JP2020016007A - Polyethylene fiber - Google Patents
Polyethylene fiber Download PDFInfo
- Publication number
- JP2020016007A JP2020016007A JP2019093563A JP2019093563A JP2020016007A JP 2020016007 A JP2020016007 A JP 2020016007A JP 2019093563 A JP2019093563 A JP 2019093563A JP 2019093563 A JP2019093563 A JP 2019093563A JP 2020016007 A JP2020016007 A JP 2020016007A
- Authority
- JP
- Japan
- Prior art keywords
- component
- polyethylene
- temperature
- polyethylene fiber
- less
- 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.)
- Granted
Links
- -1 Polyethylene Polymers 0.000 title claims abstract description 222
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 220
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 210
- 239000000835 fiber Substances 0.000 title claims abstract description 151
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000005481 NMR spectroscopy Methods 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 12
- 230000006698 induction Effects 0.000 claims abstract description 10
- 238000005259 measurement Methods 0.000 claims description 51
- 239000000203 mixture Substances 0.000 claims description 51
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 230000004927 fusion Effects 0.000 claims description 20
- 239000000460 chlorine Substances 0.000 claims description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 230000004899 motility Effects 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 230000014759 maintenance of location Effects 0.000 abstract description 13
- 238000005299 abrasion Methods 0.000 abstract description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 61
- 238000006116 polymerization reaction Methods 0.000 description 46
- 239000002245 particle Substances 0.000 description 40
- 239000002904 solvent Substances 0.000 description 32
- 239000000243 solution Substances 0.000 description 31
- 239000002002 slurry Substances 0.000 description 26
- 239000003054 catalyst Substances 0.000 description 25
- 238000012360 testing method Methods 0.000 description 21
- 238000001035 drying Methods 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- 229940057995 liquid paraffin Drugs 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011949 solid catalyst Substances 0.000 description 11
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 8
- 239000005977 Ethylene Substances 0.000 description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 7
- 239000003426 co-catalyst Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000003078 antioxidant effect Effects 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000004611 light stabiliser Substances 0.000 description 4
- 230000033001 locomotion Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- VNEBWJSWMVTSHK-UHFFFAOYSA-L disodium;3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C=C2C=C(S([O-])(=O)=O)C(O)=CC2=C1 VNEBWJSWMVTSHK-UHFFFAOYSA-L 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 125000002734 organomagnesium group Chemical group 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000010558 suspension polymerization method 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
- 239000004711 α-olefin Substances 0.000 description 3
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000010908 decantation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 150000002901 organomagnesium compounds Chemical class 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- 239000012085 test solution Substances 0.000 description 2
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- GPWOHFPQKGNSON-UHFFFAOYSA-N (4-hydroxyphenoxy)-(2,3,4,5,6-pentafluorophenoxy)borinic acid Chemical compound FC=1C(F)=C(F)C(F)=C(F)C=1OB(O)OC1=CC=C(O)C=C1 GPWOHFPQKGNSON-UHFFFAOYSA-N 0.000 description 1
- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- ZZLCFHIKESPLTH-UHFFFAOYSA-N 4-Methylbiphenyl Chemical compound C1=CC(C)=CC=C1C1=CC=CC=C1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
- NGKNMHFWZMHABQ-UHFFFAOYSA-N 4-chloro-2h-benzotriazole Chemical compound ClC1=CC=CC2=NNN=C12 NGKNMHFWZMHABQ-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- DFSWNYUWLQKNQP-UHFFFAOYSA-N [Ti].CC=CC=C Chemical compound [Ti].CC=CC=C DFSWNYUWLQKNQP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- YHNWUQFTJNJVNU-UHFFFAOYSA-N magnesium;butane;ethane Chemical compound [Mg+2].[CH2-]C.CCC[CH2-] YHNWUQFTJNJVNU-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002530 phenolic antioxidant Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920006027 ternary co-polymer Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003613 toluenes Chemical class 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical class [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Artificial Filaments (AREA)
Abstract
Description
本発明は、ポリエチレン繊維に関する。 The present invention relates to polyethylene fibers.
ポリエチレン繊維は軽量かつ強度に優れることから、従来より、ロープ、ネット、釣り糸、手袋、布地、積層体等様々な用途に使用されている。特に、船舶係留用のロープに代表されるように、海洋の環境下、長期間、高い負荷がかかる用途においては超高分子量ポリエチレンからなる繊維が用いられている。船舶係留用ロープに求められる特性としては、強度、耐クリープ性、耐摩耗性、耐候性等が挙げられる（例えば、特許文献１参照）。特に近年、耐クリープ性への要求が一層高まっている。このため、ポリエチレン繊維の耐クリープ性を高める方法として、従来から種々の方法が提案されている（例えば、特許文献２参照）。 Polyethylene fibers have been used in various applications such as ropes, nets, fishing lines, gloves, fabrics, and laminates because of their light weight and excellent strength. In particular, as is typified by ropes for mooring ships, fibers made of ultra-high molecular weight polyethylene are used in applications where a high load is applied for a long period of time in a marine environment. Properties required for a ship mooring rope include strength, creep resistance, wear resistance, weather resistance, and the like (for example, see Patent Document 1). Particularly in recent years, the demand for creep resistance has been further increased. For this reason, various methods have conventionally been proposed as methods for increasing the creep resistance of polyethylene fibers (see, for example, Patent Document 2).
ポリエチレン繊維の耐クリープ性向上のためにはポリエチレンの分子鎖にコモノマーを導入する方法はあるが、強度を上げられない他、結晶性が低下するため、耐摩耗性、耐候性の低下が課題である。また、ポリエチレン繊維の耐候性向上のためには耐候剤が処方されるが、さらなる改善が望まれており、特に塩水の近傍や海水雰囲気下で使用される際の強度保持の観点で改善が望まれている。その理由としては、塩水の近傍や海水雰囲気下で使用する際は、ポリエチレン繊維を束にして使用する場合が多いが、このような環境下ではポリエチレン繊維の一本の糸の強度が低下して破断することで、破断していない他の糸にかかる負荷が大きくなり、束としても破断やクリープが加速してしまうためである。 To improve the creep resistance of polyethylene fiber, there is a method of introducing a comonomer into the polyethylene molecular chain, but the strength cannot be increased and the crystallinity decreases. is there. Further, a weathering agent is formulated to improve the weather resistance of the polyethylene fiber, but further improvement is desired, particularly from the viewpoint of maintaining strength when used near salt water or in a seawater atmosphere. It is rare. The reason is that when used in the vicinity of salt water or in a seawater atmosphere, polyethylene fibers are often used in bundles, but in such an environment, the strength of one thread of polyethylene fibers is reduced. This is because the breaking increases the load applied to other yarns that have not been broken, and accelerates breaking and creep even as a bundle.
そこで本発明は、例えば、海洋で使用した際に優れた耐クリープ性、高い強度保持率、及び耐摩耗性を有するポリエチレン繊維を提供することを目的とする。 Therefore, an object of the present invention is to provide, for example, a polyethylene fiber having excellent creep resistance, high strength retention, and abrasion resistance when used in the ocean.
本発明者は、上述した従来技術の課題を解決するべく鋭意研究を進めた結果、高運動性成分の組成分率及び緩和時間が特定の範囲のポリエチレン繊維が、上記の課題を解決することができることを見出し、本発明を完成するに至った。 The inventor of the present invention has conducted intensive studies to solve the above-mentioned problems of the prior art. As a result, polyethylene fibers having a specific range of the composition ratio and relaxation time of the high mobility component can solve the above problems. They have found that they can do this and have completed the present invention.
すなわち、本発明は以下の通りである。
［１］
パルス核磁気共鳴（ＮＭＲ）のソリッドエコー法で測定された９０℃におけるポリエチレン繊維の自由誘導減衰（Ｍ（ｔ））を、下記式１を用いてフィッティングさせることにより、最も運動性の低い成分（α）、中間の運動性の成分（β）及び最も運動性の高い成分（γ）の３成分に近似した場合において、最も運動性の高い成分（γ）の組成分率が１％以上１０％以下であり、最も運動性の高い成分（γ）の緩和時間が１００μｓ以上１０００μｓ以下である、ポリエチレン繊維。
Ｍ（ｔ）＝αｅｘｐ（−（１／２）（ｔ／Ｔα）2）ｓｉｎｂｔ／ｂｔ＋βｅｘｐ（−（１／Ｗａ）（ｔ／Ｔβ）Wa）＋γｅｘｐ（−ｔ／Ｔγ） 式１
α：成分（α）の組成分率（％）
Ｔα：成分（α）の緩和時間（ｍｓｅｃ）
β：成分（β）の組成分率（％）
Ｔβ：成分（β）の緩和時間（ｍｓｅｃ）
γ：成分（γ）の組成分率（％）
Ｔγ：成分（γ）の緩和時間（ｍｓｅｃ）
ｔ：観測時間（ｍｓｅｃ）
Ｗａ：形状係数（１＜Ｗａ＜２）
ｂ：形状係数（０．１＜ｂ＜０．２）
［２］
極限粘度（η）が１１以上３０以下である、［１］に記載のポリエチレン繊維。
［３］
示差走査熱量計（ＤＳＣ）を用いた下記（i）〜（iii）の測定条件によって得られる２回目の昇温過程（測定条件（iii））のＤＳＣ曲線において、１５２℃以上の範囲に吸熱ピークが検出されない、［１］又は［２］に記載のポリエチレン繊維。
（ＤＳＣ測定条件）
（i）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（ii）１８０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（iii）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
［４］
示差走査熱量計（ＤＳＣ）を用いた下記（I）の測定条件によって得られる昇温過程のＤＳＣ曲線において、１６０℃〜１７０℃の範囲に検出される融解熱量（Ａ）と、ＤＳＣを用いた下記（II）〜（IV）の測定条件によって得られる２回目の昇温過程（測定条件（IV））のＤＳＣ曲線において、１６０℃〜１７０℃の範囲に検出される融解熱量（Ｂ）との比（Ｂ）／（Ａ）が１以上３以下である、［１］から［３］のいずれかに記載のポリエチレン繊維。
（ＤＳＣ測定条件）
（I）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（II）５０℃で１分間保持後、１０℃／分の昇温速度で１４０℃まで昇温。
（III）１４０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（IV）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
［５］
最も運動性の高い成分（γ）の組成分率が２％以上５％以下であり、最も運動性の高い成分（γ）の緩和時間が２００μｓ以上５００μｓ以下である、［１］に記載のポリエチレン繊維。
［６］
極限粘度（η）が１５以上３０以下である、［１］に記載のポリエチレン繊維。
［７］
示差走査熱量計（ＤＳＣ）を用いた下記（I）の測定条件によって得られる昇温過程のＤＳＣ曲線において、１６０℃〜１７０℃の範囲に検出される融解熱量（Ａ）と、ＤＳＣを用いた下記（II）〜（IV）の測定条件によって得られる２回目の昇温過程（測定条件（IV））のＤＳＣ曲線において、１６０℃〜１７０℃の範囲に検出される融解熱量（Ｂ）との比（Ｂ）／（Ａ）が１．５以上２．７以下である、［１］に記載のポリエチレン繊維。
（ＤＳＣ測定条件）
（I）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（II）５０℃で１分間保持後、１０℃／分の昇温速度で１４０℃まで昇温。
（III）１４０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（IV）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
［８］
塩素（Ｃｌ）の含有量が、５０ｐｐｍ以下である、［１］に記載のポリエチレン繊維。
［９］
アルミニウム（Ａｌ）の含有量が、５ｐｐｍ以下である、［１］に記載のポリエチレン繊維。
［１０］
塩素（Ｃｌ）の含有量が、５ｐｐｍ以下である、［１］に記載のポリエチレン繊維。
［１１］
パルス核磁気共鳴（ＮＭＲ）のソリッドエコー法で測定された９０℃におけるポリエチレン繊維の自由誘導減衰（Ｍ（ｔ））を、下記式１を用いてフィッティングさせることにより、最も運動性の低い成分（α）、中間の運動性の成分（β）及び最も運動性の高い成分（γ）の３成分に近似した場合において、最も運動性の高い成分（γ）の組成分率が１％以上１０％以下であり、最も運動性の高い成分（γ）の緩和時間が１００μｓ以上１０００μｓ以下である、ポリエチレン繊維の海洋での使用。
Ｍ（ｔ）＝αｅｘｐ（−（１／２）（ｔ／Ｔα）2）ｓｉｎｂｔ／ｂｔ＋βｅｘｐ（−（１／Ｗａ）（ｔ／Ｔβ）Wa）＋γｅｘｐ（−ｔ／Ｔγ） 式１
α：成分（α）の組成分率（％）
Ｔα：成分（α）の緩和時間（ｍｓｅｃ）
β：成分（β）の組成分率（％）
Ｔβ：成分（β）の緩和時間（ｍｓｅｃ）
γ：成分（γ）の組成分率（％）
Ｔγ：成分（γ）の緩和時間（ｍｓｅｃ）
ｔ：観測時間（ｍｓｅｃ）
Ｗａ：形状係数（１＜Ｗａ＜２）
ｂ：形状係数（０．１＜ｂ＜０．２）
That is, the present invention is as follows.
