JPH01280013A - Production of ultra-high-molecular weight polyolefin drawn product - Google Patents
Production of ultra-high-molecular weight polyolefin drawn productInfo
- Publication number
- JPH01280013A JPH01280013A JP10317988A JP10317988A JPH01280013A JP H01280013 A JPH01280013 A JP H01280013A JP 10317988 A JP10317988 A JP 10317988A JP 10317988 A JP10317988 A JP 10317988A JP H01280013 A JPH01280013 A JP H01280013A
- Authority
- JP
- Japan
- Prior art keywords
- molecular weight
- ultra
- high molecular
- stretching
- weight polyolefin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 238000002844 melting Methods 0.000 claims abstract description 17
- 230000008018 melting Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 abstract description 35
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 abstract description 31
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 abstract description 31
- 239000000203 mixture Substances 0.000 abstract description 17
- 238000010035 extrusion spinning Methods 0.000 abstract description 6
- 239000012188 paraffin wax Substances 0.000 abstract description 6
- 235000012438 extruded product Nutrition 0.000 abstract 1
- 239000000835 fiber Substances 0.000 description 35
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 22
- -1 polypropylene Polymers 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 239000001993 wax Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 9
- 239000005977 Ethylene Substances 0.000 description 9
- 229910000077 silane Inorganic materials 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- 239000013032 Hydrocarbon resin Substances 0.000 description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 229920006270 hydrocarbon resin Polymers 0.000 description 6
- 125000001931 aliphatic group Chemical group 0.000 description 5
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 3
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920006240 drawn fiber Polymers 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- PWATWSYOIIXYMA-UHFFFAOYSA-N Pentylbenzene Chemical compound CCCCCC1=CC=CC=C1 PWATWSYOIIXYMA-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical class C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- RZJRJXONCZWCBN-UHFFFAOYSA-N octadecane Chemical compound CCCCCCCCCCCCCCCCCC RZJRJXONCZWCBN-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003505 terpenes Chemical class 0.000 description 2
- 235000007586 terpenes Nutrition 0.000 description 2
- POOSGDOYLQNASK-UHFFFAOYSA-N tetracosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC POOSGDOYLQNASK-UHFFFAOYSA-N 0.000 description 2
- HLZKNKRTKFSKGZ-UHFFFAOYSA-N tetradecan-1-ol Chemical compound CCCCCCCCCCCCCCO HLZKNKRTKFSKGZ-UHFFFAOYSA-N 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- FIGVVZUWCLSUEI-UHFFFAOYSA-N tricosane Chemical compound CCCCCCCCCCCCCCCCCCCCCCC FIGVVZUWCLSUEI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WTARULDDTDQWMU-RKDXNWHRSA-N (+)-β-pinene Chemical compound C1[C@H]2C(C)(C)[C@@H]1CCC2=C WTARULDDTDQWMU-RKDXNWHRSA-N 0.000 description 1
- WTARULDDTDQWMU-IUCAKERBSA-N (-)-Nopinene Natural products C1[C@@H]2C(C)(C)[C@H]1CCC2=C WTARULDDTDQWMU-IUCAKERBSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 1
- ZMXIYERNXPIYFR-UHFFFAOYSA-N 1-ethylnaphthalene Chemical compound C1=CC=C2C(CC)=CC=CC2=C1 ZMXIYERNXPIYFR-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 240000007124 Brassica oleracea Species 0.000 description 1
- 239000005632 Capric acid (CAS 334-48-5) Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000001293 FEMA 3089 Substances 0.000 description 1
- 239000004831 Hot glue Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- OIZXRZCQJDXPFO-UHFFFAOYSA-N Octadecyl acetate Chemical compound CCCCCCCCCCCCCCCCCCOC(C)=O OIZXRZCQJDXPFO-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- WTARULDDTDQWMU-UHFFFAOYSA-N Pseudopinene Natural products C1C2C(C)(C)C1CCC2=C WTARULDDTDQWMU-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XCPQUQHBVVXMRQ-UHFFFAOYSA-N alpha-Fenchene Natural products C1CC2C(=C)CC1C2(C)C XCPQUQHBVVXMRQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RJTJVVYSTUQWNI-UHFFFAOYSA-N beta-ethyl naphthalene Natural products C1=CC=CC2=CC(CC)=CC=C21 RJTJVVYSTUQWNI-UHFFFAOYSA-N 0.000 description 1
- 229930006722 beta-pinene Natural products 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- WVIIMZNLDWSIRH-UHFFFAOYSA-N cyclohexylcyclohexane Chemical group C1CCCCC1C1CCCCC1 WVIIMZNLDWSIRH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PYBNTRWJKQJDRE-UHFFFAOYSA-L dodecanoate;tin(2+) Chemical compound [Sn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O PYBNTRWJKQJDRE-UHFFFAOYSA-L 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- LCWMKIHBLJLORW-UHFFFAOYSA-N gamma-carene Natural products C1CC(=C)CC2C(C)(C)C21 LCWMKIHBLJLORW-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229940116335 lauramide Drugs 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 229940043348 myristyl alcohol Drugs 0.000 description 1
- YDLYQMBWCWFRAI-UHFFFAOYSA-N n-Hexatriacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCCC YDLYQMBWCWFRAI-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- BNIXVQGCZULYKV-UHFFFAOYSA-N pentachloroethane Chemical compound ClC(Cl)C(Cl)(Cl)Cl BNIXVQGCZULYKV-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LGWZGBCKVDSYPH-UHFFFAOYSA-N triacontane Chemical compound [CH2]CCCCCCCCCCCCCCCCCCCCCCCCCCCCC LGWZGBCKVDSYPH-UHFFFAOYSA-N 0.000 description 1
- OLTHARGIAFTREU-UHFFFAOYSA-N triacontane Natural products CCCCCCCCCCCCCCCCCCCCC(C)CCCCCCCC OLTHARGIAFTREU-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
- Artificial Filaments (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
【発明の詳細な説明】
１旦立茨歪立１
本発明は、高弾性率および高強度を有する超高分子量ポ
リオレフィン延伸物の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a drawn ultra-high molecular weight polyolefin product having high elastic modulus and high strength.
Ｂの ０ｍＪｌｒらびに のＩ＋題
高弾性率および高強度を有する超高分子量ポリオレフィ
ン延伸物の製造方法については、数多くの特許が公開さ
れている。超高分子量ポリオレフィンのゲル状４ｍ維を
延伸して、高弾性率および高強度を有する繊維を得る方
法については、たとえば特開昭５６−１５４０８号公報
、特開昭６０−１９４１０９号公報には、超高分子量ポ
リエチレンの例が、特開昭５８−５２２８号公報、特開
昭６１−６１０号公報には、超高分子量ポリエチレン、
ポリプロピレンなと超高分子量ポリオレフィンの例が示
されており、さらに特開昭６２−４１３４１号公報には
、ポリオレフィン、ポリアミド、ポリエステル、ポリア
クリロニトリル、ポリ（フッ化ビニリデン）、ポリにル
アルコール等の超高分子量重合体の例が示されている。A number of patents have been published regarding methods for producing drawn ultra-high molecular weight polyolefin products having high elastic modulus and high strength. Regarding the method of drawing gel-like 4m fibers of ultra-high molecular weight polyolefin to obtain fibers having high elastic modulus and high strength, for example, JP-A-56-15408 and JP-A-60-194109, Examples of ultra-high molecular weight polyethylene are listed in JP-A-58-5228 and JP-A-61-610.
Examples of ultra-high molecular weight polyolefins such as polypropylene are shown, and JP-A No. 62-41341 discloses ultra-high molecular weight polyolefins such as polyolefins, polyamides, polyesters, polyacrylonitrile, poly(vinylidene fluoride), and polyalcohols. Examples of high molecular weight polymers are shown.
また特開昭６１−２５２３１２号公報には、超高分子量
ポリエチレンの高濃度混合″！ＩＡ＜１５〜５０重量部
）の例が示されている。Further, JP-A-61-252312 discloses an example of a high-concentration mixture of ultra-high molecular weight polyethylene (!IA<15-50 parts by weight).
しかしこれらの方法は、延伸速度が低く、例えば特開昭
５８−５２２８号公報に開示されている方法では延伸給
糸速度がｌ０ＣＩ／分以下と非常に低く、生産性に乏し
いという問題点があった。However, these methods have a problem in that the drawing speed is low; for example, in the method disclosed in JP-A-58-5228, the drawing yarn feeding speed is very low at less than 10 CI/min, resulting in poor productivity. Ta.
