WO2003044088A1 - Composition a base de resine plastique d'ingenierie decomposable a basse temperature et procede de production d'un objet moule a partir de cette composition - Google Patents
Composition a base de resine plastique d'ingenierie decomposable a basse temperature et procede de production d'un objet moule a partir de cette composition Download PDFInfo
- Publication number
- WO2003044088A1 WO2003044088A1 PCT/JP2002/012147 JP0212147W WO03044088A1 WO 2003044088 A1 WO2003044088 A1 WO 2003044088A1 JP 0212147 W JP0212147 W JP 0212147W WO 03044088 A1 WO03044088 A1 WO 03044088A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- low
- temperature
- engineering plastic
- decomposable engineering
- fluorine
- Prior art date
Links
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 170
- 239000000203 mixture Substances 0.000 title claims abstract description 77
- 239000000088 plastic resin Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title description 32
- 230000008569 process Effects 0.000 title description 7
- 238000002844 melting Methods 0.000 claims abstract description 36
- 230000008018 melting Effects 0.000 claims abstract description 35
- 125000000524 functional group Chemical group 0.000 claims abstract description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 19
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 12
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 11
- 125000004429 atom Chemical group 0.000 claims abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 7
- 229910052731 fluorine Inorganic materials 0.000 claims description 97
- 239000011737 fluorine Substances 0.000 claims description 88
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 87
- 229920005989 resin Polymers 0.000 claims description 84
- 239000011347 resin Substances 0.000 claims description 84
- 238000000465 moulding Methods 0.000 claims description 81
- 229920000642 polymer Polymers 0.000 claims description 53
- 238000002156 mixing Methods 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 34
- 229920002313 fluoropolymer Polymers 0.000 claims description 29
- 239000004811 fluoropolymer Substances 0.000 claims description 29
- 238000004519 manufacturing process Methods 0.000 claims description 23
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 23
- 229920001577 copolymer Polymers 0.000 claims description 17
- 229920006324 polyoxymethylene Polymers 0.000 claims description 16
- 229930182556 Polyacetal Natural products 0.000 claims description 14
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 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 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 9
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 238000010137 moulding (plastic) Methods 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 abstract description 49
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 abstract description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052740 iodine Inorganic materials 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 abstract 1
- 229910052794 bromium Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- 239000011630 iodine Substances 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 19
- 238000009864 tensile test Methods 0.000 description 18
- 238000001746 injection moulding Methods 0.000 description 16
- 239000008188 pellet Substances 0.000 description 15
- 239000000155 melt Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- -1 Polytetrafluoroethylene Polymers 0.000 description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical group O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000006116 polymerization reaction Methods 0.000 description 8
- 239000006057 Non-nutritive feed additive Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 238000011282 treatment Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 229920001684 low density polyethylene Polymers 0.000 description 4
- 239000004702 low-density polyethylene Substances 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 230000001603 reducing effect Effects 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 229920006038 crystalline resin Polymers 0.000 description 3
- 150000004292 cyclic ethers Chemical group 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000008187 granular material Substances 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 description 2
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- 229920004943 Delrin® Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 229920006127 amorphous resin Polymers 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000012779 reinforcing material Substances 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- YGZQJYIITOMTMD-UHFFFAOYSA-N 1-propoxybutane Chemical compound CCCCOCCC YGZQJYIITOMTMD-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XBFMJHQFVWWFLA-UHFFFAOYSA-N hexane;pentane Chemical compound CCCCC.CCCCCC XBFMJHQFVWWFLA-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 239000012768 molten material Substances 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
- 150000005673 monoalkenes Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000005824 oxyalkoxy group Chemical group 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920013745 polyesteretherketone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009717 reactive processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 102220294630 rs1158271855 Human genes 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000005336 safety glass Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 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
- 230000003068 static effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920002397 thermoplastic olefin Polymers 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
- C08L59/02—Polyacetals containing polyoxymethylene sequences only
-
- 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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/002—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds
- C08G65/005—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens
- C08G65/007—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from unsaturated compounds containing halogens containing fluorine
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08G2650/46—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen
- C08G2650/48—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing halogen containing fluorine, e.g. perfluropolyethers
Definitions
- the present invention relates to a low-temperature decomposable engineering plastic resin composition capable of improving the molding processability of a low-temperature decomposable engineering plastic and a method for producing a low-temperature decomposable engineering plastic molded body using the low-temperature decomposable engineering plastic resin composition. . ⁇
- Polymers that can be molded are usually molded by heating and melting in a molding machine, shaping the resulting melt in a mold or the like, and cooling.
- the molding method include extrusion molding. In this case, the melt is extruded through a barrel of an extruder with a rotating screw into a die and molded.
- the extrusion pressure and the extrusion torque generally increase with an increase in the friction between the extrudate and the die when compared between polymers having the same melt fluidity. If the extrusion pressure or torque is too high, it may cause industrial production problems such as the extruder automatically shutting down due to overload exceeding the limit of the extruder.
- U.S. Pat.No. 5,010,130 discloses a resin composition in which an auxiliary agent is blended, the main component of which is a resin that is difficult to melt mold, and the viscosity at 200 ° C. is 4 OOP a ⁇ s as another component.
- Polytetrafluoroethylene [PTFE] or a tetrafluoroethylene which is melted at the molding temperature in the case of a crystalline resin and has a glass transition point (Tg) or more in the case of an amorphous resin The use of a copolymer of [TFE] is disclosed.
- this technology is for a resin that is difficult to be melt-molded, and the above fluororesin is regarded as a resin having a melting point lower than that of the main resin.
- U.S. Pat.No. 3,125,547 discloses the use of a small amount of fluorinated carbon polymer as a continuous replenishment slip agent in extrusion molding of hydrocarbon polymers such as low density polyethylene [LDPE], which is solid at processing temperatures.
- LDPE low density polyethylene
- the fluororesin is said to have little or no improvement in the extrusion properties of hydrocarbon polymers.
- U.S. Pat.No. 4,855,360 uses poly (oxy-alkoxy) olefins to improve the flow on the die for the purpose of reducing melt defects in the extrudate, with a weight ratio of 1 /
- a thermoplastic olefin resin composition is disclosed in which a fluororesin is blended at a ratio of 0.005 to 0.2% by weight with respect to 1 to 1/10 or the polyolefin resin composition.
- U.S. Pat. No. 52666 39 discloses an intrinsic infrared ratio (HFP index) of 6.4 to 9.0 and a melt viscosity of 0 to prevent melt fracture and shorten the molding start time. l X 1 0 3 to 1 0 X 10 3 poise TF E / hexa It is disclosed that fluoropropylene [HFP] copolymer [FEP] is used as a molding aid for polyolefin.
- HFP index intrinsic infrared ratio
- FEP fluoropropylene
- US Pat. No. 5,477,761 discloses a technique for coating polyolefin with FEP having an HFP index of 6.4 to 9.0 and a Tm of 180 to 255 ° C.
- U.S. Pat.No. 5,770,569 discloses a method for extruding a polyolefin composition having a divalent or trivalent metal ion and an organic or inorganic anion for the purpose of eliminating the action of Ca2 +.
- these technologies are for polyolefin polymers obtained by butyl polymerization such as polyethylene and polypropylene, and improve the molding processability of engineering plastics such as polyamide and polyester ether ketone. Therefore, a technique using a fluoropolymer is not disclosed.
- U.S. Pat.No. 5,32,368 discloses a nylon 66 with FEP or irradiated PTFE as a blend of a melt-difficult polymer and a fluoropolymer processing aid to which 0.002 to 0.5% by weight of this polymer is added.
- the blend is illustrated. While by force, this Furuoroporima has foremost chain end C_ ⁇ _OH, ionic groups or one COF such as one S_ ⁇ 3 H, certain polar functional groups at least 100 ratio of per million carbon atoms
- the processing aid is chemically and physically bonded to the metal or metal oxide die surface to reduce the resistance to the flow of the polymer melt on the die surface, and the polar end groups are humidified heat treatment, etc.
- U.S. Pat. No. 6,380,033 discloses that a fluororesin, which is essential to have a perfluorobule ether unit, is used as a processing aid for a thermoplastic resin such as LDPE. Yes.
- a fluororesin which is essential to have a perfluorobule ether unit
- LDPE thermoplastic resin
- Low-temperature decomposable engineering plastics such as polyacetal as a melt-processible polymer
- the fluororesin has a polar functional group.