[1]
By fitting the free induction decay (M (t)) of the polyethylene fiber at 90 ° C. measured by the solid echo method of pulsed nuclear magnetic resonance (NMR) using the following equation 1, the component having the lowest mobility ( α), the intermediate motility component (β) and the most motility component (γ), when the three components are approximated, the composition fraction of the most motility component (γ) is 1% or more and 10% Polyethylene fiber, wherein the relaxation time of the component (γ) having the highest mobility is 100 μs or more and 1000 μs or less.
M (t) = αexp (− (１ ／) (t / Tα) 2 ) sinbt / bt + βexp (− (1 / Wa) (t / Tβ) Wa ) + γexp (−t / Tγ) Formula 1
α: composition ratio of component (α) (%)
Tα: relaxation time (msec) of component (α)
β: Composition fraction of component (β) (%)
Tβ: relaxation time of component (β) (msec)
γ: composition ratio (%) of component (γ)
Tγ: relaxation time (msec) of component (γ)
t: Observation time (msec)
Wa: shape factor (1 <Wa <2)
b: Shape factor (0.1 <b <0.2)
[2]
The polyethylene fiber according to [1], wherein the intrinsic viscosity (η) is 11 or more and 30 or less.
[3]
In a DSC curve of a second heating process (measurement condition (iii)) obtained by the following measurement conditions (i) to (iii) using a differential scanning calorimeter (DSC), an endothermic peak is in a range of 152 ° C or more. The polyethylene fiber according to [1] or [2], wherein is not detected.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(Ii) After holding at 180 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(Iii) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
[4]
In the DSC curve of the heating process obtained under the following measurement conditions (I) using a differential scanning calorimeter (DSC), the heat of fusion (A) detected in the range of 160 ° C to 170 ° C and the DSC were used. In the DSC curve of the second heating process (measurement condition (IV)) obtained under the following measurement conditions (II) to (IV), the difference between the heat of fusion (B) detected in the range of 160 ° C to 170 ° C. The polyethylene fiber according to any one of [1] to [3], wherein the ratio (B) / (A) is 1 or more and 3 or less.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(II) After holding at 50 ° C. for 1 minute, the temperature was raised to 140 ° C. at a rate of 10 ° C./min.
(III) After holding at 140 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(IV) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
[5]
The polyethylene according to [1], wherein the composition fraction of the component (γ) having the highest mobility is 2% or more and 5% or less, and the relaxation time of the component (γ) having the highest mobility is 200 μs or more and 500 μs or less. fiber.
[6]
The polyethylene fiber according to [1], wherein the intrinsic viscosity (η) is 15 or more and 30 or less.
[7]
In the DSC curve of the heating process obtained under the following measurement conditions (I) using a differential scanning calorimeter (DSC), the heat of fusion (A) detected in the range of 160 ° C to 170 ° C and the DSC were used. In the DSC curve of the second heating process (measurement condition (IV)) obtained under the following measurement conditions (II) to (IV), the difference between the heat of fusion (B) detected in the range of 160 ° C to 170 ° C. The polyethylene fiber according to [1], wherein the ratio (B) / (A) is 1.5 or more and 2.7 or less.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(II) After holding at 50 ° C. for 1 minute, the temperature was raised to 140 ° C. at a rate of 10 ° C./min.
(III) After holding at 140 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(IV) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
[8]
The polyethylene fiber according to [1], wherein the content of chlorine (Cl) is 50 ppm or less.
[9]
The polyethylene fiber according to [1], wherein the content of aluminum (Al) is 5 ppm or less.
[10]
The polyethylene fiber according to [1], wherein the content of chlorine (Cl) is 5 ppm or less.
[11]
By fitting the free induction decay (M (t)) of the polyethylene fiber at 90 ° C. measured by the solid echo method of pulsed nuclear magnetic resonance (NMR) using the following equation 1, the component having the lowest mobility ( α), the intermediate motility component (β) and the most motility component (γ), when the three components are approximated, the composition fraction of the most motility component (γ) is 1% or more and 10% The use of polyethylene fibers in the ocean, wherein the relaxation time of the component (γ) having the highest mobility is 100 μs or more and 1000 μs or less.
M (t) = αexp (− (１ ／) (t / Tα) 2 ) sinbt / bt + βexp (− (1 / Wa) (t / Tβ) Wa ) + γexp (−t / Tγ) Formula 1
α: composition ratio of component (α) (%)
Tα: relaxation time (msec) of component (α)
β: Composition fraction of component (β) (%)
Tβ: relaxation time (msec) of component (β)
γ: composition ratio (%) of component (γ)
Tγ: relaxation time (msec) of component (γ)
t: Observation time (msec)
Wa: shape factor (1 <Wa <2)
b: Shape factor (0.1 <b <0.2)
本発明によれば、例えば、海洋で使用した際に優れた耐クリープ性、高い強度保持率及び耐摩耗性を有するポリエチレン繊維を提供可能である。 According to the present invention, for example, a polyethylene fiber having excellent creep resistance, high strength retention, and wear resistance when used in the ocean can be provided.
以下、本発明を実施するための形態（以下、「本実施形態」という。）について、詳細に説明する。なお、本発明は以下の記載に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, a mode for carrying out the present invention (hereinafter, referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following description, and can be implemented with various modifications within the scope of the gist.
〔ポリエチレン繊維〕
本実施形態のポリエチレン繊維は、パルス核磁気共鳴（ＮＭＲ）のソリッドエコー法で測定された９０℃における自由誘導減衰を３成分近似した場合において、最も運動性の高い成分（γ）の組成分率が１％以上１０％以下であり、最も運動性の高い成分（γ）の緩和時間が１００μｓ以上１０００μｓ以下である。
(Polyethylene fiber)
The polyethylene fiber of the present embodiment has a composition fraction of the component (γ) having the highest mobility when the free induction decay at 90 ° C. measured by the solid echo method of pulsed nuclear magnetic resonance (NMR) is approximated by three components. Is 1% or more and 10% or less, and the relaxation time of the component (γ) having the highest mobility is 100 μs or more and 1000 μs or less.
以下、本実施形態のポリエチレン繊維の要件について説明する。 Hereinafter, requirements of the polyethylene fiber of the present embodiment will be described.
〔パルスＮＭＲのソリッドエコー法で測定された９０℃における自由誘導減衰の３成分近似〕
本実施形態のポリエチレン繊維は、パルスＮＭＲのソリッドエコー法で測定された９０℃における、該ポリエチレン繊維の自由誘導減衰（Ｍ（ｔ））を、下記式１を用いてフィッティングさせることにより、最も運動性の低い成分（α）、中間の運動性の成分（β）及び最も運動性の高い成分（γ）の３成分に近似する。
[Three-component approximation of free induction decay at 90 ° C. measured by solid echo method of pulse NMR]
The polyethylene fiber of the present embodiment has the highest motion by fitting the free induction decay (M (t)) of the polyethylene fiber at 90 ° C. measured by the solid echo method of pulse NMR using the following equation 1. It approximates to three components: a component with low mobility (α), a component with intermediate mobility (β), and a component with the highest mobility (γ).
Ｍ（ｔ）＝αｅｘｐ（−（１／２）（ｔ／Ｔα）2）ｓｉｎｂｔ／ｂｔ＋βｅｘｐ（−（１／Ｗａ）（ｔ／Ｔβ）Wa）＋γｅｘｐ（−ｔ／Ｔγ） 式１ M (t) = αexp (− (１ ／) (t / Tα) 2 ) sinbt / bt + βexp (− (1 / Wa) (t / Tβ) Wa ) + γexp (−t / Tγ) Formula 1
α：成分（α）の組成分率（％）
Ｔα：成分（α）の緩和時間（ｍｓｅｃ）
β：成分（β）の組成分率（％）
Ｔβ：成分（β）の緩和時間（ｍｓｅｃ）
γ：成分（γ）の組成分率（％）
Ｔγ：成分（γ）の緩和時間（ｍｓｅｃ）
ｔ：観測時間（ｍｓｅｃ）
Ｗａ：形状係数（１＜Ｗａ＜２）
ｂ：形状係数（０．１＜ｂ＜０．２）
α: composition ratio of component (α) (%)
Tα: relaxation time (msec) of component (α)
β: Composition fraction of component (β) (%)
Tβ: relaxation time of component (β) (msec)
γ: composition ratio (%) of component (γ)
Tγ: relaxation time (msec) of component (γ)
t: Observation time (msec)
Wa: shape factor (1 <Wa <2)
b: Shape factor (0.1 <b <0.2)
より具体的には、実施例に記載の方法により測定することができる。 More specifically, it can be measured by the method described in Examples.
〔最も運動性の高い成分（γ）の組成分率及び緩和時間〕
本実施形態のポリエチレン繊維は、パルスＮＭＲのソリッドエコー法で測定された９０℃における、該ポリエチレン繊維の自由誘導減衰を３成分に近似した場合において、最も運動性の高い成分（γ）（以下、単に、成分（γ）や最も運動性の高い成分（γ）ともいう）の組成分率が１％以上１０％以下であり、好ましくは２％以上７％以下、より好ましくは２％以上５％以下である。また、最も運動性の高い成分（γ）の緩和時間は１００μｓ以上１０００μｓ以下であり、好ましくは２００μｓ以上７００μｓ以下。より好ましくは２００μｓ以上５００μｓ以下である。
本実施形態のポリエチレン繊維は、成分（γ）の組成分率が１％以上であることにより、高温時における高運動性成分の量が十分なものとなり、塩乾サイクル試験における、高温高湿度状態から高温乾燥状態への環境変化による分子運動の変化で生じる分子間のクラック発生が抑制されるため、例えば、海洋使用時の強度保持率に優れる。一方、本実施形態のポリエチレン繊維は、成分（γ）の組成分率が１０％以下であることにより、繊維の表面強度が十分なものとなり、塩乾サイクル試験における鉄パイプの錆や塩分の付着による摩耗に強くなり、束として使用する際も束内部で結晶化した塩分により糸同士が強く擦れることによる摩耗に強くなるため、例えば、海洋使用時の耐摩耗性に優れる。
また、本実施形態のポリエチレン繊維は、成分（γ）の緩和時間が１００μｓ以上であることにより、高温時における高運動性成分の分子運動性が十分なものとなり、塩乾サイクル試験における、高温高湿度状態から高温乾燥状態への環境変化による分子運動の変化で生じる歪を緩和させることができるため、例えば、海洋使用時の強度保持率に優れる。一方、本実施形態のポリエチレン繊維は、成分（γ）の緩和時間が１０００μｓ以下であることにより分子の運動性が十分に抑制され、高温で応力がかかった際にも分子の動きが抑制されるため、例えば、海洋使用時の耐クリープ性が良好になる。
最も運動性の高い成分（γ）の組成分率及び緩和時間を制御する方法としては、特に限定されないが、ポリエチレン繊維を分子運動性の異なる３成分に分けた際に、それぞれの成分の量を適切に制御することが好ましい。そのためには、ポリエチレンの分子鎖を高度に延伸させ、伸び切り鎖結晶にさせつつも、適度に絡み合いを発生させることが好ましい。このようなポリエチレン繊維は、結晶構造が特定の状態にあると言え、そのためには用いる原料ポリエチレン及びポリエチレンの繊維化加工工程を工夫することにより得ることができる。
具体的には、特に限定されないが、例えば、原料となるポリエチレンの絡み合いを適切に制御する観点から、助触媒に有機マグネシウムを用いること、触媒と該助触媒とを接触させた後に重合器へフィードすること、また繊維加工におけるポリエチレンの絡み合いを制御する観点から、脱溶媒後、５０℃の雰囲気下で２倍延伸した後に高温で延伸すること、１４０℃で延伸後、２５℃まで１０℃／分の速度で冷却すること等が挙げられる。延伸時の分子鎖の絡み合い部分と、伸びきり鎖部分とを均一に分布させ、かつ絡み合い部分の拘束を制御することにより、成分（γ）の組成分率及び緩和時間を制御することができる。
なお、本実施形態において、成分（γ）の組成分率及び緩和時間は、実施例に記載の方法により測定することができる。
[Composition fraction and relaxation time of component (γ) having the highest mobility]
The polyethylene fiber of the present embodiment has the highest mobility component (γ) (hereinafter referred to as “γ”) when the free induction attenuation of the polyethylene fiber at 90 ° C. measured by the solid echo method of pulse NMR is approximated to three components. The component fraction of the component (γ) or the component having the highest mobility (γ) is 1% or more and 10% or less, preferably 2% or more and 7% or less, more preferably 2% or more and 5%. It is as follows. The relaxation time of the component (γ) having the highest mobility is 100 μs or more and 1000 μs or less, preferably 200 μs or more and 700 μs or less. More preferably, it is 200 μs or more and 500 μs or less.
In the polyethylene fiber of the present embodiment, when the composition fraction of the component (γ) is 1% or more, the amount of the high mobility component at a high temperature is sufficient, and the high temperature and high humidity state in the salt drying cycle test is obtained. Since the generation of cracks between molecules caused by a change in molecular motion due to an environmental change from a dry state to a high-temperature dry state is suppressed, for example, the strength retention rate at the time of marine use is excellent. On the other hand, the polyethylene fiber of the present embodiment has a sufficient surface strength of the fiber when the composition fraction of the component (γ) is 10% or less, and rust and salt adhesion of the iron pipe in the salt drying cycle test. When the fibers are used as a bundle, the fibers are strongly rubbed against each other due to the salt crystallized inside the bundle, so that the yarns are excellent in abrasion resistance when used, for example, at sea.