このような問題点を解決するため、高倍率で延伸し、給
糸速度を高くする方法として、延伸時ヒーターを給糸速
度が速くなるほど長くする方法が特開昭６０−１６７９
１８号公報に開示されており、また延伸時のヒーター長
を給糸速度が速くなるほど長くし、かつ連続的に多段延
伸する方法が特開昭６０−１９４１０９号公報に開示さ
れている。ところがこれらの公報には、工業的生産を行
う際に大切なマルチフィラメントを用いた長時間の延伸
安定性に関しては言及されていない。In order to solve these problems, as a method of drawing at a high magnification and increasing the yarn feeding speed, there is a method of increasing the length of the heater during drawing as the yarn feeding speed increases, as disclosed in Japanese Patent Application Laid-Open No. 60-1679.
18, and JP-A-60-194109 discloses a method in which the length of the heater during drawing is made longer as the yarn feeding speed increases, and continuous multi-stage drawing is carried out. However, these publications do not mention long-term stretching stability using multifilaments, which is important in industrial production.
しかしながら本発明者らの検討によれば、超高分子量ポ
リオレフィンの延伸滞留時間が同じでも、延伸される前
の粂件で延伸性および長時間の延伸安定性が大きく異な
ることが見い出された。However, according to studies conducted by the present inventors, it has been found that even if the stretching residence time of ultra-high molecular weight polyolefins is the same, the stretchability and long-term stretching stability vary greatly depending on the shape of the polyolefin before being stretched.
また上記のような特開昭６０−１６７９’１８号公報あ
るいは特開昭６０−１９４１０９号公報に開示された方
法を改良し、より工業的に超高分子量ポリエチレン繊維
を生産する方法として、非連続多段延伸する方法が特開
昭６２−１８４１１２号公報に開示されている。しかし
ながらこの特開昭６２−１８４１１２号公報に開示され
ているような超高分子量ポリオレフィン延伸物をこの途
中で一旦巻取る方法は、操作が繁雑であるため、連続的
に延伸するプロセスが工業的には好ましい。In addition, as a method for producing ultra-high molecular weight polyethylene fibers more industrially by improving the method disclosed in JP-A-60-1679'18 or JP-A-60-194109, a discontinuous method is proposed. A multi-stage stretching method is disclosed in JP-A-62-184112. However, the method of winding up a stretched ultra-high molecular weight polyolefin product midway through the process, as disclosed in JP-A-62-184112, requires complicated operations, and therefore the continuous stretching process is not suitable for industrial use. is preferable.
凡肌立旦週
本発明は、上記のような従来技術に伴う問題点を解決し
ようとするものであって、高弾性率および高強度を有す
る超高分子量ポリオレフィン延伸物を、高い延伸速度で
しかも長時間の延伸安定性を伴って、工業的な規模で生
産性および操作性よく製造しうるような、超高分子量ポ
リオレフィン延伸物の製造方法を提供することを目的と
している。The present invention is an attempt to solve the problems associated with the prior art as described above, and is to produce a drawn product of ultra-high molecular weight polyolefin having a high elastic modulus and high strength at a high drawing speed. The object of the present invention is to provide a method for producing a stretched ultra-high molecular weight polyolefin product that has long-term stretching stability and can be produced on an industrial scale with good productivity and operability.
ユ皿しｌｌ歴
本発明に係る超高分子量ポリオレフィン延伸物の製造方
法は、極限粘度［η］が少なくとも５ｄｊ ／ を以上
である超高分子量ポリオレフィン（Ａ）と、融点が超高
分子量ポリオレフィン（Ａ）の融点より低い流動性改良
剤（Ｂ）とから成る混合物を、超高分子量ポリオレフィ
ン（Ａ）の融点以上の温度で溶融混練してダイより押出
延伸し、得られる押出物を多段工程で延伸するに際し、
第ｎ段の延伸工程と前段の延伸工程との間に、延伸張力
が少なくとも前段の延伸張力の０．１〜５０％であり、
かつ０．１〜４０ｔ／フイラメントである張力緩和ゾー
ンを設けることを特徴としている。The method for producing a drawn ultra-high molecular weight polyolefin product according to the present invention comprises: ultra-high molecular weight polyolefin (A) having an intrinsic viscosity [η] of at least 5 dj/ or more; and ultra-high molecular weight polyolefin (A) having a melting point ) and a fluidity improver (B) having a lower melting point than the ultra-high molecular weight polyolefin (A), the mixture is melt-kneaded at a temperature higher than the melting point of the ultra-high molecular weight polyolefin (A) and extruded and stretched through a die, and the resulting extrudate is stretched in a multi-stage process. In doing so,
Between the n-th drawing step and the previous drawing step, the drawing tension is at least 0.1 to 50% of the drawing tension of the previous step,
It is also characterized by providing a tension relief zone of 0.1 to 40 t/filament.
良悪］１頭調朋
以下本発明に係る超高分子量ポリオレフィン延伸物の製
造方法について、具体的に説明する。Quality/Badness] The method for producing the drawn ultra-high molecular weight polyolefin product according to the present invention will be specifically explained below.
超＝ 量ポリオレフ４ン Ａ
本発明で用いられる超高分子量ポリオレフィン（Ａ）は
、デカリン溶媒中１３５℃で測定した極限粘度［η］が
少なくとも５ｄｊ／ｇ以上、好ましくは７〜３０ｄｊ／
ｒである。この極限粘度［η］が５ｄｊ／＋ｒ未満であ
ると、容易に流動性改良剤（Ｂ）と均一な混合物を調製
できるが、分子原が短いため、高弾性率および高強度特
性を有する延伸物を得ることが難しくなる傾向にあるた
め好ましくない、一方、極限粘度［η］の上限はとくに
限定されないが、３０６ｊ／ｇを超えると、流動性改良
剤（Ｂ）を添加しても溶融粘度が高過ぎて押出成形性に
劣る傾向にあるなめ好ましくない。The ultra-high molecular weight polyolefin (A) used in the present invention has an intrinsic viscosity [η] of at least 5 dj/g or more, preferably 7 to 30 dj/g, as measured at 135° C. in a decalin solvent.
It is r. When the intrinsic viscosity [η] is less than 5dj/+r, a homogeneous mixture with the fluidity improver (B) can be easily prepared, but because the molecular base is short, a stretched product with high elastic modulus and high strength properties cannot be obtained. On the other hand, the upper limit of the intrinsic viscosity [η] is not particularly limited, but if it exceeds 306j/g, the melt viscosity will decrease even if the fluidity improver (B) is added. It is not preferable because it is too high and tends to lead to poor extrusion moldability.
本発明における超高分子量ポリオレフィン（Ａ）として
は、たとえばエチレン、プロピレン、１−ブテン、１−
ペンテン、１−ヘキセン、１−オクテン、１−デセン、
４−メチル−１−ペンテンなとのα−オレフィンの単独
重合体または共重合体が用いられる。Examples of the ultra-high molecular weight polyolefin (A) in the present invention include ethylene, propylene, 1-butene, 1-
Pentene, 1-hexene, 1-octene, 1-decene,
Homopolymers or copolymers of α-olefins such as 4-methyl-1-pentene are used.
これらの中では、超高分子量ポリエチレンもしくはエチ
レンと他のα−オレフィンとのエチレンを主体とした共
重合体たとえば超高分子量ポリエチレン・プロピレン共
重合体、超高分子量エチレン・１−ブテン共重合体、超
高分子量エチレン・４−メチル−１−ペンテン共重合体
、超高分子量エチレン・１−ヘキセン共重合体、超高分
子量エチレン・１−オクテン共重合体、超高分子量エチ
レン・１−デセン共重合体であって、高結晶性の超高分
子量ポリオレフィンが、高弾性率および高引張強度を有
する延伸物が得られるので好ましい、なお上記のような
エチレンと他のα−オレフィンとからなる超高分子量エ
チレン・α−オレフィン共重合体では、α−オレフィン
の含有量は、０．０１〜３モル％好ましくは０．１〜１
．５モル％であることが望ましい。Among these, ultra-high molecular weight polyethylene or ethylene-based copolymers of ethylene and other α-olefins, such as ultra-high molecular weight polyethylene/propylene copolymers, ultra-high molecular weight ethylene/1-butene copolymers, Ultra-high molecular weight ethylene/4-methyl-1-pentene copolymer, ultra-high molecular weight ethylene/1-hexene copolymer, ultra-high molecular weight ethylene/1-octene copolymer, ultra-high molecular weight ethylene/1-decene copolymer A highly crystalline ultra-high molecular weight polyolefin is preferable because a drawn product having a high elastic modulus and a high tensile strength can be obtained. In the ethylene/α-olefin copolymer, the α-olefin content is 0.01 to 3 mol%, preferably 0.1 to 1
．． The content is preferably 5 mol%.
また本発明では、超高分子量ポリオレフィン（Ａ＞とし
て、超高分子量ポリオレフィンにビニルトリエトキシシ
ランなどのシラン化合物を、２．５−ジメチル−２，５
−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキサンなどの重
合開始剤の存在下にグラフトさせたシラングラフト化超
高分子量ポリオレフィンを用いることもできる。Furthermore, in the present invention, as the ultra-high molecular weight polyolefin (A>), a silane compound such as vinyltriethoxysilane is added to the ultra-high molecular weight polyolefin with 2,5-dimethyl-2,5
Silane-grafted ultra-high molecular weight polyolefins grafted in the presence of a polymerization initiator such as -di(tert-butylperoxy)hexane can also be used.
