の存在下で共重合する方法である。
本発明の含フッ素共重合体の製造方法としては、前記単量体を、ラジカル重合開始剤の存在下、かつ、ヨウ素原子を含む連鎖移動剤の非存在下で、共重合する方法であることが好ましい。ヨウ素原子を含む連鎖移動剤の非存在下で重合することの効果は、上述の通りである。
含フッ素共重合体の製造を乳化重合より行う場合、例えば、水性媒体、乳化剤、ラジカル重合開始剤の存在下、上記単量体を加熱することにより実施できる。
水溶性有機溶媒としては、tert-ブタノール、プロピレングリコール、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、トリプロピレングリコール等が挙げられる。特に、tert-ブタノール、ジプロピレングリコールモノメチルエーテルが好ましい。
水性媒体が水溶性有機溶媒を含む場合、水溶性有機溶媒の含有量は、水の100質量部に対して。1~40質量部が好ましく、3~30質量部がより好ましい。
アニオン性乳化剤の具体例としては、ラウリル硫酸ナトリウム、ドデシルベンゼンスルホン酸ナトリウム等の炭化水素系乳化剤、ペルフルオロオクタン酸アンモニウム、ペルフルオロオクタン酸ナトリウム、ペルフルオロヘキサン酸アンモニウム等の含フッ素脂肪酸塩が挙げられる。また、F(CF2)pO(CF(X3)CF2O)qCF(Y)COOA(式中、X3、Yはそれぞれ独立にフッ素原子または炭素原子数1~3のペルフルオロアルキル基を示し、Aは水素原子、アルカリ金属原子またはNH4を示し、pは1~10の整数を示し、qは0~3の整数を示す。)で表される含フッ素乳化剤も好ましい。Aにおけるアルカリ金属原子の具体例としては、ナトリウム、カリウムが挙げられる。
水溶性重合開始剤の具体例としては、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸類、ジコハク酸過酸化物、アゾビスイソブチルアミジン二塩酸塩等の有機系重合開始剤類が挙げられ、これらの中でも、過硫酸類が好ましく、過硫酸アンモニウムがより好ましい。
レドックス重合開始剤としては、過硫酸類と還元剤を組み合せた重合開始剤が挙げられる。このうち、重合温度が0~80℃の範囲で各単量体を重合可能な重合開始剤が好ましい。レドックス重合開始剤を構成する過硫酸塩の具体例としては、過硫酸アンモニウム、過硫酸ナトリウム、過硫酸カリウム等の過硫酸のアルカリ金属塩が挙げられ、過硫酸アンモニウムが好ましい。過硫酸類と組み合わせる還元剤の具体例としては、チオ硫酸塩、亜硫酸塩、亜硫酸水素塩、ピロ亜硫酸塩、ヒドロキシメタンスルフィン酸塩が挙げられ、ヒドロキシメタンスルフィン酸塩が好ましく、ヒドロキシメタンスルフィン酸ナトリウム塩が特に好ましい。
凝集方法としては、金属塩の添加、塩酸、硫酸または硝酸等の無機酸の添加が挙げられ、得られる含フッ素共重合体に金属の混入が少なくなり半導体製造装置が有する部材(例えば、Oリング)に好適に使用できる点から、無機酸の添加が好ましい。
ただし、本発明の含フッ素共重合体の製造時において、ヨウ素原子を含む連鎖移動剤を使用しないことが好ましい。これにより、G’0.3/G’0.03を上述の範囲内に調節することが容易となる。
本発明の含フッ素共重合体組成物は、上述の含フッ素共重合体と、架橋剤とを含む。
ジアルキルパーオキシド類の具体例としては、1,1-ジ(tert-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、2,5-ジメチルヘキサン-2,5-ジヒドロキシパーオキシド、tert-ブチルクミルパーオキシド、ジクミルパーオキシド、2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(tert-ブチルパーオキシ)-3-ヘキシン、tert-ブチルパーオキシマレイン酸、tert-ブチルパーオキシソプロピルカーボネートが挙げられる。
架橋剤の含有量の下限値は、含フッ素共重合体の100質量部に対して、0.01質量部以上が好ましく、0.1質量部以上がより好ましく、0.2質量部以上がさらに好ましく、0.4質量部以上が最も好ましい。架橋剤の含有量が上記範囲であれば、架橋物品の離型性がより優れる。