- the object of the present invention is to mold extrusion pressure, extrusion torque, etc. in molding process of meltable low-temperature decomposable engineering plastic, not resin difficult to be melt-molded as shown in the above patents or polyolefin resin.
- An object of the present invention is to provide a resin composition capable of improving processability and stably obtaining molding processability in extrusion pressure, extrusion torque, and the like.
- the present invention is a resin composition obtained by blending a low-temperature decomposable engineering plastic and a fluorine-containing resin.
- the low-temperature decomposable engineering plastic has a melting point of 200 ° C. or lower and a decomposition temperature of 300 ° C.
- a resin comprising a fluorine-containing polymer bonded with a fluorine atom, and the fluorine-containing polymer has substantially no polar functional group having reactivity with the low-temperature decomposable engineering plastic.
- a low-temperature decomposable engineering plastic resin composition characterized by
- the present invention is a method for producing a low-temperature decomposable engineering plastic resin composition, wherein the low-temperature decomposable engineering plastic resin composition is produced by blending a low-temperature decomposable engineering plastic and a fluorine-containing resin.
- the present invention also provides a method for producing a low-temperature decomposable 4 engineering plastic molded product, characterized in that the low-temperature decomposable engineering plastic resin composition is melted and molded.
- the low temperature decomposable engineering plastic resin composition of the present invention is obtained by blending a fluorine-containing resin and a low temperature decomposable engineering plastic.
- a fluorine atom is bonded to at least one atom selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom, on a non-terminal carbon atom constituting the main chain.
- It is a resin comprising a fluoropolymer.
- the “non-terminal carbon atom” means a carbon atom constituting the main chain of the fluoropolymer that is different from the carbon atom present at the terminal.
- Such fluorine-containing resins usually have a low melting point, and can be suitably used as a processing aid for low-temperature decomposable engineering plastics.
- at least one atom selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and an iodine atom is bonded to a non-terminal carbon atom constituting the main chain and a fluorine atom.
- an atom other than these such as an oxygen atom, a nitrogen atom, a silicon atom, or a sulfur atom, may be bonded to the non-terminal carbon atom constituting the main chain.
- the oxygen atom is usually ether oxygen.
- fluorine-containing polymer examples include, as monomer components, perfluoromonomers such as tetrafluoroethylene [TFE], hexafluoropropylene [HFP], and perfluorovinyl ether [PFVE]; Fluorovinyl monomer such as trifluoroethylene [CTFE]; vinylidene fluoride [VdF], fluorinated buluyl, trifluoroethylene, the following general formula (i)
- X 1 represents a hydrogen atom or a fluorine atom
- X 2 represents a hydrogen atom, a fluorine atom or a chlorine atom
- n represents an integer of 1 to 10
- examples thereof include polymers obtained by polymerizing one or more fluorine-containing monomers such as other fluorine-containing monomer other than the above.
- examples of the PFVE include perfluoro (alkyl vinyl ether) [P AV E] and the like.
- the monomer component include ethylene [E t], propylene [P r] and the like.
- One or two or more types of bulle monomers not containing fluorine may be included.
- the fluorine-containing polymer is obtained by polymerization using each of the above-mentioned monomers.
- a hydrogen atom, a chlorine atom, a bromine atom is added to a non-terminal carbon atom constituting the main chain. It goes without saying that at least one atom selected from the group consisting of silicon atoms and fluorine atoms are bonded to fluorine atoms.
- the perfluoromonomer is a monomer having a main chain composed of a carbon atom, a fluorine atom, and optionally an oxygen atom, and a hydrogen atom is not bonded to a carbon atom of the main chain.
- Perfluorovinyl monomers such as TFE and HFP; PAVE monomers such as perfluoro (propyl butyl ether) [PPVE].
- the oxygen atom is usually ether oxygen.
- fluoropolymer examples include polyvinylidene fluoride [PVdF], TFEZHFP / VdF copolymer [THV], VdF / TFE copolymer [VT], VdF / HFP copolymer [VdFZHFP], VdF
- VdF polyvinylidene fluoride
- TV TFEZHFP / VdF copolymer
- VT VdF / TFE copolymer
- VdFZHFP VdF
- VdF examples include V d F polymers containing V d F as monomer components such as / TFE / HFP copolymer [V d F / TFE / HF P].
- the fluoropolymer further include TFE polymers such as an E tZTFE copolymer [ETF E] and an E tZTFEZHFP copolymer [EFEP]; an E t ZCTFE copolymer [ECTFE] and the like.
- TFE polymers such as an E tZTFE copolymer [ETF E] and an E tZTFEZHFP copolymer [EFEP]; an E t ZCTFE copolymer [ECTFE] and the like.
- EFE E E
- E tZTFEZHFP copolymer E tZTFEZHFP copolymer
- ECTFE E t ZCTFE copolymer
- the fluorine-containing polymer examples include the above-mentioned fluorine-containing monomer; a vinyl monomer that does not contain fluorine, such as Et, P, and the like; and a single monomer having a cyclic structure. It may be obtained by polymerizing one or more comonomer such as a monomer in a small amount.
- the cyclic structure is not particularly limited, and examples thereof include a cyclic ether structure such as a cyclic acetal structure.
- at least two carbon atoms constituting the cyclic ether structure are the main chain of the fluoropolymer. Are becoming part of.
- the fluorine-containing polymer obtained by copolymerizing a small amount of a comonomer in addition to the comonomer essential for the copolymer as a monomer component For example, it may be obtained by copolymerizing a small amount of PAVE such as P PVE and / or a monomer represented by the above general formula (i).
- the comonomer for copolymerizing the small amount is preferably 5% by mass or less of the total amount of the monomer components. 5 mass. If it exceeds / 0 , the desired copolymer properties may not be obtained.
- the fluorine-containing polymer is preferably obtained by polymerizing a monomer component substantially free of perfluorovinyl ether [PFVE].
- PFVE perfluorovinyl ether
- the phrase “substantially free of PFVE” means that PFVE is less than 1% by mass of the total amount of the monomer components.
- the PFVE is 0.1 mass out of the total amount of the monomer components. /. Is preferably less than 0.05% by mass.
- the fluoropolymer may be a melt-formable fluororesin such as ETFE, ECTFE, EFEP, PVd F, THV, VT, etc. from the viewpoint of meltability, elasticity, application, and the like.
- fluoropolymer 1 type (s) or 2 or more types can be used.
- the fluoropolymer As the fluoropolymer, the TFE polymer, ECTFE and the V d F polymer as a resin are preferable, the TFE polymer is more preferable, and the EFEP is more preferable.
- the fluoropolymer may contain TFE as a monomer component from the viewpoint of enhancing the moldability of the low-temperature decomposable engineering plastic resin composition, although it varies depending on the application.
- a resin containing TFE as a body component is preferred.
- the fluoropolymer a polymer obtained by polymerizing a monomer component comprising TFE and HFP is more preferable.
- the fluorine-containing polymer can be obtained by polymerizing a monomer component containing TFE and HFP.
- TFE and HFP are different; fluorine Vinyl monomers that do not contain a monomer; they may be obtained by polymerizing a comonomer such as a monomer having a cyclic structure.
- the above-mentioned fluoropolymer is present at the main terminal and side chain, and has very few 14 functional groups that have reactivity with low-temperature decomposable engineering plastics.
- the above Is not particularly limited as the polar functional groups having reactivity with the low temperature decomposable engineering plastics, for example, one COF one 'CO OM one S_ ⁇ 3 M, - OS 0 3 M , one CH 2 OH, etc.
- M represents a hydrogen atom, a metal cation, or a quaternary ammonium ion. More preferably, the fluoropolymer is substantially free of polar functional groups having reactivity with the low-temperature decomposable engineering plastic.
- the phrase “having substantially no polar functional group” means that the polar functional group does not function as a polar functional group even when the polar functional group is slightly present at the main chain end or side chain. Yes, it means that it does not participate in the reaction with the above low-temperature decomposable engineering plastic.
- the number of polar functional groups that the fluoropolymer may have per 100,000 carbon atoms is 50 or less, preferably 30 or less, and more preferably 10 or less.
- the fluoropolymer has substantially no polar functional group having a reaction 4 with the low-temperature decomposable engineering plastic, so that it can be prepared or molded at a low-temperature decomposable engineering plastic resin composition to be described later. Reactions such as hydrolysis of the above-mentioned low-temperature-decomposable engineering plastics during processing can be suppressed, and generation of decomposition products can be suppressed, so that yellowing of the resulting molded product can be prevented. The moldability can be stabilized, and the inherent characteristics of the low-temperature decomposable engineering plastic can be fully utilized.