また本発明では、超高分子量ポリオレフィン（Ａ）とし
て、超高分子量ポリオレフィンに不飽和カルボン酸また
はその誘導体、不飽和エポキシ単量体、オレフィン性不
飽和結合を有するシラン単Ｊｊｌを、ジクミルペルオキ
シド、２．５−ジメチル−２，５−ジ（ｔｅｒｔ−ブチ
ルペルオキシ）ヘキサンなどのラジカル開始剤の存在下
にグラフトさせたグラフト化超高分子量ポリオレフィン
を用いることもできる。Further, in the present invention, as the ultra-high molecular weight polyolefin (A), an unsaturated carboxylic acid or its derivative, an unsaturated epoxy monomer, a silane single Jjl having an olefinic unsaturated bond, dicumyl peroxide, dicumyl peroxide, Grafted ultra-high molecular weight polyolefins grafted in the presence of a radical initiator such as 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane can also be used.
このような超高分子量ポリオレフィン（Ａ）は、粒状で
用いられることが好ましく、その粒径は通常１〜５００
μｍ好ましくは５〜３００μｍである。Such ultra-high molecular weight polyolefin (A) is preferably used in the form of particles, and the particle size is usually 1 to 500.
μm Preferably 5 to 300 μm.
ゞ 性改良剤（Ｂ）
本発明で用いられる流動性改良剤（Ｂ）は、融点が超高
分子量ポリオレフィン（Ａ）の融点より低い低分子量化
合物である。このような流動性改良剤（Ｂ）としては、
超高分子量ポリオレフィン（Ａ）を溶解しうる溶剤ある
いは超高分子量ポリオレフィン（Ａ）に対して相溶性を
有する各種ワックス類が使用される。Property Improver (B) The fluidity improver (B) used in the present invention is a low molecular weight compound whose melting point is lower than the melting point of the ultra-high molecular weight polyolefin (A). As such a fluidity improver (B),
A solvent that can dissolve the ultra-high molecular weight polyolefin (A) or various waxes that are compatible with the ultra-high molecular weight polyolefin (A) are used.
上記のような溶剤は、好ましくは前記超高分子量ポリエ
チレンの融点以上、さらに好ましくは前記超高分子量ポ
リエチレンの融点よりも２０’Ｃ以上高い沸点を有する
ことが望ましい。It is desirable that the above-mentioned solvent preferably has a boiling point higher than the melting point of the ultra-high molecular weight polyethylene, and more preferably 20'C or more higher than the melting point of the ultra-high molecular weight polyethylene.
このような溶剤としては、具体的にはｎ−ノナン、ｎ−
デカン、ｎ−ウンデカン、ｎ−ドデカン、ｎ−テトラデ
カン、ｎ−オクタデカンあるいは流動パラフィン、灯油
などの脂肪族炭化水素系溶媒、キシレン、ナフタリン、
テトラリン、ブチルベンゼン、ｐ−シメン、シクロヘキ
シルベンゼン、ジエチルベンゼン、ペンチルベンゼン、
ドデシルベンゼン、ビシクロヘキシル、デカリン、メチ
ルナフタリン、エチルナフタリン等の芳香族炭化水素系
溶媒あるいはその水素化誘導体、１，１，２．２−テト
ラクロロエタン、ペンタクロロエタン、ヘキサクロロエ
タン、１．２Ｉ３−トリクロロプロパン、ジクロロベン
ゼン、１，２゜４−トリクロロベンゼン、ブロモベンゼ
ン等のハロゲン化炭化水素溶媒、パラフィン系プロセス
オイル、ナフテン系プロセスオイル、芳香族系プロセス
オイル等の鉱油が挙げられる。Specifically, such solvents include n-nonane, n-
Decane, n-undecane, n-dodecane, n-tetradecane, n-octadecane or liquid paraffin, aliphatic hydrocarbon solvents such as kerosene, xylene, naphthalene,
Tetralin, butylbenzene, p-cymene, cyclohexylbenzene, diethylbenzene, pentylbenzene,
Aromatic hydrocarbon solvents such as dodecylbenzene, bicyclohexyl, decalin, methylnaphthalene, and ethylnaphthalene, or hydrogenated derivatives thereof, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, 1.2I3-trichloropropane , halogenated hydrocarbon solvents such as dichlorobenzene, 1,2°4-trichlorobenzene, and bromobenzene, mineral oils such as paraffinic process oils, naphthenic process oils, and aromatic process oils.
また上記のようなワックス類としては、脂肪族炭化水素
化合物あるいはその誘導体が使用される。Further, as the above-mentioned waxes, aliphatic hydrocarbon compounds or derivatives thereof are used.
ワックス類としての脂肪族炭化水素化合物としては、具
体的には、飽和脂肪族炭化水素化合物を主体とし、通常
、分子量が２０００以下、好ましくは１０００以下、さ
らに好ましくは８００以下のパラフィン系ワックスが用
いられる。これら脂肪族炭化水素化合物としては、具体
的には、トコサン、トリコサン、テトラコサン、トリア
コンタン等の炭素数２２以上のｎ−アルカンあるいはこ
れらを主成分とした低級ｎ−アルカンとの混合物、石油
から分離精製されたいわゆるパラフィンワックス、エチ
レンあるいはエチレンと他のα−オレフィンとを共重合
して得られる低分子量重合体である中・低圧ポリエチレ
ンワックス、高圧法ポリエチレンワックス、エチレン共
重合ワックスあるいは中・低圧法ポリエチレン、高圧法
ポリエチレン等のポリエチレンを熱減成等により分子量
を低下させたワックスおよびそれらのワックスの酸化物
あるいはマレイン酸変性等の酸化ワックス、マレイン酸
変性ワックス等が挙げられる。As the aliphatic hydrocarbon compound as the wax, specifically, a paraffinic wax mainly composed of saturated aliphatic hydrocarbon compounds and having a molecular weight of 2000 or less, preferably 1000 or less, more preferably 800 or less is used. It will be done. Specifically, these aliphatic hydrocarbon compounds include n-alkanes having 22 or more carbon atoms such as tocosan, tricosane, tetracosane, triacontane, mixtures of these with lower n-alkanes as main components, and mixtures separated from petroleum. Purified so-called paraffin wax, medium/low pressure polyethylene wax which is a low molecular weight polymer obtained by copolymerizing ethylene or ethylene with other α-olefins, high pressure process polyethylene wax, ethylene copolymer wax, or medium/low pressure process Examples include waxes obtained by reducing the molecular weight of polyethylene such as polyethylene and high-pressure polyethylene by thermal degradation, oxides of these waxes, oxidized waxes modified with maleic acid, and waxes modified with maleic acid.
脂肪族炭化水素化合物誘導体としては、たとえば脂肪族
炭化水素基（アルキル基、アルケニル基）の末端もしく
は内部に１個またはそれ以上、好ましくは１〜２個、特
に好ましくは１個のカルボキシル基、水酸基、カルバモ
イル基、エステル基、メルカプト基、カルボニル基等の
官能基を有する化合物である炭素数８以上、好ましくは
炭素数１２〜５０または分子量１３０〜２０００、好ま
しくは２００〜８００の脂肪酸、脂肪族アルコール、脂
肪酸アミド、脂肪酸エステル、脂肪族メルカプタン、脂
肪族アルデヒド、脂肪族ゲトン等を挙げることができる
。Examples of aliphatic hydrocarbon compound derivatives include one or more, preferably one to two, particularly preferably one, carboxyl group or hydroxyl group at the terminal or inside of an aliphatic hydrocarbon group (alkyl group, alkenyl group). , fatty acids and aliphatic alcohols having 8 or more carbon atoms, preferably 12 to 50 carbon atoms, or molecular weights 130 to 2,000, preferably 200 to 800, which are compounds having functional groups such as carbamoyl groups, ester groups, mercapto groups, and carbonyl groups. , fatty acid amide, fatty acid ester, aliphatic mercaptan, aliphatic aldehyde, aliphatic getone, and the like.
具体的には、脂肪酸としてカプリン酸、ラウリン酸、ミ
リスチン酸、バルミチン酸、ステアリン酸、オレイン酸
等、脂肪族アルコールとしてラウリンアルコール、ミリ
スチルアル、コール、セチルアルコール、ステアリルア
ルコール等、脂肪酸アミドとしてカプリンアミド、ラウ
リンアミド、パルミチンアミド、ステアリルアミド等、
脂肪酸エステルとしてステアリル酢酸エステル等を例示
することができる。Specifically, fatty acids include capric acid, lauric acid, myristic acid, balmitic acid, stearic acid, oleic acid, etc., fatty alcohols include lauric alcohol, myristyl alcohol, kohl, cetyl alcohol, stearyl alcohol, etc., and fatty acid amides include caprinamide. , lauramide, palmitinamide, stearylamide, etc.