含フッ素共重合体組成物は、本発明の効果が損なわれない範囲で、上記以外の成分を含んでいてもよい。他の成分としては、架橋助剤(例えば、トリアリルシアヌレート、トリアリルイソシアヌレート、トリメタリルイソシアヌレート)、受酸剤(例えば、脂肪酸エステル、脂肪酸金属塩、2価金属の酸化物(酸化マグネシウム、酸化カルシウム、酸化亜鉛、酸化鉛等))、充填剤および補強材(例えば、カーボンブラック、硫酸バリウム、メタケイ酸カルシウム、炭酸カルシウム、酸化チタン、二酸化珪素、クレー、タルク)、スコーチ遅延剤(例えば、ビスフェノールA等のフェノール性水酸基含有化合物類、ハイドロキノン等のキノン類、2,4-ジ(3-イソプロピルフェニル)-4-メチル-1-ペンテン等のα-メチルスチレンダイマー類)、クラウンエーテル(例えば、18-クラウン-6)、離型剤(例えば、ステアリン酸ナトリウム)が挙げられる。
ここで、「含フッ素共重合体組成物が離型剤を実質的に含まない」とは、離型剤の含有量が、含フッ素共重合体の100質量部に対して、0.1質量部以下であるのを意味し、0.01質量部以下であるのが好ましく、0質量部であるのが特に好ましい。
また、上記各成分を混合した混合物を得た後、混合物を成形してもよい。混合物の成形方法の具体例としては、圧縮成形、射出成形、押し出し成形、カレンダー成形、または、溶剤に溶かして基板等にディッピングもしくはコーティングして成形する方法が挙げられる。
本発明の架橋ゴム物品は、上述の含フッ素共重合体組成物中の含フッ素共重合体を架橋したゴム物品である。
含フッ素共重合体組成物中の含フッ素共重合体の架橋方法としては、含フッ素共重合体組成物を加熱することによって架橋する方法が好ましい。
加熱による架橋方法の具体例としては、加熱プレス架橋、スチーム架橋、熱風架橋が挙げられる。これらの方法から、含フッ素共重合体または含フッ素共重合体組成物の形状や用途を考慮して適宜選択すればよい。
加熱条件は、100~400℃で1秒~24時間が好ましい。
2次架橋を行う際の加熱条件は、80~350℃で30分間~48時間が好ましい。
架橋ゴム物品の引張強度(引張破断強度)は、ゴム特性に優れる点から、15~40MPaが好ましく、21~35MPaが特に好ましい。
架橋ゴム物品の100%モジュラス(100%伸びでの引張応力)は、ゴム特性に優れる点から、3.0~5.0MPaが好ましく、3.5~4.4MPaが特に好ましい。
架橋ゴム物品の引張伸度(切断時伸び率)は、ゴム特性に優れる点から、100~250%が好ましく、180~215%が特に好ましい。
架橋ゴム物品の引張強度、100%モジュラスおよび切断時伸び率は、JIS K 6251:2010(対応国際規格ISO 37:2005)に準拠する方法にて測定される値である。
架橋ゴム物品の硬度(Shore-A)は、架橋ゴム物品の板状の成形物(厚み1mm)を用いて、JIS K6253-1:2012に準拠して、タイプAデュロメータを用いて測定される値である。
架橋ゴム物品の300℃における圧縮永久歪みの下限値は、0%が好ましい。
架橋ゴム物品の320℃における圧縮永久歪みは、35%以下が好ましく、含フッ素共重合体が良好に架橋しており、架橋ゴム物品の加圧後の形状回復が優れる点から、30%以下がより好ましく、29%以下がさらに好ましく、24%以下が特に好ましい。
架橋ゴム物品の320℃における圧縮永久歪みの下限値は、0%が好ましい。
架橋ゴム物品の325℃における圧縮永久歪みは、35%以下が好ましく、含フッ素共重合体が良好に架橋しており、架橋ゴム物品の加圧後の形状回復が優れる点から、30%以下がより好ましく、29%以下がさらに好ましく、27%以下が特に好ましい。
架橋ゴム物品の325℃における圧縮永久歪みの下限値は、0%が好ましい。
架橋ゴム物品の300℃、320℃および325℃における圧縮永久歪みは、架橋ゴム物品の板状の成形物(厚み1mm)を用いて、JIS K6301に準拠して測定される値である。
