TWI810327B - 含氟樹脂組成物及其製造方法 - Google Patents
含氟樹脂組成物及其製造方法 Download PDFInfo
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- TWI810327B TWI810327B TW108122493A TW108122493A TWI810327B TW I810327 B TWI810327 B TW I810327B TW 108122493 A TW108122493 A TW 108122493A TW 108122493 A TW108122493 A TW 108122493A TW I810327 B TWI810327 B TW I810327B
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- liquid crystal
- fluorine
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- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 39
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000011737 fluorine Substances 0.000 title claims abstract description 36
- 239000011342 resin composition Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 229920000106 Liquid crystal polymer Polymers 0.000 claims abstract description 42
- 239000004974 Thermotropic liquid crystal Substances 0.000 claims abstract description 34
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims abstract description 28
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims abstract description 28
- -1 polychlorotrifluoroethylene Polymers 0.000 claims abstract description 24
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 238000004898 kneading Methods 0.000 claims abstract description 9
- 239000000155 melt Substances 0.000 claims description 12
- 229920001577 copolymer Polymers 0.000 claims description 10
- 239000004973 liquid crystal related substance Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 6
- 230000000977 initiatory effect Effects 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 claims description 2
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 11
- 239000000178 monomer Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 description 8
- 238000005452 bending Methods 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 4
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- HNEGQIOMVPPMNR-IHWYPQMZSA-N citraconic acid Chemical compound OC(=O)C(/C)=C\C(O)=O HNEGQIOMVPPMNR-IHWYPQMZSA-N 0.000 description 4
- 229940018557 citraconic acid Drugs 0.000 description 4
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
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- 125000005010 perfluoroalkyl group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 2