In addition, the polyethylene fiber of the present embodiment has a sufficiently high molecular mobility of the high mobility component at a high temperature because the relaxation time of the component (γ) is 100 μs or more. Since strain caused by a change in molecular motion due to an environmental change from a humidity state to a high-temperature dry state can be relaxed, for example, the strength retention rate at the time of marine use is excellent. On the other hand, in the polyethylene fiber of the present embodiment, since the relaxation time of the component (γ) is 1000 μs or less, the mobility of the molecule is sufficiently suppressed, and even when a stress is applied at a high temperature, the movement of the molecule is suppressed. Therefore, for example, the creep resistance at the time of marine use is improved.
The method of controlling the composition fraction and the relaxation time of the component (γ) having the highest mobility is not particularly limited, but when the polyethylene fiber is divided into three components having different molecular mobility, the amount of each component is reduced. Appropriate control is preferred. For this purpose, it is preferable that the molecular chains of polyethylene are highly stretched to form extended chain crystals, and that entanglements are generated appropriately. It can be said that such a polyethylene fiber has a specific crystal structure, and for that purpose, it can be obtained by devising a raw material polyethylene to be used and a step of fibrillating polyethylene.
Specifically, although not particularly limited, for example, from the viewpoint of appropriately controlling the entanglement of polyethylene as a raw material, using organomagnesium as a cocatalyst, feeding the catalyst to the polymerization reactor after contacting the cocatalyst with the cocatalyst, From the viewpoint of controlling the entanglement of polyethylene in the fiber processing, from the viewpoint of controlling the entanglement of the polyethylene in the fiber processing, after the solvent is removed, the film is stretched twice in an atmosphere of 50 ° C. and then stretched at a high temperature. Cooling at a speed of, for example. By uniformly distributing the entangled portion of the molecular chain and the extended chain portion during stretching and controlling the constraint of the entangled portion, the composition fraction and the relaxation time of the component (γ) can be controlled.
In the present embodiment, the composition fraction and the relaxation time of the component (γ) can be measured by the methods described in Examples.
〔極限粘度〕
本実施形態のポリエチレン繊維の極限粘度（η）は、１１以上３０以下であることが好ましく、より好ましくは１３以上３０以下であり、更に好ましくは１５以上３０以下である。本実施形態のポリエチレン繊維は、極限粘度（η）が１１以上であると、高延伸させるのに十分な分子量が確保でき、強度がより上げられる。一方で、本実施形態のポリエチレン繊維は、極限粘度（η）が３０以下であると、工業的な条件で生産がより可能となる。
(Intrinsic viscosity)
The intrinsic viscosity (η) of the polyethylene fiber of the present embodiment is preferably 11 or more and 30 or less, more preferably 13 or more and 30 or less, and further preferably 15 or more and 30 or less. When the intrinsic viscosity (η) of the polyethylene fiber of the present embodiment is 11 or more, a sufficient molecular weight for high stretching can be secured, and the strength is further increased. On the other hand, when the intrinsic viscosity (η) is 30 or less, the polyethylene fiber of the present embodiment can be produced under industrial conditions.
本実施形態のポリエチレン繊維の極限粘度（η）は、オレフィン系重合用触媒を用いて、重合条件等を適宜調整することで制御できる。具体的には、重合系に水素を存在させたり、重合温度を変化させたりすること等によって極限粘度（η）を制御できる。 The intrinsic viscosity (η) of the polyethylene fiber of the present embodiment can be controlled by appropriately adjusting polymerization conditions and the like using an olefin-based polymerization catalyst. Specifically, the intrinsic viscosity (η) can be controlled by allowing hydrogen to be present in the polymerization system or by changing the polymerization temperature.
本実施形態のポリエチレン繊維の極限粘度（η）は、具体的には、例えば、デカリン中にポリエチレン繊維を異なる濃度で溶解した溶液を用意し、当該溶液の１３５℃における溶液粘度を測定し、測定された溶液粘度から計算される還元粘度を所望の式に代入して求めることができる。具体的には、実施例に記載の方法により測定することができる。 Specifically, the intrinsic viscosity (η) of the polyethylene fiber of the present embodiment is determined, for example, by preparing solutions in which polyethylene fibers are dissolved at different concentrations in decalin, and measuring the solution viscosity of the solution at 135 ° C. The reduced viscosity calculated from the obtained solution viscosity can be obtained by substituting it into a desired equation. Specifically, it can be measured by the method described in Examples.
（ＤＳＣを用いた２回目の昇温過程における１５２℃以上の範囲の吸熱ピーク）
本実施形態のポリエチレン繊維は、示差走査熱量計（ＤＳＣ）を用いた下記（i）〜（iii）の測定条件によって得られる２回目の昇温過程（測定条件（iii））のＤＳＣ曲線において、１５２℃以上の範囲に吸熱ピークが検出されないことが好ましい。
（ＤＳＣ測定条件）
（i）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（ii）１８０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（iii）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
ＤＳＣを用いた２回目の昇温過程（測定条件（iii））のＤＳＣ曲線において、１５２℃以上の範囲に吸熱ピークが検出されないと、繊維中に伸びきり鎖と分子の絡み合いが均一に分布するため、繊維に優れた強度保持性を付与できる。なお、ＤＳＣを用いた２回目の昇温過程（測定条件（iii））のＤＳＣ曲線における１５２℃以上の範囲の吸熱ピークの有無は、後述する実施例に記載の方法により測定できる。
(Endothermic peak in the range of 152 ° C. or more in the second heating process using DSC)
The polyethylene fiber of the present embodiment has a DSC curve of a second heating process (measurement condition (iii)) obtained by the following measurement conditions (i) to (iii) using a differential scanning calorimeter (DSC): It is preferable that an endothermic peak is not detected in the range of 152 ° C. or higher.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(Ii) After holding at 180 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(Iii) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
If no endothermic peak is detected in the range of 152 ° C. or more in the DSC curve of the second heating process (measurement condition (iii)) using DSC, the entanglement of the extended chains and molecules is uniformly distributed in the fiber. Therefore, excellent strength retention can be imparted to the fiber. The presence or absence of an endothermic peak in the range of 152 ° C. or more in the DSC curve in the second heating process (measurement condition (iii)) using DSC can be measured by the method described in Examples described later.
ＤＳＣを用いた２回目の昇温過程（測定条件（iii））のＤＳＣ曲線における１５２℃以上の範囲の吸熱ピークが検出されないポリエチレン繊維は、溶媒によってポリエチレン粒子を高濃度のスラリーにした状態で押出機に入れた後に、溶媒をさらに追加して濃度調整し、押出したり、押出機のＬ／Ｄを極度に長くしたり、低濃度のスラリーを押出機に入れた後に、ベントにより溶媒を取り除いて濃度調整したりすることにより得ることが可能である。 The polyethylene fiber in which the endothermic peak in the range of 152 ° C. or more is not detected in the DSC curve in the second heating process (measurement condition (iii)) using DSC is extruded in a state where the polyethylene particles are made into a high-concentration slurry with a solvent. After putting into the extruder, the solvent was further added to adjust the concentration, and extruded, the L / D of the extruder was extremely lengthened, or the low concentration slurry was put into the extruder, and then the solvent was removed by venting. It can be obtained by adjusting the concentration.
（融解熱量の比（（Ｂ）／（Ａ）））
本実施形態のポリエチレン繊維は、示差走査熱量計（ＤＳＣ）を用いた下記（I）の測定条件によって得られる昇温過程のＤＳＣ曲線において、１６０℃〜１７０℃の範囲に検出される融解熱量（Ａ）と、ＤＳＣを用いた下記（II）〜（IV）の測定条件によって得られる２回目の昇温過程（測定条件（IV））のＤＳＣ曲線において、１６０℃〜１７０℃の範囲に検出される融解熱量（Ｂ）との比（Ｂ）／（Ａ）が１以上３以下であることが好ましい。
（ＤＳＣ測定条件）
（I）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（II）５０℃で１分間保持後、１０℃／分の昇温速度で１４０℃まで昇温。
（III）１４０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（IV）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
融解熱量（Ａ）及び（Ｂ）の比（（Ｂ）／（Ａ））は、１．０以上３．０以下であることが好ましく、より好ましくは１．３以上２．７以下、更に好ましくは１．５以上２．７以下である。本実施形態のポリエチレン繊維は、融解熱量の比（（Ｂ）／（Ａ））が、１．０以上であると、工業的な条件で生産がより可能となる。一方で本実施形態のポリエチレン繊維は、融解熱量の比（（Ｂ）／（Ａ））が、３．０以下であると、延伸時に応力がかからずに伸びきり鎖に移行できなかった局所的な延伸ムラを抑制でき、耐クリープ性により優れる。
融解熱量の比（（Ｂ）／（Ａ））を制御する方法としては、特に限定されないが、例えば、紡糸後に１２０℃の流動パラフィンに接触させて冷却させる方法、低吐出で紡糸する方法等が挙げられる。
なお、融解熱量の比（（Ｂ）／（Ａ））は、後述する実施例に記載の方法により測定できる。
(Ratio of heat of fusion ((B) / (A)))
The polyethylene fiber of the present embodiment has a heat of fusion detected in the range of 160 ° C. to 170 ° C. in a DSC curve in a temperature rising process obtained under the following measurement conditions (I) using a differential scanning calorimeter (DSC). A) and the DSC curve of the second heating process (measurement condition (IV)) obtained under the following measurement conditions (II) to (IV) using DSC, detected in the range of 160 ° C. to 170 ° C. The ratio (B) / (A) to the heat of fusion (B) is preferably 1 or more and 3 or less.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(II) After holding at 50 ° C. for 1 minute, the temperature was raised to 140 ° C. at a rate of 10 ° C./min.
(III) After holding at 140 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(IV) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
The ratio of the heats of fusion (A) and (B) ((B) / (A)) is preferably 1.0 or more and 3.0 or less, more preferably 1.3 or more and 2.7 or less. Is not less than 1.5 and not more than 2.7. When the ratio of the heat of fusion ((B) / (A)) is 1.0 or more, the polyethylene fiber of the present embodiment can be produced under industrial conditions. On the other hand, in the polyethylene fiber of the present embodiment, when the ratio of the heat of fusion ((B) / (A)) is 3.0 or less, no local stress was applied at the time of drawing and the localized fiber could not be transferred to the chain. And uniform stretching unevenness can be suppressed, and the creep resistance is excellent.
The method of controlling the ratio of the heats of fusion ((B) / (A)) is not particularly limited, and examples thereof include a method of contacting with a liquid paraffin at 120 ° C. to cool after spinning, and a method of spinning at low discharge. No.
The ratio of the heats of fusion ((B) / (A)) can be measured by the method described in Examples described later.
（ポリエチレン繊維に含まれる塩素含有量）
本実施形態のポリエチレン繊維における塩素（Ｃｌ）の含有量は、ポリエチレン繊維全体に対し、重量換算で、好ましくは５０ｐｐｍ以下であり、より好ましくは２５ｐｐｍ以下であり、さらに好ましくは５ｐｐｍ以下である。本実施形態のポリエチレン繊維は、塩素含有量が５０ｐｐｍ以下であると、糸強度が向上する傾向にある。塩素含有量の下限は、特に限定されないが、例えば、１．０ｐｐｍである。なお、塩素含有量は、後述する実施例に記載の方法により測定できる。
(Chlorine content in polyethylene fiber)
The content of chlorine (Cl) in the polyethylene fiber of the present embodiment is preferably not more than 50 ppm, more preferably not more than 25 ppm, and still more preferably not more than 5 ppm, in terms of weight, based on the entire polyethylene fiber. When the chlorine content of the polyethylene fiber of this embodiment is 50 ppm or less, the yarn strength tends to be improved. The lower limit of the chlorine content is not particularly limited, but is, for example, 1.0 ppm. In addition, the chlorine content can be measured by a method described in Examples described later.
ポリエチレン繊維における塩素含有量は、後述する触媒を用いるか、単位触媒あたりの生産性を高めることで低減できる。 The chlorine content in the polyethylene fiber can be reduced by using a catalyst described later or by increasing the productivity per unit catalyst.
（ポリエチレン繊維に含まれるアルミニウム含有量）
本実施形態のポリエチレン繊維におけるアルミニウム（Ａｌ）の含有量は、ポリエチレン繊維全体に対し、重量換算で、好ましくは５ｐｐｍ以下であり、より好ましくは３ｐｐｍ以下であり、さらに好ましくは２ｐｐｍ以下である。本実施形態のポリエチレン繊維は、アルミニウム含有量が５ｐｐｍ以下であると、糸強度が向上する傾向にある。アルミニウム含有量の下限は、特に限定されないが、例えば、０．５ｐｐｍである。なお、アルミニウム含有量は、後述する実施例に記載の方法により測定できる。
(Aluminum content in polyethylene fiber)
The content of aluminum (Al) in the polyethylene fiber of the present embodiment is preferably not more than 5 ppm, more preferably not more than 3 ppm, and still more preferably not more than 2 ppm, in terms of weight, based on the entire polyethylene fiber. When the aluminum content of the polyethylene fiber of this embodiment is 5 ppm or less, the yarn strength tends to be improved. The lower limit of the aluminum content is not particularly limited, but is, for example, 0.5 ppm. The aluminum content can be measured by a method described in Examples described later.