架橋ゴム物品は、O-リング、シート、ガスケット、オイルシール、ダイヤフラム、V-リング等の材料に好適である。また、耐熱性耐薬品性シール材、耐熱性耐油性シール材、電線被覆材、半導体装置用シール材、液晶ディスプレイパネル製造装置用シール材、発光ダイオード製造装置用シール材、耐蝕性ゴム塗料、耐ウレア系グリース用シール材等、ゴム塗料、接着ゴム、ホース、チューブ、カレンダーシート(ロール)、スポンジ、ゴムロール、石油掘削用部材、放熱シート、溶液架橋体、ゴムスポンジ、ベアリングシール(耐ウレアグリース等)、ライニング(耐薬品)、自動車用絶縁シート、電子機器向け絶縁シート、時計向けゴムバンド、内視鏡用パッキン(耐アミン)、蛇腹ホース(カレンダーシートからの加工)、給湯器パッキン/弁、防舷材(海洋土木、船舶)、繊維・不織布(防護服等)、基盤シール材、ゴム手袋、一軸偏心ねじポンプのステータ、尿素SCRシステム用部品、防振剤、制振剤、シーリング剤、他材料への添加剤、玩具の用途にも適用できる。
含フッ素共重合体の全単位に対する単量体A単位の含有量(モル%)は、含フッ素共重合体の製造に際して使用された単量体Aの量(単量体Aの使用量)に基づいて算出した。
また、含フッ素共重合体の全単位に対する、TFE単位、PAVE単位、RCN単位の含有量(モル%)は、19F-核磁気共鳴(NMR)分析に基づいて算出した。
重合後のラテックスを凝集して含フッ素共重合体を取り出した後のろ液およびラテックスの洗浄のあとに残ったろ液をディスクフィルターでろ過し、得られた液体をイオンクロマトグラフ測定装置(ダイアインスツルメンツ社製、自動試料燃焼装置イオンクロマトグラフ用前処理装置AQF-100型とイオンクロマトグラフを組み合わせた装置)で分析した。
単量体Aの仕込み量に対して3質量%以上のフッ化物イオンが検出された場合は、単量体Aの使用量には、反応器に添加した単量体Aの量(単量体Aの仕込み量)から、上記イオンクロマトグラフの測定結果に基づいて算出した液体中の単量体Aの量を差し引いた値を用いた。
一方で、単量体Aの仕込み量に対して3質量%以上のフッ化物イオンが検出されない場合は、仕込みに使用した単量体Aはすべて重合されたものとして、単量体Aの使用量には、単量体Aの仕込み量を用いた。
このようにして得られた単量体A単位の使用量に基づいて、含フッ素共重合体の全単位に対する単量体A単位の含有量(モル%)を算出した。
仕込んだDIBがすべて重合されたものとして、含フッ素共重合体の全質量に対する、仕込んだDIBに含まれるヨウ素原子の質量の割合(質量%)を、含フッ素共重合体である後述の共重合体4中のヨウ素原子の含有量とした。
含フッ素共重合体である後述の共重合体1~3、5および6は、ヨウ素原子を含む原料を使用せずに重合するので、ヨウ素原子を含まない。
ゴム加工解析装置(Alpha Technologies社製、RPA2000)を用いて、ASTM D6204にしたがい、温度:140℃、角周波数0.3rad/sの条件で測定した値を含フッ素共重合体のG’0.3とした。
角周波数を0.03rad/sに変更した以外は、上記G’0.3の測定方法と同様にして、含フッ素共重合体のG’0.03を測定した。
得られた値に基づいて、含フッ素共重合体のG’0.3/G’0.03を算出した。
含フッ素共重合体組成物について、ゴム加工解析装置(Alpha Technologies社製、RPA2000)を用いて177℃で12分間、振幅3度、振動数毎分100回の条件で、MHとMLを測定した。
測定されるMHはトルクの最大値を示し、MLはトルクの最小値を示し、MH-ML(MHからMLを差し引いた値)は架橋度(単位:dNm)を示す。架橋度は、含フッ素共重合体の架橋反応性の目安となり、MH-MLの値が大きいほど、架橋反応性に優れることを示す。
架橋ゴム物品について、比重計(新光電子社製)を用いて、JIS K 6220-1:2015に準じて比重を測定した。
板状の架橋ゴム物品(厚み1mm)を4号ダンベルで打ち抜いた試験片を用いて、JIS K6251:2010(対応国際規格ISO 37:2005)に準拠して、引張強度、100%モジュラスおよび引張伸度を測定した。
なお、測定装置には、データ処理付引張試験機(クイックリーダー TS-2530、上島製作所社製)を用いた。
また、各試験はそれぞれ3枚の試験片を用いて実施して、3枚の試験片の測定値を算術平均した値を記録した。
架橋ゴム物品の試験片を用いて、JIS K6253-3:2012に準拠して、タイプAデュロメータを用いて硬度(Shore-A)を測定した。
なお、測定装置には、ゴム用自動硬度計(デジテスト ショアーA、H・バーレイス試験機社製)を用いた。
また、試験は3枚の試験片を用いて実施して、3枚の試験片の測定値を算術平均した値を記録した。
