WO2022211072A1 - フッ素樹脂組成物、及び、成形体 - Google Patents
フッ素樹脂組成物、及び、成形体 Download PDFInfo
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- WO2022211072A1 WO2022211072A1 PCT/JP2022/016765 JP2022016765W WO2022211072A1 WO 2022211072 A1 WO2022211072 A1 WO 2022211072A1 JP 2022016765 W JP2022016765 W JP 2022016765W WO 2022211072 A1 WO2022211072 A1 WO 2022211072A1
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- WO
- WIPO (PCT)
- Prior art keywords
- fluororesin
- mass
- fluororesin composition
- composition according
- melting point
- Prior art date
Links
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 51
- 239000011737 fluorine Substances 0.000 title claims abstract description 43
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000011342 resin composition Substances 0.000 title abstract 4
- 238000002844 melting Methods 0.000 claims abstract description 81
- 230000008018 melting Effects 0.000 claims abstract description 81
- 238000010557 suspension polymerization reaction Methods 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims description 126
- 239000000843 powder Substances 0.000 claims description 81
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 72
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 72
- 239000000178 monomer Substances 0.000 claims description 56
- 239000002245 particle Substances 0.000 claims description 50
- 239000011163 secondary particle Substances 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 24
- 238000000748 compression moulding Methods 0.000 claims description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims description 13
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000945 filler Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 230000001747 exhibiting effect Effects 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract 3
- 229920005989 resin Polymers 0.000 abstract 3
- 125000004432 carbon atom Chemical group C* 0.000 description 28
- 239000004094 surface-active agent Substances 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 239000002253 acid Substances 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 16
- 125000000129 anionic group Chemical group 0.000 description 15
- 238000009826 distribution Methods 0.000 description 15
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 15
- 238000005469 granulation Methods 0.000 description 14
- 230000003179 granulation Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 125000000962 organic group Chemical group 0.000 description 9
- 238000010298 pulverizing process Methods 0.000 description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical class OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 description 6
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- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
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- RRZIJNVZMJUGTK-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenoxy)ethene Chemical compound FC(F)=C(F)OC(F)=C(F)F RRZIJNVZMJUGTK-UHFFFAOYSA-N 0.000 description 4
- 238000011088 calibration curve Methods 0.000 description 4
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- 125000002947 alkylene group Chemical group 0.000 description 3
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- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000011549 displacement method Methods 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
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- 238000005192 partition Methods 0.000 description 3
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical class C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 2
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- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
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- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 2
- 150000004693 imidazolium salts Chemical class 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- FBUKVWPVBMHYJY-UHFFFAOYSA-N nonanoic acid Chemical compound CCCCCCCCC(O)=O FBUKVWPVBMHYJY-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 description 1
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 1
- GYSCBCSGKXNZRH-UHFFFAOYSA-N 1-benzothiophene-2-carboxamide Chemical compound C1=CC=C2SC(C(=O)N)=CC2=C1 GYSCBCSGKXNZRH-UHFFFAOYSA-N 0.000 description 1
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 1
- FYQFWFHDPNXORA-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C FYQFWFHDPNXORA-UHFFFAOYSA-N 0.000 description 1
- AWQSAIIDOMEEOD-UHFFFAOYSA-N 5,5-Dimethyl-4-(3-oxobutyl)dihydro-2(3H)-furanone Chemical compound CC(=O)CCC1CC(=O)OC1(C)C AWQSAIIDOMEEOD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- GHVNFZFCNZKVNT-UHFFFAOYSA-N Decanoic acid Natural products CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
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- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
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- 125000005005 perfluorohexyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- 125000005008 perfluoropentyl group Chemical group FC(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)* 0.000 description 1
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 238000004080 punching Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000000243 solution Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- 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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/005—Processes for mixing polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- 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
- C08F114/00—Homopolymers 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
- C08F114/18—Monomers containing fluorine
- C08F114/26—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
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Definitions
- the present disclosure relates to a fluororesin composition and a molded article.
- PTFE Polytetrafluoroethylene
- Patent Literatures 1 and 2 describe techniques for recycling PTFE pulverized after sintering and heated PTFE.
- An object of the present disclosure is to provide a fluororesin composition that is excellent in handleability even though it contains a fluororesin that has been heated to a temperature above the melting point, and a molded article obtained from the fluororesin composition.
- the present disclosure includes a fluororesin A that has a history of being heated to a temperature above the melting point and does not exhibit melt fluidity, and a fluororesin that is polymerized by suspension polymerization and has no history of being heated to a temperature above the melting point and does not exhibit melt fluidity.
- B and having an apparent density of 0.42 g/ml or more.
- the fluororesin composition contains tetrafluoroethylene units and modified monomer units based on modified monomers copolymerizable with tetrafluoroethylene, and the amount of the modified monomer units is 1.0% by mass with respect to all polymerized units. The following are preferable.
- the fluororesin composition preferably has one or more melting points in the temperature range below 333°C and one or more melting points in the temperature range of 333 to 360°C.
- the fluororesin A is preferably polytetrafluoroethylene.
- the maximum linear length of the fluororesin A particles is preferably smaller than the maximum linear length of the fluororesin B particles.
- the fluororesin composition preferably has an angle of repose of less than 40°.
- the fluororesin composition preferably has an average secondary particle size of 5 to 700 ⁇ m.
- the content of the low-molecular-weight fluorine-containing compound is preferably 1 ppm by mass or less relative to the fluororesin composition.
- the fluororesin composition is preferably powder.
- the fluororesin composition preferably has a tensile strength at break of 10 MPa or more.
- the fluororesin composition preferably has a tensile strain at break of 150% or more.
- the fluororesin composition preferably further contains a filler.
- the present disclosure also provides a molded article obtained by compression molding and baking the fluororesin composition.
- the present disclosure includes a fluororesin A that has a history of being heated to a temperature above the melting point and does not exhibit melt fluidity, and a fluororesin that is polymerized by suspension polymerization and has no history of being heated to a temperature above the melting point and does not exhibit melt fluidity.
- B and comprising tetrafluoroethylene units and modified monomer units based on modified monomers copolymerizable with tetrafluoroethylene.
- the fluororesin composition preferably has an apparent density of 0.42 g/ml or more.
- a fluororesin composition that is excellent in handleability despite containing a fluororesin that has been heated to a temperature equal to or higher than its melting point, and a molded article obtained from the fluororesin composition. can be done.
- the present disclosure includes a fluororesin A that has a history of being heated to a temperature above the melting point and does not exhibit melt fluidity, and a fluororesin that is polymerized by suspension polymerization and has no history of being heated to a temperature above the melting point and does not exhibit melt fluidity. and B and having an apparent density of 0.42 g/ml or more (hereinafter also referred to as a first fluororesin composition).
- the first fluororesin composition contains fluororesin B polymerized by suspension polymerization without a history of heating to a temperature above the melting point, and has an apparent density within a specific range. In spite of containing fluororesin A that has been heated, it is excellent in handleability (for example, handleability during transportation and compression molding). In addition, the first fluororesin composition has good tensile properties (eg, tensile strength at break, tensile strain at break).
- the first fluororesin composition preferably has one or more melting points in the temperature range below 333°C and one or more melting points in the temperature range of 333 to 360°C.
- the temperature range of less than 333°C is more preferably less than 332°C, further preferably less than 331°C, preferably 100°C or higher, more preferably 140°C or higher, and 160°C. It is more preferable that it is above.
- the temperature range of 333 to 360° C. is more preferably 334° C. or higher, still more preferably 335° C., more preferably 355° C. or lower, and even more preferably 350° C. or lower. .
- the fluororesin composition is a fluororesin A that has a history of being heated to a temperature above the melting point and does not exhibit melt fluidity, and a melting point that has no history of being heated to a temperature above the melting point.
- Fluororesin B that does not show fluidity is included.
- the fluororesin A has a history of being heated to a temperature equal to or higher than its melting point.
- Examples of the heating include heating for molding, heat treatment, and the like.
- the fluororesin A preferably has a melting point of 100°C or higher and lower than 333°C, more preferably lower than 332°C, and even more preferably lower than 331°C.
- the lower limit is not limited, it is more preferably 140°C, and even more preferably 180°C or higher.
- the fluororesin A preferably has one or more melting points in the temperature range below 333°C.
- the temperature range of less than 333° C. is more preferably less than 332° C., further preferably less than 331° C., preferably 100° C. or higher, more preferably 140° C. or higher, It is more preferably 180°C or higher.
- the fact that the melting point is within the above range indicates that there is a history of heating to a temperature equal to or higher than the melting point.
- the fluororesin A may also have a melting point in the temperature range of 333° C. or higher.
- the melting point of the fluororesin is the heat of fusion obtained by performing differential scanning calorimetry [DSC] at a heating rate of 10° C./min using X-DSC7000 (manufactured by Hitachi High-Tech Science Co., Ltd.). is the temperature corresponding to the minimum point on the curve. If there are two or more local minimum points in one melting peak, each point is taken as the melting point.
- the fluororesin A does not exhibit melt fluidity.
- the term "not exhibiting melt fluidity” means that the melt flow rate (MFR) is less than 0.25 g/10 minutes, preferably less than 0.10 g/10 minutes, and more preferably 0.05 g/10 minutes or less. It means that there is In this specification, MFR is defined by the type of fluororesin using a melt indexer according to ASTM D1238, the measurement temperature (for example, 372 ° C. for PFA and FEP, 297 ° C.
- load eg, 5 kg for PFA, FEP and ETFE
- load eg, 5 kg for PFA, FEP and ETFE
- PTFE it is a value obtained by measuring under the same measurement conditions as PFA.
- the reduction rate of the thickness after heating relative to the thickness before heating is 20%. If it is less than or the thickness after heating is greater than the thickness before heating, it also means that the fluororesin does not exhibit melt fluidity.
- polytetrafluoroethylene [PTFE] is preferable.
- the PTFE may be high molecular weight PTFE.
- the PTFE as the fluororesin A may be a homopolymer of TFE, or may be a polymer unit based on 99.0% by mass or more of TFE and a polymer unit based on 1.0% by mass or less of a modified monomer (hereinafter referred to as (also referred to as "modified monomer units").
- the modified PTFE may be composed only of polymerized units based on TFE and modified monomer units.
- the content of modified monomer units in the modified PTFE is preferably in the range of 0.00001 to 1.0% by mass based on the total polymerized units.
- the lower limit of the modified monomer unit content is more preferably 0.0001% by mass, still more preferably 0.001% by mass, even more preferably 0.005% by mass, and particularly preferably 0.010% by mass.
- the upper limit of the modified monomer unit content is preferably 0.90% by mass, more preferably 0.50% by mass, still more preferably 0.40% by mass, even more preferably 0.30% by mass, and 0.20% by mass. % by weight is particularly preferred, and 0.10% by weight is particularly preferred.
- the modified monomer unit means a part of the molecular structure of PTFE that is derived from the modified monomer.