Examples of fatty acid esters include stearyl acetate and the like.
これら流動性改良剤（Ｂ）の中でも、常温固体のワック
ス類が、貯蔵性、輸送性の面で好ましい。Among these fluidity improvers (B), waxes that are solid at room temperature are preferred in terms of storage and transportability.
本発明に用いる流動性改良剤（Ｂ）としては、本発明の
目的を損わない範囲で、軟化点が５０〜１２０°Ｃの低
軟化点炭化水素重合体、具体的には、通常、粘着付与樹
脂として粘着テープ、塗料、およびホットメルト接着剤
用分野に用いられており、重合されるモノマー源の違い
により次のような樹脂、たとえば、石油、ナフサ等の分
解によって得られるＣ 留分、Ｃ５留分、これらの混合
物あるいはこれらの任意の留分、例えばＣ５留分中のイ
ソプレンおよび１．３−ペンタジェンなどを主原料とす
る脂肪族系炭化水素樹脂、石油、ナフサ等の分解によっ
て得られるＣ９留分中のスチレン誘導体およびインデン
顕を主原料とする芳香族系炭化水素樹脂、Ｃ−Ｃ５留分
の任意の留分とＣ９留分を共重合した脂肪族・芳香族共
重合炭化水素樹脂、芳香族系炭化水素樹脂を水素添加し
た脂環族系炭化水素樹脂、脂肪族、脂環族および芳香族
を含む構造をもつ合成テルペン系炭化水素樹脂、テレベ
ン油中のα、β−ピネンを原料とするテルペン系炭化水
素樹脂、コールタール系ナフサ中のインデンおよびスチ
レン類を原料とするクマロンインデン系炭化水素樹脂、
低分子量スチレン系樹脂およびロジン系炭化水素樹脂な
どを添加した混合系の流動性改良剤を用いることもでき
る。As the fluidity improver (B) used in the present invention, a low softening point hydrocarbon polymer having a softening point of 50 to 120°C is generally used, as long as it does not impair the purpose of the present invention. It is used as a coating resin in the fields of adhesive tapes, paints, and hot-melt adhesives, and depending on the monomer source to be polymerized, the following resins may be used: For example, C fraction obtained by decomposing petroleum, naphtha, etc. A C5 fraction, a mixture thereof, or any fraction thereof, such as an aliphatic hydrocarbon resin whose main raw materials are isoprene and 1,3-pentadiene in the C5 fraction, obtained by decomposition of petroleum, naphtha, etc. An aromatic hydrocarbon resin whose main raw materials are styrene derivatives and indene in the C9 fraction, and an aliphatic/aromatic copolymerized hydrocarbon resin obtained by copolymerizing any fraction of the C-C5 fraction with the C9 fraction. , alicyclic hydrocarbon resin obtained by hydrogenating aromatic hydrocarbon resin, synthetic terpene hydrocarbon resin with a structure containing aliphatic, alicyclic and aromatic groups, α, β-pinene in turpentine oil. Terpene hydrocarbon resin as raw material, coumaron indene hydrocarbon resin as raw material from indene and styrene in coal tar naphtha,
A mixed fluidity improver containing a low molecular weight styrene resin, a rosin hydrocarbon resin, or the like may also be used.
１庄盈豆
本発明では、まず、上記のような超高分子量ポリオレフ
ィン（Ａ）と、流動性改良剤ＣＢ）とからなる混合物を
、超高分子量ポリオレフィン（Ａ）の融点以上の温度で
ダイより押出紡糸して超高分子量ポリオレフィン押出物
を調製する。1. In the present invention, first, a mixture consisting of the above-mentioned ultra-high molecular weight polyolefin (A) and a fluidity improver CB) is passed through a die at a temperature higher than the melting point of the ultra-high molecular weight polyolefin (A). Ultra-high molecular weight polyolefin extrudates are prepared by extrusion spinning.
超高分子量ポリオレフィン（Ａ）と流動性改良剤（Ｂ）
との混合割合は、通常、超高分子量ポリオレフィン（Ａ
）が５〜ＳＣ１量％、好ましくは２０〜６０重量％、換
言すれば流動・注改良剤（Ｂ）が２０〜９５重量％、好
ましくは４０〜８０重量％の範囲であることが望ましい
。Ultra-high molecular weight polyolefin (A) and fluidity improver (B)
The mixing ratio with ultra-high molecular weight polyolefin (A
) is in the range of 5 to 1% by weight, preferably 20 to 60% by weight, in other words, the flow/pouring improver (B) is preferably in the range of 20 to 95% by weight, preferably 40 to 80% by weight.
ここで、押出紡糸して得られる超高分子量ポリオレフィ
ンの押出物は、空気雰囲気中または不活性気体中で押出
されたものであり、この押出物は未延伸の状態であって
も良いし、延伸された状態でも良い、この押出物が延伸
された状態にある場合には、その延伸倍率は、３〜６０
倍、好ましくは２０〜５０倍であり、その際の温度は１
７０〜２３０℃、好ましくは１８０〜２１０’Ｃである
。Here, the extrudate of ultra-high molecular weight polyolefin obtained by extrusion spinning is extruded in an air atmosphere or an inert gas, and this extrudate may be in an unstretched state or in a stretched state. When this extrudate is in a stretched state, the stretching ratio is 3 to 60.
times, preferably 20 to 50 times, at a temperature of 1
The temperature is 70-230°C, preferably 180-210'C.
このようにして得られる超高分子量ポリオレフィンの押
出物を、下記のような条件で延伸すると、超高分子量ポ
リオレフィン延伸物がｆＭ遺される。When the ultra-high molecular weight polyolefin extrudate thus obtained is stretched under the following conditions, the ultra-high molecular weight polyolefin drawn product is left with fM.
すなわち、超高分子量ポリオレフィン押出物を該押出物
中に含まれる流動性改良剤（Ｂ）を除去しながら多段工
程で延伸する。超高分子量ポリオレフィン押出物の延伸
は、一般に１０〜２００ｇ／フィラメントの延伸張力で
行なわれる。That is, the ultra-high molecular weight polyolefin extrudate is stretched in multiple steps while removing the fluidity improver (B) contained in the extrudate. Stretching of ultra-high molecular weight polyolefin extrudates is generally carried out at a stretching tension of 10 to 200 g/filament.
本発明では、この際第ｎ段の延伸工程と前段の延伸工程
の間に、延伸張力が少なくとも前段の延伸張力の０．１
〜５０％、好ましくは０．３〜２０％、さらに好ましく
は０．５〜１０％の張力緩和ゾーンを設置して、超高分
子量ポリオレフィン押出物の延伸を行なう。In the present invention, at this time, between the n-th drawing step and the previous drawing step, the drawing tension is at least 0.1 of the drawing tension of the previous step.
A strain relief zone of ~50%, preferably 0.3-20%, more preferably 0.5-10% is provided to effect the stretching of the ultra-high molecular weight polyolefin extrudate.
具体的には第ｎ段の延伸工程と前段の延伸工程との間に
、少なくとも３秒以上好ましくは５秒以上さらに好まし
くは５〜１２０秒間、前段の延伸張力の０．５〜１０％
であり、かつ延伸張力が１０ｇ／フィラメント以下であ
る張力緩和ゾーンに超高分子量ポリオレフィン押出物を
通過させる。Specifically, between the n-th stretching step and the previous stretching step, the stretching tension is at least 3 seconds or more, preferably 5 seconds or more, more preferably 5 to 120 seconds, and 0.5 to 10% of the stretching tension in the previous step.
The ultra-high molecular weight polyolefin extrudate is passed through a strain relief zone where the stretch tension is 10 g/filament or less.
また第ｎ段の延伸工程を前段の延伸工程より少なくとも
３℃高い温度条件下で行うことが好ましい。Further, it is preferable that the n-th stretching step is performed at a temperature that is at least 3° C. higher than the previous stretching step.
さらに具体的には、前記超高分子量ポリオレフィン押出
物を、１〜７段好ましくは２〜５段で延伸し、この際第
ｎ段の延伸工程は、前段の延伸工程よりも３〜３５゛Ｃ
と高い温度で行い、かつ各延伸工程の間に３秒以上好ま
しくは５秒以上さらに好ましくは５〜１２０秒間、前段
の延伸張力の０．５〜１０％であり、かつ延伸張力がＬ
ｏｇ／フィラメント以下である張力緩和ゾーンに、超高
分子量ポリオレフィン押出物を通過させる。More specifically, the ultra-high molecular weight polyolefin extrudate is stretched in 1 to 7 stages, preferably 2 to 5 stages, with the nth stage stretching step being 3 to 35°C lower than the previous stretching step.
and at a high temperature, and the stretching tension is 0.5 to 10% of the previous stage stretching tension for 3 seconds or more, preferably 5 seconds or more, and more preferably 5 to 120 seconds between each stretching step, and the stretching tension is L
The ultra high molecular weight polyolefin extrudate is passed through a strain relief zone that is less than or equal to og/filament.