架橋ゴム物品の試験片を用いて、JIS K 6301に準拠して、試験片を300℃70時間保持した際の圧縮永久歪み(%)、320℃70時間保持した際の圧縮永久歪み(%)および、325℃70時間保持した際の圧縮永久歪み(%)をそれぞれ測定した。圧縮永久歪みの値が小さいほど、架橋ゴム物品の回復性が優れること、つまり、良好に架橋していることを示す。
また、試験は3枚の試験片を用いて実施して、3枚の試験片の測定値を算術平均した値を記録した。
架橋ゴム物品の試験片の厚みをシックネスゲージによって測定した後、試験片を空気雰囲気下において300℃で70時間加熱した(熱老化)。
熱老化後の試験片を室温まで冷却した後、冷却後の試験片を用いて、上述の試験方法と同様の条件にて、熱老化後における引張強度および引張伸度を測定した。
試験は3枚の試験片を用いて実施して、3枚の試験片の測定値を算術平均した値を記録した。
熱老化を行っていない試験片の測定値(常態試験値)と、熱老化後の試験片の測定値(熱老化後の試験値)と、に基づいて、以下の式にしたがって熱老化試験前後における変化率(熱老化試験変化率)を算出した。変化率が0%に近いほど、耐熱性に優れることを示す。
熱老化試験変化率(%)=100×{(常態試験値)-(熱老化後の試験値)}/(常態試験値)
シート状の金型に、含フッ素共重合体組成物を導入して、含フッ素共重合体組成物を180℃で20分間架橋して、金型に付着した状態の架橋ゴム物品(縦100mm×横60mm×厚み1mm)を得た。架橋反応終了後、直ちに、エアーガン(製品名サイクロンダスター、中央空機株式会社製)を用いて、架橋ゴム物品と金型との界面に空気を噴射して、以下の評価基準にて、離型性の評価を行った。
なお、架橋反応終了後、直ちに空気を噴射しているため、空気噴射時の架橋物品の温度は180℃に近い温度であると考えられる。
<エアーガンによる空気の噴射条件>
圧力:0.5MPa
空気の噴射時間:3秒
<評価基準>
○:架橋ゴム物品が金型から脱離した。
×:架橋ゴム物品が金型から脱離しなかった。
<含フッ素共重合体の製造>
アンカー翼を備えた内容積20Lのステンレス製耐圧反応器を脱気した後、超純水の7.2L、乳化剤であるC2F5OCF2CF2OCF2COONH4の30質量%水溶液の880g、8CNVEの7.3g、C3DVEの6.8g、リン酸水素二ナトリウム・12水和物の5質量%水溶液の15.9gを仕込んだ。アンカー翼を用いて撹拌しながら、TFEの137g、PMVEの635gを容器内に仕込んだ後、内温を80℃まで昇温した。反応器内圧は0.90MPa[gauge]であった。過硫酸アンモニウム(APS)の3質量%水溶液の40mLを添加し、重合を開始した。重合開始前に圧入した単量体を、以下、「初期添加単量体」ともいう。
反応器内圧が0.89MPa[gauge]に低下した時点でTFE、8CNVE、PMVEを圧入し、反応器内圧を0.90MPa[gauge]に昇圧させた。反応器内圧が0.89MPa[gauge]に低下するたびにこれを繰り返した。
重合速度が低下してきたところで、APSの3質量%水溶液を適宜加えた。重合開始後に加えたAPSの3質量%水溶液の合計は、40mLであった。
TFEの総添加質量が1193gとなった時点で、後添加単量体の添加を停止し、反応器内温を冷却し、重合反応を停止させ、含フッ素共重合体を含むラテックスを得た。重合時間は429分間であった。また、各後添加単量体の総添加質量は、TFEが1193g、PMVEが668g、8CNVEが66.7gであった。
使用した単量体の種類、初期添加単量体の添加量、後添加単量体の添加量、および重合開始剤の添加量等を表1に示す通りに変更した以外は、例1-1と同様にして含フッ素共重合体を得た。以下、例1-2において得られた含フッ素共重合体を「共重合体2」、例1-3において得られた含フッ素共重合体を「共重合体3」、例1-5において得られた含フッ素共重合体を「共重合体5」、および、例1-6において得られた含フッ素共重合体を「共重合体6」、という。
使用した単量体の種類、初期添加単量体の添加量、後添加単量体の添加量、および重合開始剤の添加量等を表1に示す通りに変更し、超純水、乳化剤、8CNVE、C3DVE、リン酸水素二ナトリウム・12水和物と共に連鎖移動剤であるDIBの3.8gを重合開始前の重合槽に仕込んだ以外は、例1-1と同様にして含フッ素共重合体を得た。例1-4において得られた含フッ素共重合体を、以下「共重合体4」という。