- each polymerized unit described above can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer.
- the modified monomer is not particularly limited as long as it can be copolymerized with TFE.
- examples include perfluoroolefin such as hexafluoropropylene [HFP]; hydrogen such as trifluoroethylene and vinylidene fluoride [VDF]. Containing fluoroolefin; perhaloolefin such as chlorotrifluoroethylene; perfluorovinyl ether: perfluoroallyl ether; (perfluoroalkyl)ethylene, ethylene and the like.
- one type of modifying monomer may be used, or a plurality of types thereof may be used.
- Rf represents a perfluoro organic group
- perfluoro organic group means an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms.
- the perfluoro organic group may have an ether oxygen.
- perfluorovinyl ether examples include perfluoro(alkyl vinyl ether) [PAVE] in which Rf is a perfluoroalkyl group having 1 to 10 carbon atoms in the general formula (A).
- the perfluoroalkyl group preferably has 1 to 5 carbon atoms.
- Examples of the perfluoroalkyl group in PAVE include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group and the like.
- Rf is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and Rf is the following formula:
- Rf is the following formula:
- n an integer of 1 to 4.
- PFAE Perfluoroalkylethylene
- examples thereof include (perfluorobutyl)ethylene (PFBE) and (perfluorohexyl)ethylene.
- Rf 1 is preferably a perfluoroalkyl group having 1 to 10 carbon atoms or a perfluoroalkoxyalkyl group having 1 to 10 carbon atoms.
- the above PTFE as the fluororesin A preferably has a standard specific gravity (SSG) of 2.280 or less, more preferably 2.10 or less. Moreover, it is preferably 1.50 or more, and more preferably 1.60 or more.
- SSG is measured by a water displacement method in accordance with ASTM D-792 using a sample molded in accordance with ASTM D 4895-89.
- the above PTFE as the fluororesin A usually has non-melt secondary processability.
- the above non-melt secondary processability means the property that the melt flow rate cannot be measured at a temperature higher than the melting point in accordance with ASTM D-1238 and D-2116, in other words, the property that does not flow easily even in the melting temperature range. do.
- One of the melting points of PTFE (high molecular weight PTFE) as the fluororesin A is preferably 310°C or higher, more preferably 320°C or higher, and preferably lower than 333°C. It may also have a melting point in the temperature range of 333° C. or higher.
- the first fluororesin composition may contain fluororesin A particles.
- the particles of the fluororesin A may be secondary particles of the fluororesin A.
- Particles of the fluororesin A preferably have an average secondary particle size of 1 to 200 ⁇ m from the viewpoint of further improving the handleability of the fluororesin composition.
- the average secondary particle size is more preferably 5 ⁇ m or more, further preferably 10 ⁇ m or more, more preferably 150 ⁇ m or less, further preferably 100 ⁇ m or less, and 70 ⁇ m or less. is even more preferable, particularly preferably 50 ⁇ m or less, and most preferably 30 ⁇ m or less.
- the average secondary particle diameter is measured using a Beckman Coulter laser diffraction particle size distribution analyzer (LS13 320) in a dry manner at a vacuum pressure of 20 mH 2 O, and 50% of the integrated particle size distribution (volume basis). be equal to the particle size corresponding to
- the particles of the fluororesin A preferably have a D90 of 10 ⁇ m or more, more preferably 30 ⁇ m or more, and even more preferably 50 ⁇ m or more, in order to further improve the handleability of the fluororesin composition. Also, it is preferably 600 ⁇ m or less, more preferably 500 ⁇ m or less, and even more preferably 400 ⁇ m or less.
- the above D90 is measured using a Beckman Coulter laser diffraction particle size distribution analyzer (LS13 320) in a dry manner at a vacuum pressure of 20 mH 2 O, and the particles corresponding to 90% of the integrated particle size distribution (volume basis). equal to the diameter.
- the particles of the fluororesin A are obtained, for example, by compression-molding a fluororesin that has not been heated to a temperature above its melting point and does not exhibit melt fluidity, and pulverizing the shavings of the molded product obtained by firing. be able to.
- the pulverization can be performed with a pulverizer or the like. After coarsely pulverizing, it may be pulverized.
- the shape of compression molding is not particularly limited.
- the firing temperature should be higher than the melting point of the fluororesin.
- the pulverizer is not particularly limited as long as it can pulverize (preferably refine) the cutting waste. Examples include air jet mills, hammer mills, force mills, stone mills, freeze grinders, and the like.
- the particles of the fluororesin A are obtained by heating the fluororesin powder, which has no history of heating to a temperature above the melting point and does not exhibit melt fluidity, to a temperature above the melting point without compression molding, and then pulverizing the powder using a pulverizer.
- the crusher is the same as above.
- the fluororesin B has no history of being heated to a temperature above its melting point.
- the fluororesin B preferably has a melting point of 100 to 360°C.
- the melting point is more preferably 140° C. or higher, still more preferably 160° C. or higher, and more preferably 355° C. or lower, even more preferably 350° C. or lower.
- the fluororesin B preferably has one or more melting points in the temperature range of 333-360°C.
- the temperature range is more preferably 334° C. or higher, still more preferably 335° C. or higher, and more preferably 355° C. or lower, further preferably 350° C. or lower.
- the fact that the melting point is within the above range indicates that there is no history of heating to a temperature above the melting point.
- it may also have a melting point in a temperature range below 333°C.
- the fluororesin B does not exhibit melt fluidity.
- the melt fluidity is as described above.
- PTFE is preferable.
- the PTFE may be high molecular weight PTFE.
- the above-mentioned PTFE (high molecular weight PTFE) as the fluororesin B has a heat of fusion curve when the temperature is raised at a rate of 10°C/min using a differential scanning calorimeter [DSC]. It is preferable that one or more endothermic peaks appear and the heat of fusion at 290 to 350° C. calculated from the heat of fusion curve is 62 mJ/mg or more.
- the above PTFE as the fluororesin B preferably has a standard specific gravity (SSG) of 2.130 to 2.280.
- the standard specific gravity is measured by a water displacement method according to ASTM D792 using a sample molded according to ASTM D489589.
- "High molecular weight" for PTFE that has never been heated above its melting point means that the standard specific gravity is within the above range.
- Non-melt secondary processability is as described above.
- the PTFE as the fluororesin B may be a homopolymer of TFE, or may contain 99.0% by mass or more of polymerized units based on TFE and 1.0% by mass or less of polymerized units based on a modified monomer (modified It may be a modified PTFE containing a monomer unit).
- modified PTFE may be composed only of polymerized units based on TFE and modified monomer units. Modified PTFE is preferable in terms of obtaining a fluororesin composition having a higher apparent density and more excellent handleability and a fluororesin composition having more excellent tensile properties.
- the content of modified monomer units in the modified PTFE is preferably in the range of 0.00001 to 1.0% by mass based on the total polymerized units.
- the lower limit of the modified monomer unit content is more preferably 0.0001% by mass, still more preferably 0.001% by mass, even more preferably 0.005% by mass, and particularly preferably 0.010% by mass.
- the upper limit of the modified monomer unit content is preferably 0.90% by mass, more preferably 0.50% by mass, still more preferably 0.40% by mass, even more preferably 0.30% by mass, and 0.20% by mass. % by weight is particularly preferred, and 0.10% by weight is particularly preferred.
- Modification monomers that can be used in the above PTFE as the fluororesin B are the same as those exemplified for PTFE (high molecular weight PTFE) as the fluororesin A.
- the fluororesin B is polymerized by suspension polymerization.
- a fluororesin polymerized by suspension polymerization that does not exhibit melt flowability is less likely to be fibrillated, so that the apparent density of the fluororesin composition can be increased, and the handleability can be improved.
- the fluororesin B polymerized by suspension polymerization and exhibiting no melt fluidity preferably satisfies all of the following.
- the proportion of particles having a particle diameter of 1 ⁇ m or less as determined by image processing with a scanning electron microscope (SEM) is 30% or less.
- the amount of the anionic fluorine-containing surfactant measured by a liquid chromatograph mass spectrometer (LC/MS/MS) using an extract obtained by Soxhlet extraction with methanol is 1 mass ppm or less.
- the above suspension polymerization can be carried out by a known method. For example, by using no or a limited amount of an anionic fluorine-containing surfactant, dispersing a polymerization initiator in an aqueous medium, and polymerizing the monomers necessary for composing the fluororesin B, fluorine A granular powder of Resin B can be isolated directly.
- a powder directly obtained by the above suspension polymerization may be used, or a powder obtained by pulverizing and/or granulating the above powder may be used.
- the pulverization may be performed by a known method, and can be performed by a method of pulverizing using a pulverizer such as a hammer mill, pin mill, jet mill, or cutter mill.
- the granulation may also be performed by a known method, such as underwater granulation, hot water granulation, emulsification dispersion granulation, emulsified hot water granulation, solvent-free granulation, and dry solvent granulation. be able to.
- the first fluororesin composition may contain fluororesin B particles.
- the particles of the fluororesin B may be secondary particles of the fluororesin B.
- the particles of the fluororesin B preferably have an average secondary particle size of 1 to 700 ⁇ m.
- the average secondary particle size is more preferably 5 ⁇ m or more, still more preferably 10 ⁇ m or more, and even more preferably 20 ⁇ m or more. Moreover, it is more preferably 500 ⁇ m or less, still more preferably 150 ⁇ m or less, and even more preferably 100 ⁇ m or less.
- the average secondary particle diameter is measured using a Beckman Coulter laser diffraction particle size distribution analyzer (LS13 320) in a dry manner at a vacuum pressure of 20 mH 2 O, and 50% of the integrated particle size distribution (volume basis). be equal to the particle size corresponding to
- the particles of the fluororesin B preferably have a D90 of 10 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 50 ⁇ m or more, and preferably 600 ⁇ m or less, and 500 ⁇ m or less. is more preferable, and 400 ⁇ m or less is even more preferable.
- the above D90 is measured using a Beckman Coulter laser diffraction particle size distribution analyzer (LS13 320) in a dry manner at a vacuum pressure of 20 mH 2 O, and the particles corresponding to 90% of the integrated particle size distribution (volume basis). equal to the diameter.
- the first fluororesin composition has an apparent density of 0.42 g/ml or more. When the apparent density is within the above range, the first fluororesin composition is excellent in handleability.
- the apparent density is preferably 0.45 g/ml or more, more preferably 0.47 g/ml or more, from the viewpoint of better handleability.
- the upper limit is not particularly limited, it may be 1.00 g/ml.
- the apparent density is measured according to JIS K 6891.
- the content of the fluororesin A in the first fluororesin composition is preferably 10 to 90% by mass relative to the above fluororesin composition, in order to further improve the tensile properties.