以下延伸工程を３段に分けて行なう場合について説明す
る。A case where the stretching process is performed in three stages will be described below.
すなわち超高分子量ポリオレフィン押出物の延伸を、第
１段延伸工程では、２０〜１００ｇ／フィラメントの延
伸張力で、９５〜１２５”Ｃの温度で２〜８倍の延伸倍
率で行ない、次いで得られた延伸物を第２段延伸工程の
前で１０秒間１００°Ｃで延伸張力５ｇ／フィラメント
の張力緩和ゾーンに通過させ、次いで第２段延伸工程を
、４０〜１８０ ｇ／フィラメントの延伸張力で１１０
℃〜１４０℃の温度、１〜３倍の延伸倍率で行なう。That is, the ultra-high molecular weight polyolefin extrudate was drawn in the first stage drawing step at a drawing tension of 20 to 100 g/filament at a temperature of 95 to 125"C and a drawing ratio of 2 to 8 times. The drawn product was passed through a strain relief zone at 100 °C for 10 seconds with a drawing tension of 5 g/filament before the second drawing step, and then a second drawing step was carried out at 110° C. with a drawing tension of 40 to 180 g/filament.
It is carried out at a temperature of 140°C to 140°C and a stretching ratio of 1 to 3 times.
上記のようにして得られた延伸物を、さらに第３段延伸
工程の前に５秒間、１００’Ｃで延伸張力３ｇ／フィラ
メントの張力緩和ゾーンに通過させ、次いで第３段延伸
工程を、１０〜８０ｇ／フィラメントの延伸張力で１３
０〜１５５℃の温度１〜４倍の延伸倍率で行なう、この
際第２段延伸工程では、第１段延伸工程よりも５〜２０
℃高い温度で行ない、第３段延伸工程では第２段延伸工
程よりも３〜３０℃高い温度で行なう。The drawn product obtained as described above is further passed through a tension relaxation zone with a drawing tension of 3 g/filament at 100'C for 5 seconds before the third drawing step, and then the third drawing step is carried out for 10 seconds. ~13 at a drawing tension of ~80g/filament
It is carried out at a temperature of 0 to 155°C and a stretching ratio of 1 to 4 times. In this case, in the second stage stretching step, the stretching ratio is 5 to 20 times higher than that in the first stage stretching step.
The third drawing step is carried out at a temperature 3 to 30° C. higher than the second drawing step.
上記延伸時の熱媒は空気、水蒸気、溶媒のいずれを用い
ても高弾性率かつ高強度の延伸物が得られるが、熱媒と
して流動性改良剤（Ｂ）を溶出あるいは滲出除去するこ
とができる溶媒で、沸点が組成物の融点以上のもの、具
体的には例えばデカリン、デカン、灯油を用いると延伸
時に過剰の流動性改良剤（Ｂ）の除去ができ、延伸時の
延伸むらの低減ならびに高延伸倍率の達成が可能となる
ので好ましい。また超高分子量ポリオレフィン（Ａ＞の
延伸物から流動性改良剤（Ｂ）を除去する手段としては
、前記の方法に限らず、未延伸物をヘキサン、ヘプタン
、熱エタノール、クロロホルム、ベンゼン等の溶剤で処
理後延伸する方法、延伸物をヘキサン、ヘプタン、熱エ
タノール、クロロホルム、ベンゼン等の溶剤で処理する
方法によっても流動性改良剤（Ｂ）を抽出除去でき、し
かも高弾性率かつ高強度の延伸物が得られる。A drawn product with high elastic modulus and high strength can be obtained by using air, water vapor, or a solvent as the heating medium during the above-mentioned stretching, but the fluidity improver (B) cannot be removed by elution or exudation as the heating medium. Using a solvent with a boiling point higher than the melting point of the composition, specifically, for example, decalin, decane, or kerosene, can remove excess fluidity improver (B) during stretching, reducing stretching unevenness during stretching. In addition, it is possible to achieve a high stretching ratio, which is preferable. In addition, as a means for removing the fluidity improver (B) from the drawn product of ultra-high molecular weight polyolefin (A>), the method is not limited to the above-mentioned method. The fluidity improver (B) can also be extracted and removed by a method in which the stretched product is treated with a solvent such as hexane, heptane, hot ethanol, chloroform, benzene, etc. You can get things.
なお超高分子量ポリオレフィン（Ａ）の押出紡糸工程は
、通常、空気中で行なわれ、この際押出物は１０〜５０
倍の延伸倍率（ドラフト比率）に延伸されている。The extrusion spinning process of the ultra-high molecular weight polyolefin (A) is usually carried out in air, and at this time the extrudate is
It is stretched to a stretching ratio (draft ratio) of 2 times.
超高分子量ポリオレフィン（Ａ）と流動性改良剤（Ｂ）
等との混合時には、耐熱安定剤、耐候安定剤、顔料、染
料、無機充填剤等、通常、ポリオレフィンに添加される
配合剤を本発明の目的を損なわない範囲で添加すること
ができる。Ultra-high molecular weight polyolefin (A) and fluidity improver (B)
When mixing with polyolefins, additives that are usually added to polyolefins, such as heat stabilizers, weather stabilizers, pigments, dyes, and inorganic fillers, can be added to the extent that the purpose of the present invention is not impaired.
九哩立宏】
本発明によれば、超高分子量ポリオレフィンから成る繊
維を、多段工程で延伸する際、第ｎ段の延伸工程と前段
の延伸工程の間に、好ましくは少なくとも３秒以上、前
段の延伸張力の０．１〜２０％であり、かつ延伸張力が
０．１〜４０ｇ／フィラメントである張力緩和ゾールを
設けて、この張力緩和ゾーンに超高分子量ポリオレフィ
ン押出物を通過させているので、前段の延伸工程におい
て生じた分子レベルの歪が緩和され、延伸速度を速くで
きるとともに、延伸倍率を高くでき、工業的規模で高弾
性率かつ高強度の延伸物を得ることができる。According to the present invention, when a fiber made of ultra-high molecular weight polyolefin is drawn in a multi-stage process, between the n-th drawing process and the previous drawing process, the first drawing process is preferably performed for at least 3 seconds or more. A tension relaxation sol with a stretching tension of 0.1 to 20% of the stretching tension of 0.1 to 40 g/filament is provided, and the ultra-high molecular weight polyolefin extrudate is passed through this tension relaxation zone. The strain at the molecular level caused in the previous stretching process is relaxed, the stretching speed can be increased, the stretching ratio can be increased, and a stretched product with high elastic modulus and high strength can be obtained on an industrial scale.
［実施例〕
次に実施例を挙げて本発明をより詳しく説明するが、本
発明はその要旨を越えない限り、これらの例に何ら制約
されるものではない。[Examples] Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples unless the gist thereof is exceeded.
火」自引上
紘ＪαＬ程
超高分子量ポリエチレン（［η］＝８．２６ｄＪｌ／ｇ
、平均粒径＝２００．ｕｍ）粉末とパラフィンワックス
（日本＠製、商品名ニルパックス、融点：６９℃）粉末
とをヘンシェルミキサーで５分間混合し、超高分子量ポ
リエチレンの濃度が４０重量％の混合物を調製した。Ultra-high molecular weight polyethylene ([η] = 8.26 dJl/g
, average particle size=200. um) powder and paraffin wax (manufactured by Japan@, trade name Nilpax, melting point: 69°C) powder were mixed for 5 minutes in a Henschel mixer to prepare a mixture having an ultra-high molecular weight polyethylene concentration of 40% by weight.
続いて該混合物を、−軸押比ｍ＜モダンマシーナリー社
製、スクリュー径４０市、Ｌ／Ｄ＝３０）を用いて、供
給部で３０℃に、溶融部で１３０’Ｃに、圧縮部分で２
００℃に温度設定し、スクリュー回転数を１５ Ｏｒ、
Ｉ）、１として、滞留時間５分で溶融混練した。Subsequently, the mixture was heated to 30°C in the supply section, 130'C in the melting section, and 130'C in the compression section using -axial pressing ratio m < Modern Machinery Co., Ltd., screw diameter 40 mm, L/D = 30). 2
Set the temperature to 00℃, screw rotation speed to 15 Or,
I), 1 was melt-kneaded with a residence time of 5 minutes.
引き続き該溶融物をオリフィス径２市のダイより１．７
４ｃｃ／分の速度で押出紡糸した。紡糸繊維は２８０ａ
ａのエアーギャップで室温の空気にて冷却固化し、超高
分子量ポリエチレン繊維とした′。Subsequently, the melt was passed through a die with an orifice diameter of 1.7 mm.