- the fluorine-containing polymer does not substantially have a polar functional group
- the fluorine-containing polymer can be used together with the low-temperature-decomposable engineering plastic on the die surface, screw surface, barrel inner wall, etc. of an extruder, for example. Reduces friction and lubrication 1 ”does not hinder the production, so it is possible to reduce extrusion pressure and torque and to reduce these fluctuations, and to improve the molding processability of the low temperature degradable engineering plastic resin composition of the present invention. it can.
- the mechanism for reducing the friction is not clear, it is considered as follows. That is, in the molding machine, many of the low-temperature angularity engineering plastics have polar parts such as amide bonds in the main chain structure. Such low-temperature decomposable engineering plastics are molding machines such as dies, screws, and barrels. On the surface of a part of Adhesiveness to parts made of a certain metal or metallic acid is high, but the adhesive property is very low. The adhesive strength between the low-temperature decomposable engineering plastic resin composition and the molding machine can be reduced by entering between the engineering plastic and the metal part.
- the fluorine-containing polymer has substantially no polar functional group, but is present in a portion made of metal or metal oxide on the inner surface of the molding machine, and lubricates the flow of the low-temperature decomposable engineering plastic. Demonstrate its properties throughout the molding process.
- the fluorine-containing polymer can be located on the surface of the metal or metal oxide because of the interfacial tension, and what is phase-separated is due to the force to reduce the interface with the partner component even a little. Conceivable. Therefore, the above fluoropolymer does not need to have a polar functional group by itself when it is supplied stably.
- the number of the polar functional groups possessed by the fluoropolymer can be determined by, for example, the method described in US Pat. No. 5,13,3,368. That is, using a film obtained by compression molding the fluoropolymer, the absorbance was measured with an infrared spectrophotometer, and the calibration factor (CF) determined by measuring the model compound containing the polar functional group was used.
- the number of terminal groups per 1 million carbon atoms of the fluorine-containing polymer can be obtained from the following formula. ⁇ ⁇ Atom 10 6 Crane officer.
- the thickness of fill J The wavelength of the polar functional group ( ⁇ ⁇ ) and the calibration factor of the model compound are, for example, 5.3 1 ⁇ ⁇ for 1 COF, 4 0 6, 5.5 2 ⁇ for —COOH, respectively. 3 3 5; — For COOCH 3 , 5.5 7 ⁇ m, 3 68, etc.
- the fluorine-containing polymer can be synthesized by polymerizing the monomer components using usual polymerization methods such as emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, and gas phase polymerization. it can.
- a chain transfer agent may be used.
- the chain transfer agent is not particularly limited.
- Methanol is preferred.
- the chain transfer agent can be preferably used.
- the polar functional group is used at the chain end.
- a polymer having the above-mentioned polar functional group can be eliminated by subjecting this polymer to treatment such as steam treatment to stabilize the chain ends.
- the polar functional group can be converted to one CF 3 or one CONH 2 by, for example, fluorine gas [F 2 ] treatment or ammonia treatment, and to one CF 2 H by the above steam treatment or hydrogen treatment. You can also Therefore, the fluoropolymer may have one CF 3 , one CONH 2 , one CF 2 H, or the like. Above-CF 3 , 1 CONH 2 , 1 CF 2 H, etc. are different from the above polar functional groups. In the case of suspension polymerization, a polymer having substantially no polar functional group can be obtained without performing these treatments.
- the melting point of the fluoropolymer is not particularly limited, but it is preferable that the polymer is already melted at a temperature at which the low-temperature decomposable engineering plastic used in the molding machine melts.
- the temperature is preferably lower than the processing temperature of the plastic, and more preferably lower than the melting point of the low-temperature decomposable engineering plastic used.
- the low-temperature decomposable engineering plastic resin blended with the fluoropolymer in the low-temperature decomposable engineering plastic resin composite of the present invention usually has excellent properties such as heat resistance, high strength, and high dimensional stability. However, it is a resin that can be used as a substitute material for metals depending on the case. For example, mechanical properties such as machinery, equipment parts, electrical and electronic parts, etc. It includes resins that can be used for materials and the like.
- the low-temperature decomposable engineering plastic is a high-performance plastic suitable for structural members and mechanical members, and is mainly used for industrial use, including those used for textiles. Absent.
- Engineering plastics generally have a heat resistance of 10 ° C or higher, Tensile strength is 49 MP a (5 kgf 'mm— 2 ) or more and flexural modulus is 2 GP a
- the above heat resistance of 100 ° C or higher means that the melting point in the case of a crystalline resin and the glass transition point in the case of non-crystalline cocoon are not less than 100 ° C and less than 100 ° c. It means that the mechanical strength does not deteriorate at the temperature of.
- the deflection temperature under load (DTUL; ASTM D 648) is usually used.
- the deflection temperature under load is the temperature at which the test bar obtained by using the resin to be measured is heated by applying a load of 1.82 MPa or 0.45 MPa and the test bar begins to deform.
- the above engineering plastics usually have heat resistance of 150 ° C or higher, and include those called special engineering plastics or super engineering plastics (super engineering plastics).
- the tensile strength is the maximum stress until it breaks due to the tensile load, and is the value obtained by dividing the maximum load by the original cross-sectional area of the test piece.
- the tensile strength is determined by a method based on ASTM D 638-00 (2000).
- the above engineering plastics usually have a standard composition of raw resin and the above tensile strength is 49 to 20 OMPa as data without reinforcement.
- the flexural modulus is the elastic modulus calculated using the load-deflection curve obtained for the test piece in the 3-point bending test and 4-point bending test.
- the flexural modulus is obtained by performing a method according to ASTM D 790-00 (2000).
- ASTM D 790-00 As the above-mentioned engineering plastics, those having a flexural modulus of 2 to 7 GPa as a standard composition of raw resin and without reinforcing materials are usually preferable.
- the lower limit of the flexural modulus is more preferably 2.4 GPa.
- the low-temperature decomposable engineering plastic resin yarn composition of the present invention is described later. As a matter of course, it is a thermoplastic resin.
- the low-temperature-decomposable engineering plastic has the melting point of 200 ° C or lower and the decomposition temperature of 300 ° C or lower among the engineering plastics. is there.
- the melting point of the low-temperature decomposable engineering plastic has a more preferable upper limit of 190 ° C.
- the upper limit of the decomposition temperature of the low-temperature decomposable engineering plastic is more preferably 2500 ° C.
- the low-temperature decomposable engineering plastic preferably has a resin temperature during molding of 1550 to 2500C.
- the resin temperature has a more preferred lower limit of 1700 ° C, a more preferred lower limit of 1800 ° C, a more preferred upper limit of 2400 ° C, and a more preferred upper limit of 2300 ° C. It is.
- the low-temperature decomposable engineering plastic is usually a plastic obtained by polymerization of carbonyl groups such as formaldehyde such as polyacetal.
- the polyacetal include, for example, a homopolymer obtained by polymerizing formaldehyde as a raw material using various catalysts, a cyclic ether different from trioxane at the time of ring-opening polymerization of trioxane, which is a trimer of formaldehyde, and the like. And a copolymer obtained by adding and polymerizing.
- the polyacetal include polyoxymethylene [POM]. When the polyacetal is made of a homopolymer, it has higher crystallinity and a higher melting point than those made of a copolymer, but has a poor thermal stability and a high tendency to low temperature decomposability.
- the low-melting-point engineering plastic one having self-lubricating property is preferable.
- the above low-melting engineering plastics are usually excellent in lubricity under low load if they have self-lubricating properties, but this characteristic is generally determined by the main chain and the atoms bonded to this main chain. It is considered that the surface of the polymer chain to be formed can be expressed due to the fact that there are few irregularities. For example, the static friction coefficient and the dynamic friction coefficient can be reduced.
- the low-temperature decomposable engineering plastic includes the above melting point (non-crystalline tree In the case of fat, there is no particular limitation as long as it has a glass transition point) and a decomposition temperature.
- a low-temperature decomposable engineering plastic made of a polymer having no phenylene group in the main chain skeleton, etc. Examples of such materials include polyacetal homopolymers and copolymers made from formaldehyde.
- the low-temperature decomposable engineering plastic one or more kinds can be used.
- the low-temperature angle-divergence engineering plastic can be synthesized by, for example, a conventionally known method according to each type.
- the fluorine-containing resin is 0.05 to 1% by mass of the total of the mass of the low-temperature-decomposable engineering plastic and the mass of the fluorine-containing resin. preferable.