- the content is more preferably 20% by mass or more, still more preferably 30% by mass or more, even more preferably 40% by mass or more, and particularly preferably 50% by mass or more, Further, it is more preferably 85% by mass or less, still more preferably 80% by mass or less, even more preferably less than 80% by mass, even more preferably 75% by mass or less, and 70% by mass. % or less is particularly preferable.
- the content of the fluororesin B in the first fluororesin composition is preferably 10 to 90% by mass relative to the above fluororesin composition in order to further improve the tensile properties.
- the content is more preferably 15% by mass or more, still more preferably 20% by mass or more, even more preferably more than 20% by mass, and even more preferably 25% by mass or more.
- It is particularly preferably 30% by mass or more, more preferably 80% by mass or less, still more preferably 70% by mass or less, even more preferably 60% by mass or less, and 50% by mass % or less is particularly preferred.
- the total amount of the fluororesins A and B in the first fluororesin composition is preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass, relative to the fluororesin composition. It is more preferably 95% by mass or more, even more preferably 95% by mass or more, and particularly preferably 98% by mass or more.
- the first fluororesin composition contains TFE units and modified monomer units based on modified monomers copolymerizable with TFE, and the amount of the modified monomer units is 1.0% by mass or less with respect to the total polymerization units. Preferably. Moreover, it is preferable that the amount of TFE units is 99.0% by mass or more.
- the lower limit of the content of the modified monomer unit in the first fluororesin composition may be 0% by mass, more preferably 0.0001% by mass, still more preferably 0.001% by mass, and 0.005% by mass. % is even more preferred, and 0.010% by weight is even more preferred.
- the upper limit of the modified monomer unit content is preferably 0.90% by mass, more preferably 0.50% by mass, still more preferably 0.40% by mass, even more preferably 0.30% by mass, and 0.20% by mass. % by weight is particularly preferred, and 0.10% by weight is particularly preferred.
- the content of modified monomer units can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer. Moreover, when the raw material composition is known, it can be obtained by calculation from the raw material composition.
- the fluororesin B is a TFE homopolymer
- the content of the fluororesin A is 50% by mass or more and 80% by mass of the fluororesin composition. It should be less than % by mass.
- the content of the fluororesin A is more preferably 75% by mass or less, still more preferably 70% by mass or less, relative to the fluororesin composition.
- the content of the fluororesin A is 50% by mass or more relative to the fluororesin composition
- the tensile strength of the fluororesin composition is The breaking strength is 20 MPa or more.
- the tensile strength at break was measured by putting 35 g of the fluororesin composition into a mold of ⁇ 100 mm, compressing it under the conditions of a pressure of 30 MPa and 1 minute, raising the temperature from room temperature to 300 ° C. in 3 hours, and then 300 ° C. The temperature is raised from 370°C to 370°C in 4 hours, held at 370°C for 12 hours, then lowered to 300°C in 5 hours, and then lowered to room temperature in 1 hour. and measured according to ASTM D1708.
- the fluororesin B is a homopolymer of TFE.
- the present disclosure includes a fluororesin A that has a history of being heated to a temperature above the melting point and does not exhibit melt fluidity, and a fluororesin that is polymerized by suspension polymerization and has no history of being heated to a temperature above the melting point and does not exhibit melt fluidity.
- a fluororesin composition (hereinafter also referred to as a second fluororesin composition) containing TFE units and modified monomer units based on modified monomers copolymerizable with TFE is also provided. Since the second fluororesin composition has a specific monomer composition, even though it contains fluororesin A that has been heated to a temperature above the melting point, it is easy to handle (for example, during transportation and compression molding). (handleability). Also, the second fluororesin composition has good tensile properties (eg, tensile strength at break, tensile strain at break).
- the second fluororesin composition preferably has one or more melting points in the temperature range below 333°C and one or more melting points in the temperature range of 333 to 360°C.
- the temperature range of less than 333°C is more preferably less than 332°C, further preferably less than 331°C, preferably 100°C or higher, more preferably 140°C or higher, and 160°C. It is more preferable that it is above.
- the temperature range of 333 to 360° C. is more preferably 334° C. or higher, still more preferably 335° C., more preferably 355° C. or lower, and even more preferably 350° C. or lower. .
- the fluororesin composition is a fluororesin A that has a history of being heated to a temperature above the melting point and does not exhibit melt fluidity, and a melting point that has no history of being heated to a temperature above the melting point.
- Fluororesin B that does not show fluidity is included.
- the same fluororesin A as in the first fluororesin composition can be used.
- the same fluororesin B as in the first fluororesin composition can be used, and 99.0% by mass or more of polymerized units based on TFE (TFE units) and polymerized units (with modified monomer units) based on modified monomers in an amount of 1.0% by mass or less are preferred.
- the fluororesin B may consist of only TFE units and modified monomer units.
- the modified monomer include the monomers described above for the modified PTFE as the fluororesin B in the first fluororesin composition.
- the preferred range of content of modified monomer units is also the same as the range described for the first fluororesin composition.
- the configuration of the fluororesin B in the second fluororesin composition other than the composition is the same as that of the fluororesin B in the first fluororesin composition.
- the second fluororesin composition contains TFE units and modified monomer units based on modified monomers copolymerizable with TFE.
- the second fluororesin composition may contain only TFE units and modified monomer units as polymerized units.
- the content of the modified monomer units is preferably 1.0% by mass or less with respect to the total polymerized units constituting the fluororesin composition.
- the lower limit of the modified monomer unit content is preferably 0.00001% by mass, more preferably 0.0001% by mass, still more preferably 0.001% by mass, still more preferably 0.005% by mass, and 0.010% by mass. % by weight is particularly preferred.
- the upper limit of the modified monomer unit content is preferably 0.90% by mass, more preferably 0.50% by mass, still more preferably 0.40% by mass, even more preferably 0.30% by mass, and 0.20% by mass. % by weight is particularly preferred, and 0.10% by weight is particularly preferred.
- the second fluororesin composition preferably contains 99.0% by mass or more of TFE units with respect to all polymerized units.
- the content of polymerized units constituting the second fluororesin composition can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and fluorescent X-ray analysis depending on the type of monomer. Moreover, when the raw material composition is known, it can be obtained by calculation from the raw material composition.
- the contents of the fluororesins A and B and the total amount of the fluororesins A and B in the second fluororesin composition are the same as those described for the first fluororesin composition.
- the second fluororesin composition preferably has an apparent density of 0.42 g/ml or more, more preferably 0.45 g/ml or more, more preferably 0.47 g/ml, in terms of better handleability. ml or more is more preferable. Although the upper limit is not particularly limited, it may be 1.00 g/ml.
- the apparent density is measured according to JIS K 6891.
- first and second fluororesin compositions are not particularly limited, powders are preferred.
- the maximum linear length of the fluororesin A particles is preferably smaller than the maximum linear length of the fluororesin B particles.
- the maximum linear length of the particles of the fluororesins A and B satisfies the above relationship, the apparent density of the fluororesin composition can be increased, and the handleability is further improved.
- the manufacturing cost of the fluororesin composition can be reduced.
- the first and second fluororesin compositions preferably satisfy all of the following.
- the proportion of particles having a particle diameter of 1 ⁇ m or less as determined by image processing with a scanning electron microscope (SEM) is 30% or less.
- the amount of the anionic fluorine-containing surfactant measured by a liquid chromatograph mass spectrometer (LC/MS/MS) using an extract obtained by Soxhlet extraction with methanol is 1 mass ppm or less.
- the first and second fluororesin compositions preferably have an angle of repose of less than 40°, more preferably less than 38°, and less than 35° in terms of excellent fluidity and even better handleability. is more preferable.
- the angle of repose is a funnel with a total height of 115 mm, a leg diameter of ⁇ 26 mm, a leg length of 35 mm, and an intake opening of 60°. It is a value obtained by dropping a 40 g sample from a funnel and measuring the angle of the lower half of the pile of the dropped sample with a protractor.
- the first and second fluororesin compositions preferably have an average secondary particle size of 5 to 700 ⁇ m.
- the average secondary particle size is more preferably 10 ⁇ m or more, further preferably 20 ⁇ m or more, more preferably 600 ⁇ m or less, more preferably 500 ⁇ m or less, and still more preferably 400 ⁇ m or less.
- the average secondary particle diameter is measured using a Beckman Coulter laser diffraction particle size distribution analyzer (LS13 320) in a dry manner at a vacuum pressure of 20 mH 2 O, and 50% of the integrated particle size distribution (volume basis). be equal to the particle size corresponding to
- D90 of the first and second fluororesin compositions is preferably 10 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 50 ⁇ m or more, and preferably 600 ⁇ m or less, It is more preferably 500 ⁇ m or less, even more preferably 400 ⁇ m or less.
- the above D90 is measured using a Beckman Coulter laser diffraction particle size distribution analyzer (LS13 320) in a dry manner at a vacuum pressure of 20 mH 2 O, and the particles corresponding to 90% of the integrated particle size distribution (volume basis). equal to the diameter.
- the content (total amount) of the low-molecular-weight fluorine-containing compound in the first and second fluororesin compositions is preferably 1 ppm by mass or less relative to the fluororesin composition, in order to further improve the tensile properties. , more preferably 500 mass ppb or less, more preferably 100 mass ppb or less, even more preferably 50 mass ppb or less, even more preferably 25 mass ppb or less, and 10 mass ppb It is particularly preferably 5 mass ppb or less, particularly preferably 5 mass ppb or less, even more preferably 1 mass ppb or less, and most preferably less than 1 mass ppb.
- the content of the low-molecular-weight fluorine-containing compound is measured by a liquid chromatograph mass spectrometer (LC/MS/MS) after Soxhlet extraction of the sample with methanol.
- low-molecular-weight fluorine-containing compounds include fluorine-containing carboxylic acids having 4 or more carbon atoms and salts thereof, fluorine-containing sulfonic acids having 4 or more carbon atoms and salts thereof, and the like, all of which contain an ether bond (-O-) may have
- Examples of the low-molecular-weight fluorine-containing compound include anionic fluorine-containing surfactants.
- the anionic fluorine-containing surfactant may be, for example, a surfactant containing a fluorine atom having a total carbon number of 20 or less in the portion excluding the anionic group.
- the anionic fluorine-containing surfactant may also be a fluorine-containing surfactant whose anionic portion has a molecular weight of 800 or less.
- the "anionic portion” means the portion of the fluorine-containing surfactant excluding the cation. For example, in the case of F(CF 2 ) n1 COOM represented by formula (I), which will be described later, it is the “F(CF 2 ) n1 COO” portion.
- the low-molecular-weight fluorine-containing compound also includes a fluorine-containing surfactant having a LogPOW of 3.5 or less.
- the above LogPOW is the partition coefficient between 1-octanol and water, and LogP [wherein P is the octanol/water (1:1) mixture containing the fluorine-containing surfactant during phase separation. represents the concentration ratio of the fluorine-containing surfactant/the concentration of the fluorine-containing surfactant in water].