Extrusion spinning was carried out at a speed of 4 cc/min. Spun fiber is 280a
It was cooled and solidified in air at room temperature in the air gap of a to obtain an ultra-high molecular weight polyethylene fiber.
この繊維は５１０デニールであり、紡糸時のドラフト比
率は４０であった。またこの際の巻取速度は２８ｍ／分
であった。This fiber had a denier of 510, and the draft ratio during spinning was 40. Further, the winding speed at this time was 28 m/min.
ｌ應工ｌ
前記の方法で超高分子量ポリエチレン混合物から紡糸さ
れた１００本の繊維を、次の条件で延伸し、配向延伸繊
維を得た。６台のゴデツトロールを用いて、ｎ−デカン
およびトリエチレングリコールを熱媒とした延伸槽にて
３段延伸を行った。このとき第１延伸槽の熱媒はｎ−デ
カンであり、延伸温度は１１０℃であり、延伸張力は８
０ｇ／フィラメントであり、また第２延沖槽の熱媒はｎ
−デカンであり、延伸温度は１２０℃であり、延伸張力
は１２０ｇ／フィラメントであり、さらに第３延伸槽の
熱媒はトリエチレングリコールであり、延伸温度は１４
６℃であり、延伸張力は４０ｇ／フィラメントであり、
槽の有効長はそれぞれ６ｍであった。延伸に際しては第
１ゴデツトロールの回転速度を５．０ｍ／分として、第
６ゴデツトロールの回転速度を変更することにより所望
の延伸比の繊維を得た。また第２および第４ゴデツトロ
ールの回転速度は安定延伸可能な範囲で適宜選択した。1.100 fibers spun from the ultra-high molecular weight polyethylene mixture by the above method were drawn under the following conditions to obtain oriented drawn fibers. Three stages of stretching were performed in a stretching tank using six godet rolls and using n-decane and triethylene glycol as heating media. At this time, the heating medium in the first drawing tank was n-decane, the drawing temperature was 110°C, and the drawing tension was 8
0g/filament, and the heat medium of the second Nobuki tank is n
- decane, the drawing temperature is 120°C, the drawing tension is 120 g/filament, and the heating medium in the third drawing tank is triethylene glycol, the drawing temperature is 14
6°C, the drawing tension was 40g/filament,
The effective length of each tank was 6 m. During stretching, the rotation speed of the first godet roll was set at 5.0 m/min, and the rotation speed of the sixth godet roll was changed to obtain fibers with a desired drawing ratio. Further, the rotational speeds of the second and fourth godet rolls were appropriately selected within a range that allowed stable stretching.
ただし延伸比は第１ゴデツトロールと第６ゴデゲトロー
ルとの回転速度比により計算して求めた。However, the stretching ratio was calculated based on the rotational speed ratio of the first godetrol and the sixth godetrol.
第２ゴデツトロールと第３ゴデツトロールとの間に第１
張力緩和ゾーンを設け、この第１張力緩和ゾーンでは温
度はｉｏｏ’ｃであり、延伸張力は２ｇ／フィラメント
であり、その有効長は１０ｍであった。この第１張力緩
和ゾーンにおける超高分子量ポリオレフィン押出物の滞
留時間は２０秒であった。また第４コデツトロールと第
５コデツトロールとの間に第２張力緩和ゾールを設け、
この第２張力緩和ゾーンでは温度は１１０℃であり、延
伸張力は３ｇ／フィラメントであり、その有効長は１０
ｍであった。この第２張力緩和ゾールにおける超高分子
量ポリオレフィン押出物の滞留時間は１０秒であった。between the second godets troll and the third godets troll
A strain relief zone was provided, in which the temperature was ioo'c, the drawing tension was 2 g/filament, and its effective length was 10 m. The residence time of the ultra-high molecular weight polyolefin extrudate in this first strain relief zone was 20 seconds. Further, a second tension relieving sol is provided between the fourth codetroll and the fifth codetroll,
In this second strain relief zone, the temperature is 110°C, the drawing tension is 3 g/filament, and the effective length is 10
It was m. The residence time of the ultra high molecular weight polyolefin extrudate in this second strain relief sol was 10 seconds.
上記のような張力緩和ゾーンでの延伸張力は、第３コデ
ツトロールおよび第４コデツトロールの回転速度を調節
することにより調節した。なお、この延伸張力の測定に
はテンションメーター（英光測器製、Ｈ３−４０００）
を用いた。The stretching tension in the tension relaxation zone as described above was adjusted by adjusting the rotational speed of the third codet roll and the fourth codetroll. To measure this stretching tension, use a tension meter (manufactured by Eikoh Sokki, H3-4000).
was used.
得られた延伸繊維の引張弾性率、引張強度および破断点
伸度をインテスコ万能試験Ｒ２００５型（インテスコ社
製）を用いて、室温（２３℃）にて測定した。クランプ
間の試料長は２５４市、引張速度は２５４ｍｍ／分とし
た。ただし引張弾性率は初期弾性率である。計算に必要
な繊維断面積はポリエチレンの密度を０．９６ｇ／ｄｌ
として繊維の重量と長さを測定して求めた。このように
して得られた延伸超高分子量ポリエチレン繊維の物性を
表１に示す。The tensile modulus, tensile strength, and elongation at break of the obtained drawn fibers were measured at room temperature (23° C.) using an Intesco Universal Test R2005 model (manufactured by Intesco). The sample length between the clamps was 254 mm, and the tensile speed was 254 mm/min. However, the tensile modulus is the initial modulus. The fiber cross-sectional area required for calculation is based on the density of polyethylene of 0.96 g/dl.
It was determined by measuring the weight and length of the fiber. Table 1 shows the physical properties of the drawn ultra-high molecular weight polyethylene fiber thus obtained.
表 １
後述する比較例１の結果（表２）に比べ延伸性、強度お
よび弾性率に優れていることがわかる。Table 1 It can be seen that the film is superior in stretchability, strength, and elastic modulus compared to the results of Comparative Example 1 (Table 2), which will be described later.
比較例１
紡 糸
実施例１の方法と同様にして未延伸超高分子量ポリエチ
レン繊維の紡糸を行った。Comparative Example 1 Spinning An undrawn ultra-high molecular weight polyethylene fiber was spun in the same manner as in Example 1.
ｌ−一皇
実施例１と同様にして延伸を行った。ただし第１延伸槽
と第２延伸槽の間および第２延伸槽と第３延伸槽の間に
張力緩和ゾーンを設けず、第２ゴデツトロールと第３ゴ
デツトロールおよび第４ゴデゾトロールと第５ゴデツト
ロールの回転速度は各々同一とした。ところが延伸操作
中に糸切れが頻発し、延伸倍率も１６倍までしか上らな
かった。l-Ikko Stretching was carried out in the same manner as in Example 1. However, no tension relaxation zone is provided between the first and second drawing tanks and between the second and third drawing tanks, and the rotational speeds of the second and third godetrolls, and the fourth and fifth godetrolls are were the same for each. However, thread breakage occurred frequently during the stretching operation, and the stretching ratio could only be increased to 16 times.
結果を表２に示す。The results are shown in Table 2.
表 ２
グラフトイおよび ７、
超高分子量ポリエチレン（［η］−８．７ｄＮ／ｇ、平
均粒径＝１８０μｍ）粉末を、溶融後１００”Ｃに保っ
たパラフィンワックス（日木精蝋製、商品名：ルバッタ
ス、融点：６９℃）中に投入した後、３０分間攪拌し、
超高分子量ポリエチレンの濃度が３０重量％の分散体を
調製した。Table 2 Graft toy and 7. Paraffin wax (manufactured by Hiki Seiro Co., Ltd., product name: Rubattas, melting point: 69°C), stirred for 30 minutes,
A dispersion with an ultra-high molecular weight polyethylene concentration of 30% by weight was prepared.
続いて、該分散体に、超高分子量ポリエチレン１００重
量部に対して５重量部のビニルトリエトキシシラン（信
越化学製）と、０．０５重量部の２．５−ジメチル−２
，５−ジ（ｔｅｒｔ−ブチルペルオキシ）ヘキサン（日
本油脂製、商品名：パーへキサ２５Ｂ）と添加して１０
分攪拌混合し、分散体を得た。Subsequently, 5 parts by weight of vinyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) and 0.05 parts by weight of 2.5-dimethyl-2 were added to the dispersion based on 100 parts by weight of ultra-high molecular weight polyethylene.
,5-di(tert-butylperoxy)hexane (manufactured by NOF Corporation, trade name: Perhexa 25B) and
The mixture was stirred and mixed for several minutes to obtain a dispersion.
