JP6059233B2 - 難燃性熱可塑性樹脂組成物 - Google Patents
難燃性熱可塑性樹脂組成物 Download PDFInfo
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- JP6059233B2 JP6059233B2 JP2014532952A JP2014532952A JP6059233B2 JP 6059233 B2 JP6059233 B2 JP 6059233B2 JP 2014532952 A JP2014532952 A JP 2014532952A JP 2014532952 A JP2014532952 A JP 2014532952A JP 6059233 B2 JP6059233 B2 JP 6059233B2
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- 229920005992 thermoplastic resin Polymers 0.000 title claims description 72
- 239000011342 resin composition Substances 0.000 title claims description 46
- 239000003063 flame retardant Substances 0.000 title claims description 25
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims description 22
- 229920001169 thermoplastic Polymers 0.000 claims description 45
- 239000004416 thermosoftening plastic Substances 0.000 claims description 45
- -1 perfluoro Chemical group 0.000 claims description 30
- 239000000178 monomer Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 14
- 238000012360 testing method Methods 0.000 claims description 13
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 13
- 239000000155 melt Substances 0.000 claims description 10
- 238000002485 combustion reaction Methods 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 5
- 125000001033 ether group Chemical group 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 4
- 229920005989 resin Polymers 0.000 description 27
- 239000011347 resin Substances 0.000 description 27
- 125000003118 aryl group Chemical group 0.000 description 21
- 239000000047 product Substances 0.000 description 18
- 229920001643 poly(ether ketone) Polymers 0.000 description 16
- 229910052731 fluorine Inorganic materials 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 11
- 239000004696 Poly ether ether ketone Substances 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- 229920002530 polyetherether ketone Polymers 0.000 description 11
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 239000008188 pellet Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 238000001746 injection moulding Methods 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052755 nonmetal Inorganic materials 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920001652 poly(etherketoneketone) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001955 polyphenylene ether Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- DEQUKPCANKRTPZ-UHFFFAOYSA-N (2,3-dihydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1O DEQUKPCANKRTPZ-UHFFFAOYSA-N 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000006585 (C6-C10) arylene group Chemical group 0.000 description 1
- 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 1