- fluorine-containing surfactant examples include US Patent Application Publication No. 2007/0015864, US Patent Application Publication No. 2007/0015865, US Patent Application Publication No. 2007/0015866, and US Patent US2007/0276103, US2007/0117914, US2007/142541, US2008/0015319, US3250808 Specification, US Patent No. 3271341, JP 2003-119204, WO 2005/042593, WO 2008/060461, WO 2007/046377, JP 2007-119526 Publications, WO 2007/046482, WO 2007/046345, US Patent Application Publication No. 2014/0228531, WO 2013/189824, WO 2013/189826 etc.
- anionic fluorine-containing surfactant As the anionic fluorine-containing surfactant, the following general formula (N 0 ): X n0 ⁇ Rf n0 ⁇ Y 0 (N 0 ) (In the formula, X n0 is H, Cl or and F. Rf n0 has 3 to 20 carbon atoms, is chain-shaped, branched-chain or cyclic, and some or all of H is substituted by F. The alkylene group may contain one or more ether bonds, and some H may be substituted with Cl. Y 0 is an anionic group.) Compound represented by is mentioned.
- the anionic group of Y 0 may be -COOM, -SO 2 M, or -SO 3 M, and may be -COOM or -SO 3 M.
- M is H, a metal atom, NR 74 , optionally substituted imidazolium, optionally substituted pyridinium or optionally substituted phosphonium ; is H or an organic group.
- the metal atom include alkali metals (group 1) and alkaline earth metals (group 2), such as Na, K, and Li.
- R 7 may be H or a C 1-10 organic group, may be H or a C 1-4 organic group, may be H or a C 1-4 alkyl group.
- M may be H, a metal atom or NR 7 4 , may be H, an alkali metal (group 1), an alkaline earth metal (group 2) or NR 7 4 , H, Na, K, Li or NH4 .
- Rf n0 50% or more of H may be substituted with fluorine.
- N 1 As the compound represented by the general formula (N 0 ), the following general formula (N 1 ): X n0 ⁇ (CF 2 ) m1 ⁇ Y 0 (N 1 ) (Wherein, X n0 are H, Cl and F, m1 is an integer of 3 to 15, and Y 0 is as defined above.)
- Rf n5 is a linear or branched partially or fully fluorinated alkylene group which may contain an ether bond having 1 to 3 carbon atoms, and L is a linking group; , Y 0 are as defined above, provided that the total number of carbon atoms of X n2 , X n3 , X n4 and Rf n5 is 18 or less.
- the compounds represented by the general formula (N 0 ) include perfluorocarboxylic acids (I) represented by the following general formula (I), ⁇ -H represented by the following general formula (II) Perfluorocarboxylic acid (II), perfluoroethercarboxylic acid (III) represented by the following general formula (III), perfluoroalkylalkylenecarboxylic acid (IV) represented by the following general formula (IV), the following general formula Alkoxyfluorocarboxylic acid (V) represented by (V), perfluoroalkylsulfonic acid (VI) represented by the following general formula (VI), ⁇ -H perfluorosulfone represented by the following general formula (VII) Acid (VII), perfluoroalkylalkylenesulfonic acid (VIII) represented by the following general formula (VIII), alkylalkylenecarboxylic acid (IX) represented by the following general formula (IX), and the following general formula (X) Fluorocarboxylic acids
- the perfluorocarboxylic acid (I) has the following general formula (I): F( CF2 ) n1COOM (I) (Wherein, n1 is an integer of 3 to 14 , M is H, a metal atom, NR 74 , imidazolium optionally having substituents, pyridinium optionally having substituents or It is a phosphonium which may have a substituent, and R 7 is H or an organic group.).
- the ⁇ -H perfluorocarboxylic acid (II) has the following general formula (II): H(CF2) n2COOM ( II ) (wherein n2 is an integer of 4 to 15, and M is as defined above).
- the perfluoroether carboxylic acid (III) has the following general formula (III): Rf 1 -O-(CF(CF 3 )CF 2 O) n3 CF(CF 3 )COOM (III) (Wherein, Rf 1 is a perfluoroalkyl group having 1 to 5 carbon atoms, n3 is an integer of 0 to 3, and M is as defined above.) .
- the perfluoroalkylalkylenecarboxylic acid (IV) has the following general formula (IV): Rf2(CH2)n4Rf3COOM ( IV ) (wherein Rf 2 is a perfluoroalkyl group having 1 to 5 carbon atoms, Rf 3 is a linear or branched perfluoroalkylene group having 1 to 3 carbon atoms, n4 is a is an integer, and M is as defined above.
- the alkoxyfluorocarboxylic acid (V) has the following general formula (V): Rf4 - O - CY1Y2CF2 - COOM (V) (In the formula, Rf 4 is a linear or branched partially or fully fluorinated alkyl group which may contain an ether bond and/or a chlorine atom having 1 to 12 carbon atoms, and Y 1 and Y 2 are the same or different and are H or F, and M is as defined above.
- the perfluoroalkylsulfonic acid (VI) has the following general formula (VI): F( CF2)n5SO3M ( VI ) (wherein n5 is an integer of 3 to 14, and M is as defined above).
- the ⁇ -H perfluorosulfonic acid (VII) has the following general formula (VII): H( CF2)n6SO3M ( VII ) (wherein n6 is an integer of 4 to 14, and M is as defined above).
- the perfluoroalkylalkylenesulfonic acid (VIII) has the following general formula (VIII): Rf5 ( CH2 ) n7SO3M ( VIII) (Wherein, Rf 5 is a perfluoroalkyl group having 1 to 13 carbon atoms, n7 is an integer of 1 to 3, and M is as defined above.) .
- the alkylalkylenecarboxylic acid (IX) has the following general formula (IX): Rf6 ( CH2 ) n8COOM (IX) (wherein Rf 6 is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond with 1 to 13 carbon atoms, n8 is an integer of 1 to 3, M is defined above.).
- the fluorocarboxylic acid (X) has the following general formula (X): Rf7 - O - Rf8 - O-CF2-COOM(X) (Wherein, Rf 7 is a linear or branched partially or fully fluorinated alkyl group that may contain an ether bond and/or a chlorine atom having 1 to 6 carbon atoms, and Rf 8 is a carbon A linear or branched, partially or fully fluorinated alkyl group of numbers 1 to 6, wherein M is as defined above.).
- the alkoxyfluorosulfonic acid (XI) has the following general formula (XI): Rf9 -O - CY1Y2CF2 - SO3M (XI) (In the formula, Rf 9 is a linear or branched chain that may contain an ether bond having 1 to 12 carbon atoms, and may contain chlorine, and is a partially or fully fluorinated alkyl group; 1 and Y 2 are the same or different and are H or F, and M is as defined above.
- the above compound (XII) has the following general formula (XII): (Wherein, X 1 , X 2 and X 3 may be the same or different, and may contain H, F and an ether bond having 1 to 6 carbon atoms, a linear or branched partially or fully fluorinated Rf 10 is a perfluoroalkylene group having 1 to 3 carbon atoms, L is a linking group, and Y 0 is an anionic group.).
- Y 0 can be -COOM, -SO 2 M, or -SO 3 M, and can be -SO 3 M, or COOM, where M is as defined above.
- Examples of L include a single bond, a partially fluorinated alkylene group which may contain an ether bond having 1 to 10 carbon atoms, and the like.
- the above compound (XIII) has the following general formula (XIII): Rf 11 —O—(CF 2 CF(CF 3 )O) n9 (CF 2 O) n10 CF 2 COOM (XIII) (wherein Rf 11 is a chlorine-containing fluoroalkyl group having 1 to 5 carbon atoms, n9 is an integer of 0 to 3, n10 is an integer of 0 to 3, and M is the above-defined It is represented by Compound (XIII) includes CF2ClO ( CF2CF ( CF3 )O) n9 ( CF2O ) n10CF2COONH4 ( a mixture having an average molecular weight of 750, wherein n9 and n10 are as defined above). There is.)
- anionic fluorine-containing surfactant examples include carboxylic acid-based surfactants, sulfonic acid-based surfactants, and the like.
- the fluorine-containing surfactant may be a single fluorine-containing surfactant or a mixture containing two or more fluorine-containing surfactants.
- fluorine-containing surfactant examples include compounds represented by the following formulas.
- a fluorine-containing surfactant may be a mixture of these compounds.
- the first and second fluororesin compositions preferably further contain a filler.
- a filler include glass fiber, glass beads, carbon fiber, spherical carbon, carbon black, graphite, silica, alumina, mica, silicon carbide, boron nitride, titanium oxide, bismuth oxide, cobalt oxide, molybdenum disulfide, Bronze, gold, silver, copper, nickel, aromatic polyester, polyimide, polyphenylene sulfide and the like can be mentioned, and one or more of them can be used.
- at least one selected from the group consisting of glass fiber, carbon fiber, graphite and bronze is preferable.
- the content of the filler is preferably 0 to 80% by mass with respect to the fluororesin composition.
- the content is more preferably 1% by mass or more, further preferably 5% by mass or more, even more preferably 10% by mass or more, and particularly preferably 12% by mass or more, Further, it is more preferably 70% by mass or less, still more preferably 60% by mass or less, even more preferably 50% by mass or less, even more preferably 40% by mass or less, and 30% by mass. % or less, and most preferably 25 mass % or less.
- the first and second fluororesin compositions can be produced, for example, by mixing fluororesin A powder and fluororesin B particles.
- the particles of the fluororesin B are preferably mixed with the powder of the fluororesin A in the form of powder.
- a mixing method is not particularly limited, and a known method can be adopted. Mixing can also take place in a grinder. From the viewpoint of easily obtaining a fluororesin composition having a higher apparent density and more excellent handleability, it is preferable that the maximum linear length of the particles of the fluororesin A is smaller than the maximum linear length of the particles of the fluororesin B. .
- the obtained fluororesin composition may be pulverized.
- the pulverization may be carried out by a known method, for example, using a pulverizer such as an air jet mill, a hammer mill, a force mill, a stone mill type pulverizer, or a freeze pulverizer.
- a pulverizer such as an air jet mill, a hammer mill, a force mill, a stone mill type pulverizer, or a freeze pulverizer.
- the obtained fluororesin composition may be granulated.
- a fluororesin composition having a higher apparent density and more excellent handleability can be obtained.
- the granulation method include known methods such as underwater granulation, hot water granulation, emulsification dispersion granulation, emulsified hot water granulation, solvent-free granulation, and dry solvent granulation. mentioned.
- the first and second fluororesin compositions preferably have a tensile strength at break of 10 MPa or more, more preferably 11 MPa or more, still more preferably 15 MPa or more, and particularly preferably 20 MPa or more. .
- the upper limit is not particularly limited, it may be, for example, 30 MPa.