本実施形態のポリエチレン繊維におけるアルミニウム含有量は、後述する触媒を用いるか、単位触媒あたりの生産性を高めることで低減できる。 The aluminum content in the polyethylene fiber of the present embodiment can be reduced by using a catalyst described later or by increasing the productivity per unit catalyst.
（ポリエチレン）
本実施形態のポリエチレン繊維を構成するポリエチレンとしては、以下に限定されないが、例えば、エチレン単独重合体、又はエチレンと、他の１種以上のモノマーとの共重合体（例えば、二元又は三元共重合体）が挙げられる。共重合体の結合形式は、ランダムでもブロックであってもよい。他のモノマーとしては、以下に限定されないが、例えば、α−オレフィン、ビニル化合物が挙げられ、前記α−オレフィンとしては、以下に限定されないが、例えば、プロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン等の炭素数３〜２０のα−オレフィンが挙げられ、前記ビニル化合物としては、以下に限定されないが、例えば、ビニルシクロヘキサン、スチレン及びその誘導体等が挙げられる。また、必要に応じて、他のモノマーとして、１，５−ヘキサジエン、１，７−オクタジエン等の非共役ポリエンを使用できる。これらの他のモノマーは１種を単独で、又は２種以上を組み合わせて用いることができる。
(polyethylene)
The polyethylene constituting the polyethylene fiber of the present embodiment is not limited to the following. For example, ethylene homopolymer or a copolymer of ethylene and one or more other monomers (for example, binary or ternary) Copolymer). The bonding form of the copolymer may be random or block. Examples of the other monomer include, but are not limited to, α-olefins and vinyl compounds. Examples of the α-olefin include, but are not limited to, propylene, 1-butene, and 4-methyl-1. Α-olefins having 3 to 20 carbon atoms such as -pentene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, and 1-tetradecene; Examples of the vinyl compound include, but are not limited to, vinylcyclohexane, styrene, and derivatives thereof. If necessary, non-conjugated polyenes such as 1,5-hexadiene and 1,7-octadiene can be used as other monomers. These other monomers can be used alone or in combination of two or more.
（添加剤）
さらに、本実施形態のポリエチレン繊維は、中和剤、酸化防止剤、及び耐光安定剤等の添加剤を含有してもよい。
(Additive)
Further, the polyethylene fiber of the present embodiment may contain additives such as a neutralizer, an antioxidant, and a light stabilizer.
中和剤はポリエチレン中に含まれる塩素キャッチャー、又は成形加工助剤等として使用される。中和剤としては、以下に限定されないが、例えば、カルシウム、マグネシウム、バリウム等のアルカリ土類金属のステアリン酸塩が挙げられる。中和剤の含有量は、特に限定されないが、ポリエチレン全体に対し、質量換算で、好ましくは３０００ｐｐｍ以下であり、より好ましくは１０００ｐｐｍ以下、さらに好ましくは５００ｐｐｍ以下である。 The neutralizing agent is used as a chlorine catcher contained in polyethylene, a molding aid, or the like. Examples of the neutralizing agent include, but are not limited to, stearates of alkaline earth metals such as calcium, magnesium, and barium. The content of the neutralizing agent is not particularly limited, but is preferably 3,000 ppm or less, more preferably 1,000 ppm or less, and still more preferably 500 ppm or less in terms of mass with respect to the whole polyethylene.
酸化防止剤としては、以下に限定されないが、例えば、ジブチルヒドロキシトルエン、ペンタエリスチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］、オクタデシル−３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート等のフェノール系酸化防止剤が挙げられる。酸化防止剤の含有量は、特に限定されないが、ポリエチレン全体に対し、質量換算で、１質量％以下が好ましく、より好ましくは０．５質量％以下であり、さらに好ましくは０．１質量％以下である。 Examples of the antioxidant include, but are not limited to, dibutylhydroxytoluene, pentaerythyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( Phenolic antioxidants such as 3,5-di-t-butyl-4-hydroxyphenyl) propionate. The content of the antioxidant is not particularly limited, but is preferably not more than 1% by mass, more preferably not more than 0.5% by mass, and still more preferably not more than 0.1% by mass, based on the whole polyethylene. It is.
耐光安定剤としては、以下に限定されないが、例えば、２−（５−メチル−２−ヒドロキシフェニル）ベンゾトリアゾール、２−（３−ｔ−ブチル−５−メチル−２−ヒドロキシフェニル）−５−クロロベンゾトリアゾール等のベンゾトリアゾール系耐光安定剤；ビス（２，２，６，６−テトラメチル−４−ピペリジン）セバケート、ポリ［｛６−（１，１，３，３−テトラメチルブチル）アミノ−１，３，５−トリアジン−２，４−ジイル｝｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝ヘキサメチレン｛（２，２，６，６−テトラメチル−４−ピペリジル）イミノ｝］等のヒンダードアミン系耐光安定剤が挙げられる。耐光安定剤の含有量は、特に限定されないが、ポリエチレン粒子全体に対し、質量換算で、好ましくは５０００ｐｐｍ以下であり、より好ましくは４０００ｐｐｍ以下、さらに好ましくは３０００ｐｐｍ以下である。 Examples of the light stabilizer include, but are not limited to, 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5- Benzotriazole-based light stabilizers such as chlorobenzotriazole; bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, poly [@ 6- (1,1,3,3-tetramethylbutyl) amino -1,3,5-triazine-2,4-diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6-tetramethyl-4 -Piperidyl) imino}] and the like. The content of the light stabilizer is not particularly limited, but is preferably 5,000 ppm or less, more preferably 4,000 ppm or less, and still more preferably 3,000 ppm or less, in terms of mass, based on the whole polyethylene particles.
本実施形態では、上記のような各成分以外にもポリエチレン繊維の製造に有用な他の公知の成分を含むことができる。 In the present embodiment, other known components useful for the production of polyethylene fibers can be included in addition to the above components.
本実施形態のポリエチレン繊維は、１種のポリエチレンで構成されてもよく、異なる２種以上のポリエチレンで構成されてもよい。２種以上の場合には、例えば、粘度平均分子量が異なるポリエチレンを組み合わせてもよい。また、本実施形態のポリエチレン繊維を構成するポリエチレンとしては、超高分子量ポリエチレンが好ましく、ポリエチレン繊維は、ポリエチレンとして超高分子量ポリエチレン単独で構成してもよく、超高分子量ポリエチレンと、他の樹脂とを組み合わせてもよい。他の樹脂としては、特に限定されず、例えば、低密度ポリエチレン、線状低密度ポリエチレンなどの他のポリエチレン、ポリプロピレン、ポリスチレンなどが挙げられる。これらの他の樹脂は、一種を単独で、又は２種以上を組み合わせてもよい。 The polyethylene fiber of the present embodiment may be composed of one kind of polyethylene or two or more different kinds of polyethylene. In the case of two or more types, for example, polyethylenes having different viscosity average molecular weights may be combined. Further, as the polyethylene constituting the polyethylene fiber of the present embodiment, ultra-high molecular weight polyethylene is preferable, and the polyethylene fiber may be composed of ultra-high molecular weight polyethylene alone as polyethylene, ultra-high molecular weight polyethylene, and other resins. May be combined. The other resin is not particularly limited, and examples thereof include other polyethylene such as low-density polyethylene and linear low-density polyethylene, polypropylene, and polystyrene. These other resins may be used alone or in combination of two or more.
［ポリエチレンの製造方法］
本実施形態のポリエチレン繊維に用いるポリエチレンは特に限定されないが、一般的なチーグラー・ナッタ触媒を用いて製造することが好ましい。
[Polyethylene production method]
The polyethylene used for the polyethylene fiber of the present embodiment is not particularly limited, but is preferably produced using a general Ziegler-Natta catalyst.
ポリエチレンの製造方法における重合法は、懸濁重合法或いは気相重合法により、エチレン、又はエチレンを含む単量体を（共）重合させる方法が挙げられる。このなかでも、重合熱を効率的に除熱できる懸濁重合法が好ましい。懸濁重合法においては、媒体として不活性炭化水素媒体を用いることができ、さらにオレフィン自身を溶媒として用いることもできる。 Examples of the polymerization method in the method for producing polyethylene include a method in which ethylene or a monomer containing ethylene is (co) polymerized by a suspension polymerization method or a gas phase polymerization method. Among these, a suspension polymerization method capable of efficiently removing heat of polymerization is preferable. In the suspension polymerization method, an inert hydrocarbon medium can be used as a medium, and the olefin itself can be used as a solvent.
上記不活性炭化水素媒体としては、特に限定されないが、具体的には、例えば、プロパン、ブタン、イソブタン、ペンタン、イソペンタン、ヘキサン、ヘプタン、オクタン、デカン、ドデカン、灯油等の脂肪族炭化水素；シクロペンタン、シクロヘキサン、メチルシクロペンタン等の脂環式炭化水素；ベンゼン、トルエン、キシレン等の芳香族炭化水素；エチルクロライド、クロルベンゼン、ジクロロメタン等のハロゲン化炭化水素及びこれらの混合物等を挙げることができる。 The inert hydrocarbon medium is not particularly limited, but specifically, for example, aliphatic hydrocarbons such as propane, butane, isobutane, pentane, isopentane, hexane, heptane, octane, decane, dodecane, and kerosene; Alicyclic hydrocarbons such as pentane, cyclohexane and methylcyclopentane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as ethyl chloride, chlorobenzene and dichloromethane, and mixtures thereof; .
ポリエチレンの製造方法における重合温度は、通常、３０℃以上１００℃以下が好ましく、３５℃以上９０℃以下がより好ましく、４０℃以上８０℃以下がさらに好ましい。重合温度が３０℃以上であれば、工業的に効率的な製造が可能である。一方、重合温度が１００℃以下であれば、連続的に安定運転が可能である。 In general, the polymerization temperature in the method for producing polyethylene is preferably from 30 ° C to 100 ° C, more preferably from 35 ° C to 90 ° C, even more preferably from 40 ° C to 80 ° C. When the polymerization temperature is 30 ° C. or higher, industrially efficient production is possible. On the other hand, when the polymerization temperature is 100 ° C. or lower, stable operation can be continuously performed.
ポリエチレンの製造方法における重合圧力は、通常、好ましくは０．１ＭＰａ以上２ＭＰａ以下、より好ましくは０．１ＭＰａ以上１．５ＭＰａ以下、さらに好ましくは０．１ＭＰａ以上１．０ＭＰａ以下である。常圧以上であることにより残留触媒灰分が低いエチレン重合体が得られる傾向にあり、２ＭＰａ以下であることにより、塊状のスケールを発生させることがなく、ポリエチレンを安定的に生産できる傾向にある。 The polymerization pressure in the method for producing polyethylene is usually preferably 0.1 MPa or more and 2 MPa or less, more preferably 0.1 MPa or more and 1.5 MPa or less, and still more preferably 0.1 MPa or more and 1.0 MPa or less. When the pressure is equal to or higher than normal pressure, an ethylene polymer having a low residual catalyst ash content tends to be obtained, and when the pressure is 2 MPa or less, polyethylene tends to be stably produced without generating massive scale.
本実施形態のポリエチレン繊維は、前述のとおり最も運動性の高い成分（γ）の組成分率が１％以上１０％以下であり、最も運動性の高い成分（γ）の緩和時間が１００μｓ以上１０００μｓ以下である。すなわち、ポリエチレン繊維を分子運動性の異なる３成分に分けた際に、それぞれの成分の量を適切に制御することが好ましい。そのためには、ポリエチレンの分子鎖を高度に延伸させ、伸び切り鎖結晶にさせつつも、適度に絡み合いを発生させることが好ましい。
ポリエチレンの絡み合いを抑制する方法としては、特に限定されないが、例えば、助触媒には有機マグネシウムを用いること、該助触媒と触媒を接触させた後に重合器へフィードすること、該助触媒と触媒を同一ラインから間欠フィードすること等が挙げられる。助触媒として有機マグネシウムを用いることによりポリエチレン鎖の成長と結晶化を適度に制御することができる。さらに、触媒と助触媒とを接触させた後に重合器へフィードすることにより、ポリエチレン粒子間の絡み合いのムラを抑制することができる。
また、分子の絡み合いを発生させる方法としては、特に限定されないが、例えば、重合系内のスラリー濃度を制御すること、重合器に邪魔板を設置しないこと、撹拌翼以外のノズルは触媒フィードノズルとスラリー抜きノズルのみにすること等が挙げられる。重合系内のスラリー濃度は、好ましくは３０質量％以上５０質量％以下、より好ましくは４０質量％以上５０質量％以下とする。スラリー濃度を３０質量％以上とすることにより、重合時において触媒上の反応点付近の温度を適度に高く保持し、分子の絡み合いを促進することにより分子間の拘束を高めることができる傾向にある。一方、スラリー濃度を５０質量％以下とすることにより、塊状のスケールを発生させることがなく、エチレン重合体を安定的に生産できる傾向にある。
As described above, the polyethylene fiber of the present embodiment has a composition fraction of the component (γ) having the highest mobility of 1% or more and 10% or less, and a relaxation time of the component (γ) having the highest mobility of 100 μs or more and 1000 μs or less. It is as follows. That is, when the polyethylene fiber is divided into three components having different molecular motility, it is preferable to appropriately control the amount of each component. For this purpose, it is preferable that the molecular chains of polyethylene are highly stretched to form extended chain crystals, and that entanglements are generated appropriately.