- 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 2
- BLTXWCKMNMYXEA-UHFFFAOYSA-N 1,1,2-trifluoro-2-(trifluoromethoxy)ethene Chemical compound FC(F)=C(F)OC(F)(F)F BLTXWCKMNMYXEA-UHFFFAOYSA-N 0.000 description 2
- ADTHJEKIUIOLBX-UHFFFAOYSA-N 1,1,3,4,4,5,5,6,6,6-decafluoro-3-(trifluoromethyl)hex-1-ene Chemical compound FC(C(F)(F)F)(C(C(C(F)(F)F)(C=C(F)F)F)(F)F)F ADTHJEKIUIOLBX-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229940091181 aconitic acid Drugs 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000001530 fumaric acid Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- HNEGQIOMVPPMNR-NSCUHMNNSA-N mesaconic acid Chemical compound OC(=O)C(/C)=C/C(O)=O HNEGQIOMVPPMNR-NSCUHMNNSA-N 0.000 description 2
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000012783 reinforcing fiber Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- RMHCWMIZBMGHKV-UHFFFAOYSA-N 1,1,2,3,3,4,4,5,5,6,6,6-dodecafluorohex-1-ene Chemical group FC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RMHCWMIZBMGHKV-UHFFFAOYSA-N 0.000 description 1
- UPHOPMSGKZNELG-UHFFFAOYSA-N 2-hydroxynaphthalene-1-carboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=C(O)C=CC2=C1 UPHOPMSGKZNELG-UHFFFAOYSA-N 0.000 description 1
- GENYBPRYOMJDAG-UHFFFAOYSA-N 3,4-dioctylphthalic acid Chemical compound CCCCCCCCC1=CC=C(C(O)=O)C(C(O)=O)=C1CCCCCCCC GENYBPRYOMJDAG-UHFFFAOYSA-N 0.000 description 1
- 125000005274 4-hydroxybenzoic acid group Chemical group 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 150000001409 amidines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- WXBLLCUINBKULX-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1.OC(=O)C1=CC=CC=C1 WXBLLCUINBKULX-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000004203 carnauba wax Substances 0.000 description 1
- 235000013869 carnauba wax Nutrition 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005796 dehydrofluorination reaction Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
- C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- 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
- C08F114/24—Trifluorochloroethene
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones
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Abstract
本發明提供一種流動性得到較大改善之含氟樹脂組成物及其製造方法。本發明係關於一種含氟樹脂組成物,其特徵在於含有:99.99〜97質量%之熔點為205〜225℃之氟樹脂、及0.01〜2質量%之熱致液晶聚合物。又,本發明係關於一種含氟樹脂組成物之製造方法,其包含以285〜320℃將聚氯三氟乙烯、及熱致液晶聚合物混練之步驟。
Description
本發明係關於一種含氟樹脂組成物及其製造方法。
專利文獻1中,揭示有一種由氟樹脂及熱致液晶聚合物構成之組成物。然而,實施例中,研究了熱致液晶聚合物之含量最低為10質量%,且僅對機械物性進行評價。
專利文獻2中,揭示有一種由氟樹脂及熱致液晶聚合物構成之組成物。然而,僅揭示了熱致液晶聚合物之含量為40〜60質量%者。
專利文獻3中,揭示有一種由氟樹脂及熱致液晶聚合物構成之組成物。然而,僅揭示了熱致液晶聚合物之含量為20〜80質量%者。
專利文獻4中,揭示有一種由通用塑膠或工程塑膠及熱致液晶聚合物構成之組成物。然而,揭示了熱致液晶聚合物之含量為3〜90質量%,但並未提及氟樹脂。
[先前技術文獻]
[專利文獻]
專利文獻1:日本特開平2-110156號公報
專利文獻2:日本特開平2-32147號公報
專利文獻3:日本特開昭63-230756號公報
專利文獻4:日本特開昭56-115357號公報
[發明所欲解決之課題]
本發明之目的在於:提供一種流動性得到較大改善之含氟樹脂組成物及其製造方法。
[解決課題之技術手段]
本發明係關於一種含氟樹脂組成物,其含有:99.99〜97質量%之熔點為205〜225℃之氟樹脂、及0.01〜3質量%之熱致液晶聚合物。
氟樹脂較佳為聚氯三氟乙烯。
較佳為含有99.9〜98質量%之聚氯三氟乙烯、及0.1〜2質量%之熱致液晶聚合物。
聚氯三氟乙烯於280℃之熔體流動速率MFR為0.1〜1.0g/10分鐘。
熱致液晶聚合物之液晶轉移起始溫度較佳為200〜260℃。
熱致液晶聚合物較佳為對羥苯甲酸(para-oxybenzoic acid)與對苯二甲酸乙二酯(ethylene terephthalate)之共聚物。
又,本發明係關於一種含氟樹脂組成物,其含有:90質量%以上之聚氯三氟乙烯,且於280℃之熔體流動速率MFR為3〜40g/10分鐘。
又,本發明係關於一種上述含氟樹脂組成物之製造方法,其包含:以285〜320℃混練聚氯三氟乙烯、及熱致液晶聚合物之步驟。
[發明之效果]
本發明之含氟樹脂組成物因少量含有熱致液晶聚合物,故可維持著氟樹脂之優異特性而較大地改善流動性。因而,擠出成形性得到改善,且亦可進行原本射出成形困難之氟樹脂之射出成形。另一方面,因僅少量含有熱致液晶聚合物,故可無損氟樹脂之特性(例如聚氯三氟乙烯所具有之機械性強度或水蒸氣穿透性)而較大地改善成形性。
本發明人發現可藉由對含氟樹脂少量添加熱致液晶聚合物而大幅地改善流動性,遂完成了本發明之含氟樹脂組成物。
以下,具體地說明本發明。
本發明之含氟樹脂組成物之特徵在於含有:99.99〜97質量%之熔點為205〜225℃之氟樹脂、及0.01〜3質量%之熱致液晶聚合物。
氟樹脂之熔點為205〜225℃,但較佳為210〜216℃。此處,熔點指使用示差掃描熱量計(DSC)以10℃/分鐘之速度升溫時對應熔解熱曲線中之極大值的溫度。
作為熔點為205〜225℃之氟樹脂,只要滿足熔點則並無特別限制,但可列舉例如聚氯三氟乙烯(PCTFE)、乙烯-四氟乙烯(ETFE)、四氟乙烯-六氟丙烯-偏二氟乙烯(THV)等。其中,於氟樹脂之流動性較低,流動性之改善效果變高之方面,較佳為聚氯三氟乙烯。
作為本發明使用之PCTFE,可列舉氯三氟乙烯(CTFE)均聚物、及基於CTFE之聚合單位(「CTFE單位」)與基於可與CTFE聚合之單體(α)之聚合單位(「單體(α)單位」)之共聚物。
PCTFE較佳係CTFE單位為90〜100莫耳%。於防濕性更優異之方面,CTFE單位更佳為98〜100莫耳%,CTFE單位進而較佳為99〜100莫耳%。
於PCTFE為CTFE單位與單體(α)單位之共聚物之情形時,作為單體(α),若為可與CTFE共聚合之單體則並無特別限定,例如,可列舉四氟乙烯(TFE)、乙烯(Et)、偏二氟乙烯(VdF)、全氟(烷基乙烯基)醚(PAVE)、以下述通式(I):
CX3
X4
=CX1
(CF2
)n
X2
(I)
(式中,X1
、X3
及X4
相同或不同,且表示氫原子或氟原子,X2
表示氫原子、氟原子或氯原子,n表示1〜10之整數)所表示之乙烯基單體、及以下述通式(II)
CF2
=CF-OCH2
-Rf (II)
(式中,Rf為碳數1〜5之全氟烷基)所表示之烷基全氟乙烯基醚衍生物等。
作為上述PAVE,可列舉全氟(甲基乙烯基醚)〔PMVE〕、全氟(乙基乙烯基醚)〔PEVE〕、全氟(丙基乙烯基醚)〔PPVE〕、及全氟(丁基乙烯基醚)。
作為以上述通式(I)所表示之乙烯基單體,並無特別限定,可列舉例如六氟丙烯(HFP)、全氟(1,1,2-三氫-1-己烯)、全氟(1,1,5-三氫-1-戊烯)、以下述通式(III):
H2
C=CX5
Rf5
(III)
(式中,X5
為H、F或CF3
,Rf5