- the tensile strength at break was measured by putting 35 g of the fluororesin composition into a mold of ⁇ 100 mm, compressing it under the conditions of a pressure of 30 MPa and 1 minute, raising the temperature from room temperature to 300 ° C. in 3 hours, and then 300 ° C. The temperature is raised from 1 to 370°C in 4 hours, held at 370°C for 12 hours, then lowered to 300°C in 5 hours, and then lowered to room temperature in 1 hour. and measured according to ASTM D1708.
- the first and second fluororesin compositions preferably have a tensile breaking strain of 150% or more, more preferably 170% or more, even more preferably 200% or more, and 250% or more. is even more preferable, 330% or more is particularly preferable, and 350% or more is particularly preferable. Although the upper limit is not particularly limited, it may be 600%, for example.
- the above tensile breaking strain is obtained by putting 35 g of the above fluororesin composition into a mold of ⁇ 100 mm, compression molding under the conditions of a pressure of 30 MPa and 1 minute, heating from room temperature to 300 ° C. in 3 hours, and then 300 ° C. The temperature is raised from 1 to 370°C in 4 hours, held at 370°C for 12 hours, then lowered to 300°C in 5 hours, and then lowered to room temperature in 1 hour. and measured according to ASTM D1708.
- the first and second fluororesin compositions can be suitably used as molding materials.
- the method for molding the fluororesin composition is not particularly limited, but compression molding, ram extrusion molding, isostatic molding and the like can be mentioned. Among them, compression molding is preferred.
- the first and second fluororesin compositions are preferably powders for compression molding.
- the present disclosure also provides molded bodies obtained by compression molding and baking the first and second fluororesin compositions.
- the molded article of the present disclosure has excellent tensile properties even though it contains a fluororesin that has been heated to a temperature equal to or higher than its melting point.
- the compression molding can be performed, for example, by maintaining a pressure of 10 to 50 MPa for 1 minute to 30 hours.
- the firing can be performed, for example, by heating at a temperature of 350 to 380° C. for 0.5 to 50 hours.
- the molded article of the present disclosure preferably has a tensile strength at break of 10 MPa or more, more preferably 11 MPa or more, even more preferably 15 MPa or more, and particularly preferably 20 MPa or more.
- the upper limit is not particularly limited, it may be, for example, 30 MPa.
- the tensile strength at break is measured according to ASTM D1708.
- the molded article of the present disclosure preferably has a tensile breaking strain of 150% or more, more preferably 170% or more, still more preferably 200% or more, and even more preferably 250% or more. , is particularly preferably 330% or more, and particularly preferably 350% or more. Although the upper limit is not particularly limited, it may be 600%, for example.
- the tensile breaking strain is measured according to ASTM D1708.
- Molded articles obtained from the first and second fluororesin compositions include lining sheets, packings, gaskets, diaphragm valves, heat-resistant wires, heat-resistant insulating tapes for vehicle motors and generators, release sheets, sealing materials, casings, It can be suitably used for sleeves, bellows, hoses, piston rings, butterfly valves, square tanks, wafer carriers and the like.
- melting point (melting point) Using X-DSC7000 (manufactured by Hitachi High-Tech Science Co., Ltd.), differential scanning calorimetry [DSC] was performed at a heating rate of 10 ° C./min. Obtained as the temperature corresponding to the minimum point in the heat of fusion curve . When there were two or more local minimum points in one melting peak, each was taken as the melting point.
- a funnel with a total height of 115 mm, a leg diameter of ⁇ 26 mm, a leg length of 35 mm, and an intake opening of 60° is installed so that the height from the bottom of the funnel to the sample drop surface is 100 mm, and a 40 g sample is placed in the funnel.
- a protractor was used to measure the angle of the lower half of the mountain of the dropped sample, which was taken as the angle of repose.
- a peak of a compound that can be identified as a fluorine compound having a molecular weight of 800 or less was extracted from the accurate mass, and an extraction chromatogram was drawn.
- an aqueous solution containing perfluorooctanoic acid with a known concentration prepare aqueous solutions with four levels of content, analyze the aqueous solution with each content, and plot the content and the relationship between the area area and the content. , the calibration curve was drawn.
- the content of fluorine-containing compounds having a molecular weight of 800 or less in the extract was calculated in terms of perfluorooctanoic acid using the above extraction chromatogram and calibration curve.
- Production Example 1 (Preparation of fluororesin powder A-1) 35 g of PTFE molding powder (standard specific gravity (SSG): 2.159, melting point: 345.0°C) obtained by pulverizing coarse homo-PTFE powder obtained by suspension polymerization of only TFE monomer with a pulverizer is used. Then, it was compression-molded in a mold of ⁇ 100 mm at 30 MPa for 1 minute, and fired at 370° C. for 3 hours to obtain a molded product. After cutting the obtained molded product, it was pulverized with a pulverizer to obtain a fluororesin powder A-1.
- SSG standard specific gravity
- the fluororesin powder A-1 had a melting point of 328° C., an average secondary particle size of 23 ⁇ m, a D10 of 8 ⁇ m, a D90 of 48 ⁇ m, an apparent density of 0.64 g/ml, and a maximum linear length of 94 ⁇ m.
- Production Example 2 (Preparation of fluororesin powder A-2) A molded article obtained in the same manner as in Production Example 1 was cut and then pulverized with a pulverizer to obtain fluororesin powder A-2.
- the fluororesin powder A-2 had a melting point of 328° C., an average secondary particle size of 37 ⁇ m, a D10 of 7 ⁇ m, a D90 of 87 ⁇ m, an apparent density of 0.53 g/ml, and a maximum linear length of 129 ⁇ m.
- Fluororesin powder B-1 A homo-PTFE coarse powder obtained by suspension polymerization of only the TFE monomer was pulverized with a pulverizer to obtain fluororesin powder B-1.
- the fluororesin powder B-1 has an apparent density of 0.34 g/ml, an average secondary particle diameter of 24 ⁇ m, a D90 of 55 ⁇ m, a standard specific gravity (SSG) of 2.163, a melting point of 345.0° C., and a maximum linear length. was 112 ⁇ m.
- Fluororesin powder B-2 A coarse powder of modified PTFE obtained by suspension polymerization of TFE and perfluoropropyl vinyl ether (PPVE) was pulverized with a pulverizer to obtain fluororesin powder B-2.
- the fluororesin powder B-2 has an apparent density of 0.33 g/ml, an average secondary particle diameter of 28 ⁇ m, a D90 of 77 ⁇ m, a standard specific gravity (SSG) of 2.168, a melting point of 341.5° C., and an amount in PPVE units. was 0.09% by mass, and the maximum linear length was 156 ⁇ m.
- Example 1 50 g of fluororesin powder A-1 and 50 g of fluororesin powder B-1 were mixed using a wonder crusher WC-3 at a rotation speed of 6900 rpm for 60 seconds to obtain a PTFE powder (fluororesin composition). rice field.
- the obtained PTFE powder had an average secondary particle size of 24 ⁇ m, D10 of 7 ⁇ m, D90 of 58 ⁇ m, an apparent density of 0.50 g/ml, and an angle of repose of 32°, indicating excellent handleability.
- the PTFE powder contained 100% by mass of TFE units with respect to all polymerized units.
- the PTFE powder has a melting point of 329° C.
- a tensile strength at break of 21 MPa was 1 mass ppm or less.
- Example 2 A PTFE powder and a molded product were obtained in the same manner as in Example 1 except that the fluororesin powder B-2 was used instead of the fluororesin powder B-1.
- the obtained PTFE powder had an average secondary particle size of 27 ⁇ m, a D10 of 7 ⁇ m, a D90 of 72 ⁇ m, an apparent density of 0.49 g/ml, and an angle of repose of 30°, showing excellent handleability.
- the PTFE powder contained 99.955% by mass of TFE units and 0.045% by mass of PPVE units based on the total polymerized units.
- the PTFE powder had a melting point of 329° C. and 342° C., a tensile strength at break of 23 MPa, and a tensile strain at break of 427%.
- Example 3 A PTFE powder was obtained in the same manner as in Example 2 except that 70 g of the fluororesin powder A-1 and 30 g of the fluororesin powder B-2 were used.
- the obtained PTFE powder had an average secondary particle size of 29 ⁇ m, a D10 of 9 ⁇ m, a D90 of 76 ⁇ m, an apparent density of 0.52 g/ml, and an angle of repose of 36°, indicating excellent handleability.
- the PTFE powder contained 99.973% by mass of TFE units and 0.027% by mass of PPVE units based on the total polymerized units.
- the PTFE powder had a melting point of 329° C. and 342° C., a tensile strength at break of 18 MPa, and a tensile strain at break of 374%.
- Example 4 A PTFE powder was obtained in the same manner as in Example 1 except that 70 g of the fluororesin powder A-1 and 30 g of the fluororesin powder B-1 were used.
- the obtained PTFE powder had an average secondary particle size of 33 ⁇ m, a D10 of 10 ⁇ m, a D90 of 103 ⁇ m, an apparent density of 0.56 g/ml, and an angle of repose of 37°, indicating excellent handleability.
- the PTFE powder contained 100% by mass of TFE units with respect to all polymerized units.
- the PTFE powder had a melting point of 329° C. and 345° C., a tensile strength at break of 11 MPa, and a tensile strain at break of 229%.
- Example 5 PTFE powder was obtained in the same manner as in Example 1 using 70 g of fluororesin powder A-2 and 30 g of fluororesin powder B-1.
- the obtained PTFE powder had an average secondary particle size of 36 ⁇ m, D10 of 10 ⁇ m, D90 of 105 ⁇ m, an apparent density of 0.68 g/ml, and an angle of repose of 37°, indicating excellent handleability.
- the PTFE powder contained 100% by mass of TFE units with respect to all polymerized units.
- the PTFE powder had a melting point of 329° C. and 345° C., a tensile strength at break of 12 MPa, and a tensile strain at break of 224%.
- Example 6 PTFE powder was obtained in the same manner as in Example 2 using 40 g of fluororesin powder A-1, 45 g of fluororesin powder B-2, and 15 g of glass fiber (PF E-001 manufactured by Nitto Boseki Co., Ltd.).
- the obtained PTFE powder had an apparent density of 0.45 g/ml, an angle of repose of 34°, and was excellent in handleability.
- the PTFE powder contained 99.959% by mass of TFE units and 0.041% by mass of PPVE units based on the total polymerized units.
- the PTFE powder had a melting point of 329° C. and 342° C., a tensile strength at break of 15 MPa, and a tensile strain at break of 342%.
- Example 7 PTFE powder was obtained in the same manner as in Example 2 using 40 g of fluororesin powder A-1, 45 g of fluororesin powder B-2, and 15 g of bronze powder (Bro-AT-200 manufactured by Fukuda Metal Foil & Powder Co., Ltd.).
- the obtained PTFE powder had an apparent density of 0.53 g/ml, an angle of repose of 34°, and was excellent in handleability.
- the PTFE powder contained 99.959% by mass of TFE units and 0.041% by mass of PPVE units based on the total polymerized units.