The method for suppressing the entanglement of polyethylene is not particularly limited, for example, using organomagnesium as a co-catalyst, feeding the co-catalyst and the catalyst to a polymerization reactor after contacting the co-catalyst, and Intermittent feed from the same line is mentioned. By using organomagnesium as a co-catalyst, the growth and crystallization of polyethylene chains can be controlled appropriately. Furthermore, by feeding the catalyst and the co-catalyst to the polymerization reactor after the catalyst and the co-catalyst are brought into contact with each other, unevenness of entanglement between the polyethylene particles can be suppressed.
Further, the method of generating the entanglement of the molecule is not particularly limited, for example, to control the slurry concentration in the polymerization system, not to install a baffle plate in the polymerization vessel, nozzles other than the stirring blade and the catalyst feed nozzle For example, only a slurry removal nozzle may be used. The slurry concentration in the polymerization system is preferably 30% by mass or more and 50% by mass or less, more preferably 40% by mass or more and 50% by mass or less. When the slurry concentration is 30% by mass or more, the temperature near the reaction point on the catalyst is maintained at a moderately high temperature during the polymerization, and the entanglement of the molecules is promoted, whereby the constraint between the molecules tends to be increased. . On the other hand, when the slurry concentration is 50% by mass or less, there is a tendency that an ethylene polymer can be stably produced without generating a massive scale.
ポリエチレンの製造方法における溶媒分離は、特に限定されないが、例えば、デカンテーション法、遠心分離法、フィルター濾過法等によって行うことができ、エチレン重合体と溶媒との分離効率の観点から、遠心分離法が好ましい。溶媒分離後にエチレン重合体に含まれる溶媒の量は、特に限定されないが、エチレン重合体の質量に対して、好ましくは７０質量％以下であり、より好ましくは６０質量％以下であり、さらに好ましくは５０質量％以下である。 Solvent separation in the method for producing polyethylene is not particularly limited, for example, can be performed by a decantation method, a centrifugation method, a filter filtration method, etc., from the viewpoint of separation efficiency between the ethylene polymer and the solvent, centrifugation method Is preferred. The amount of the solvent contained in the ethylene polymer after the solvent separation is not particularly limited, but is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably the mass of the ethylene polymer. It is 50% by mass or less.
ポリエチレンを合成するために使用した触媒の失活は、特に限定されないが、ポリエチレンと溶媒とを分離した後に実施することが好ましい。溶媒と分離した後に触媒を失活させるための薬剤を導入することにより、溶媒中に含まれる低分子量成分や触媒成分等の析出を低減することができる。 Deactivation of the catalyst used for synthesizing the polyethylene is not particularly limited, but is preferably performed after separating the polyethylene and the solvent. By introducing an agent for deactivating the catalyst after separation from the solvent, precipitation of low molecular weight components, catalyst components, and the like contained in the solvent can be reduced.
触媒系を失活させる薬剤としては、特に限定されないが、例えば、酸素、水、アルコール類、グリコール類、フェノール類、一酸化炭素、二酸化炭素、エーテル類、カルボニル化合物、アルキン類等を挙げることができる。 The agent that deactivates the catalyst system is not particularly limited, and includes, for example, oxygen, water, alcohols, glycols, phenols, carbon monoxide, carbon dioxide, ethers, carbonyl compounds, alkynes, and the like. it can.
ポリエチレンの製造方法における乾燥温度は、通常、５０℃以上１５０℃以下が好ましく、５０℃以上１３０℃以下がより好ましく、５０℃以上１００℃以下がさらに好ましい。乾燥温度が５０℃以上であれば、効率的な乾燥が可能である。一方、乾燥温度が１５０℃以下であれば、エチレン重合体の分解や架橋を抑制した状態で乾燥することが可能である。 In general, the drying temperature in the method for producing polyethylene is preferably from 50 ° C to 150 ° C, more preferably from 50 ° C to 130 ° C, and still more preferably from 50 ° C to 100 ° C. When the drying temperature is 50 ° C. or higher, efficient drying is possible. On the other hand, if the drying temperature is 150 ° C. or lower, it is possible to dry the ethylene polymer in a state where decomposition and crosslinking of the ethylene polymer are suppressed.
（ポリエチレン繊維の製造方法）
以下、本実施形態のポリエチレン繊維の製造方法の一例について説明する。
(Method for producing polyethylene fiber)
Hereinafter, an example of the method for producing the polyethylene fiber of the present embodiment will be described.
（ポリエチレンと溶媒とのスラリー溶液調製）
ポリエチレン粒子と溶媒、必要に応じて酸化防止剤等の添加剤を配合してスラリー溶液を調製する。
(Preparation of slurry solution of polyethylene and solvent)
A slurry solution is prepared by blending polyethylene particles, a solvent, and if necessary, additives such as an antioxidant.
溶媒としては、紡糸に適切な溶媒であれば限定されないが、例えば、大気圧にて１００℃超の沸点を有する炭化水素等が挙げられる。溶媒としては、特に限定されないが、具体的には、例えば、ハロゲン化炭化水素、鉱油、流動性パラフィン、デカリン、テトラリン、ナフタレン、キシレン、トルエン、ドデカン、ウンデカン、デカン、ノナン、オクテン、シス−デカヒドロナフタレン、トランス−デカヒドロナフタレン、低分子量ポリエチレンワックス、及びこれらの混合物等が挙げられる。これらの中でも、鉱油、流動性パラフィン、及びこれらの混合物が好ましい。
ポリエチレン粒子と溶媒との配合比としては、ポリエチレン粒子が２０質量％以上４０質量％以下、溶媒が６０質量％以上８０質量％以下であることが好ましい。また、スラリー溶液は１１０℃以上１２５℃以下に加熱した状態で押出機に導入することが好ましい。
The solvent is not limited as long as it is a solvent suitable for spinning, and includes, for example, hydrocarbons having a boiling point of more than 100 ° C. at atmospheric pressure. The solvent is not particularly limited, but specifically, for example, halogenated hydrocarbons, mineral oil, liquid paraffin, decalin, tetralin, naphthalene, xylene, toluene, dodecane, undecane, decane, nonane, octene, cis-deca Examples include hydronaphthalene, trans-decahydronaphthalene, low molecular weight polyethylene wax, and mixtures thereof. Of these, mineral oil, liquid paraffin, and mixtures thereof are preferred.
The mixing ratio of the polyethylene particles to the solvent is preferably 20% by mass or more and 40% by mass or less, and the solvent is preferably 60% by mass or more and 80% by mass or less. Further, it is preferable to introduce the slurry solution into an extruder in a state where the slurry solution is heated to 110 ° C. or more and 125 ° C. or less.
スラリー溶液を押出機に導入した後、押出機出口におけるポリエチレン粒子と溶媒との配合比をポリエチレン粒子が５質量％以上１５質量％以下、溶媒が８５質量％以上９５質量％以下となるように液添設備により溶媒を押出機の途中から導入することが好ましい。また、液添により導入する溶媒は２００℃以上に加熱した状態で導入することが好ましい。 After introducing the slurry solution into the extruder, the mixture ratio of the polyethylene particles and the solvent at the outlet of the extruder is adjusted so that the polyethylene particles are 5% by mass or more and 15% by mass or less and the solvent is 85% by mass or more and 95% by mass or less. It is preferable that the solvent is introduced from the middle of the extruder by the addition equipment. Further, it is preferable that the solvent introduced by liquid addition be introduced while being heated to 200 ° C. or higher.
スラリー溶液が導入される押出機は、いかなる押出機であってもよく、例えば、同方向回転二軸押出機等の二軸押出機が挙げられる。
スラリー溶液を押出すことによる混合物の形成は、ポリエチレン粒子が溶融する温度よりも高い温度で行ってよい。押出機で形成されるポリエチレン粒子及び溶媒の混合物は、従って、溶融ポリエチレン粒子及び溶媒の液体混合物であってよい。溶融ポリエチレン粒子及び溶媒の液体混合物が押出機中で形成される温度は、１４０℃以上３２０℃以下が好ましく、より好ましくは２００℃以上３００℃以下、さらに好ましくは２２０℃以上２８０℃以下である。また、押出機内での溶融滞留時間としては５分以上３０分以下が好ましく、より好ましくは１０分以上２５分以下であり、さらに好ましくは１５分以上２０分以下である。
The extruder into which the slurry solution is introduced may be any extruder, for example, a twin-screw extruder such as a co-rotating twin-screw extruder.
The formation of the mixture by extruding the slurry solution may be performed at a temperature higher than the temperature at which the polyethylene particles melt. The mixture of polyethylene particles and solvent formed in the extruder may therefore be a liquid mixture of molten polyethylene particles and solvent. The temperature at which the liquid mixture of the molten polyethylene particles and the solvent is formed in the extruder is preferably from 140 ° C to 320 ° C, more preferably from 200 ° C to 300 ° C, even more preferably from 220 ° C to 280 ° C. The melt residence time in the extruder is preferably 5 minutes or more and 30 minutes or less, more preferably 10 minutes or more and 25 minutes or less, and even more preferably 15 minutes or more and 20 minutes or less.
こうして得られた液体混合物を紡糸口金に通して紡糸する。紡糸口金の温度は１４０℃以上３２０℃以下が好ましく、より好ましくは２００℃以上３００℃以下、さらに好ましくは２２０℃以上２８０℃以下である。また、紡糸口金の孔径は０．３ｍｍ以上１．５ｍｍ以下が好ましく、吐出速度は１ｍ／分以上３ｍ／分以下が好ましい。 The liquid mixture thus obtained is passed through a spinneret and spun. The temperature of the spinneret is preferably from 140 ° C. to 320 ° C., more preferably from 200 ° C. to 300 ° C., even more preferably from 220 ° C. to 280 ° C. Further, the hole diameter of the spinneret is preferably 0.3 mm or more and 1.5 mm or less, and the discharge speed is preferably 1 m / min or more and 3 m / min or less.
吐出した溶媒を含む糸は、徐冷しながら巻き取ることが好ましい。具体的には、例えば１〜５ｃｍのエアギャップを介して１２０℃以上１２５℃以下のスラリー溶液を作製したものと同じ溶媒中に投入し、徐冷しながら巻き取ることが可能である。巻取速度としては、３ｍ/分以上６０ｍ/分以下が好ましく、より好ましくは３ｍ/分以上５０ｍ/分以下であり、さらに好ましくは５ｍ/分以上４０ｍ/分以下である。
ついで、該糸から溶媒を除去する。溶媒を除去する方法は紡糸溶液の種類によって異なり、例えば、流動性パラフィンの場合は、ヘキサン等の溶媒に該糸を浸漬させ、抽出作業を行った後、３０℃以上５０℃以下の条件で１時間以上乾燥させる。
得られた繊維は、一般的には延伸加工が施される。延伸加工されたポリエチレン繊維の結晶構造は、延伸工程条件の影響を受けることになる。一般には糸温度１００℃程度で延伸加工するが、その前工程として糸温度が３０℃以上５０℃以下になるように恒温槽で加熱し、１．５倍〜３．０倍にプレ延伸することが好ましい。次に、糸温度が１００℃以上１４０℃以下になるように恒温槽で加熱し、５．０倍〜５０倍に一次延伸し延伸糸を巻き取る。ついで、該延伸糸を一次延伸糸が１４０℃以上１６０℃以下になるように恒温槽で加熱し、更に二次延伸し、ポリエチレン繊維を得ることができる。
It is preferable to wind the yarn containing the discharged solvent while gradually cooling it. Specifically, for example, it is possible to put the slurry solution having a temperature of 120 ° C. or more and 125 ° C. or less into the same solvent through an air gap of 1 to 5 cm, and to wind the slurry solution while gradually cooling it. The winding speed is preferably from 3 m / min to 60 m / min, more preferably from 3 m / min to 50 m / min, even more preferably from 5 m / min to 40 m / min.
Next, the solvent is removed from the yarn. The method of removing the solvent varies depending on the type of the spinning solution. For example, in the case of liquid paraffin, the yarn is immersed in a solvent such as hexane and the extraction operation is performed. Let dry for at least an hour.
The obtained fiber is generally subjected to a drawing process. The crystal structure of the drawn polyethylene fiber is affected by the drawing process conditions. In general, drawing is performed at a yarn temperature of about 100 ° C., but as a pre-process, the yarn is heated in a constant temperature bath so that the temperature is 30 ° C. or more and 50 ° C. or less, and pre-drawn 1.5 to 3.0 times. Is preferred. Next, the yarn is heated in a thermostat so that the yarn temperature becomes 100 ° C. or more and 140 ° C. or less, and the yarn is primarily stretched to 5.0 to 50 times, and the stretched yarn is wound. Next, the drawn yarn is heated in a constant temperature bath so that the temperature of the primary drawn yarn becomes 140 ° C. or more and 160 ° C. or less, and further subjected to secondary drawing, thereby obtaining a polyethylene fiber.