為碳數1〜10之全氟烷基)所表示之全氟(烷基)乙烯等。作為上述全氟(烷基)乙烯,較佳為全氟(丁基)乙烯。
作為以上述通式(II)所表示之烷基全氟***衍生物,較佳為Rf為碳數1〜3之全氟烷基者,更佳為CF2
=CF-OCH2
-CF2
CF3
。
作為可與上述CTFE聚合之單體(α),較佳為TFE、Et、VdF、PAVE、及選自由上述通式(I)所表示之乙烯基單體所構成之群中之至少1個。又,上述單體(α)亦可為1種或2種以上。
作為上述單體(α),又,亦可使用可與CTFE共聚合之不飽和羧酸類。作為上述不飽和羧酸類,並無特別限定,可列舉例如(甲基)丙烯酸、丁烯酸、順丁烯二酸、反丁烯二酸、衣康酸、檸康酸、中康酸、烏頭酸等碳數3〜6之不飽和脂肪族羧酸類等,亦可為碳數3〜6之不飽和脂肪族聚羧酸類。
作為上述不飽和脂肪族聚羧酸類,並無特別限定,例如,可列舉順丁烯二酸、反丁烯二酸、衣康酸、檸康酸、中康酸、烏頭酸等,且順丁烯二酸、衣康酸、檸康酸等可為酸酐者亦可為酸酐。
上述單體(α)亦可為2種以上,但其中1種為VdF、PAVE及/或HFP之情形時,亦可與衣康酸、檸康酸及其等之酸酐併用。
上述PCTFE較佳為熔體流動速率(MFR)為0.1〜1g/10分鐘。MFR係依據ASTM D3307,於溫度280℃、負載10.0kg之條件下測定所得之值。
氟樹脂之含量於含氟樹脂組成物中為99.99〜97質量%,但較佳為99.9〜98質量%。另一方面,熱致液晶聚合物之含量為0.01〜3質量%,較佳為0.1〜2質量%。氟樹脂之含量未達97質量%之情況下,存在機械強度低下之傾向,而若超過99.99質量%,則存在流動性改善效果變低之傾向。
熱致液晶聚合物若為經加熱成為向列型等液晶狀態之聚合物,則並無特別限定,例如,可列舉
I型液晶聚合物(雙酚/安息香酸/對羥苯甲酸(POB)共聚物等)
II型液晶聚合物(羥基萘甲酸(HNA)/POB共聚物等)
III型液晶聚合物(POB/對苯二甲酸乙二酯共聚物等)等。其中,根據混練溫度與液晶轉移溫度之觀點而言,較佳為POB/對苯二甲酸乙二酯共聚物等III型液晶聚合物。
POB/對苯二甲酸乙二酯共聚物中之POB單位之共聚合量並無特別限定,較佳為20〜80莫耳%,更佳為30〜70莫耳%。未達20莫耳%之情況下,存在不再具有充分之液晶性之傾向,而若超過80莫耳%,則存在聚合物之分子鏈變得過於剛直,液晶起始溫度變得過高之傾向。
熱致液晶聚合物之液晶轉移起始溫度並無特別限定,較佳為氟樹脂之加工溫度以下,例如PCTFE係加工溫度為280℃以上,故較佳為280℃以下,更佳為200〜260℃,進而較佳為210〜240℃。未達200℃之情況下,存在液晶聚合物於混練溫度下容易分解,從而容易損及分散效果之傾向,若超過260℃,則存在混練溫度下之熔融黏度較高,無法獲得流動性改善效果之傾向。此處,液晶起始溫度係指將熱致液晶聚合物載置於偏光顯微鏡之試樣台,升溫加熱,於剪切應力下發出乳白光之溫度。
本發明之含氟樹脂組成物之熔體流動速率MFR無特別限定,於280℃,較佳為3〜40g/10分鐘,更佳為5〜30g/10分鐘。於未達3g/10分鐘之情況下,熔融黏度變高,於射出成形時成為不良要因,而若超過40g/10分鐘,則存在機械強度低下之傾向。
又,本發明之含氟樹脂組成物之特徵在於含有90質量%以上之聚氯三氟乙烯,且於280℃之熔體流動速率MFR為3〜40g/10分鐘。
本發明之含氟樹脂組成物可含有氟樹脂及熱致液晶聚合物以外之其他成分。作為其他成分,可列舉強化纖維、填充劑、塑化劑、加工助劑、脫模劑、顏料、難燃劑、潤滑劑、光穩定劑、耐候穩定劑、導電劑、抗靜電劑、紫外線吸收劑、抗氧化劑、發泡劑、香料、油、軟化劑、脫氟化氫劑、成核劑等。作為上述強化纖維,可列舉碳纖維、玻璃纖維、玄武岩纖維等。作為填充劑,可列舉聚四氟乙烯、雲母、二氧化矽(silica)、滑石、矽藻土、黏土、氧化鈦、硫酸鋇等。作為導電劑,可列舉碳黑等。作為塑化劑,可列舉二辛基鄰苯二甲酸、新戊四醇等。作為加工助劑,可列舉巴西棕櫚蠟、碸化合物、低分子量聚乙烯、氟系助劑等。作為脫氟化氫劑,可列舉有機鎓、脒類等。
又,本發明之含氟樹脂組成物之製造方法之特徵在於包含:以285〜320℃混練聚氯三氟乙烯及熱致液晶聚合物之步驟。
混練方法並無特別限定,可使用爐碾壓機、班布里混合機、加壓捏合機、擠出機等,但於可施加高剪切力之方面,較佳為採用加壓捏合機或雙軸擠出機等擠出機。
較佳為於PCTFE之熔點以上且分解溫度以下之溫度進行熔融混練。具體而言,較佳為於250〜360℃進行,更佳為285〜320℃。於未達250℃之情況下,存在變得難以分散之傾向,而超過360℃,則存在含氟樹脂之分子量下降,強度降低之傾向。
本發明之含氟樹脂組成物或利用其製造方法所得之含氟樹脂組成物可藉由擠出成形、射出成形等而賦形。所得之成形品可用於半導體相關行業、醫藥用覆膜、阻隔膜、產業機器、電子零件、汽車用零件等多種用途。
實施例
繼而,列舉實施例而說明本發明,但本發明不僅限於此等實施例。
以下表示實施例及比較例中使用之材料。
聚氯三氟乙烯:CTFE100莫耳%、熔點211℃、於280℃之MFR:0.49g/10分鐘
熱致液晶聚合物:X7G(Eastman Kodak公司製造)、液晶起始溫度:245℃、對羥苯甲酸單元之共聚合量:40莫耳%
實施例1〜2