- the PTFE powder had a melting point of 329° C. and 342° C., a tensile strength at break of 14 MPa, and a tensile strain at break of 364%.
- Example 8 Example using 40 g of fluororesin powder A-1, 40 g of fluororesin powder B-2, 15 g of glass fiber (PF E-001 manufactured by Nitto Boseki Co., Ltd.), and 5 g of graphite (CPB manufactured by Nippon Graphite Industry Co., Ltd.)
- a PTFE powder was obtained in the same manner as in 2.
- the obtained PTFE powder had an apparent density of 0.49 g/ml and an angle of repose of 38°, and was excellent in handleability.
- the PTFE powder contained 99.964% by mass of TFE units and 0.036% by mass of PPVE units based on the total polymerized units.
- the PTFE powder had a melting point of 329° C. and 342° C., a tensile strength at break of 9 MPa, and a tensile strain at break of 80%.
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Abstract
Description
第1のフッ素樹脂組成物は、融点以上の温度に加熱した履歴のない懸濁重合で重合されたフッ素樹脂Bを含み、かつ見掛密度が特定の範囲内にあるので、融点以上の温度に加熱した履歴のあるフッ素樹脂Aを含むにもかかわらず、取り扱い性(例えば、運搬時や圧縮成形時の取り扱い性)に優れる。
また、第1のフッ素樹脂組成物は、良好な引張特性(例えば、引張破断強度、引張破断歪)を有する。
上記333℃未満の温度領域は、332℃未満であることがより好ましく、331℃未満であることが更に好ましく、100℃以上であることが好ましく、140℃以上であることがより好ましく、160℃以上であることが更に好ましい。
上記333~360℃の温度領域は、334℃以上であることがより好ましく、335℃であることが更に好ましく、また、355℃以下であることがより好ましく、350℃以下であることが更に好ましい。
上記2つの温度領域に融点を有することは、フッ素樹脂組成物が、融点以上の温度に加熱した履歴のある溶融流動性を示さないフッ素樹脂Aと、融点以上の温度に加熱した履歴のない溶融流動性を示さないフッ素樹脂Bとを含むことを示す。
下限は限定されないが、140℃であることがより好ましく、180℃以上であることが更に好ましい。
融点が上記範囲内にあることは、融点以上の温度に加熱した履歴があることを示す。
フッ素樹脂Aは、333℃以上の温度領域にも融点を有していてもよい。
本明細書において、溶融流動性を示さないとは、メルトフローレート(MFR)が0.25g/10分未満、好ましくは0.10g/10分未満、より好ましくは0.05g/10分以下であることを意味する。
本明細書において、MFRは、ASTM D1238に従って、メルトインデクサーを用いて、フッ素樹脂の種類によって定められた測定温度(例えば、PFAやFEPの場合は372℃、ETFEの場合は297℃)、荷重(例えば、PFA、FEP及びETFEの場合は5kg)において内径2.095mm、長さ8mmのノズルから10分間あたりに流出するポリマーの質量(g/10分)として得られる値である。PTFEの場合は、PFAと同様の測定条件で測定して得られる値である。
本明細書において、上記変性モノマー単位とは、PTFEの分子構造の一部分であって変性モノマーに由来する部分を意味する。
CF2=CF-ORf (A)
(式中、Rfは、パーフルオロ有機基を表す。)で表されるパーフルオロ不飽和化合物等が挙げられる。本明細書において、上記「パーフルオロ有機基」とは、炭素原子に結合する水素原子が全てフッ素原子に置換されてなる有機基を意味する。上記パーフルオロ有機基は、エーテル酸素を有していてもよい。
CF2=CF-CF2-ORf1 (B)
(式中、Rf1は、パーフルオロ有機基を表す。)で表されるフルオロモノマーが挙げられる。
上記平均二次粒子径は、ベックマン・コールター製レーザー回折式粒度分布測定装置(LS13 320)を用いて、乾式で、バキューム圧20mH2Oで測定を行ない、粒度分布積算(体積基準)の50%に対応する粒子径に等しいとする。
上記D90は、ベックマン・コールター製レーザー回折式粒度分布測定装置(LS13 320)を用いて、乾式で、バキューム圧20mH2Oで測定を行ない、粒度分布積算(体積基準)の90%に対応する粒子径に等しいとする。
圧縮成形の形状は特に問わない。焼成する温度はフッ素樹脂の融点以上であれば良い。粉砕機は特に限定されず、切削屑を粉砕(好ましくは微細化)することができるものであればよい。例えば、エアジェットミル、ハンマーミル、フォースミル、石臼型の粉砕機、凍結粉砕機等が挙げられる。
融点が上記範囲内にあることは、融点以上の温度に加熱した履歴がないことを示す。
なお、上記融点とともに、333℃未満の温度領域にも融点を有していても構わない。
融点以上の温度に加熱した履歴のないPTFEについての「高分子量」とは、上記標準比重が上記の範囲内にあることを意味する。
見掛密度が一層高く、取り扱い性に一層優れるフッ素樹脂組成物が得られる点、及び、引張特性に一層優れるフッ素樹脂組成物が得られる点では、変性PTFEが好ましい。
(i)走査電子顕微鏡(SEM)の画像処理による粒子径が1μm以下の粒子の割合が30%以下である。
(ii)メタノールでソックスレー抽出した抽出液を用いた液体クロマトグラフ質量計(LC/MS/MS)により測定されるアニオン性含フッ素界面活性剤の量が1質量ppm以下である。
上記粉砕は公知の方法により行ってよく、ハンマーミル、ピンミル、ジェットミル、カッターミル等の粉砕機を用いて粉砕する方法により行うことができる。
上記造粒も公知の方法により行ってよく、水中造粒法、温水造粒法、乳化分散造粒法、乳化温水造粒法、無溶剤造粒法、乾式溶剤造粒法等の方法により行うことができる。
上記平均二次粒子径は、ベックマン・コールター製レーザー回折式粒度分布測定装置(LS13 320)を用いて、乾式で、バキューム圧20mH2Oで測定を行ない、粒度分布積算(体積基準)の50%に対応する粒子径に等しいとする。
上記D90は、ベックマン・コールター製レーザー回折式粒度分布測定装置(LS13 320)を用いて、乾式で、バキューム圧20mH2Oで測定を行ない、粒度分布積算(体積基準)の90%に対応する粒子径に等しいとする。
取り扱い性に一層優れる点で、上記見掛密度は、0.45g/ml以上であることが好ましく、0.47g/ml以上であることがより好ましい。上限は特に限定されないが、1.00g/mlであっても構わない。
上記見掛密度は、JIS K 6891に準拠して測定する。
上記変性モノマー単位の含有量は、NMR、FT-IR、元素分析、蛍光X線分析を単量体の種類によって適宜組み合わせることで算出できる。また、原料組成が分かっている場合は、原料組成から計算により求めることもできる。
上記引張破断強度は、φ100mmの金型に35gの上記フッ素樹脂組成物を投入し、30MPaの圧力、1分間の条件で圧縮成形し、室温から300℃まで3時間で昇温し、その後300℃から370℃まで4時間で昇温し、370℃で12時間保持した後、300℃まで5時間で降温したのち、室温まで1時間で降温する工程により焼成した成形体を打ち抜いて作成したダンベルを用いて、ASTM D1708に準じて測定する。
この態様において、フッ素樹脂BがTFEの単独重合体であることも好ましい。
第2のフッ素樹脂組成物は、特定の単量体組成を有するので、融点以上の温度に加熱した履歴のあるフッ素樹脂Aを含むにもかかわらず、取り扱い性(例えば、運搬時や圧縮成形時の取り扱い性)に優れる。
また、第2のフッ素樹脂組成物は、良好な引張特性(例えば、引張破断強度、引張破断歪)を有する。
上記333℃未満の温度領域は、332℃未満であることがより好ましく、331℃未満であることが更に好ましく、100℃以上であることが好ましく、140℃以上であることがより好ましく、160℃以上であることが更に好ましい。
上記333~360℃の温度領域は、334℃以上であることがより好ましく、335℃であることが更に好ましく、また、355℃以下であることがより好ましく、350℃以下であることが更に好ましい。
上記2つの温度領域に融点を有することは、フッ素樹脂組成物が、融点以上の温度に加熱した履歴のある溶融流動性を示さないフッ素樹脂Aと、融点以上の温度に加熱した履歴のない溶融流動性を示さないフッ素樹脂Bとを含むことを示す。
上記変性モノマーとしては、第1のフッ素樹脂組成物におけるフッ素樹脂Bとしての変性PTFEについて上述した単量体が挙げられる。変性モノマー単位の含有量の好適な範囲も第1のフッ素樹脂組成物について説明した範囲と同様である。
上記見掛密度は、JIS K 6891に準拠して測定する。
(i)走査電子顕微鏡(SEM)の画像処理による粒子径が1μm以下の粒子の割合が30%以下である。
(ii)メタノールでソックスレー抽出した抽出液を用いた液体クロマトグラフ質量計(LC/MS/MS)により測定されるアニオン性含フッ素界面活性剤の量が1質量ppm以下である。
上記安息角は、全高115mm、足部径φ26mm、足部長さ35mm、取込部の開きが60°の漏斗を、漏斗の底面から試料落下面までの高さが100mmとなるように設置し、40gの試料を漏斗から落とし、落下した試料の山の下半分の角度を分度器で測定して得られる値である。
上記平均二次粒子径は、ベックマン・コールター製レーザー回折式粒度分布測定装置(LS13 320)を用いて、乾式で、バキューム圧20mH2Oで測定を行ない、粒度分布積算(体積基準)の50%に対応する粒子径に等しいとする。
上記D90は、ベックマン・コールター製レーザー回折式粒度分布測定装置(LS13 320)を用いて、乾式で、バキューム圧20mH2Oで測定を行ない、粒度分布積算(体積基準)の90%に対応する粒子径に等しいとする。
上記低分子量含フッ素化合物の含有量は、試料をメタノールでソックスレー抽出した後、液体クロマトグラフ質量計(LC/MS/MS)により測定する。
なお、上記「アニオン性部分」は、上記含フッ素界面活性剤のカチオンを除く部分を意味する。例えば、後述する式(I)で表されるF(CF2)n1COOMの場合には、「F(CF2)n1COO」の部分である。