本実施形態のポリエチレン繊維は種々の用途に使用でき、ロープ、ネット、釣り糸、手袋、布地、防弾チョッキ、装甲車の防弾カバー、積層体、スポーツ用品、縫合糸等が挙げられる。中でも、本実施形態のポリエチレン繊維は、海洋での使用が好ましく、特に、船舶係留ロープ、ヨットロープ、釣り糸、漁網として好適に利用できる。 The polyethylene fiber of the present embodiment can be used for various uses, and examples thereof include a rope, a net, a fishing line, a glove, a fabric, a bulletproof vest, a bulletproof cover of an armored car, a laminate, a sporting goods, and a suture. Among them, the polyethylene fiber of the present embodiment is preferably used in the ocean, and can be particularly suitably used as a mooring rope for a ship, a yacht rope, a fishing line, and a fishing net.
以下、実施例及び比較例を用いて本発明をさらに詳しく説明するが、本発明は以下の実施例により何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.
〔実施例、比較例において用いた各種特性及び物性の測定方法〕
（１）パルス核磁気共鳴（ＮＭＲ）のソリッドエコー法
パルスＮＭＲのソリッドエコー法で測定された９０℃におけるポリエチレン繊維の自由誘導減衰（Ｍ（ｔ））を、下記条件で測定した。
測定装置：日本電子社製 ＪＮＭ−Ｍｕ２５
サンプル量：約４００ｍｇ
観測核：1Ｈ
測定：Ｔ2
測定法：ソリッドエコー法
パルス幅：２．２〜２．３μｓ
パルス間隔：７．０μｓ〜９．２μｓ
積算回数：２５６回
測定温度：３０℃、５０℃、７０℃、９０℃（測定温度はサンプル内部の温度であり、装置温度が設定温度に達してから５分後にサンプル内部温度が測定温度になるように装置温度を調整し、測定を開始した）
繰り返し時間：３ｓ
[Methods for measuring various properties and physical properties used in Examples and Comparative Examples]
(1) Solid Echo Method of Pulse Nuclear Magnetic Resonance (NMR) The free induction decay (M (t)) of polyethylene fiber at 90 ° C. measured by the solid echo method of pulse NMR was measured under the following conditions.
Measuring device: JNM-Mu25 manufactured by JEOL Ltd.
Sample amount: about 400mg
Observed nucleus: 1 H
Measurement: T 2
Measurement method: Solid echo method Pulse width: 2.2 to 2.3 μs
Pulse interval: 7.0 μs to 9.2 μs
Number of integration: 256 times Measurement temperature: 30 ° C., 50 ° C., 70 ° C., 90 ° C. (The measurement temperature is the temperature inside the sample, and the temperature inside the sample becomes the measurement temperature 5 minutes after the device temperature reaches the set temperature. Adjusted the device temperature and started the measurement)
Repetition time: 3s
解析方法：下記式１を用いて、解析ソフト（ＩＧＯＲ Ｐｒｏ６．３）によりフィッティングを行い、最も運動性の低い成分（α）、中間の運動性の成分（β）及び最も運動性の高い成分（γ）の３成分に近似した場合において、３成分の組成分率及び緩和時間を求めた。 Analysis method: Using the following equation 1, fitting is performed by analysis software (IGOR Pro 6.3), and the component with the lowest mobility (α), the component with the middle mobility (β), and the component with the highest mobility ( When approximated to the three components of γ), the composition fraction and relaxation time of the three components were determined.
Ｍ（ｔ）＝αｅｘｐ（−（１／２）（ｔ／Ｔα）2）ｓｉｎｂｔ／ｂｔ＋βｅｘｐ（−（１／Ｗａ）（ｔ／Ｔβ）Wa）＋γｅｘｐ（−ｔ／Ｔγ） 式１ M (t) = αexp (− (1/2) (t / Tα) 2 ) sinbt / bt + βexp (− (1 / Wa) (t / Tβ) Wa ) + γexp (−t / Tγ) Formula 1
α：成分（α）の組成分率（％）
Ｔα：成分（α）の緩和時間（ｍｓｅｃ）
β：成分（β）の組成分率（％）
Ｔβ：成分（β）の緩和時間（ｍｓｅｃ）
γ：成分（γ）の組成分率（％）
Ｔγ：成分（γ）の緩和時間（ｍｓｅｃ）
ｔ：観測時間（ｍｓｅｃ）
Ｗａ：形状係数（１＜Ｗａ＜２）
ｂ：形状係数（０．１＜ｂ＜０．２）
α: composition ratio of component (α) (%)
Tα: relaxation time (msec) of component (α)
β: Composition fraction of component (β) (%)
Tβ: relaxation time of component (β) (msec)
γ: composition ratio (%) of component (γ)
Tγ: relaxation time (msec) of component (γ)
t: Observation time (msec)
Wa: shape factor (1 <Wa <2)
b: Shape factor (0.1 <b <0.2)
（２）極限粘度（η）の測定
実施例及び比較例で製造したポリエチレン繊維の極限粘度を、ＩＳＯ１６２８−３：２０１０を参照し、以下に示す方法によって求めた。
まず、溶解管にポリエチレン繊維４．５ｍｇを秤量し、溶解管を窒素置換した後、２０ｍＬのデカヒドロナフタレン（２，６−ジ−ｔ−ブチル−４−メチルフェノールを１ｇ／Ｌ加えたもの）を加え、１５０℃で１．５時間、撹拌子を用いて攪拌しながらポリエチレン繊維を溶解させた。その溶液を１３５℃の恒温槽で、キャノンフェンスケタイプの粘度計を用いて、標線間の落下時間（ｔs）を測定した。同様に、ブランクとしてポリエチレン繊維を入れていないデカリンのみの落下時間（ｔb）を測定した。
以下の式２に従って求めたポリマーの還元粘度（ηｓｐ／Ｃ）を式３に代入し、極限粘度（η）を求めた。
(2) Measurement of intrinsic viscosity (η) The intrinsic viscosity of the polyethylene fibers produced in Examples and Comparative Examples was determined by the method shown below with reference to ISO1628-3: 2010.
First, 4.5 mg of polyethylene fiber was weighed into a dissolving tube, and the dissolving tube was purged with nitrogen. Then, 20 mL of decahydronaphthalene (1 g / L of 2,6-di-t-butyl-4-methylphenol was added). Was added thereto, and the polyethylene fibers were dissolved while stirring at 150 ° C. for 1.5 hours using a stirrer. The falling time (t s ) of the solution was measured in a thermostat at 135 ° C. using a Cannon-Fenske type viscometer. Similarly, the fall time (t b ) of only decalin containing no polyethylene fiber as a blank was measured.
The intrinsic viscosity (η) was determined by substituting the reduced viscosity (ηsp / C) of the polymer determined according to the following equation 2 into the equation 3.
（ηｓｐ／Ｃ）＝（ｔs／ｔb−１）／（（ｍ／１０００）／（２０＊１．１０７）＊１００） （単位：ｄＬ／ｇ） 式２
ｍ：サンプル質量（ｍｇ）
Ｃ：サンプル溶液濃度 （ｍ／１０００／（２０＊１．１０７）＊１００）（ｇ／１００ｍＬ）
(Ηsp / C) = (t s / t b -1) / ((m / 1000) / (20 * 1.107) * 100) ( Unit: dL / g) Equation 2
m: Sample mass (mg)
C: Sample solution concentration (m / 1000 / (20 * 1.107) * 100) (g / 100 mL)
（η）＝（ηｓｐ／Ｃ）／（１＋０．２７＊Ｃ＊（ηｓｐ／Ｃ）） 式３
Ｃ：サンプル溶液濃度（ｇ／１００ｍＬ）
(Η) = (ηsp / C) / (1 + 0.27 * C * (ηsp / C)) Equation 3
C: Sample solution concentration (g / 100 mL)
（３）示差走査熱量計（ＤＳＣ）の２回目昇温過程のＤＳＣ曲線における１５２℃以上の範囲の吸熱ピークの有無
実施例及び比較例で製造したポリエチレン繊維についてＤＳＣ（パーキンエルマー社製、商品名：ＤＳＣ８０００）を用いて測定を行なった。具体的には８〜１０ｍｇのポリエチレン繊維をアルミニウムパンに挿填し、ＤＳＣに設置した後、以下の（i）〜（iii）の測定条件で測定を行った。
（ＤＳＣ測定条件）
（i）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（ii）１８０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（iii）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
２回目の昇温過程（測定条件（iii））のＤＳＣ曲線において１５２℃以上の範囲に吸熱ピークが検出（観察）されるか否かを測定した。
(3) Existence of endothermic peak in the range of 152 ° C. or more in the DSC curve in the second heating process of the differential scanning calorimeter (DSC) For the polyethylene fibers produced in Examples and Comparative Examples, DSC (trade name, manufactured by PerkinElmer, Inc.) : DSC8000). Specifically, after inserting 8 to 10 mg of polyethylene fiber into an aluminum pan and setting it on a DSC, measurement was performed under the following measurement conditions (i) to (iii).
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(Ii) After holding at 180 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(Iii) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
It was measured whether or not an endothermic peak was detected (observed) in the range of 152 ° C. or higher in the DSC curve in the second heating process (measurement condition (iii)).
（４）示差走査熱量計（ＤＳＣ）の昇温過程のＤＳＣ曲線において１６０℃〜１７０℃の範囲に検出される融解熱量（Ａ）と、１４０℃保温後の昇温過程のＤＳＣ曲線において１６０℃〜１７０℃の範囲に検出される融解熱量（Ｂ）との比（Ｂ）／（Ａ）
実施例及び比較例で製造したポリエチレン繊維についてＤＳＣ（パーキンエルマー社製、商品名：ＤＳＣ８０００）を用いて測定を行なった。具体的には８〜１０ｍｇのポリエチレン繊維をアルミニウムパンに挿填し、ＤＳＣに設置した後、以下の（I）の測定条件での測定及び（II）〜（IV）の測定条件での測定を行った。
（ＤＳＣ測定条件）
（I）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（II）５０℃で１分間保持後、１０℃／分の昇温速度で１４０℃まで昇温。
（III）１４０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（IV）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
測定条件（I）の昇温過程のＤＳＣ曲線において１６０℃から１７０℃の範囲に検出される融解熱量（Ａ）と、測定条件（II）〜（IV）の２回目の昇温過程（測定条件（IV））のＤＳＣ曲線において１６０℃から１７０℃の範囲に検出される融解熱量（Ｂ）とを測定し、（Ｂ）／（Ａ）を求めた。
(4) The amount of heat of fusion (A) detected in the range of 160 ° C. to 170 ° C. in the DSC curve of the differential scanning calorimeter (DSC) during the heating process, and 160 ° C. in the DSC curve of the heating process after keeping the temperature at 140 ° C. Ratio (B) / (A) to heat of fusion (B) detected in the range of -170 ° C
The polyethylene fibers produced in Examples and Comparative Examples were measured using DSC (trade name: DSC8000, manufactured by PerkinElmer). Specifically, after inserting 8 to 10 mg of polyethylene fiber into an aluminum pan and installing it on a DSC, the measurement under the following measurement conditions (I) and the measurement under the measurement conditions (II) to (IV) are performed. went.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(II) After holding at 50 ° C. for 1 minute, the temperature was raised to 140 ° C. at a rate of 10 ° C./min.
(III) After holding at 140 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(IV) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
The heat of fusion (A) detected in the range of 160 ° C. to 170 ° C. in the DSC curve of the heating process under measurement condition (I) and the second heating process under measurement conditions (II) to (IV) (measurement condition) The heat of fusion (B) detected in the range of 160 ° C. to 170 ° C. in the DSC curve of (IV)) was measured, and (B) / (A) was determined.
（５）強度
ポリエチレン繊維の強度は、下記装置及び測定条件で最大荷重値（単位：ｃＮ）を測定し、繊度で割ることで算出した。なお、繊度は糸１×１０4ｍ当たりの質量であり、単位はｄｔｅｘで表す。
装置：エーアンドデイ社製 テンシロン
チャック間距離：５００ｍｍ
引張速度：２５０ｍｍ／分
(5) Strength The strength of the polyethylene fiber was calculated by measuring the maximum load value (unit: cN) using the following apparatus and measuring conditions, and dividing the measured value by the fineness. The fineness is the mass per 1 × 10 4 m of yarn, and the unit is represented by dtex.
Apparatus: A & D Tensilon Distance between chucks: 500mm
Pulling speed: 250mm / min
（６）塩乾サイクル試験下での耐クリープ性
塩乾サイクル試験下におけるポリエチレン繊維の耐クリープ性は、以下のとおり算出した。下記装置及び試験条件でポリエチレン繊維を破断応力の３０％になるように荷重をかけ、ポリエチレン繊維（糸）が伸びて破断するまでの時間を耐クリープ性として算出した。なお、破断応力は（５）の引張試験における最大荷重値をポリエチレン繊維の断面積で割って算出した。評価基準は、以下のとおりである。
装置：スガ試験機製 塩乾湿複合サイクル試験機 ＩＳＯ−３−ＣＹ．Ｒ
塩乾サイクル試験条件：７０℃５％塩水１２時間噴霧後、７０℃相対湿度５０％１２時間。
（評価基準）
◎：３サイクル破断しなかった
○：２サイクル破断しなかったが、３サイクル完了前に破断した
×：２サイクル完了前に破断した
(6) Creep resistance under salt drying cycle test The creep resistance of polyethylene fibers under the salt drying cycle test was calculated as follows. A load was applied to the polyethylene fiber so as to be 30% of the breaking stress under the following apparatus and test conditions, and the time required for the polyethylene fiber (yarn) to elongate and break was calculated as creep resistance. The breaking stress was calculated by dividing the maximum load value in the tensile test of (5) by the cross-sectional area of the polyethylene fiber. The evaluation criteria are as follows.