<含フッ素共重合体組成物の製造>
共重合体1の100質量部、MT-C(Cancarb社製、MTカーボン)の5質量部、および、BOAP(2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン、架橋剤)の0.5質量部の割合で各成分を調合して、2本ロールで混練し、含フッ素共重合体組成物を得た。得られた含フッ素共重合体組成物を、以下、「含フッ素共重合体組成物1」という。
含フッ素共重合体組成物1を180℃で20分間架橋および成型して、縦100mm×横60mm×厚み1mmの架橋ゴムシートを得た(1次架橋)。そして、窒素雰囲気下において、架橋ゴムシートを90℃で3時間加熱した後、5時間かけて305℃まで昇温し、305℃を保ったまま、さらに13時間加熱した(2次架橋)。
得られた2次架橋後の架橋ゴムシートを室温まで冷却した後、JIS K 6251で規定された4号ダンベル状に打ち抜いて、架橋ゴム物品の試験片を3枚得た。得られた架橋ゴム物品を、以下、「架橋ゴム物品1」という。
表3-1および表3-2に示す含フッ素共重合体、架橋剤、およびカーボンブラックを使用した以外は、含フッ素共重合体組成物1の製造と同様にして、含フッ素共重合体組成物2~12を得た。また、含フッ素共重合体組成物2~12を用いた以外は、架橋ゴム物品1の製造と同様にして、架橋ゴム物品2~12の試験片を得た。
なお、例2-9における架橋ゴム物品9は、300℃70時間保持した際の圧縮永久歪みを測定したあとに、小さいひびが観察された。また、例2-11おける架橋ゴム物品11および例2-12おける架橋ゴム物品12は、325℃70時間保持した際の圧縮永久歪みを測定したあとに、小さいひびが観察された。
なお、2021年04月12日に出願された日本特許出願2021-066993号の明細書、特許請求の範囲および要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- テトラフルオロエチレンに基づく単位と、パーフルオロ(アルキルビニルエーテル)に基づく単位と、フッ素原子と2個以上の重合性不飽和結合とを有する単量体に基づく単位と、ニトリル基とフッ素原子とを有する単量体に基づく単位と、を有する、含フッ素共重合体であって、
140℃での動的粘弾性測定によって求められる、角周波数0.3rad/sにおける前記含フッ素共重合体の貯蔵弾性率をG’0.3、角周波数0.03rad/sにおける前記含フッ素共重合体の貯蔵弾性率をG’0.03とした場合、G’0.3/G’0.03が1.00~1.45である、含フッ素共重合体。 - 前記ニトリル基とフッ素原子とを有する単量体に基づく単位の含有量に対する、前記フッ素原子と2個以上の重合性不飽和結合とを有する単量体に基づく単位の含有量のモル比が、0.002~7である、請求項1に記載の含フッ素共重合体。
- 前記パーフルオロ(アルキルビニルエーテル)が、下式(1)で表される単量体である、請求項1または2に記載の含フッ素共重合体。
CF2=CF-O-Rf1 (1)
式(1)中、Rf1は、炭素数1~10のパーフルオロアルキル基を示す。 - 前記フッ素原子と2個以上の重合性不飽和結合とを有する単量体が、下式(2)で表される単量体である、請求項1~3のいずれか1項に記載の含フッ素共重合体。
(CR21R22=CR23-)a1R24 (2)
式(2)中、R21、R22およびR23はそれぞれ独立に、水素原子、フッ素原子、メチル基またはトリフルオロメチル基を示し、a1は2~6の整数を示し、R24は、a1価の炭素数1~10のパーフルオロ炭化水素基または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。複数のR21、複数のR22および複数のR23はそれぞれ、互いに同一であっても異なっていてもよい。 - 前記式(2)で表される単量体が、下式(3)で表される単量体または下式(4)で表される単量体である、請求項4に記載の含フッ素共重合体。
(CF2=CF-)2R31 (3)
式(3)中、R31は、2価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。
(CH2=CH-)2R41 (4)