以表1中所示之液晶聚合物之摻合量,使用雙軸擠出機,以圓筒溫度290〜315℃進行混練,製作含氟樹脂組成物。將所得之含氟樹脂組成物,利用設定為圓筒溫度270〜300℃、噴嘴溫度300℃、模具溫度100℃之射出成型機進行射出成形,而成形啞鈴型試驗片及彎曲試驗片。
比較例1
將PCTFE利用設定為圓筒溫度300〜330℃、噴嘴溫度330℃、模具溫度100℃之射出成型機進行射出成形,而成形啞鈴型試驗片及彎曲試驗片。
<熔體流動速率(MFR)>
依據ASTM D1238,使用熔融指數測定儀(東洋精機公司製造),以280℃保持5分鐘後,將10kg負載下自內徑2.095mm、長度8mm之噴嘴流出10分鐘之聚合物之質量(g/10分鐘)設為MFR。
<拉伸物性>
使用所得之啞鈴型試驗片,藉由Tensilon萬能試驗機(A&D公司製造)以50mm/分鐘之速度進行拉伸試驗,依據ASTM D638,求出拉伸斷裂強度及拉伸斷裂伸長率。
<彎曲物性>
使用所得之彎曲試驗片,藉由Tensilon萬能試驗機(A&D公司製造)以2mm/分鐘之速度進行彎曲試驗,依據ASTM D790,求出彎曲強度及彎曲彈性模數。
<負載撓曲溫度>
使用所得之彎曲試驗片,藉由熱變形試驗機(安田精機公司製造),將1.83MPa之負載下達到0.254mm之撓曲之溫度參照ASTM D648,求出負載撓曲溫度。
<水蒸氣穿透性>
將利用壓縮成形製作而成之膜切割成50mm×50mm之尺寸,基於JIS K7129(A法),利用水蒸氣穿透度計L80-5000(Dr.Lyssy公司製造),施以Ф30mm之過濾器,測定膜之水蒸氣穿透度。
[表1]
實施例1之含氟樹脂組成物中,即便含有僅0.5質量份之液晶聚合物,聚氯三氟乙烯之MFR0.49g/10分鐘亦增大約25倍為14.8g/10分鐘,流動性顯著改善。其結果,即便PCTFE之成形溫度320〜330℃下降至300℃亦可進行射出成形。
又,對於機械物性而言,彎曲彈性模數提高,而拉伸強度、彎曲強度、負載撓曲溫度、水蒸氣穿透性則幾乎未變化。
實施例2之含氟樹脂組成物中,即便含有僅1質量份之液晶聚合物,MFR亦增大約50倍,流動性顯著改善。又,對於機械物性而言,彎曲彈性模數提高,而拉伸強度、彎曲強度、負載撓曲溫度、水蒸氣穿透性則幾乎未變。
[產業上之可利用性]
本發明之含氟樹脂組成物係流動性得到較大改善,可較佳地適用於擠出成形或射出成形。
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Claims (10)
- 一種含氟樹脂組成物,其含有:99.5~99.99質量%之熔點為205~225℃之氟樹脂、及0.01~0.5質量%之熱致液晶聚合物,熱致液晶聚合物之液晶轉移起始溫度為200~280℃。
- 如請求項1所述之含氟樹脂組成物,其中,氟樹脂係聚氯三氟乙烯。
- 如請求項2所述之含氟樹脂組成物,其含有99.5~99.9質量%之聚氯三氟乙烯、及0.1~0.5質量%之熱致液晶聚合物。
- 如請求項2所述之含氟樹脂組成物,其中,聚氯三氟乙烯於280℃之熔體流動速率MFR為0.1~1.0g/10分鐘。
- 如請求項3所述之含氟樹脂組成物,其中,聚氯三氟乙烯於280℃之熔體流動速率MFR為0.1~1.0g/10分鐘。
- 如請求項1至5中任一項所述之含氟樹脂組成物,其中,熱致液晶聚合物之液晶轉移起始溫度為200~260℃。
- 如請求項1至5中任一項所述之含氟樹脂組成物,其中,熱致液晶聚合物為對羥苯甲酸(para-oxybenzoic acid)與對苯二甲酸乙二酯(ethylene terephthalate)之共聚物。
- 如請求項6所述之含氟樹脂組成物,其中,熱致液晶聚合物為對羥苯甲酸與對苯二甲酸乙二酯之共聚物。
- 一種含氟樹脂組成物,其含有:99.5質量%以上之聚氯三氟乙烯、及液晶轉移起始溫度為200~280℃之熱致液晶聚合物,且於280℃之熔體流動速率MFR為3~40g/10分鐘。
- 一種請求項1至9中任一項所述之含氟樹脂組成物之製造方法,其包含:以285~320℃混練聚氯三氟乙烯、及熱致液晶聚合物之步驟。
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CN110669302A (zh) | 2020-01-10 |
TW202006052A (zh) | 2020-02-01 |
JP7152726B2 (ja) | 2022-10-13 |
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KR102442817B1 (ko) | 2022-09-14 |
EP3795631A4 (en) | 2022-03-09 |
EP3795631A1 (en) | 2021-03-24 |
KR20210013115A (ko) | 2021-02-03 |
US20210253841A1 (en) | 2021-08-19 |
CN112352015B (zh) | 2022-11-18 |
CN112352015A (zh) | 2021-02-09 |
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