- the above fluorine-containing resin is 0.05 mass. If it is less than 0 , the reduction in extrusion pressure and extrusion torque will be insufficient, and if the fluororesin exceeds 1% by mass, the resulting molded product may become opaque or cloudy. An effect commensurate with the increase in the amount of the fluorine-containing resin is not obtained so that it becomes uneconomical.
- the lower limit of the fluorine-containing resin is more preferably 0.1% by mass of the total mass of the low-temperature decomposable engineering plastic and the mass of the fluorine-containing resin, and an upper limit of 0.5% by mass is more preferable. It is.
- a fluororesin composed of a fluoropolymer obtained by polymerizing the monomer component composed of the above-mentioned TFE and HFP, and polyacetal Yarn alignment is preferred.
- a combination of EFEP and polyacetal is more preferable in that the moldability can be stabilized and yellowing of the resulting molded article can be prevented.
- it may be obtained by copolymerizing a small amount of PAVE and Pino such as PPVE or the monomer represented by the above general formula (i).
- Polyacetal is a resin that is easily decomposed and highly reactive, and it has been difficult to mold stably.
- the low-temperature-decomposable engineering plastic resin composition of the present invention can be stably molded by using the above-mentioned fluororesin even when the low-temperature-decomposable engineering plastic is polyacetal. Be Yellowing of the molded product can be prevented.
- the low-temperature decomposable engineering plastic resin composition of the present invention may be blended with other components, if necessary, together with the above-mentioned fluorine-containing resin and the above-mentioned low-temperature decomposable engineering plastic.
- the above-mentioned other components are not particularly limited.
- whisker such as potassium titanate, glass fiber, aspect fiber, carbon fiber, other high-strength fiber, reinforcing material such as glass powder; mineral, flakes, etc.
- Stabilizer such as silicone oil, molybdenum disulfide; Pigment; Power Conductive agent such as Bonbon Black; Impact resistance improver such as rubber; Other additives can be used.
- the method for producing a low temperature decomposable engineering plastic resin composition of the present invention is a method for producing the low temperature decomposable engineering plastic resin composition by blending a low temperature decomposable engineering plastic and a fluorine-containing resin.
- the method for preparing the low-temperature decomposable engineering plastic resin composition of the present invention is not particularly limited.
- a conventionally known method can be used.
- the fluororesin and the low-temperature decomposable engineering plastic can be used. Examples include a method of blending at an appropriate ratio so as to achieve the above-mentioned mixing ratio, adding and mixing the above-mentioned other components as required, and preparing the mixture by melting and kneading the mixture under heating as necessary. .
- the other components may be added to and mixed with the fluororesin and Z or the low-temperature decomposable engineering plastic in advance, or the fluororesin and the low-temperature decomposability. It may be added when blending engineering plastics.
- the fluorine-containing resin and the low-temperature decomposable engineering plastic need only have a blending ratio within the above range when the resulting low-temperature decomposable engineering plastic resin composition of the present invention is molded.
- the blending is not particularly limited, for example, a method of blending the fluororesin and the low-temperature decomposable engineering plastic so that the blending ratio is within the above range from the beginning, or first the fluororesin The fluorine-containing resin, the low-temperature decomposable engineering plastic, and the essential component so that the content of the resin is higher than the blending ratio within the above range.
- the ratio of the low-temperature decomposition '14 engineering plastic to the fluorine-containing resin is within the above range.
- the low-temperature decomposable engineering plastic is added to the composition (1) before or during the molding process, and stepwise blended so as to prepare the yarn and the composition (2).
- the composition (1) may be referred to as a masterbatch, and the fluororesin in the composition (1) is composed of the mass of the low temperature decomposable engineering plastic and the above It is preferably more than 0.05% by mass of the total of the fluororesin and 20% by mass or less, more preferably the lower limit is 1% by mass, and the more preferable lower limit is 2% by mass. There is a more preferred upper limit of 10% by mass.
- the composition (2) is sometimes referred to as a premix.
- the mixing method is not particularly limited.
- the mixing can be performed under normal conditions using a mixer such as various mills that are usually used for mixing a resin composition such as a molding composition.
- a mixer such as various mills that are usually used for mixing a resin composition such as a molding composition.
- the particles made of the fluorine-containing resin are evenly dispersed among the particles made of the low-temperature decomposable engineering plastic, the resulting low-temperature decomposable engineering plastic resin of the present invention is extruded when molding the material. Since the effects of improving the moldability such as reduction in torque and extrusion pressure tend to be exhibited well, the particles made of the fluororesin are almost uniformly distributed on the surface of each particle made of the low-temperature decomposable engineering plastic. It is preferable to mix thoroughly to adhere.
- the above “compounding” means the ability to mix a low temperature decomposable engineering plastic and a fluorine-containing resin, or preparation of a master batch prior to preparation of a premix.
- the above blending may be performed by melting (melting and kneading) the low-temperature decomposable engineering plastic and / or fluorine-containing resin, or may be performed by mixing these materials without melting, for example, by a mill.
- the low-temperature decomposable engineering plastic and the fluorine-containing resin may be powder, granules, pellets, etc., respectively, but the fluorine-containing resin is efficiently and uniformly present on the surface of the low-temperature decomposable engineering plastic (the pellet). Therefore, the low temperature decomposable engineering plastic is preferably a pellet, and the fluororesin is preferably a powder. In this case, the mixing is preferably performed without melting the low-temperature decomposable engineering plastic and the fluorine-containing resin.
- the low-temperature decomposable engineering plastic and the fluorine-containing resin both of which are powders, are melt-kneaded and blended or blended without melting, and both are pellets.
- the fluorine-containing resin can be present between the low-temperature-decomposable engineering plastic and the molding machine more efficiently than mixing the low-temperature decomposable engineering plastic and the fluorine-containing resin without melting them.
- the low-temperature decomposable engineering plastic and the fluorine-containing resin may be in any form such as powder, granule, pellet, etc.
- the low-temperature decomposable engineering plastic may be a pellet.
- the fluorine-containing resin may be a pellet or a powder.
- the fluororesin is preferably a powder from the viewpoint that the mixing can be performed sufficiently uniformly.
- the particles made of the fluororesin adhering to the surface of the low-temperature decomposable engineering plastic are used in the molding process of the resulting low-temperature decomposable engineering plastic resin composition of the present invention, in particular the low-temperature decomposable engineering plastic.
- the low temperature decomposable engineering plastic resin composition exhibits a sufficient lubricating effect due to the presence of a large number on the surface inside the machine, It is presumed that the low-temperature decomposable engineering plastic resin composition can be smoothly transferred in the molding machine. As a result, it is thought that molding processability is improved, such as enabling a significant decrease in extrusion torque and extrusion pressure.
- the surface inside the machine with which the low-temperature decomposable engineering plastic resin composition comes into contact is a screw in a melt-extrusion section, a barrel around the screw and storing and rotating the screw.
- the surface of the die or the like at the extrusion destination is a screw in a melt-extrusion section, a barrel around the screw and storing and rotating the screw.
- heat the compound obtained by the above compounding It may be melted and kneaded.
- the heating is usually performed at a temperature equal to or higher than the melting point of the low-temperature decomposable engineering plastic, and the low-temperature decomposable engineering plastic is melted, and the particles made of the fluorine-containing resin are uniformly dispersed in the melt. It is preferable to do so.
- the fluorine-containing resin is present on the surface of the pellet and the like, and also exists inside the pellet and the like depending on the concentration. Therefore, the particles comprising the fluororesin exude from the inside of the pellet or the like after the molding process of the low-temperature-decomposable engineering plastic resin composition of the present invention, particularly after the start of melting of the pellet or the like. Accordingly, the interaction between the molecules constituting the low-temperature decomposable engineering plastic and the intermolecular segments is reduced to prevent such blocking, and the low-temperature decomposable engineering plastic and thus the low-temperature decomposable engine.
- the low-temperature decomposable engineered plastic resin composition comprising a nearing plastic can be easily transferred in a molding machine. As a result, it is thought to contribute to the improvement of molding processability, such as reducing the extrusion torque and extrusion pressure.
- the particle size may be adjusted as necessary.
- the low-temperature decomposable engineering plastic resin composition of the present invention may be in any form such as powder, granule, pellet and the like.
- the low-temperature decomposable engineering plastic resin composition of the present invention thus obtained can be used as a molding material.
- the method for producing a low-temperature decomposable engineering plastic molded body of the present invention is to produce a molded body by melting and molding the low-temperature decomposable engineering plastic resin composition.