式(4)中、R41は、2価の炭素数1~10のパーフルオロ炭化水素基、または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。 - 前記ニトリル基とフッ素原子とを有する単量体が、下式(5)で表される単量体である、請求項1~5のいずれか1項に記載の含フッ素共重合体。
CR51R52=CR53-R54-CN (5)
式(5)中、R51、R52およびR53はそれぞれ独立に、水素原子、フッ素原子またはメチル基を示し、R54は、2価の炭素数1~10のパーフルオロ炭化水素基または該パーフルオロ炭化水素基の末端もしくは炭素-炭素結合間にエーテル性酸素原子を有する基を示す。 - 前記R51、R52およびR53の全てがフッ素原子であるかまたはそれら全てが水素原子であり、前記R54がエーテル性酸素原子を有しかつエーテル性酸素原子の数が1~3個である、請求項6に記載の含フッ素共重合体。
- ヨウ素原子を実質的に含まない、請求項1~7のいずれか1項に記載の含フッ素共重合体。
- 請求項1~8のいずれか1項に記載の含フッ素共重合体を製造する方法であって、テトラフルオロエチレンと、パーフルオロ(アルキルビニルエーテル)と、フッ素原子と2個以上の重合性不飽和結合とを有する単量体と、ニトリル基とフッ素原子とを有する単量体を、ラジカル重合開始剤の存在下で共重合する、含フッ素共重合体の製造方法。
- ヨウ素原子を含む連鎖移動剤の非存在下で共重合する、請求項9に記載の含フッ素共重合体の製造方法。
- 請求項1~8のいずれか1項に記載の含フッ素共重合体と、架橋剤と、を含む、含フッ素共重合体組成物。
- 前記架橋剤が2個以上のアミノ基を有する化合物である、請求項11に記載の含フッ素共重合体組成物。
- 前記架橋剤の含有量が、前記含フッ素共重合体の100質量部に対して、1.0質量部未満である、請求項11または12に記載の含フッ素共重合体組成物。
- 請求項11~13のいずれか1項に記載の含フッ素共重合体組成物中の含フッ素共重合体を架橋してなる、架橋ゴム物品。
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Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06263952A (ja) | 1993-01-14 | 1994-09-20 | Nippon Mektron Ltd | 含フッ素エラストマ−組成物 |
JPH11510495A (ja) * | 1995-07-26 | 1999-09-14 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | フッ素化アルケニルトリアジン類及び架橋剤としてのそれらの使用 |
JP2008031195A (ja) * | 2006-07-26 | 2008-02-14 | Yunimatekku Kk | 接着剤塗布金属積層用含フッ素エラストマー |
JP2009529070A (ja) * | 2006-03-03 | 2009-08-13 | スリーエム イノベイティブ プロパティズ カンパニー | フルオロポリマー硬化組成物 |
WO2010082633A1 (ja) | 2009-01-16 | 2010-07-22 | 旭硝子株式会社 | 含フッ素弾性共重合体およびその製造方法、架橋ゴム物品 |
JP5833657B2 (ja) | 2010-09-24 | 2015-12-16 | グリーン, ツイード オブ デラウェア, インコーポレイテッド | 高温への適用に適したフッ素含有エラストマー組成物 |
JP2019500469A (ja) * | 2015-12-30 | 2019-01-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | ペルフルオロトリビニルトリアジン化合物のコポリマー及び該コポリマーの合成方法 |
WO2020114972A1 (en) * | 2018-12-06 | 2020-06-11 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomer composition for high thermal rating |