上記LogPOWは、カラム;TOSOH ODS-120Tカラム(φ4.6mm×250mm、東ソー(株)製)、溶離液;アセトニトリル/0.6質量%HClO4水=1/1(vol/vol%)、流速;1.0ml/分、サンプル量;300μL、カラム温度;40℃、検出光;UV210nmの条件で、既知のオクタノール/水分配係数を有する標準物質(ヘプタン酸、オクタン酸、ノナン酸及びデカン酸)についてHPLCを行い、各溶出時間と既知のオクタノール/水分配係数との検量線を作成し、この検量線に基づき、試料液におけるHPLCの溶出時間から算出する。
Xn0-Rfn0-Y0 (N0)
(式中、Xn0は、H、Cl又は及びFである。Rfn0は、炭素数3~20で、鎖状、分枝鎖状又は環状で、一部又は全てのHがFにより置換されたアルキレン基であり、該アルキレン基は1つ以上のエーテル結合を含んでもよく、一部のHがClにより置換されていてもよい。Y0はアニオン性基である。)で表される化合物が挙げられる。
Mは、H、金属原子、NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基である。
上記金属原子としては、アルカリ金属(1族)、アルカリ土類金属(2族)等が挙げられ、例えば、Na、K又はLiである。
R7は、H又はC1-10の有機基であってよく、H又はC1-4の有機基であってよく、H又はC1-4のアルキル基であってよい。
Mは、H、金属原子又はNR7 4であってよく、H、アルカリ金属(1族)、アルカリ土類金属(2族)又はNR7 4であってよく、H、Na、K、Li又はNH4であってよい。
Xn0-(CF2)m1-Y0 (N1)
(式中、Xn0は、H、Cl及びFであり、m1は3~15の整数であり、Y0は、上記定義したものである。)で表される化合物、下記一般式(N2):
Rfn1-O-(CF(CF3)CF2O)m2CFXn1-Y0 (N2)
(式中、Rfn1は、炭素数1~5のパーフルオロアルキル基であり、m2は、0~3の整数であり、Xn1は、F又はCF3であり、Y0は、上記定義したものである。)で表される化合物、下記一般式(N3):
Rfn2(CH2)m3-(Rfn3)q-Y0 (N3)
(式中、Rfn2は、炭素数1~13のエーテル結合及び/又は塩素原子を含み得る、部分又は完全フッ素化されたアルキル基であり、m3は、1~3の整数であり、Rfn3は、直鎖状又は分岐状の炭素数1~3のパーフルオロアルキレン基であり、qは0又は1であり、Y0は、上記定義したものである。)で表される化合物、下記一般式(N4):
Rfn4-O-(CYn1Yn2)pCF2-Y0 (N4)
(式中、Rfn4は、炭素数1~12のエーテル結合を含み得る直鎖状又は分枝鎖状の部分又は完全フッ素化されたアルキル基であり、Yn1及びYn2は、同一若しくは異なって、H又はFであり、pは0又は1であり、Y0は、上記定義したものである。)で表される化合物、及び、一般式(N5):
F(CF2)n1COOM (I)
(式中、n1は、3~14の整数であり、Mは、H、金属原子、NR7 4、置換基を有していてもよいイミダゾリウム、置換基を有していてもよいピリジニウム又は置換基を有していてもよいホスホニウムであり、R7は、H又は有機基である。)で表されるものである。
H(CF2)n2COOM (II)
(式中、n2は、4~15の整数であり、Mは、上記定義したものである。)で表されるものである。
Rf1-O-(CF(CF3)CF2O)n3CF(CF3)COOM (III)
(式中、Rf1は、炭素数1~5のパーフルオロアルキル基であり、n3は、0~3の整数であり、Mは、上記定義したものである。)で表されるものである。
Rf2(CH2)n4Rf3COOM (IV)
(式中、Rf2は、炭素数1~5のパーフルオロアルキル基であり、Rf3は、直鎖状又は分岐状の炭素数1~3のパーフルオロアルキレン基、n4は、1~3の整数であり、Mは、上記定義したものである。)で表されるものである。
Rf4-O-CY1Y2CF2-COOM (V)
(式中、Rf4は、炭素数1~12のエーテル結合及び/又は塩素原子を含み得る直鎖状又は分枝鎖状の部分又は完全フッ素化されたアルキル基であり、Y1及びY2は、同一若しくは異なって、H又はFであり、Mは、上記定義したものである。)で表されるものである。
F(CF2)n5SO3M (VI)
(式中、n5は、3~14の整数であり、Mは、上記定義したものである。)で表されるものである。
H(CF2)n6SO3M (VII)
(式中、n6は、4~14の整数であり、Mは、上記定義したものである。)で表されるものである。
Rf5(CH2)n7SO3M (VIII)
(式中、Rf5は、炭素数1~13のパーフルオロアルキル基であり、n7は、1~3の整数であり、Mは、上記定義したものである。)で表されるものである。
Rf6(CH2)n8COOM (IX)
(式中、Rf6は、炭素数1~13のエーテル結合を含み得る直鎖状または分岐鎖状の部分又は完全フッ素化されたアルキル基であり、n8は、1~3の整数であり、Mは、上記定義したものである。)で表されるものである。
Rf7-O-Rf8-O-CF2-COOM (X)
(式中、Rf7は、炭素数1~6のエーテル結合及び/又は塩素原子を含み得る直鎖状又は分枝鎖状の部分又は完全フッ素化されたアルキル基であり、Rf8は、炭素数1~6の直鎖状又は分枝鎖状の部分又は完全フッ素化されたアルキル基であり、Mは、上記定義したものである。)で表されるものである。
Rf9-O-CY1Y2CF2-SO3M (XI)
(式中、Rf9は、炭素数1~12のエーテル結合を含み得る直鎖状又は分枝鎖状であって、塩素を含んでもよい、部分又は完全フッ素化されたアルキル基であり、Y1及びY2は、同一若しくは異なって、H又はFであり、Mは、上記定義したものである。)で表されるものである。
Y0は、-COOM、-SO2M、又は、-SO3Mであってよく、-SO3M、又は、COOMであってよい(式中、Mは上記定義したものである。)。
Lとしては、例えば、単結合、炭素数1~10のエーテル結合を含みうる部分又は完全フッ素化されたアルキレン基が挙げられる。
Rf11-O-(CF2CF(CF3)O)n9(CF2O)n10CF2COOM (XIII)
(式中、Rf11は、塩素を含む炭素数1~5のフルオロアルキル基であり、n9は、0~3の整数であり、n10は、0~3の整数であり、Mは、上記定義したものである。)で表されるものである。化合物(XIII)としては、CF2ClO(CF2CF(CF3)O)n9(CF2O)n10CF2COONH4(平均分子量750の混合物、式中、n9及びn10は上記定義したものである。)が挙げられる。
F(CF2)7COOM、
F(CF2)5COOM、
H(CF2)6COOM、
H(CF2)7COOM、
CF3O(CF2)3OCHFCF2COOM、
C3F7OCF(CF3)CF2OCF(CF3)COOM、
CF3CF2CF2OCF(CF3)COOM、
CF3CF2OCF2CF2OCF2COOM、
C2F5OCF(CF3)CF2OCF(CF3)COOM、
CF3OCF(CF3)CF2OCF(CF3)COOM、
CF2ClCF2CF2OCF(CF3)CF2OCF2COOM、
CF2ClCF2CF2OCF2CF(CF3)OCF2COOM、
CF2ClCF(CF3)OCF(CF3)CF2OCF2COOM、
CF2ClCF(CF3)OCF2CF(CF3)OCF2COOM、
上記充填材としては、例えば、ガラス繊維、ガラスビーズ、炭素繊維、球状カーボン、カーボンブラック、グラファイト、シリカ、アルミナ、マイカ、炭化珪素、窒化硼素、酸化チタン、酸化ビスマス、酸化コバルト、二硫化モリブデン、ブロンズ、金、銀、銅、ニッケル、芳香族ポリエステル、ポリイミド、ポリフェニレンサルファイド等が挙げられ、1種又は2種以上を用いることができる。
なかでも、ガラス繊維、炭素繊維、グラファイト、及び、ブロンズからなる群より選択される少なくとも1種が好ましい。
見掛密度が一層高く、取り扱い性に一層優れるフッ素樹脂組成物を容易に得る点では、フッ素樹脂Aの粒子の最大直線長さを、フッ素樹脂Bの粒子の最大直線長さより小さくすることが好ましい。
上記造粒の方法としては、公知の方法が挙げられ、水中造粒法、温水造粒法、乳化分散造粒法、乳化温水造粒法、無溶剤造粒法、乾式溶剤造粒法等が挙げられる。
上記引張破断強度は、φ100mmの金型に35gの上記フッ素樹脂組成物を投入し、30MPaの圧力、1分間の条件で圧縮成形し、室温から300℃まで3時間で昇温し、その後300℃から370℃まで4時間で昇温し、370℃で12時間保持した後、300℃まで5時間で降温したのち、室温まで1時間で降温する工程によって焼成した成形体を打ち抜いて作成したダンベルを用いて、ASTM D1708に準じて測定する。
上記引張破断歪は、φ100mmの金型に35gの上記フッ素樹脂組成物を投入し、30MPaの圧力、1分間の条件で圧縮成形し、室温から300℃まで3時間で昇温し、その後300℃から370℃まで4時間で昇温し、370℃で12時間保持した後、300℃まで5時間で降温したのち、室温まで1時間で降温する工程によって焼成した成形体を打ち抜いて作成したダンベルを用いて、ASTM D1708に準じて測定する。
第1及び第2のフッ素樹脂組成物は、圧縮成形用粉末であることが好ましい。
本開示の成形体は、融点以上の温度に加熱した履歴のあるフッ素樹脂を含むにもかかわらず、引張特性に優れる。
上記引張破断強度は、ASTM D1708に準じて測定する。
上記引張破断歪は、ASTM D1708に準じて測定する。
X-DSC7000(株式会社日立ハイテクサイエンス社製)を用い、10℃/分の昇温速度で示差走査熱量測定〔DSC〕を行って得られた融解熱曲線における極小点に対応する温度として求めた。1つの融解ピーク中に極小点が2つ以上ある場合は、それぞれを融点とした。
19F-NMR法により測定した。
ベックマン・コールター製レーザー回折式粒度分布測定装置(LS13 320)を用いて、乾式で、バキューム圧20mH2Oで測定を行ない、得られた粒度分布(体積基準)に基づいて求めた。平均二次粒子径は、粒度分布積算の50%に対応する粒子径に等しいとした。10%に対応する粒子径をD10、90%に対応する粒子径をD90とした。
JIS K 6891に準拠して測定した。
ASTM D4895 89に準拠して成形されたサンプルを用い、ASTM D 792に準拠した水置換法により測定した。
全高115mm、足部径φ26mm、足部長さ35mm、取込部の開きが60°の漏斗を、漏斗の底面から試料落下面までの高さが100mmとなるように設置し、40gの試料を漏斗から落とし、落下した試料の山の下半分の角度を分度器で測定し、安息角とした。
φ100mmの金型に35gの粉末を投入し、30MPaの圧力、1分間の条件で圧縮成形し、室温から300℃まで3時間で昇温し、その後300℃から370℃まで4時間で昇温し、370℃で12時間保持した後、300℃まで5時間で降温したのち、室温まで1時間で降温する工程により焼成することで成形品を得た。この成形品を打ち抜くことでダンベルを用意し、ASTM D 1708に準じて引張試験を行い、引張破断強度、引張破断歪を測定した。
二次粒子100個以上をSEM画像を用いて観察し、二次粒子の長径をそれぞれ測定した。その中で最も大きい長径を最大直線長さとした。
原料組成から計算により求めた。