- the method for producing a low-temperature decomposable engineering plastic molding of the present invention is characterized by using the above-mentioned low-temperature decomposable engineering plastic resin composition.
- the above-mentioned “low temperature degradable engineering plastic” Hereinafter, the “molded body manufacturing method” may be simply referred to as “molded body manufacturing method”.
- the method for producing a molded body includes introducing the low-temperature decomposable engineering plastic resin composition into a molding machine such as a screw extruder.
- the production method after being put into the molding machine is not particularly limited as long as it is heat-melt molding.
- the low-temperature decomposable engineering plastic resin yarn introduced into the molding machine such as a screw extruder is used.
- the composition is heated to the molding temperature, pressurized as necessary, and the molten low-temperature decomposable engineering plastic resin composition is extruded into a die of a molding machine or injected into a mold for molding.
- a conventionally known method such as a method of obtaining a molded product having a desired shape can be used.
- the low-temperature decomposable engineering plastic resin composition of the present invention is melted in the heating section in the molding machine to become a melt, and then exits the heating section and is transferred to the cooling section. Molded.
- the low-temperature decomposable engineering plastic resin composition of the present invention can stably improve the transportability of the melt from the heating section to the cooling section in the molding machine. Workability can be improved.
- the particles made of the fluororesin are in a state of almost uniformly adhering to the surface of the pellets of the low-temperature-decomposable engineering plastic as described above. Heating in the machine is considered to melt at the same time as the low-temperature decomposable engineering plastic or before the low-temperature decomposable engineering plastic.
- the fluororesin is a powder and / or has a melting point lower than that of the low-temperature decomposable engineering plastic, it tends to melt before the low-temperature decomposable engineering plastic. Therefore, the lubricating action of the fluorine-containing resin can be sufficiently exhibited in the molding machine.
- the heating section in the molding machine is usually a melt extrusion section, and this melt extrusion section usually has a screw and a barrel, and is heated by a heater around the barrel.
- the resin composition is heated.
- the extrusion processability and the extrusion pressure Is obtained by a significant decrease. That is, in the case of extrusion molding, although depending on the composition and molding conditions of the low-temperature decomposable engineering plastic resin composition, the extrusion torque can be reduced to 20 to 95% of the value when the fluorine-containing resin is not blended.
- the extrusion pressure can be reduced to 40 to 95 ° / 0 which is a value obtained when the above-mentioned fluororesin is not blended.
- the method for producing the molded body is not particularly limited, and examples thereof include extrusion molding, injection molding, blow molding (blow molding), mold molding, rotational molding, reaction molding, and the like. Extrusion molding is preferred in order to effectively exhibit the molding processability.
- the extrusion molding is a method in which the low-temperature decomposable engineering plastic resin composition of the present invention heated and melted in an extruder is continuously extruded from a die and molded.
- the injection molding is a method in which the low-temperature decomposable engineering plastic resin composition of the present invention heated and melted in an injection molding machine is press-filled into a mold having one end closed and molded.
- the blow molding is performed by inflating a parison prepared in advance from the low-temperature decomposable engineering plastic resin composition of the present invention that has been heated and melted, using air pressure or the like in the mold, and is in close contact with the mold.
- This is a method of molding.
- the reactive molding is a method for performing compound molding while performing a chemical reaction using a molding machine having a function as a reaction apparatus, and examples thereof include reactive processing and reactive extrusion molding.
- the molding temperature is usually a temperature higher than the melting point of the low-temperature decomposable engineering plastic used. If the molding temperature is within the above range, it is usually a temperature lower than the lower one of the decomposition temperature of the fluororesin and the decomposition temperature of the low temperature decomposable engineering plastic. Examples of such a molding temperature include 2500 to 400 ° C.
- the molding temperature may be referred to as the extrusion temperature in the case of extrusion molding.
- molding with the said molded object manufacturing method can be set as various shapes, such as coating
- the use of the molded body is not particularly limited, and the low-temperature decomposable engineering used Depending on the type of plastic, for example, it can be suitably used for mechanical properties such as mechanical properties and those that mainly require heat resistance.
- Applications of the molded body include, for example, various machines and equipment such as space equipment; equipment parts such as gears and cams; electrical and electronic parts such as connectors, plugs, switches, and wire enamel; vehicles such as automobiles and aircraft Or these parts; decorative plates; various films such as magnetic tape, photographic film, gas separation membranes; optical materials such as lenses, compact discs, optical disk substrates, safety glasses; tableware such as beverage containers; various heat-resistant medical supplies Other various industrial parts.
- the present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
- the blending amount (% by mass) of the fluororesin is based on the total amount of the fluororesin and the low temperature molecular engineering plastic.
- the reaction product was washed with water and dried to obtain 95 kg of powder.
- -95 kg of the obtained powder and 100 L of pure water were placed in a 500 L stainless steel crepe, 7 kg of 28% aqueous ammonia was added, and the mixture was heated at 80 ° C for 5 hours while stirring.
- the content powder was taken out, washed with water and dried to obtain 93 kg of a fluororesin.
- the molar ratio of TFE: Et: HFP: HF-Pe in the obtained copolymer was measured by 19 F—NMR. As a result, it was 38.9: 45.9: 18.8: 0.4. It was.
- the melting point measured by a differential scanning calorimeter [DSC] (manufactured by Seiko) was 171.8 ° C.
- the content rate of the polar functional group and the melt flow rate value were measured using the following methods.
- a 0.1 mm thick polymer film obtained by compression molding of the fluororesin obtained above at 300 ° C was measured using an FT IR spectrophotometer, and the number of terminal groups per million carbon atoms was calculated using the following formula: As a result, all the polar functional groups contained only traces at the end of the polymer chain, and no polar functional group was found per million carbon atoms. Difficulty X CF
- MFR Menoleto Flow Rate
- a melt indexer manufactured by Toyo Seiki Seisakusho Co., Ltd. was used to measure the amount of polymer flowing out per unit time (10 minutes) from a nozzle with a diameter of 2 mm and a length of 8 mm under a load of 230 ° C and 5 kg. 7. I g — 10 minutes.
- Example 1 A melt indexer (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used to measure the amount of polymer flowing out per unit time (10 minutes) from a nozzle with a diameter of 2 mm and a length of 8 mm under a load of 230 ° C and 5 kg. 7. I g — 10 minutes.
- Molding was performed in the same manner as in Example 1 except that no fluorine-containing resin was blended.
- Table 1 shows the extrusion torque and extrusion pressure.
- the fluorine-containing resin obtained in Synthesis Example 1 is supplied by a vibrator-type quantitative feeder (KUBOTA) so as to be 3% by mass, and the same-direction rotating twin-screw extruder (model: Z E40A, Berstorfi, SCREEN) U-size ⁇ 4 3 mm, L / D: 3 3.5), kneaded with polyacetal (trade name: Delrin 1 50 SA, manufactured by DuPont) at a normal temperature of 1 90-200 ° C Got.
- KUBOTA vibrator-type quantitative feeder
- the resulting kneaded pellets and polyacetal were blended so that the fluorine-containing resin would be 0.05% by mass, put in a plastic bag and mixed, then an injection molding machine (Type: Crockner F85, TEC, mold: ASTM D 6 3 8 Type 1 tensile test specimen mold), barrel temperature 190 ° C, mold temperature 50 ° C, injection pressure 1 1 0-1 1 5MPa And formed.
- the obtained molded product was subjected to a tensile test using the following method, and the appearance was visually observed. The results are shown in Table 2.
- the test method is based on AS TM D 6 3 8 4 3 0 2) was used for measurement.
- the measurement conditions were a tensile speed of 5 mra / min and a distance between chucks of 115 mm. Tensile elongation was calculated from the amount of movement of the crosshead.
- Example 3
- Example 4 Molding was performed in the same manner as in Example 2 except that the amount of the fluorine-containing resin was 0.1% by mass. Table 2 shows the measurement results and appearance of the tensile test. Example 4
- Example 5 Molding was performed in the same manner as in Example 2 except that the amount of the fluorine-containing resin was changed to 0.25% by mass. Table 2 shows the measurement results and appearance of the tensile test. Example 5
- Example 6 Molding was performed in the same manner as in Example 2 except that the mold temperature of the injection molding machine was set to 120 ° C. Table 2 shows the measurement results and appearance of the tensile test. Example 6
- Example 7 Molding was performed in the same manner as in Example 2 except that the amount of the fluorine-containing resin was 0.110% by mass and the mold temperature of the injection molding machine was 120 ° C. Table 2 shows the measurement results and appearance of the tensile test.