次いで該分散体を同方向回転２軸押出機（プラスチック
工学研究所製、スクリュー径３９＋ｗ＋ｎ、Ｌ／Ｄ＝４
２）を用いて、供給部の温度を１００℃とし、その他の
部分の温度を１９０℃に設定し、スクリュー回転数を２
５０ ｒ、ｐ、ｎとし、滞留時間を１．５分として溶融
混練した。Next, the dispersion was transferred to a co-rotating twin-screw extruder (manufactured by Plastic Engineering Research Institute, screw diameter 39+w+n, L/D=4
2), set the temperature of the supply part to 100°C, set the temperature of other parts to 190°C, and set the screw rotation speed to 2.
50 r, p, n, and the residence time was 1.5 minutes for melt-kneading.
引き続き得られた溶融物を、オリフィス径１．８市のダ
イよりｉ、７４ＣＣ／分の速度で押出紡糸した。得られ
た紡糸繊維を１８０ａｏのエアーギャップで室温の空気
にて冷却固化し、未延伸超高分子量ポリエチレンシラン
グラフト繊維とした。Subsequently, the resulting melt was extrusion-spun through a die with an orifice diameter of 1.8 mm at a speed of 74 CC/min. The obtained spun fibers were cooled and solidified in air at room temperature with an air gap of 180 AO to obtain undrawn ultra-high molecular weight polyethylene silane grafted fibers.
この未延伸糸は４００デニールであり、紡糸時のドラフ
ト比率は４２であった。また、この際の巻き取り速度は
２８．３ｍ／分であった。This undrawn yarn had a denier of 400 and a draft ratio of 42 during spinning. Further, the winding speed at this time was 28.3 m/min.
シラングラフト量の 量
上記方法にて調製された未延伸グラフト繊維的８ｇを１
３５°Ｃに加熱保持したｐ−キシレン２００ＣＣに溶解
した０次いで常温にて過剰のヘキサン中に超高分子量ポ
リエチレンを析出させ、パラフィンワックスと未反応シ
ラン化合物を除去した。このようにして得られたシラン
グラフト化された超高分子量ポリエチレンのＳｉグラフ
ト量を、重合法にてＳｉ重量％で求めたところ、０．２
９重量％であった。Amount of silane graft: 8 g of undrawn grafted fiber prepared by the above method is added to 1
Ultra-high molecular weight polyethylene was dissolved in 200 cc of p-xylene heated and maintained at 35°C, and then ultra-high molecular weight polyethylene was precipitated in excess hexane at room temperature to remove paraffin wax and unreacted silane compounds. The amount of Si grafted in the silane-grafted ultra-high molecular weight polyethylene thus obtained was determined as Si weight % using a polymerization method, and was found to be 0.2
It was 9% by weight.
廷−一一仲
前記の方法で超高分子量ポリエチレン混合物から紡糸さ
れた１００本のグラフト化未延伸繊維を次の条件で延伸
し、配向延伸繊維を得た。100 grafted undrawn fibers spun from an ultra-high molecular weight polyethylene mixture by the method described above were drawn under the following conditions to obtain oriented drawn fibers.
６台のゴデツトロールを用いて、ｎ−デカンおよびトリ
エチレングリコールを熱媒とした延伸槽にて４段延伸を
行った。このとき第１延伸槽の熱媒はｎ−デカンであり
、延伸温度は１１０℃であり、延伸張力は７０ｇ／フィ
ラメントであり、第２延伸槽の熱媒はｎ−デカンであり
、延伸温度は１１８℃であり、延伸張力は１００＋ｒ／
フイラメントであり、第３延伸檀の熱媒はトリエチレン
グリコールであり、延伸温度は１４０℃であり、延伸張
力は５０ｇ／フィラメントであり、第４延伸槽の熱媒は
トリエチレングリコールであり、延伸温度は１４６ ”
Ｃであり、延伸張力は３０ｇ／フィラメントであり、槽
の有効長はそれぞれ６ｍであった。Four stages of stretching were carried out in a stretching tank using 6 godet rolls and using n-decane and triethylene glycol as heating media. At this time, the heating medium in the first drawing tank is n-decane, the drawing temperature is 110°C, the drawing tension is 70 g/filament, the heating medium in the second drawing tank is n-decane, and the drawing temperature is The temperature was 118°C, and the stretching tension was 100+r/
The heating medium in the third drawing tank is triethylene glycol, the drawing temperature is 140°C, the drawing tension is 50 g/filament, the heating medium in the fourth drawing tank is triethylene glycol, and the drawing temperature is 140°C. The temperature is 146”
C, the drawing tension was 30 g/filament, and the effective length of each tank was 6 m.
延伸に際しては第１ゴデツトロールの回転速度を４ｍ／
分として第６ゴデツトロールの回転速度を変更すること
により所望の延伸比の繊維を得な。During stretching, the rotational speed of the first godet roll was set at 4 m/
The desired draw ratio of the fiber can be obtained by changing the rotational speed of the sixth godet roll in minutes.
また第２．第４．第５ゴデツトロールの回転速度は安定
延伸可能な範囲で適宜選択しな、ただし延伸比は第１ゴ
デツトロールと第６ゴデツトロールとの回転速度比によ
り計算して求めた。Also second. 4th. The rotation speed of the fifth godet roll was appropriately selected within a range that allowed stable stretching, but the stretching ratio was calculated from the rotation speed ratio of the first godet roll and the sixth godet roll.
また第２ゴデツ１〜ロールと第３ゴデツトロールの間に
は有効長１０ｍの張力緩和ゾーンを設け、この張力緩和
ゾーンでは、温度は１００℃であり、延伸張力は３ｇ／
フィラメントとなるように第３ゴデツトロールの回転速
度を調節した。この張力緩和ゾーンにおける超高分子量
ポリオレフィン押出物の滞留時間は２５秒であった。な
おこの延伸張力の測定にはテンションメーター（英光測
器製、Ｈ３−４０００＞を用いた。In addition, a tension relaxation zone with an effective length of 10 m is provided between the second godet rolls 1 to 3 and the third godet roll, and in this tension relaxation zone, the temperature is 100°C and the stretching tension is 3 g/
The rotation speed of the third godet roll was adjusted to form a filament. The residence time of the ultra high molecular weight polyolefin extrudate in this strain relief zone was 25 seconds. Note that a tension meter (manufactured by Eikoh Sokki Co., Ltd., H3-4000) was used to measure the stretching tension.
得られた繊維を減圧下、室温にて乾燥し、延伸超高分子
ポリエチレンシラングラフト繊維とした。The obtained fibers were dried under reduced pressure at room temperature to obtain stretched ultra-high molecular weight polyethylene silane grafted fibers.
架橋触媒の含浸
前記方法で調製されたシラン化合物グラフト超高分子量
ポリエチレンの配向繊維をさらに架橋する場合には、延
伸時第２延伸槽に熱媒としてｎ−デカンおよびｎ−デカ
ンと等量のジブチル錫ジラウレートの混合物を用い、パ
ラフィンワックスを抽出するのと同時に、ジブチル錫ジ
ラウレートを繊維中に含浸した。あるいは延伸後、巻取
る直前に油剤塗布装置を用い、ｎ−デカンと等量のジブ
チル錫ジラウレートの混合物を繊維に塗布・含浸した。Impregnation of cross-linking catalyst When further cross-linking the oriented fibers of the silane compound-grafted ultra-high molecular weight polyethylene prepared by the above method, n-decane and an amount of dibutyl equivalent to n-decane are added as a heat medium to the second stretching tank during stretching. A mixture of tin dilaurate was used to impregnate dibutyltin dilaurate into the fiber at the same time as paraffin wax was extracted. Alternatively, after stretching and immediately before winding, the fiber was coated and impregnated with a mixture of n-decane and dibutyltin dilaurate in an equal amount using an oil coating device.
得られた繊維は、減圧上室温にてデカン臭のなくなるま
で乾燥した。The obtained fibers were dried under reduced pressure at room temperature until the odor of decane disappeared.
龍−一旦
この後繊維は潜水中で１２時間放置して架橋を完了させ
た。Dragon - Once this was done, the fibers were left under water for 12 hours to complete crosslinking.
ゲル分率の測定
上記方法にて得られたシラン架橋延伸超高分子量ポリエ
チレン繊維的０．４ｇをバラキシレン２００ ｍｌの入
っているコンデンサーを装置した三角フラスコに投入し
、４時間沸騰状態にて攪拌した０次いで不溶物をステン
レス製３００ ｎｅｓｈの金網で沢過した。８０°Ｃの
減圧下で乾燥後、秤量し、不溶物の重量を求めた。ゲル
分率は以下の式で求めた。Measurement of gel fraction 0.4 g of the silane cross-linked stretched ultra-high molecular weight polyethylene fiber obtained by the above method was placed in an Erlenmeyer flask equipped with a condenser containing 200 ml of free xylene, and stirred at boiling for 4 hours. Then, the insoluble matter was filtered through a stainless steel wire mesh made of 300 mesh. After drying under reduced pressure at 80°C, it was weighed to determine the weight of insoluble matter. The gel fraction was determined using the following formula.