- 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 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- OKISUZLXOYGIFP-UHFFFAOYSA-N 4,4'-dichlorobenzophenone Chemical compound C1=CC(Cl)=CC=C1C(=O)C1=CC=C(Cl)C=C1 OKISUZLXOYGIFP-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- YSYRISKCBOPJRG-UHFFFAOYSA-N 4,5-difluoro-2,2-bis(trifluoromethyl)-1,3-dioxole Chemical compound FC1=C(F)OC(C(F)(F)F)(C(F)(F)F)O1 YSYRISKCBOPJRG-UHFFFAOYSA-N 0.000 description 1
- HLRVUOFDBXRZBI-UHFFFAOYSA-N 4-fluoro-4'-hydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(F)C=C1 HLRVUOFDBXRZBI-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 239000004813 Perfluoroalkoxy alkane Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004962 Polyamide-imide Substances 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229920011301 perfluoro alkoxyl alkane Polymers 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002312 polyamide-imide Polymers 0.000 description 1
- 229920001230 polyarylate Polymers 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001470 polyketone Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/16—Condensation polymers of aldehydes or ketones with phenols only of ketones with phenols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C69/00—Combinations of shaping techniques not provided for in a single one of main groups B29C39/00 - B29C67/00, e.g. associations of moulding and joining techniques; Apparatus therefore
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/772—Articles characterised by their shape and not otherwise provided for
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
[−Ar−O−Ar−C(=O)−Ar−C(=O)−] (a2)
[−Ar−O−Ar−O−Ar−C(=O)−] (a3)
[式中、Arは2価の芳香族炭化水素環基(フェニレン基、ビフェニレン基など)を表す]
熱可塑性フッ素樹脂(B)は、ラジカル重合性パーフルオロ系単量体の共重合体、例えば、テトラフルオロエチレンとヘキサフルオロプロピレン及びパーフルオロ(C1−3アルキルビニルエーテル)から選択された少なくとも一種との共重合体であってもよい。温度390℃、剪断速度60s−1において、熱可塑性樹脂(A)と熱可塑性フッ素樹脂(B)との溶融粘度比は、前者/後者=0.3/1〜6/1であってもよい。
熱可塑性樹脂(A)は、アリーレン基とエーテル基[−O−]とカルボニル基[−C(=O)−]とで構成された繰り返し単位を含んでいる限り特に制限されず、例えば、下記式(a1)〜(a5)のいずれかで表される繰り返し単位を含んでいる。
[−Ar−O−Ar−C(=O)−] (a1)
[−Ar−O−Ar−C(=O)−Ar−C(=O)−] (a2)
[ −Ar−O−Ar−O−Ar−C(=O)−] (a3)
[−Ar−O−Ar−C(=O)−Ar−O−Ar−C(=O)−Ar−C(=O)−] (a4)
[−Ar−O−Ar−O−Ar−C(=O)−Ar−C(=O)−] (a5)
(式中、Arは置換基を有していてもよい2価の芳香族炭化水素環基を表す)
Arで表される2価の芳香族炭化水素環基としては、例えば、フェニレン基(o−、m−又はp−フェニレン基など)、ナフチレン基などのC6−10アリーレン基、ビフェニレン基(2,2’−ビフェニレン基、3,3’−ビフェニレン基、4,4’−ビフェニレン基など)などのビC6−10アリーレン基、o−、m−又はp−ターフェニレン基などのターC6−10アリーレン基などが例示できる。これらの芳香族炭化水素環基は、置換基、例えば、ハロゲン原子、アルキル基(メチル基などの直鎖状又は分岐鎖状C1−4アルキル基など)、ハロアルキル基、ヒドロキシル基、アルコキシ基(メトキシ基などの直鎖状又は分岐鎖状C1−4アルコキシ基など)、メルカプト基、アルキルチオ基、カルボキシル基、スルホ基、アミノ基、N−置換アミノ基、シアノ基などを有していてもよい。なお、繰り返し単位(a1)〜(a5)において、各Arの種類は、互いに同一であってもよく、異なっていてもよい。