フッ素樹脂組成物(粉末)を1g秤量し、アンモニア水とメタノールで調製した0.3%水酸化アンモニウムメタノール溶液(A)を10mL加え、60℃に温調した超音波洗浄機にサンプル瓶をセットし、2時間の超音波処理を行ない、抽出液を得た。抽出液中の含フッ素化合物について、液体クロマトグラフ質量分析計(Agilent社製1290 Infinity II型LC、6530型飛行時間型質量分析計)を用いて測定を行った。測定機器構成と測定条件を表1に示す。精密質量から分子量800以下のフッ素化合物と同定できる化合物をピーク抽出し、抽出クロマトグラムを描いた。濃度既知の含パーフルオロオクタン酸の水溶液を用いて、4水準の含有量の水溶液を作製し、それぞれの含有量の水溶液の分析を行ない、含有量とその含有量に対するエリア面積と関係をプロットし、検量線を描いた。上記検量線を用いて、抽出液中の分子量800以下の含フッ素化合物の含有量は、上記抽出クロマトグラムと検量線を用いて、パーフルオロオクタン酸換算で計算した。
TFEモノマーのみの懸濁重合で得られたホモPTFEの粗粉末を粉砕機で粉砕して得られたPTFEモールディングパウダー(標準比重(SSG):2.159,融点:345.0℃)35gを使用して、φ100mmの金型にて30MPa、1分間の条件で圧縮成形し、370℃で3時間焼成することで成形品を得た。得られた成形品を切削した後に、粉砕機で粉砕し、フッ素樹脂粉末A-1を得た。フッ素樹脂粉末A-1の融点は328℃、平均二次粒子径は23μm、D10は8μm、D90は48μm、見掛密度は0.64g/ml、最大直線長さは94μmであった。
製造例1と同様にして得られた成形品を切削した後に、粉砕機で粉砕し、フッ素樹脂粉末A-2を得た。フッ素樹脂粉末A-2の融点は328℃、平均二次粒子径は37μm、D10は7μm、D90は87μm、見掛密度は0.53g/ml、最大直線長さは129μmであった。
TFEモノマーのみの懸濁重合で得られたホモPTFEの粗粉末を粉砕機で粉砕し、フッ素樹脂粉末B-1を得た。フッ素樹脂粉末B-1の見掛密度は0.34g/ml、平均二次粒子径は24μm、D90が55μm、標準比重(SSG)は2.163、融点は345.0℃、最大直線長さは112μmであった。
TFEとパーフルオロプロピルビニルエーテル(PPVE)との懸濁重合で得られた変性PTFEの粗粉末を粉砕機で粉砕し、フッ素樹脂粉末B-2を得た。フッ素樹脂粉末B-2の見掛密度は0.33g/ml、平均二次粒子径は28μm、D90が77μm、標準比重(SSG)は2.168、融点は341.5℃、PPVE単位の量は0.09質量%、最大直線長さは156μmであった。
50gのフッ素樹脂粉末A-1と50gのフッ素樹脂粉末B-1とをワンダークラッシャーWC-3を用いて、回転数6900rpmで60秒間の混合を行なうことでPTFE粉末(フッ素樹脂組成物)を得た。得られたPTFE粉末の平均二次粒子径は24μm、D10は7μm、D90は58μm、見掛密度は0.50g/ml、安息角は32°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を100質量%含んでいた。上記PTFE粉末の融点は329℃及び345℃、引張破断強度は21MPa、引張破断歪は346%、低分子量含フッ素化合物(アニオン性部分の分子量が800以下のフッ素を含む界面活性剤)の含有量は1質量ppm以下であった。
フッ素樹脂粉末B-1の代わりにフッ素樹脂粉末B-2を使用したこと以外は実施例1と同様にしてPTFE粉末及び成形品を得た。得られたPTFE粉末の平均二次粒子径は27μm、D10は7μm、D90は72μm、見掛密度は0.49g/ml、安息角は30°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を99.955質量%、PPVE単位を0.045質量%含んでいた。上記PTFE粉末の融点は329℃及び342℃、引張破断強度は23MPa、引張破断歪は427%であった。
35gのフッ素樹脂粉末A-1(安息角=21°、融点328℃)だけを用いて実施例1と同様に引張試験を行なったところ引張破断強度は9MPa、引張破断歪は145%であった。
フッ素樹脂粉末A-1を70g、フッ素樹脂粉末B-2を30gとした以外は実施例2と同様にしてPTFE粉末を得た。得られたPTFE粉末の平均二次粒子径は29μm、D10は9μm、D90は76μm、見掛密度は0.52g/ml、安息角は36°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を99.973質量%、PPVE単位を0.027質量%含んでいた。上記PTFE粉末の融点は329℃及び342℃、引張破断強度は18MPa、引張破断歪は374%であった。
フッ素樹脂粉末A-1を70g、フッ素樹脂粉末B-1を30gとした以外は実施例1と同様にしてPTFE粉末を得た。得られたPTFE粉末の平均二次粒子径は33μm、D10は10μm、D90は103μm、見掛密度は0.56g/ml、安息角は37°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を100質量%含んでいた。上記PTFE粉末の融点は329℃及び345℃、引張破断強度は11MPa、引張破断歪は229%であった。
フッ素樹脂粉末A-2を70g、フッ素樹脂粉末B-1を30g用いて実施例1と同様にしてPTFE粉末を得た。得られたPTFE粉末の平均二次粒子径は36μm、D10は10μm、D90は105μm、見掛密度は0.68g/ml、安息角は37°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を100質量%含んでいた。上記PTFE粉末の融点は329℃及び345℃、引張破断強度は12MPa、引張破断歪は224%であった。
フッ素樹脂粉末A-1を40g、フッ素樹脂粉末B-2を45g、ガラス繊維(日東紡績株式会社製PF E-001)を15g用いて実施例2と同様にしてPTFE粉末を得た。得られたPTFE粉末の見掛密度は0.45g/ml、安息角は34°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を99.959質量%、PPVE単位を0.041質量%含んでいた。上記PTFE粉末の融点は329℃及び342℃、引張破断強度は15MPa、引張破断歪は342%であった。
フッ素樹脂粉末A-1を40g、フッ素樹脂粉末B-2を45g、ブロンズ粉末(福田金属箔粉工業製Bro-AT-200)を15g用いて実施例2と同様にしてPTFE粉末を得た。得られたPTFE粉末の見掛密度は0.53g/ml、安息角は34°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を99.959質量%、PPVE単位を0.041質量%含んでいた。上記PTFE粉末の融点は329℃及び342℃、引張破断強度は14MPa、引張破断歪は364%であった。
フッ素樹脂粉末A-1を40g、フッ素樹脂粉末B-2を40g、ガラス繊維(日東紡績株式会社製PF E-001)を15g、グラファイト(日本黒鉛工業株式会社製CPB)を5g用いて実施例2と同様にしてPTFE粉末を得た。得られたPTFE粉末の見掛密度は0.49g/ml、安息角は38°であり、取扱性に優れるものであった。また、上記PTFE粉末は、全重合単位に対しTFE単位を99.964質量%、PPVE単位を0.036質量%含んでいた。上記PTFE粉末の融点は329℃及び342℃、引張破断強度は9MPa、引張破断歪は80%であった。
Claims (15)
- 融点以上の温度に加熱した履歴のある溶融流動性を示さないフッ素樹脂Aと、融点以上の温度に加熱した履歴のない懸濁重合で重合された溶融流動性を示さないフッ素樹脂Bとを含み、見掛密度が0.42g/ml以上であるフッ素樹脂組成物。
- 前記フッ素樹脂組成物は、テトラフルオロエチレン単位、及び、テトラフルオロエチレンと共重合可能な変性モノマーに基づく変性モノマー単位を含み、全重合単位に対し、前記変性モノマー単位の量が1.0質量%以下である請求項1に記載のフッ素樹脂組成物。
- 333℃未満の温度領域に1つ以上、333~360℃の温度領域に1つ以上の融点を有する請求項1又は2に記載のフッ素樹脂組成物。
- フッ素樹脂Aは、ポリテトラフルオロエチレンである請求項1~3のいずれかに記載のフッ素樹脂組成物。
- フッ素樹脂Aの粒子の最大直線長さが、フッ素樹脂Bの粒子の最大直線長さより小さい請求項1~4のいずれかに記載のフッ素樹脂組成物。
- 安息角が40°未満である請求項1~5のいずれかに記載のフッ素樹脂組成物。
- 平均二次粒子径が5~700μmである請求項1~6のいずれかに記載のフッ素樹脂組成物。
- 低分子量含フッ素化合物の含有量が、前記フッ素樹脂組成物に対し1質量ppm以下である請求項1~7のいずれかに記載のフッ素樹脂組成物。
- 粉末である請求項1~8のいずれかに記載のフッ素樹脂組成物。
- 引張破断強度が10MPa以上である請求項1~9のいずれかに記載のフッ素樹脂組成物。
- 引張破断歪が150%以上である請求項1~10のいずれかに記載のフッ素樹脂組成物。
- 更に、充填材を含む請求項1~11のいずれかに記載のフッ素樹脂組成物。
- 請求項1~12のいずれかに記載のフッ素樹脂組成物を圧縮成形及び焼成して得られる成形体。
- 融点以上の温度に加熱した履歴のある溶融流動性を示さないフッ素樹脂Aと、融点以上の温度に加熱した履歴のない懸濁重合で重合された溶融流動性を示さないフッ素樹脂Bとを含み、テトラフルオロエチレン単位、及び、テトラフルオロエチレンと共重合可能な変性モノマーに基づく変性モノマー単位を含むフッ素樹脂組成物。
- 見掛密度が0.42g/ml以上である請求項14に記載のフッ素樹脂組成物。
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WO2013189826A1 (en) | 2012-06-20 | 2013-12-27 | Solvay Specialty Polymers Italy S.P.A. | Tetrafluoroethylene copolymers |
WO2013189824A1 (en) | 2012-06-20 | 2013-12-27 | Solvay Specialty Polymers Italy S.P.A. | Tetrafluoroethylene copolymers |
WO2019244433A1 (ja) | 2018-06-21 | 2019-12-26 | Blanc Bijou株式会社 | フッ素樹脂焼成体の生産方法、フッ素樹脂焼成体、フッ素樹脂ディスパージョンの生産方法、焼成体の生産方法、フッ素樹脂ディスパージョン、及び焼成体 |
WO2020138239A1 (ja) * | 2018-12-27 | 2020-07-02 | Agc株式会社 | 粒子の製造方法および成形体の製造方法 |
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JP2022159202A (ja) | 2022-10-17 |
TW202302750A (zh) | 2023-01-16 |
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US20240018349A1 (en) | 2024-01-18 |
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