試料重量 上記の調製試料のゲル分率は９５％であった。Sample weight The gel fraction of the above prepared sample was 95%.
なお、架橋前の延伸超高分子量ポリエチレンシランクラ
フト繊維のゲル分率は０％であり、グラフト反応中止の
ゲル生成は認められなかった。Note that the gel fraction of the stretched ultra-high molecular weight polyethylene silane kraft fiber before crosslinking was 0%, and no gel formation due to termination of the graft reaction was observed.
引張弾性率、引張強度および破断点伸度はインテスコ万
能試験機２００５型（インテスコ社製）を用いて室温（
２３°Ｃ）にて測定した。クランプ間の試料長はマルチ
フィラメント：２５４ｍで引張速度２５４ｎｓｍ／分と
した。ただし、引張弾性率は初期弾性率である。計算に
必要な繊維断面積はポリエチレンの密度を０．９６０／
ａＪとして繊維の重量と長さを測定して求めた。The tensile modulus, tensile strength, and elongation at break were measured at room temperature (
23°C). The sample length between the clamps was multifilament: 254 m, and the tensile speed was 254 nsm/min. However, the tensile modulus is the initial modulus. The fiber cross-sectional area required for calculation is the density of polyethylene 0.960/
aJ was determined by measuring the weight and length of the fiber.
このようにして得られたシラン架橋延伸超高分子量ポリ
エチレンｌａ維の物性を表３に示す。Table 3 shows the physical properties of the silane-crosslinked stretched ultra-high molecular weight polyethylene LA fiber thus obtained.
表 ３
後述する比較例２の結果（表４）に比べて、延伸性、強
度弾性率に優れていることがわかる。Table 3 It can be seen that the stretchability and strength-elastic modulus are superior to the results of Comparative Example 2 (Table 4) described later.
土！Ｕ江ｌ
実施例２の方法と同様にして、未延伸超高分子量ポリエ
チレンシラングラフト繊維とした。soil! In the same manner as in Example 2, an undrawn ultra-high molecular weight polyethylene silane grafted fiber was obtained.
乞う２ゴタΣヱ止」レヘ友１
実施例２の方法と同様にして未延伸グラフト繊維を分析
した結果、グラフト量は０．２９重量％であった。As a result of analyzing the undrawn grafted fibers in the same manner as in Example 2, the amount of grafting was 0.29% by weight.
１−一腫
実施例２と同様にして超高分子量ポリエチレン混合物か
ら紡糸されたグラフト化未延伸糸を延伸した。ただし第
２ゴデツトロールと第３ゴデツトロールの間に緩和ゾー
ンを設けず、第２ゴデツトロールと第３ゴデツトロール
の回転速度は同一とした。しかし延伸操作中に糸切れが
頻発し、延伸倍率は１０倍しか上からなかった。1-1 Tumor A grafted undrawn yarn spun from an ultra-high molecular weight polyethylene mixture in the same manner as in Example 2 was stretched. However, no relaxation zone was provided between the second godet roll and the third godet roll, and the rotational speeds of the second godet roll and the third godet roll were made the same. However, thread breakage occurred frequently during the stretching operation, and the stretching ratio was only 10 times higher.
カリ。 煤の パおよび加
実施例２と同様にしてシラン架橋超高分子量ポリエチレ
ンの配向繊維を得た。Cali. In the same manner as in Example 2, oriented fibers of silane-crosslinked ultra-high molecular weight polyethylene were obtained.
実施例２と同様にして求めたシラン架橋超高分子量ポリ
エチレン繊維のゲル分率は９６％であった。また該架橋
超高分子量ポリエチレン繊維の物性を表４に示す。The gel fraction of the silane-crosslinked ultra-high molecular weight polyethylene fiber determined in the same manner as in Example 2 was 96%. Further, Table 4 shows the physical properties of the crosslinked ultra-high molecular weight polyethylene fiber.
表 ４ 代理人 弁理士 銘木 俊一部Table 4 Agent Patent attorney Shunbetsu Precious Wood
Claims (1)
超高分子量ポリオレフィン（Ａ）と、融点が超高分子量
ポリオレフィン（Ａ）の融点より低い流動性改良剤（Ｂ
）とから成る混合物を、超高分子量ポリオレフィン（Ａ
）の融点以上の温度で溶融混練してダイより押出延伸し
、得られる押出物を多段工程で延伸するに際し、第ｎ段
の延伸工程と前段の延伸工程との間に、延伸張力が前段
の延伸張力の０．１〜５０％であり、かつ０．１〜４０
ｇ／フィラメントである張力緩和ゾーンを設けることを
特徴とする超高分子量ポリオレフィン延伸物の製造方法
。1) An ultra-high molecular weight polyolefin (A) having an intrinsic viscosity [η] of at least 5 dl/g or more, and a fluidity improver (B) having a melting point lower than the melting point of the ultra-high molecular weight polyolefin (A).
) and ultra-high molecular weight polyolefin (A
) is melt-kneaded at a temperature higher than the melting point of 0.1 to 50% of the stretching tension, and 0.1 to 40%
1. A method for producing a drawn ultra-high molecular weight polyolefin product, which comprises providing a tension relaxation zone which is a filament.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10317988A JPH01280013A (en) | 1988-04-26 | 1988-04-26 | Production of ultra-high-molecular weight polyolefin drawn product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10317988A JPH01280013A (en) | 1988-04-26 | 1988-04-26 | Production of ultra-high-molecular weight polyolefin drawn product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01280013A true JPH01280013A (en) | 1989-11-10 |
Family
ID=14347286
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10317988A Pending JPH01280013A (en) | 1988-04-26 | 1988-04-26 | Production of ultra-high-molecular weight polyolefin drawn product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01280013A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011219771A (en) * | 2011-07-26 | 2011-11-04 | Sumitomo Chemical Co Ltd | Polyolefin-based resin film and composition for producing the polyolefin-based resin film |
| WO2019177089A1 (en) * | 2018-03-15 | 2019-09-19 | 東洋紡株式会社 | Polyethylene fibers, and product using same |
-
1988
- 1988-04-26 JP JP10317988A patent/JPH01280013A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011219771A (en) * | 2011-07-26 | 2011-11-04 | Sumitomo Chemical Co Ltd | Polyolefin-based resin film and composition for producing the polyolefin-based resin film |
| WO2019177089A1 (en) * | 2018-03-15 | 2019-09-19 | 東洋紡株式会社 | Polyethylene fibers, and product using same |
| JPWO2019177089A1 (en) * | 2018-03-15 | 2021-02-25 | 東洋紡株式会社 | Polyethylene fiber and products using it |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5057261A (en) | Process for producing modified ultrahigh-molecular-weight polyolefins | |
| US4902460A (en) | Process for preparation of molecularly oriented, silane-crosslinked ultra-high-molecular-weight polyethylene molded article | |
| EP0168923B1 (en) | Process for producing stretched article of ultrahigh-molecular weight polyethylene | |
| EP0115192B1 (en) | Process for producing stretched filaments of ultrahigh-molecular-weight polyethylene | |
| EP0173572B1 (en) | Graft-modified ultrahigh-molecular-weight polyethylene and process for producing same | |
| WO1987003888A1 (en) | Compositions of ethylene polymers, method for the preparation and application thereof for the production of industrial articles | |
| KR950013728B1 (en) | Molecularly oriented, silane-cross linked ultra-high-molecular-weight polyethylene molded articla and process for preparation thereof | |
| JPS63182349A (en) | Production of ultrahigh molecular weight polyolefin composition | |
| JPS59130313A (en) | Manufacture of drawn ultra-high-molecular-weight polyethylene | |
| EP0316141A2 (en) | Filamentary aggregate and net composed thereof | |
| JPH01280013A (en) | Production of ultra-high-molecular weight polyolefin drawn product | |
| JPH0417132B2 (en) | ||
| JPH0226915A (en) | Production of ultra-high-molecular weight polyolefin fiber | |
| JPH0240764B2 (en) | ||
| JPH0336930B2 (en) | ||
| JPH0655628A (en) | Manufacture of modified ultra-high-molecular-weight polyolefin stretched material | |
| JPS6395234A (en) | Molded article of silane-crosslinked polyethylene having molecular orientation and production thereof | |
| JPH0482909A (en) | Production of high-molecular weight polyolefin fiber | |
| JPH06211923A (en) | Stretched modified ultrahigh-molecular-weight crystalline polyethylene | |
| JPS60190330A (en) | Manufacture of superhigh molecular weight polyethylene stretched product | |
| JPH0277452A (en) | Molecule oriented molded article of ultra-high-molecular-weight polyolefin base resin | |
| JPH04214405A (en) | Draw-formed material of polypropylene having ultra-high molecular weight and its use | |
| JPH01256335A (en) | Fishing line | |
| JPH03260112A (en) | Ultrahigh molecular weight polypropylene drawn product and its use |