Apparatus: Suga Test Machine's salt-dry / wet combined cycle tester ISO-3-CY. R
Salt drying cycle test conditions: 70 ° C., 5% salt water for 12 hours, then 70 ° C., 50% relative humidity, 50% for 12 hours.
(Evaluation criteria)
：: did not break in 3 cycles ○: did not break in 2 cycles, but broke before completion of 3 cycles ×: broke before completion of 2 cycles
（７）塩乾サイクル試験下での強度保持率
塩乾サイクル試験下におけるポリエチレン繊維の強度保持率は、以下のとおり算出した。下記装置及び試験条件で塩乾サイクル試験した後のポリエチレン繊維について、前記（５）に記載の方法により引張強度を測定し、以下の式により強度保持率を求めた。評価基準は以下のとおりである。
装置：スガ試験機製 塩乾湿複合サイクル試験機 ＩＳＯ−３−ＣＹ．Ｒ
塩乾サイクル試験条件：７０℃５％塩水１２時間噴霧後、７０℃相対湿度５０％１２時間のサイクルを３回実施。
強度保持率（％）＝（塩乾サイクル試験後の強度／塩乾サイクル試験前の強度）×１００
（評価基準）
◎：強度保持率が９０％以上であった
○：強度保持率が８０％以上９０％未満であった
×：強度保持率が８０％未満であった
(7) Strength retention rate under salt drying cycle test The strength retention rate of the polyethylene fiber under the salt drying cycle test was calculated as follows. The tensile strength of the polyethylene fiber after the salt drying cycle test was performed using the following apparatus and test conditions was measured by the method described in the above (5), and the strength retention was determined by the following equation. The evaluation criteria are as follows.
Apparatus: Suga Test Machine's salt-dry / wet combined cycle tester ISO-3-CY. R
Salt drying cycle test conditions: 70 ° C., 5% salt water was sprayed for 12 hours, and then a cycle of 70 ° C., relative humidity, 50%, 12 hours was performed three times.
Strength retention (%) = (strength after salt drying cycle test / strength before salt drying cycle test) × 100
(Evaluation criteria)
：: The strength retention was 90% or more. ：: The strength retention was 80% or more and less than 90%. X: The strength retention was less than 80%.
（８）塩乾サイクル試験下（腐食環境下）での破断耐久性（耐摩耗性）
塩乾サイクル試験下（腐食環境下）におけるポリエチレン繊維の破断耐久性は、以下のとおり算出した。下記装置及び試験条件で、１０ｍｍ径の鉄パイプにポリエチレン繊維を垂らし、破断応力の１０％の力がポリエチレン繊維にかかるよう両端に荷重をかけ、ポリエチレン繊維が破断せずに残った本数を破断耐久性（耐摩耗性）として評価した。評価基準は、以下のとおりである。
試験繊維の数：１０本
装置：スガ試験機製 塩乾湿複合サイクル試験機 ＩＳＯ−３−ＣＹ．Ｒ
塩乾サイクル試験条件：７０℃５％塩水１２時間噴霧後、７０℃相対湿度５０％１２時間を３回実施。
（評価基準）
◎：９本以上破断しなかった
○：５本以上９本未満破断しなかった
×：６本以上破断した
(8) Breaking durability (abrasion resistance) under salt drying cycle test (under corrosive environment)
The breaking durability of the polyethylene fiber under the salt drying cycle test (under a corrosive environment) was calculated as follows. With the following equipment and test conditions, a polyethylene fiber is dropped on a 10 mm diameter iron pipe, and a load is applied to both ends so that a force of 10% of the breaking stress is applied to the polyethylene fiber. (Wear resistance) was evaluated. The evaluation criteria are as follows.
Number of test fibers: 10 devices: Suga Test Machine's salt-dry / wet combined cycle tester ISO-3-CY. R
Salt drying cycle test conditions: 70 ° C., 5% salt water is sprayed for 12 hours, and then 70 ° C., 50% relative humidity, 50% is performed for 12 hours three times.
(Evaluation criteria)
：: 9 or more pieces did not break. ○: 5 to less than 9 pieces did not break. ×: 6 or more pieces broken.
（９）ポリエチレン繊維における塩素含有量
ポリエチレン繊維を自動試料燃焼装置（三菱化学アナリテック社製 ＡＱＦ−１００）で燃焼後、吸収液（Ｎａ2ＣＯ3とＮａＨＣＯ3との混合溶液）に吸収させ、その吸収液をイオンクロマトグラフ装置（ダイオネクス社製、ＩＣＳ１５００、カラム（分離カラム：ＡＳ１２Ａ、ガードカラム：ＡＧ１２Ａ）サプレッサー ＡＳＲＳ３００）に注入させ全塩素量を測定した。
(9) Chlorine content in polyethylene fiber After burning the polyethylene fiber with an automatic sample combustion device (AQF-100 manufactured by Mitsubishi Chemical Analytech Co., Ltd.), the polyethylene fiber was absorbed into an absorbing solution (a mixed solution of Na 2 CO 3 and NaHCO 3 ). The absorption solution was injected into an ion chromatograph (ICS 1500, manufactured by Dionex, column (separation column: AS12A, guard column: AG12A) suppressor ASRS300), and the total chlorine amount was measured.
（１０）ポリエチレン繊維におけるアルミニウム含有量
ポリエチレン繊維０．２ｇをテフロン（登録商標）製分解容器に秤取り、高純度硝酸を加えてマイルストーンゼネラル社製マイクロウェーブ分解装置ＥＴＨＯＳ−ＴＣにて加圧分解後、日本ミリポア社製超純水製造装置で精製した純水で全量を５０ｍＬとしたものを検液として使用した。上記検液に対し、サーモフィッシャーサイエンティフィック社製誘導結合プラズマ質量分析装置（ＩＣＰ−ＭＳ）Ｘシリーズ２を使用して、内標準法でアルミニウムの定量を行った。
(10) Aluminum content in polyethylene fiber 0.2 g of polyethylene fiber was weighed into a Teflon (registered trademark) decomposition vessel, and high-purity nitric acid was added thereto, followed by pressure decomposition with a microwave decomposer ETHOS-TC manufactured by Milestone General. Thereafter, pure water purified by an ultrapure water production apparatus manufactured by Nippon Millipore Co., Ltd. to a total volume of 50 mL was used as a test solution. Using the inductively coupled plasma mass spectrometer (ICP-MS) X series 2 manufactured by Thermo Fisher Scientific, the amount of aluminum was quantified for the test solution by an internal standard method.
［参考例１］触媒合成例
〔固体触媒成分［Ａ］の調製〕
充分に窒素置換された８Ｌステンレス製オートクレーブにヘキサン１，６００ｍＬを添加した。０℃で攪拌しながら１ｍｏｌ／Ｌの四塩化チタンヘキサン溶液８００ｍＬと１ｍｏｌ／Ｌの組成式ＡｌＭｇ5（Ｃ4Ｈ9）11（ＯＳｉ（Ｃ2Ｈ5）Ｈ）2で表される有機マグネシウム化合物のヘキサン溶液８００ｍＬとを３時間かけて同時に添加した。添加後、ゆっくりと昇温し、５℃で１時間反応を継続させた。反応終了後、上澄み液を１，６００ｍＬ除去し、ヘキサン１，６００ｍＬで５回洗浄することにより、固体触媒成分［Ａ］を調製した。
[Reference Example 1] Catalyst synthesis example [Preparation of solid catalyst component [A]]
1,600 mL of hexane was added to an 8 L stainless steel autoclave sufficiently purged with nitrogen. With stirring at 0 ° C., 800 mL of a 1 mol / L hexane solution of titanium tetrachloride and 1 mol / L of an organomagnesium compound represented by a composition formula of AlMg 5 (C 4 H 9 ) 11 (OSi (C 2 H 5 ) H) 2 And hexane solution (800 mL) were added simultaneously over 3 hours. After the addition, the temperature was slowly raised, and the reaction was continued at 5 ° C. for 1 hour. After completion of the reaction, 1,600 mL of the supernatant was removed, and the solid catalyst component [A] was prepared by washing five times with 1,600 mL of hexane.
［参考例６］触媒合成例
〔固体触媒成分［Ｆ］の調製〕
（１）原料のシリカ成分［ｆ−１］の合成
平均粒子径が７μｍ、表面積が７００ｍ2／ｇ、粒子内細孔容積が１．９ｍＬ／ｇの球状シリカを、窒素雰囲気下、５００℃で５時間焼成し、脱水した。
窒素雰囲気下、容量１．８Ｌのオートクレーブ内で、この脱水シリカ４０ｇをヘキサン８００ｍＬ中に分散させ、スラリーを得た。
得られたスラリーを攪拌下２０℃に保ちながらトリエチルアルミニウムのヘキサン溶液（濃度１ｍｏｌ／Ｌ）１００ｍＬを１時間で滴下し、その後、同温度で２時間攪拌した。その後、得られた反応混合物中をデカンテーションによって、上澄み液中の未反応のトリエチルアルミニウムを除去した。このようにしてトリエチルアルミニウムで処理されたシリカ成分［ｆ−１］のヘキサンスラリー８００ｍＬを得た。
（２）原料のチタニウム錯体成分［ｆ−２］の調製
［（Ｎ−ｔ−ブチルアミド）（テトラメチル−η５−シクロペンタジエニル）ジメチルシラン］チタニウム−１，３−ペンタジエン（以下、「チタニウム錯体」と記載する。）２００ｍｍｏｌをアイソパーＥ［エクソンケミカル社（米国）製の炭化水素混合物の商品名］１２５０ｍＬに溶解し、予めトリエチルアルミニウム及びブチルエチルマグネシウムより合成した、Ｍｇ6（Ｃ2Ｈ5）6（ｎ−Ｃ4Ｈ9）6Ａｌ（Ｃ2Ｈ5）3の１ｍｏｌ／Ｌヘキサン溶液を２５ｍＬ加え、さらにヘキサンを加えてチタニウム錯体濃度を０．１ｍｏｌ／Ｌに調整し、チタニウム錯体成分［ｆ−２］を得た。
（３）原料の反応混合物［ｆ−３］の調製
ビス（水素化タロウアルキル）メチルアンモニウム−トリス（ペンタフルオロフェニル）（４−ヒドロキシフェニル）ボレート（以下、「ボレート」と記載する。）５．７ｇをトルエン５０ｍＬに添加して溶解し、ボレートの１００ｍｍｏｌ／Ｌトルエン溶液を得た。このボレートのトルエン溶液にエトキシジエチルアルミニウムの１ｍｏｌ／Ｌヘキサン溶液５ｍＬを室温で加え、さらにヘキサンを加えて溶液中のボレート濃度が７０ｍｍｏｌ／Ｌとなるようにした。その後、室温で１時間攪拌し、ボレートを含む反応混合物［ｆ−３］を得た。
（４）固体触媒成分［Ｆ］の合成
上記（１）で得られたシリカ成分［ｆ−１］のスラリー８００ｍＬを、２０℃で攪拌しながら、上記（２）で得られたチタニウム錯体成分［ｆ−２］のうち３２ｍＬと上記（３）で得られたボレートを含むこの反応混合物［ｆ−３］４６ｍＬとを、同時に１時間で添加し、さらに同温度で１時間攪拌し、チタニウム錯体とボレートとを反応させた。反応終了後、上澄み液を除去し、ヘキサンで未反応の触媒原料を除去することにより、触媒活性種が該シリカ上に形成されている固体触媒成分［Ｆ］を得た。
[Reference Example 6] Catalyst synthesis example [Preparation of solid catalyst component [F]]
(1) Synthesis of Raw Material Silica Component [f-1] Spherical silica having an average particle diameter of 7 μm, a surface area of 700 m 2 / g, and a pore volume in particles of 1.9 mL / g was obtained at 500 ° C. under a nitrogen atmosphere. It was baked for 5 hours and dehydrated.
Under a nitrogen atmosphere, in a 1.8 L autoclave, 40 g of the dehydrated silica was dispersed in 800 mL of hexane to obtain a slurry.
While maintaining the obtained slurry at 20 ° C. with stirring, 100 mL of a hexane solution of triethylaluminum (concentration: 1 mol / L) was added dropwise over 1 hour, and then stirred at the same temperature for 2 hours. Thereafter, unreacted triethylaluminum in the supernatant was removed by decantation in the obtained reaction mixture. Thus, 800 mL of a hexane slurry of the silica component [f-1] treated with triethylaluminum was obtained.
(2) Preparation of Titanium Complex Component [f-2] as Raw Material [(Nt-butylamide) (tetramethyl-η5-cyclopentadienyl) dimethylsilane] titanium-1,3-pentadiene (hereinafter, “titanium complex 200 mmol was dissolved in 1250 mL of Isopar E (trade name of a hydrocarbon mixture manufactured by Exxon Chemical Co., USA), and Mg 6 (C 2 H 5 ) was synthesized in advance from triethylaluminum and butylethylmagnesium. 25 mL of a 1 mol / L hexane solution of 6 (nC 4 H 9 ) 6 Al (C 2 H 5 ) 3 was added, and hexane was further added to adjust the titanium complex concentration to 0.1 mol / L. f-2] was obtained.