- Example 7
- Example 8 Molding was performed in the same manner as in Example 2 except that the amount of the fluorine-containing resin was 0.25% by mass and the mold temperature of the injection molding machine was 120 ° C. Table 2 shows the measurement results and appearance of the tensile test.
- Example 8
- Example 9 Molding was carried out in the same manner as in Example 2 except that the barrel temperature of the injection molding machine was 2 10 ° C. Table 2 shows the measurement results and appearance of the tensile test. Example 9
- Example 1 Molding was carried out in the same manner as in Example 2 except that the blending amount of the fluorine-containing resin was 0.110% by mass and the barrel temperature of the injection molding machine was 2110 ° C. Table 2 shows the measurement results and appearance of the tensile test.
- Example 1 0
- Example 1 Molding was performed in the same manner as in Example 2 except that the blending amount of the fluorine-containing resin was 0.25% by mass and the barrel temperature of the injection molding machine was 2110 ° C. Table 2 shows the measurement results and the II state of the tensile test.
- Example 1 1
- Example 1 2 Molding was carried out in the same manner as in Example 2 except that the barrel temperature of the injection molding machine was 2 10 ° C and the mold temperature was 120 ° C. Table 2 shows the measurement results and appearance of the tensile test.
- Example 1 2 the barrel temperature of the injection molding machine was 2 10 ° C and the mold temperature was 120 ° C. Table 2 shows the measurement results and appearance of the tensile test.
- Example 1 3 The amount of the fluorine-containing resin 0.1 and 0 mass 0/0, the barrel temperature of the injection molding machine and 2 1 0 ° C, except that the mold temperature was set to 1 2 0 ° C, as in Example 2 To be molded. Table 2 shows the measurement results and appearance of the tensile test.
- Example 1 3 The amount of the fluorine-containing resin 0.1 and 0 mass 0/0, the barrel temperature of the injection molding machine and 2 1 0 ° C, except that the mold temperature was set to 1 2 0 ° C, as in Example 2 To be molded. Table 2 shows the measurement results and appearance of the tensile test.
- Example 1 3 The amount of the fluorine-containing resin 0.1 and 0 mass 0/0, the barrel temperature of the injection molding machine and 2 1 0 ° C, except that the mold temperature was set to 1 2 0 ° C, as in Example 2 To be molded. Table 2 shows the measurement results and appearance of the tensile test.
- Example 2 The same as in Example 2 except that the blending amount of the fluorinated resin was 0.25% by mass, the barrel temperature of the injection molding machine was 2 10 ° C, and the mold temperature was 120 ° C. And molded. Table 2 shows the measurement results and appearance of the tensile test. Comparative Example 2
- Molding was performed in the same manner as in Example 2 except that no fluorine-containing resin was blended and the mold temperature of the injection molding machine was set to 120 ° C. Table 2 shows the measurement results and appearance of the tensile test. Comparative Example 4.
- Molding was carried out in the same manner as in Example 2 except that the fluorine-containing resin was not blended, the barrel temperature of the injection molding machine was set to 210 ° C, and the mold temperature was set to 120 ° C.
- Table 2 shows the measurement results and appearance of the tensile test.
- Screw rotation pressure bar 100 95 95 100 95 95 95 95 95 95 95 90 85 95 90 85 120 120 100 95 Yield strength MPa 66 66 67 69 66 66 69 69 66 70 66 69 Yield elongation K 15.7 17.7 17.8 17.3 17.8 14.6 20.7 16.7 Elastic modulus GPa 3.0 3.0 3.0 3.4 3.0 2.9 3.5 3.4 3.4 3.0 3.3 3.0 3.3
- the low-temperature decomposable engineering plastic resin composition of the present invention is obtained by blending the above-mentioned fluorine-containing resin at a content within a specific range, the above-mentioned heating part in the molding machine to the above cooling part It is possible to improve the transportability of the molten material until the end of the manufacturing process, and to achieve stable production of molded products, improved yield, and improved productivity, and industrial production of low-temperature decomposable engineering plastic molded products. It works favorably. ⁇
- the mechanism by which the low-temperature decomposable engineering plastic resin composition of the present invention exhibits such advantageous effects is not clear, but the fluororesin is mainly used during transfer from the heating section to the cooling section. This is thought to be due to the fact that it functions as a lubricant on the contact surface with the melt inside the molding machine. In the case of extrusion molding, the fluorine-containing resin is considered to exert the lubricating action on the surface of the rotary screw in the extruder and the surface of the barrel around it.
- the fluorine-containing resin exhibiting such a lubricating action for example, EFEP is used and melted like EFEP in a melt obtained by setting the molding temperature to a temperature equal to or higher than the melting point of EFEP.
- EFEP may be used and it may not be melted like EFEP in a melt obtained by setting the molding temperature to a temperature lower than the melting start point of EFEP.
- the fluorine-containing resin is melted at the molding temperature, it is a resin that is not compatible with the low-temperature decomposable engineering plastic in order to effectively exert the lubricating action. Are preferred.
- the low-temperature decomposable engineering plastic resin composition of the present invention a wide variety of fluorine-containing resins are used as described above, such as there is often no need to particularly select the melting point in relation to the molding temperature. Can expand the range of material selection. .
- the lubricating action can be obtained only by blending a very small amount of the fluororesin within the specific range described above.
- the low-temperature decomposable engineering plastic resin composition of the present invention can not only improve the moldability in industrial production of low-temperature decomposable engineering plastics by a simple method, but the above-mentioned fluororesin is usually Since it is expensive, it is advantageous for industrial production because it is effective in a very small amount.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2003545722A JPWO2003044088A1 (ja) | 2001-11-21 | 2002-11-21 | 低温分解性エンジニアリングプラスチック樹脂組成物、及び当該組成物からなる成形体の製造方法 |
EP02785943A EP1452562A1 (en) | 2001-11-21 | 2002-11-21 | Low-temperature-decomposable engineering plastic resin composition and process for producing molded object of the composition |
US10/380,825 US20040242771A1 (en) | 2001-11-21 | 2002-11-21 | Low-temperature-decomposable engineering plastic resin composition and production method of molding using the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/989,160 | 2001-11-21 | ||