熱可塑性フッ素樹脂(B)は、通常、火種及び融液の落下(ドリップ)を抑制するために用いられるが、本発明では、意外にも前記熱可塑性樹脂(A)との組み合わせにおいて少量で難燃性を大きく向上させる機能を有する。
熱可塑性樹脂組成物は、相分離構造を有しており、連続相を構成する熱可塑性樹脂(A)中に、分散相を構成する熱可塑性フッ素樹脂(B)が粒子状に分散している。分散相は、等方形状であってもよく、異方形状であってもよい。
PEEK:ダイセル・エボニック(株)製、ベスタキープ−J ZV7403、ポリエーテルエーテルケトン
FEP:テトラフルオロエチレン−ヘキサフルオロプロピレン系共重合体(組成重量比;テトラフルオロエチレン/ヘキサフルオロプロピレン/パーフルオロ(プロピルビニルエーテル)=87.5/11.5/1.0、MFR;27g/10分)
PFA:テトラフルオロエチレン−パーフルオロアルキルビニルエーテル系共重合体(組成重量比;テトラフルオロエチレン/パーフルオロ(プロピルビニルエーテル)=94.5/5.5、MFR;23g/10分)
[曲げ弾性率]
曲げ弾性率は、ASTM D790に準じて測定した。
比較例又は実施例の樹脂組成物で形成したプレスシートを、ウルトラミクロトーム(ライカ社製、ULTRACUT S)の試料ホルダーに固定し、チャンバー内を液体窒素で−80℃に冷却し、厚み90nmの薄切片を切り出した。得られた薄切片を、20%エタノール溶液を付着させた白金リングにて回収し、銅製シートメッシュ(応研商事社製、200A)に付着させた。透過型電子顕微鏡(日立製作所社製、H7100FA)を用いて、銅製シートメッシュに付着した薄切片を観察してネガフィルムを作製し、このネガフィルムをスキャナー(EPSON社製、GT−9400UF)にて電子画像化し、光学解析装置(ニレコ社製、LUZEX AP)を用いて電子像の二値化処理を行い、分散相の平均粒径を算出した。
比較例又は実施例の樹脂組成物で形成した射出成形品を用いて、UL94Vに準じて測定した。
シャーレの中央部にステンレス(SUS316)製の金属円板(φ50mm、厚み2mm)を積層した積層体を2組用意し、これらの積層体を、金属円板が内側になるように対向させて、2枚の金属円板の間に、比較例又は実施例の樹脂組成物で形成した1cm3のペレットを挟んで試験体を作製した。この試験体を、オーブン内にて390℃、42時間加熱し、金属の腐食を以下の基準により評価した。
3…ペレットを置いた部分が一部変色しているものの、凹凸は生成していない
2…ペレットを置いた部分が一部変色し、凹凸が生成している
1…ペレットを置いた部分が全て変色し、凹凸が生成している。
垂直燃焼試験用の試験片(0.8mm厚)について成形を行い、金型を開いて突き出しピンによってイジェクトした時に、試験片が移動側又は稼動側に残った場合を離型不良、残らずイジェクトできた場合を離型良として、10回の成形のうちの離型不良の回数により金型離型性を評価した。
JSW社製 TEX44αIIを用いて、PEEKとFEP又はPEEKとPFAを表3〜5に示す割合(重量比)でドライブレンドした後、表1〜2に示す条件で溶融混練し、樹脂組成物を調製した。この樹脂組成物をペレタイザーによりペレット化し、ペレットを作製した。また、前記樹脂組成物を熱プレス機により380℃及び5MPaの条件下でプレスし、厚み1.4mmのプレスシートを作製した。さらに、前記樹脂組成物を射出成形し、厚み0.8mmの射出成形品を作製した。結果を表3〜5に示す。
Claims (9)
- 厚み1.5mm以下の薄肉部を有する薄肉成形体を形成するための難燃性熱可塑性樹脂組成物であって、
アリーレン基とエーテル基とカルボニル基とで構成された繰り返し単位を含む熱可塑性樹脂(A)と、熱可塑性フッ素樹脂(B)とを含んでおり、
熱可塑性フッ素樹脂(B)が、テトラフルオロエチレンと、ヘキサフルオロプロピレン及びパーフルオロ(C 1−3 アルキルビニルエーテル)から選択された少なくとも一種との共重合体であり、
熱可塑性樹脂(A)と熱可塑性フッ素樹脂(B)との重量割合が、前者/後者=95/5〜99/1であり、
熱可塑性フッ素樹脂(B)が熱可塑性樹脂(A)中に粒子状に分散し、分散相を形成しており、分散相の平均粒子径が0.01〜0.8μmである難燃性熱可塑性樹脂組成物。 - 熱可塑性樹脂(A)と熱可塑性フッ素樹脂(B)との重量割合が、前者/後者=96/4〜98/2である請求項1記載の難燃性熱可塑性樹脂組成物。
- 熱可塑性フッ素樹脂(B)の分散相の平均粒子径が0.01〜0.7μmである請求項1又は2記載の難燃性熱可塑性樹脂組成物。
- 熱可塑性樹脂(A)が、下記式(a1)〜(a3)のいずれかで表される繰り返し単位を含む熱可塑性樹脂である請求項1〜3のいずれかに記載の難燃性熱可塑性樹脂組成物。
[−Ar−O−Ar−C(=O)−] (a1)
[−Ar−O−Ar−C(=O)−Ar−C(=O)−](a2)
[−Ar−O−Ar−O−Ar−C(=O)−] (a3)
(式中、Arは2価の芳香族炭化水素環基を表す) - 熱可塑性フッ素樹脂(B)が、ラジカル重合性パーフルオロ系単量体の共重合体である請求項1〜4のいずれかに記載の難燃性熱可塑性樹脂組成物。
- 温度390℃、剪断速度60s−1において、熱可塑性樹脂(A)と熱可塑性フッ素樹脂(B)との溶融粘度比が、前者/後者=0.3/1〜6/1である請求項1〜5のいずれかに記載の難燃性熱可塑性樹脂組成物。
- 厚み0.8mmの試験片を、UL94に準拠した垂直燃焼試験に供したとき、一回目及び二回目の着火時間の合計が10秒以下である請求項1〜6のいずれかに記載の難燃性熱可塑性樹脂組成物。
- 請求項1〜7のいずれかに記載の難燃性熱可塑性樹脂組成物で形成された薄肉成形体。
- 請求項1〜7のいずれかに記載の難燃性熱可塑性樹脂組成物を溶融混練して、熱可塑性樹脂(A)中に熱可塑性フッ素樹脂(B)を平均粒子径が0.01〜0.8μmの粒子状に分散させ、厚み1.5mm以下の薄肉部を有する薄肉成形体を成形することにより、この薄肉成形体の難燃性を向上させる方法。
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