JP2021066993A (ja) | 2019-10-21 | 2021-04-30 | ザウラー スピニング ソリューションズ ゲー・エム・ベー・ハー ウント コー. カー・ゲーSaurer Spinning Solutions GmbH & Co. KG | 紡績機のドラフト装置用の集束装置、ならびに集束装置用のドラフト装置 |
WO2021085423A1 (ja) * | 2019-10-30 | 2021-05-06 | Agc株式会社 | 含フッ素共重合体、含フッ素共重合体組成物および架橋ゴム物品 |
-
2022
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- 2022-04-06 EP EP22788105.9A patent/EP4324861A1/en active Pending
- 2022-04-06 WO PCT/JP2022/017143 patent/WO2022220180A1/ja active Application Filing
- 2022-04-06 CN CN202280027889.5A patent/CN117222680A/zh active Pending
- 2022-04-07 TW TW111113281A patent/TW202248222A/zh unknown
-
2023
- 2023-10-04 US US18/480,619 patent/US20240026048A1/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH06263952A (ja) | 1993-01-14 | 1994-09-20 | Nippon Mektron Ltd | 含フッ素エラストマ−組成物 |
JPH11510495A (ja) * | 1995-07-26 | 1999-09-14 | イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー | フッ素化アルケニルトリアジン類及び架橋剤としてのそれらの使用 |
JP2009529070A (ja) * | 2006-03-03 | 2009-08-13 | スリーエム イノベイティブ プロパティズ カンパニー | フルオロポリマー硬化組成物 |
JP2008031195A (ja) * | 2006-07-26 | 2008-02-14 | Yunimatekku Kk | 接着剤塗布金属積層用含フッ素エラストマー |
WO2010082633A1 (ja) | 2009-01-16 | 2010-07-22 | 旭硝子株式会社 | 含フッ素弾性共重合体およびその製造方法、架橋ゴム物品 |
JP5833657B2 (ja) | 2010-09-24 | 2015-12-16 | グリーン, ツイード オブ デラウェア, インコーポレイテッド | 高温への適用に適したフッ素含有エラストマー組成物 |
JP2019500469A (ja) * | 2015-12-30 | 2019-01-10 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | ペルフルオロトリビニルトリアジン化合物のコポリマー及び該コポリマーの合成方法 |
WO2020114972A1 (en) * | 2018-12-06 | 2020-06-11 | Solvay Specialty Polymers Italy S.P.A. | Fluoroelastomer composition for high thermal rating |
JP2021066993A (ja) | 2019-10-21 | 2021-04-30 | ザウラー スピニング ソリューションズ ゲー・エム・ベー・ハー ウント コー. カー・ゲーSaurer Spinning Solutions GmbH & Co. KG | 紡績機のドラフト装置用の集束装置、ならびに集束装置用のドラフト装置 |
WO2021085423A1 (ja) * | 2019-10-30 | 2021-05-06 | Agc株式会社 | 含フッ素共重合体、含フッ素共重合体組成物および架橋ゴム物品 |
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