US09/989,160 US20030109646A1 (en) | 2001-11-21 | 2001-11-21 | Resin composition and method of producing shaped articles |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2003044088A1 true WO2003044088A1 (fr) | 2003-05-30 |
Family
ID=25534824
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/012148 WO2003044093A1 (fr) | 2001-11-21 | 2002-11-21 | Composition de resine et procede de fabrication de moules |
PCT/JP2002/012147 WO2003044088A1 (fr) | 2001-11-21 | 2002-11-21 | Composition a base de resine plastique d'ingenierie decomposable a basse temperature et procede de production d'un objet moule a partir de cette composition |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2002/012148 WO2003044093A1 (fr) | 2001-11-21 | 2002-11-21 | Composition de resine et procede de fabrication de moules |
Country Status (6)
Country | Link |
---|---|
US (2) | US20030109646A1 (ja) |
EP (2) | EP1452562A1 (ja) |
JP (2) | JPWO2003044093A1 (ja) |
CN (2) | CN1541251A (ja) |
TW (2) | TW200300430A (ja) |
WO (2) | WO2003044093A1 (ja) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005186370A (ja) * | 2003-12-25 | 2005-07-14 | Nissei Electric Co Ltd | 熱収縮チューブ |
JP2005282630A (ja) * | 2004-03-29 | 2005-10-13 | Toyox Co Ltd | 食品用積層ホース |
WO2014203727A1 (ja) | 2013-06-21 | 2014-12-24 | ダイキン工業株式会社 | 加工助剤、及び組成物 |
WO2015098867A1 (ja) | 2013-12-26 | 2015-07-02 | ダイキン工業株式会社 | ポリオレフィン用加工助剤、及び、ポリオレフィン組成物 |
EP3106482A1 (en) | 2015-06-16 | 2016-12-21 | Daikin Industries, Limited | A processing aid for polyolefins and a polyolefin composition |
Families Citing this family (26)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20040092638A1 (en) * | 2002-08-28 | 2004-05-13 | Martens Marvin M. | Polyamide compositions incorporating non-melt-processable fluoropolymers and processes associated therewith |
RU2383557C2 (ru) * | 2003-06-09 | 2010-03-10 | 3М Инновейтив Пропертиз Компани | Плавкая полимерная композиция, содержащая фторполимер, имеющий длинные боковые цепочки |
US7117961B2 (en) * | 2003-07-31 | 2006-10-10 | Smith International, Inc. | Dynamic seal with soft interface |
US20060014904A1 (en) * | 2004-07-13 | 2006-01-19 | Daikin Industries, Ltd. | Polymer compositions and method for producing a molded body |
ATE540061T1 (de) * | 2004-11-16 | 2012-01-15 | Daikin Ind Ltd | Feines pulver aus modifiziertem polytetrafluorethylen und formkörper aus modifiziertem polytetrafluorethylen |
DE102005023419B4 (de) | 2005-05-20 | 2007-02-22 | Ems-Chemie Ag | Polyamid-Oligomere und deren Verwendung |
DE102005023420A1 (de) | 2005-05-20 | 2006-11-23 | Ems-Chemie Ag | Polyamidformmassen mit verbesserter Fliessfähigkeit, deren Herstellung sowie deren Verwendung |
US20070248823A1 (en) * | 2006-04-24 | 2007-10-25 | Daikin Industries, Ltd. | Fluorine containing copolymer fiber and fabric |
WO2008047759A1 (fr) * | 2006-10-20 | 2008-04-24 | Daikin Industries, Ltd. | Copolymère contenant du fluor et article moulé de celui-ci |
GB201000182D0 (en) | 2010-01-07 | 2010-02-24 | Hexcel Composites Ltd | Novel curable resins and curing agents therefor |
CN101880436B (zh) | 2010-07-05 | 2012-05-30 | 清华大学 | 树脂组合物及其模塑品 |
CN103958608B (zh) | 2011-12-13 | 2016-08-17 | 大金工业株式会社 | 树脂组合物和成型品 |
KR20140107412A (ko) * | 2011-12-14 | 2014-09-04 | 다이킨 고교 가부시키가이샤 | 절연 전선 |
WO2014024671A1 (ja) | 2012-08-06 | 2014-02-13 | ダイキン工業株式会社 | 樹脂組成物及び成形品 |
WO2014037374A1 (en) | 2012-09-04 | 2014-03-13 | Solvay Specialty Polymers Usa, Llc | High melt flow peak compositions |
US10557057B2 (en) | 2012-09-04 | 2020-02-11 | Solvay Specialty Polymers Usa, Llc. | High melt flow PAEK compositions |
JP6494019B2 (ja) * | 2012-12-28 | 2019-04-03 | サンデンホールディングス株式会社 | 斜板式圧縮機 |
US9644080B2 (en) | 2013-04-17 | 2017-05-09 | Daicel-Evonik Ltd. | Light-resistant resin composition, and moulded body thereof |
US10246586B2 (en) | 2013-04-17 | 2019-04-02 | Daicel-Evonik Ltd. | Light-resistance improver |
CN103333443A (zh) * | 2013-07-03 | 2013-10-02 | 吴江市天源塑胶有限公司 | 一种含有聚乙烯醇缩乙醛的抗冲击耐高温塑料 |
JP6135541B2 (ja) * | 2014-02-17 | 2017-05-31 | 旭硝子株式会社 | フッ素樹脂組成物の製造方法、成形品の製造方法及び電線の製造方法 |
WO2016027702A1 (ja) | 2014-08-21 | 2016-02-25 | ダイキン工業株式会社 | 加工助剤 |
WO2017188280A1 (ja) | 2016-04-28 | 2017-11-02 | 旭硝子株式会社 | 含フッ素共重合体組成物、その製造方法、および成形体 |
JP6876276B2 (ja) * | 2016-04-28 | 2021-05-26 | Agc株式会社 | 被覆電線 |
CN111592614A (zh) * | 2020-06-04 | 2020-08-28 | 成都虹润制漆有限公司 | 一种乙烯基改性氟碳树脂及其制备方法、耐腐蚀涂料及其制备方法和应用 |
JP7174311B2 (ja) * | 2021-02-26 | 2022-11-17 | ダイキン工業株式会社 | 含フッ素共重合体 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0162455A2 (en) * | 1984-05-22 | 1985-11-27 | Daikin Industries, Limited | Ethylene/Tetrafluoroethylene Copolymer |
JPS63213546A (ja) * | 1987-02-28 | 1988-09-06 | Sanko Shoji Kk | 樹脂組成物 |
JPH06212080A (ja) * | 1992-10-29 | 1994-08-02 | Ntn Corp | 潤滑性樹脂組成物 |
EP0644209A1 (de) * | 1993-09-21 | 1995-03-22 | Hoechst Aktiengesellschaft | Polytetrafluorethylen-Mikropulver, ihre Herstellung und Verwendung |
JPH08253692A (ja) * | 1995-03-15 | 1996-10-01 | Hitachi Cable Ltd | 合成樹脂組成物 |
EP0773244A1 (en) * | 1994-07-22 | 1997-05-14 | Daikin Industries, Ltd. | Fine powder of molten high-molecular-weight fluororesin, molded article thereof, and process for producing both |
JPH10237254A (ja) * | 1997-02-26 | 1998-09-08 | Polyplastics Co | 熱可塑性樹脂とフッ素樹脂の混合方法及びフッ素樹脂含有熱可塑性樹脂組成物の製造方法 |
JPH1129691A (ja) * | 1997-07-09 | 1999-02-02 | Oiles Ind Co Ltd | ポリアセタール樹脂組成物 |
WO2000069967A1 (en) * | 1999-05-13 | 2000-11-23 | Dyneon Llc | Polymer processing additive containing a multimodalfluoropolymer and a melt processable thermoplastic polymer composition employing the same |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3125547A (en) * | 1961-02-09 | 1964-03-17 | Extrudable composition consisting of | |
US4581406A (en) * | 1985-06-11 | 1986-04-08 | E. I. Du Pont De Nemours And Company | Fluoroelastomer containing polyethylene composition and process for extruding same |
US4855360A (en) * | 1988-04-15 | 1989-08-08 | Minnesota Mining And Manufacturing Company | Extrudable thermoplastic hydrocarbon polymer composition |
US4904735A (en) * | 1988-07-08 | 1990-02-27 | E. I. Du Pont De Nemours And Company | Processing aid for polymers |
JPH0391556A (ja) * | 1989-09-04 | 1991-04-17 | Lion Corp | 導電性樹脂組成物 |
US5106911A (en) * | 1989-10-06 | 1992-04-21 | E. I. Du Pont De Nemours And Company | Process and processing aid for extruding a hydrocarbon polymer |
WO1991005013A1 (en) * | 1989-10-06 | 1991-04-18 | E.I. Du Pont De Nemours And Company | Fluoropolymer process aids containing functional groups |
US5094806A (en) * | 1989-11-06 | 1992-03-10 | The Dow Chemical Company | Blow molding of thermoplastic polymeric compositions containing a fluorinated olefin |
US5010130A (en) * | 1990-05-15 | 1991-04-23 | E. I. Du Pont De Nemours And Company | High melt viscosity fluoropolymer process aid |
US5057575A (en) * | 1990-08-29 | 1991-10-15 | E. I. Du Pont De Nemours And Company | Processing aid for polymers |
BE1004682A3 (fr) * | 1991-03-14 | 1993-01-12 | Solvay | Compositions a base de polyamides et objets faconnes a partir de ces compositions. |
CA2056839C (en) * | 1991-12-03 | 1996-11-19 | Allan Wilfred Duff | Polyolefin bottles with glossy surface |
WO1995014719A1 (en) * | 1992-08-28 | 1995-06-01 | E.I. Du Pont De Nemours And Company | Low-melting tetrafluoroethylene copolymer and its uses |
US5547761A (en) * | 1992-08-28 | 1996-08-20 | E. I. Du Pont De Nemours And Company | Low melting tetrafluoroethylene copolymer and its uses |
US5374683A (en) * | 1992-08-28 | 1994-12-20 | E. I. Du Pont De Nemours And Company | Low-melting tetrafluoroethylene copolymer and its uses |
US5266639A (en) * | 1992-08-28 | 1993-11-30 | E. I. Du Pont De Nemours And Company | Low-melting tetrafluorethylene copolymer and its uses |
EP0656912B1 (en) * | 1992-08-28 | 1996-12-04 | E.I. Du Pont De Nemours And Company | Low-melting tetrafluoroethylene copolymer and its uses |
JPH06136255A (ja) * | 1992-10-27 | 1994-05-17 | Mitsui Toatsu Chem Inc | ポリエーテル芳香族ケトン樹脂組成物 |
FR2706284B1 (fr) * | 1993-06-17 | 1995-09-29 | Roux Christiane | Prothèse cotyloïdienne, notamment pour articulation coxo-fémorale. |
US5707569A (en) * | 1994-02-15 | 1998-01-13 | E. I. Du Pont De Nemours And Company | Processing aid system for polyolefins |
US5549948A (en) * | 1994-09-02 | 1996-08-27 | Minnesota Mining And Manufacturing Company | Melt-processable fluoroplastic |
JP3149377B2 (ja) * | 1997-01-22 | 2001-03-26 | 大同メタル工業株式会社 | 湿式ラジアル軸受用摺動部材 |
US6380313B1 (en) * | 2000-06-27 | 2002-04-30 | Dyneon Llc | Polymer processing additive containing a perfluorovinylether-modified flouropolymer and a melt processable thermoplastic polymer composition employing the same |
-
2001
- 2001-11-21 US US09/989,160 patent/US20030109646A1/en not_active Abandoned
-
2002
- 2002-11-21 CN CNA028157885A patent/CN1541251A/zh active Pending
- 2002-11-21 WO PCT/JP2002/012148 patent/WO2003044093A1/ja not_active Application Discontinuation
- 2002-11-21 WO PCT/JP2002/012147 patent/WO2003044088A1/ja not_active Application Discontinuation
- 2002-11-21 EP EP02785943A patent/EP1452562A1/en not_active Withdrawn
- 2002-11-21 TW TW091133908A patent/TW200300430A/zh unknown
- 2002-11-21 CN CNA028157893A patent/CN1547603A/zh active Pending
- 2002-11-21 JP JP2003545726A patent/JPWO2003044093A1/ja not_active Withdrawn
- 2002-11-21 US US10/380,825 patent/US20040242771A1/en not_active Abandoned
- 2002-11-21 EP EP02783579A patent/EP1454963A1/en not_active Withdrawn
- 2002-11-21 JP JP2003545722A patent/JPWO2003044088A1/ja not_active Withdrawn
- 2002-11-21 TW TW091133909A patent/TW200300429A/zh unknown
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0162455A2 (en) * | 1984-05-22 | 1985-11-27 | Daikin Industries, Limited | Ethylene/Tetrafluoroethylene Copolymer |
JPS63213546A (ja) * | 1987-02-28 | 1988-09-06 | Sanko Shoji Kk | 樹脂組成物 |
JPH06212080A (ja) * | 1992-10-29 | 1994-08-02 | Ntn Corp | 潤滑性樹脂組成物 |
EP0644209A1 (de) * | 1993-09-21 | 1995-03-22 | Hoechst Aktiengesellschaft | Polytetrafluorethylen-Mikropulver, ihre Herstellung und Verwendung |
EP0773244A1 (en) * | 1994-07-22 | 1997-05-14 | Daikin Industries, Ltd. | Fine powder of molten high-molecular-weight fluororesin, molded article thereof, and process for producing both |
JPH08253692A (ja) * | 1995-03-15 | 1996-10-01 | Hitachi Cable Ltd | 合成樹脂組成物 |
JPH10237254A (ja) * | 1997-02-26 | 1998-09-08 | Polyplastics Co | 熱可塑性樹脂とフッ素樹脂の混合方法及びフッ素樹脂含有熱可塑性樹脂組成物の製造方法 |
JPH1129691A (ja) * | 1997-07-09 | 1999-02-02 | Oiles Ind Co Ltd | ポリアセタール樹脂組成物 |
WO2000069967A1 (en) * | 1999-05-13 | 2000-11-23 | Dyneon Llc | Polymer processing additive containing a multimodalfluoropolymer and a melt processable thermoplastic polymer composition employing the same |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005186370A (ja) * | 2003-12-25 | 2005-07-14 | Nissei Electric Co Ltd | 熱収縮チューブ |
JP2005282630A (ja) * | 2004-03-29 | 2005-10-13 | Toyox Co Ltd | 食品用積層ホース |
JP4696293B2 (ja) * | 2004-03-29 | 2011-06-08 | 株式会社トヨックス | 食品用積層ホース |
WO2014203727A1 (ja) | 2013-06-21 | 2014-12-24 | ダイキン工業株式会社 | 加工助剤、及び組成物 |
US9624362B2 (en) | 2013-06-21 | 2017-04-18 | Daikin Industries, Ltd. | Processing aid, and composition |
WO2015098867A1 (ja) | 2013-12-26 | 2015-07-02 | ダイキン工業株式会社 | ポリオレフィン用加工助剤、及び、ポリオレフィン組成物 |
EP3106482A1 (en) | 2015-06-16 | 2016-12-21 | Daikin Industries, Limited | A processing aid for polyolefins and a polyolefin composition |
US10358515B2 (en) | 2015-06-16 | 2019-07-23 | Daikin Industries, Ltd. | Processing aid for polyolefins and a polyolefin composition |
Also Published As
Publication number | Publication date |
---|---|
EP1452562A1 (en) | 2004-09-01 |
US20030109646A1 (en) | 2003-06-12 |
US20040242771A1 (en) | 2004-12-02 |
TW200300430A (en) | 2003-06-01 |
EP1454963A1 (en) | 2004-09-08 |
EP1454963A8 (en) | 2004-12-22 |
WO2003044093A1 (fr) | 2003-05-30 |
TW200300429A (en) | 2003-06-01 |
JPWO2003044088A1 (ja) | 2005-03-10 |
CN1547603A (zh) | 2004-11-17 |
CN1541251A (zh) | 2004-10-27 |
JPWO2003044093A1 (ja) | 2005-03-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2003044088A1 (fr) | Composition a base de resine plastique d'ingenierie decomposable a basse temperature et procede de production d'un objet moule a partir de cette composition | |
JP4406099B2 (ja) | フツ素プラステイツクスとポリエーテルケトンケトンとの配合物 | |
CN106661163B (zh) | 加工助剂 | |
EP2818516B1 (en) | Fluorine-containing copolymer composition, molded article, and electric wire | |
JP5387681B2 (ja) | 加工助剤、成形用組成物、加工助剤用マスターバッチ及び成形品 | |
JP7335685B2 (ja) | 熱溶融性フッ素樹脂組成物及びこれから成る射出成形品 | |
JPH01157827A (ja) | シリコーン侵人型重合体網状構造を含む熱可塑性物質の高められた溶融押出 | |
CA2574667C (en) | Aromatic polyimide composition and articles manufactured therefrom | |
KR20160138009A (ko) | 테트라플루오로에틸렌과 퍼플루오로(에틸 비닐 에테르)의 공중합체의 층을 갖는 복합 성형품 | |
WO1999062999A1 (fr) | Agent de micronisation de spherulites pour fluororesine cristalline et composition de fluororesine cristalline contenant cet agent de micronisation | |
WO2007123125A1 (ja) | 加工助剤及び成形用組成物 | |
US20040102572A1 (en) | Resin composition and process for producing molding | |
JP2010189599A (ja) | 熱可塑性樹脂組成物、並びに医療製品及び内視鏡操作部 | |
WO1996026980A1 (en) | Thermoplastic fluoro resin compositions and moulded articles produced therefrom | |
JP2005239902A (ja) | 摺動性改良剤、摺動用樹脂組成物及び摺動部材 | |
JPH11269383A (ja) | 樹脂組成物 | |
US20060014904A1 (en) | Polymer compositions and method for producing a molded body | |
TWI272290B (en) | Polyphenylene sulfide thermoplastic resin composition | |
JP2019025742A (ja) | フッ素樹脂ペレットおよびその製造方法、ならびに電線の製造方法 | |
JP3724257B2 (ja) | 重合体組成物およびその成形体 | |
JP3162800B2 (ja) | 熱可塑性樹脂組成物 | |
JP3120811B2 (ja) | ポリアセタール樹脂組成物 | |
CN112457613A (zh) | 一种低表面粗糙度的高性能热塑性的复合含氟树脂 | |
JPH05295209A (ja) | 熱可塑性樹脂組成物 | |
JPH05295259A (ja) | 熱可塑性樹脂組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CN JP KR US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR IE IT LU MC NL PT SE SK TR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWE | Wipo information: entry into national phase |
Ref document number: 10380825 Country of ref document: US |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2003545722 Country of ref document: JP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2002785943 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 20028157885 Country of ref document: CN |
|
WWP | Wipo information: published in national office |
Ref document number: 2002785943 Country of ref document: EP |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 2002785943 Country of ref document: EP |