(3) Preparation of reaction mixture [f-3] as raw material bis (hydrogenated tallowalkyl) methylammonium-tris (pentafluorophenyl) (4-hydroxyphenyl) borate (hereinafter referred to as “borate”) 5. 7 g was added to and dissolved in 50 mL of toluene to obtain a 100 mmol / L toluene solution of borate. 5 mL of a 1 mol / L hexane solution of ethoxydiethyl aluminum was added to this toluene solution of borate at room temperature, and hexane was further added so that the borate concentration in the solution was 70 mmol / L. Thereafter, the mixture was stirred at room temperature for 1 hour to obtain a reaction mixture [f-3] containing borate.
(4) Synthesis of Solid Catalyst Component [F] While stirring 800 mL of the silica component [f-1] slurry obtained in (1) above at 20 ° C., the titanium complex component [2] obtained in (2) above was stirred. f-2] and 46 mL of the reaction mixture [f-3] containing the borate obtained in the above (3) were simultaneously added over 1 hour, further stirred at the same temperature for 1 hour, and mixed with the titanium complex. Reacted with borate. After completion of the reaction, the supernatant was removed, and the unreacted catalyst raw material was removed with hexane to obtain a solid catalyst component [F] in which a catalytically active species was formed on the silica.
（水添触媒［Ｇ］の調製）
窒素置換した攪拌機付の容量２．０ＬのＳＵＳオートクレーブに、チタノセンジクロライド３７．３ｇをヘキサン１Ｌで導入した。５００ｒｐｍで撹拌しながら、トリイソブチルアルミニウムとジイソブチルアルミニウムハイドライドとの（トリイソブチルアルミニウム：ジイソブチルアルミニウムハイドライド＝９：１（モル比））の混合物０．７ｍｏｌ／Ｌ、４２９ｍＬを室温で、１時間かけてポンプで添加した。添加後７１ｍＬのヘキサンでラインを洗浄した。１時間撹拌を継続し、濃青色の均一な１００ｍＭ／Ｌ溶液（水添触媒［Ｇ］）を得た。
(Preparation of hydrogenation catalyst [G])
Into a 2.0 L SUS autoclave equipped with a stirrer and purged with nitrogen, 37.3 g of titanocene dichloride was introduced with 1 L of hexane. While stirring at 500 rpm, 0.7 mol / L of a mixture of triisobutylaluminum and diisobutylaluminum hydride (triisobutylaluminum: diisobutylaluminum hydride = 9: 1 (molar ratio)) and 429 mL were pumped at room temperature for 1 hour. Was added. After the addition, the line was washed with 71 mL of hexane. Stirring was continued for 1 hour to obtain a dark blue uniform 100 mM / L solution (hydrogenation catalyst [G]).
［参考例２］ポリエチレン重合例
〔ポリエチレン粒子［Ｂ］の重合〕
ヘキサン、エチレン、触媒、助触媒を、攪拌装置が付いたベッセル型３００Ｌ重合反応器に連続的に供給した。重合圧力は０．４ＭＰａであった。重合温度はジャケット冷却により８２℃に保った。固体触媒成分［Ａ］と、助触媒としてＡｌＭｇ6（Ｃ4Ｈ9）12とを使用した。ＡｌＭｇ6（Ｃ4Ｈ9）12は１０ｍｍｏｌ／時間の速度で供給し、固体触媒成分［Ａ］と接触させた後に重合器に添加した。固体触媒成分［Ａ］は、エチレン重合体の製造速度が１０ｋｇ／時間となり、重合反応器内のスラリー濃度が４０質量％になるように供給した。エチレンは圧力が保たれるように供給した。ヘキサンは液面レベルが一定に保たれるように供給した。重合スラリーは、連続的に圧力０．０５ＭＰａ、温度７０℃のフラッシュドラムに抜き、未反応のエチレンを分離した。分離されたエチレン重合体パウダーは、９０℃で窒素ブローしながら乾燥した。なお、この乾燥工程で、重合後のパウダーに対し、スチームを噴霧して、触媒及び助触媒の失活を実施した。得られたエチレン重合体パウダーを目開き４２５μｍの篩を用いて、篩を通過しなかったものを除去することでポリエチレン粒子［Ｂ］を得た。ポリエチレン粒子［Ｂ］の極限粘度は１５であった。
[Reference Example 2] Example of polyethylene polymerization [polymerization of polyethylene particles [B]]
Hexane, ethylene, a catalyst and a cocatalyst were continuously supplied to a 300-L polymerization vessel equipped with a stirrer. The polymerization pressure was 0.4 MPa. The polymerization temperature was kept at 82 ° C. by jacket cooling. Solid catalyst component [A] and AlMg 6 (C 4 H 9 ) 12 as co-catalyst were used. AlMg 6 (C 4 H 9 ) 12 was supplied at a rate of 10 mmol / hour, and was added to the polymerization reactor after being brought into contact with the solid catalyst component [A]. The solid catalyst component [A] was supplied such that the production rate of the ethylene polymer became 10 kg / hour and the slurry concentration in the polymerization reactor became 40% by mass. Ethylene was supplied so that the pressure was maintained. Hexane was supplied so that the liquid level was kept constant. The polymerization slurry was continuously discharged into a flash drum at a pressure of 0.05 MPa and a temperature of 70 ° C. to separate unreacted ethylene. The separated ethylene polymer powder was dried at 90 ° C. while blowing with nitrogen. In this drying step, the powder after polymerization was sprayed with steam to deactivate the catalyst and the cocatalyst. The obtained ethylene polymer powder was removed using a sieve having a mesh size of 425 μm, and the particles that did not pass through the sieve were removed to obtain polyethylene particles [B]. The intrinsic viscosity of the polyethylene particles [B] was 15.
［参考例３］ポリエチレン重合例
〔ポリエチレン粒子［Ｃ］の重合〕
重合温度を７８℃にした以外は参考例２と同様にして、ポリエチレン粒子［Ｃ］を得た。ポリエチレン粒子［Ｃ］の極限粘度は２０であった。
[Reference Example 3] Example of polyethylene polymerization [polymerization of polyethylene particles [C]]
Polyethylene particles [C] were obtained in the same manner as in Reference Example 2 except that the polymerization temperature was changed to 78 ° C. The intrinsic viscosity of the polyethylene particles [C] was 20.
［参考例４］ポリエチレン重合例
〔ポリエチレン粒子［Ｄ］の重合〕
重合温度を５５℃にした以外は参考例２と同様にして、ポリエチレン粒子［Ｄ］を得た。ポリエチレン粒子［Ｄ］の極限粘度は３０であった。
[Reference Example 4] Example of polyethylene polymerization [polymerization of polyethylene particles [D]]
Polyethylene particles [D] were obtained in the same manner as in Reference Example 2 except that the polymerization temperature was 55 ° C. The intrinsic viscosity of the polyethylene particles [D] was 30.
［参考例５］ポリエチレン重合例
〔ポリエチレン粒子［Ｅ］の重合〕
重合温度を５５℃にし、助触媒としてトリイソブチルアルミニウムを使用し、触媒と接触させずに別ラインより重合反応器にフィードした以外は参考例２と同様にして、ポリエチレン粒子［Ｅ］を得た。ポリエチレン粒子［Ｅ］の極限粘度は２７であった。
[Reference Example 5] Example of polyethylene polymerization [polymerization of polyethylene particles [E]]
Polyethylene particles [E] were obtained in the same manner as in Reference Example 2 except that the polymerization temperature was set to 55 ° C., triisobutylaluminum was used as a cocatalyst, and the mixture was fed to the polymerization reactor from another line without contacting with the catalyst. . The intrinsic viscosity of the polyethylene particles [E] was 27.
［参考例７］ポリエチレン重合例
〔ポリエチレン粒子［Ｈ］の重合〕
撹拌装置が付いたベッセル型３００Ｌ重合反応器を用いた。重合温度はジャケット冷却により７５℃に保った。溶媒としてノルマルヘキサンを６０Ｌ／時間で供給した。固体触媒成分［Ｆ］を重合速度が１０ｋｇ／時間となるように供給した。１ｍｏｌ／Ｌの組成式ＡｌＭｇ5（Ｃ4Ｈ9）11（ＯＳｉ（Ｃ2Ｈ5）Ｈ）2で表される有機マグネシウム化合物のヘキサン溶液をＭｇ及びＡｌの総量として６ｍｍｏｌ／時間で固体触媒成分［Ｆ］と接触させてから供給した。水素は固体触媒成分［Ｆ］のフィード配管に２ＮＬ／時間で供給した。このフィード配管に、別途水添触媒［Ｇ］を反応器内濃度が３．６μｍｏｌ／Ｌとなるように供給した。重合圧力０．８ＭＰａＧ、平均滞留時間３時間の条件で、気相部にエチレンを供給し連続重合を行ったこと以外は参考例２と同様にして、ポリエチレン粒子［Ｈ］を得た。ポリエチレン粒子［Ｈ］の極限粘度は３０であった。
［参考例８］ポリエチレン重合例
〔ポリエチレン粒子［Ｉ］の重合〕
重合温度を５０℃にし、助触媒としてトリイソブチルアルミニウムを使用し、触媒と接触させずに別ラインより重合反応器にフィードした以外は参考例２と同様にして、ポリエチレン粒子［Ｉ］を得た。ポリエチレン粒子［Ｉ］の極限粘度は２９であった。
[Reference Example 7] Example of polyethylene polymerization [polymerization of polyethylene particles [H]]
A 300 L polymerization reactor equipped with a stirrer was used. The polymerization temperature was kept at 75 ° C. by cooling the jacket. Normal hexane was supplied at a rate of 60 L / hour as a solvent. The solid catalyst component [F] was supplied such that the polymerization rate became 10 kg / hour. A solid catalyst component containing 1 mol / L of a hexane solution of an organomagnesium compound represented by the composition formula AlMg 5 (C 4 H 9 ) 11 (OSi (C 2 H 5 ) H) 2 at a total amount of 6 mmol / hour of Mg and Al [F] and then supplied. Hydrogen was supplied to the feed pipe of the solid catalyst component [F] at a rate of 2 NL / hour. A hydrogenation catalyst [G] was separately supplied to this feed pipe so that the concentration in the reactor became 3.6 μmol / L. Polyethylene particles [H] were obtained in the same manner as in Reference Example 2, except that ethylene was supplied to the gas phase and continuous polymerization was performed under the conditions of a polymerization pressure of 0.8 MPaG and an average residence time of 3 hours. The intrinsic viscosity of the polyethylene particles [H] was 30.
[Reference Example 8] Example of polyethylene polymerization [polymerization of polyethylene particles [I]]
Polyethylene particles [I] were obtained in the same manner as in Reference Example 2, except that the polymerization temperature was set to 50 ° C., triisobutylaluminum was used as a cocatalyst, and the mixture was fed to the polymerization reactor from another line without contacting the catalyst. . The intrinsic viscosity of the polyethylene particles [I] was 29.
〔実施例１〕
（ポリエチレン繊維の製造方法）
ポリエチレン粒子［Ｂ］と流動パラフィン（松村石油（株）製Ｐ−３５０（商標））とを用いてポリエチレン粒子が３０質量％になるようにスラリー溶液を調製した。さらにスラリー溶液１００質量部に対して酸化防止剤としてペンタエリスチル−テトラキス［３−（３，５−ジ−ｔ−ブチル−４−ヒドロキシフェニル）プロピオネート］を１質量部添加した。次に調製したスラリー溶液を１１０℃に加熱してから二軸押出機に導入した。さらに、押出機出口のポリエチレンの濃度が１０質量％になるように押出機中段から液添設備により２００℃の流動パラフィンを導入した。押出により得られた液体混合物は孔径１．０ｍｍの紡糸口金に通して紡糸した。なお、吐出速度１．０ｍ/分であった。次に、紡糸した繊維を、３ｃｍのエアギャップを介して１２０℃の流動パラフィンに１分間接触させた後に、室温まで冷却して巻き取った。巻取速度は、５ｍ/分であった。
次に、得られた繊維から流動パラフィンをヘキサンにより抽出し、４０℃で１時間乾燥させた。
乾燥させた繊維を糸温度が５０℃になるように恒温槽で加熱し、２．０倍にプレ延伸した。次に、糸温度が１２０℃になるように恒温槽で繊維を加熱し、１５倍に一次延伸し延伸糸を得た。ついで、該延伸糸を糸温度が１４０℃になるように恒温槽で加熱し、５倍に二次延伸し、２５℃まで１０℃／分の速度で冷却することにより、ポリエチレン繊維を得た。
[Example 1]
(Method for producing polyethylene fiber)
A slurry solution was prepared using polyethylene particles [B] and liquid paraffin (P-350 (trademark) manufactured by Matsumura Oil Co., Ltd.) so that the polyethylene particles became 30% by mass. Further, 1 part by mass of pentaerythyl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] as an antioxidant was added to 100 parts by mass of the slurry solution. Next, the prepared slurry solution was heated to 110 ° C. and introduced into a twin-screw extruder. Further, liquid paraffin at 200 ° C. was introduced from the middle stage of the extruder by a liquid addition facility so that the concentration of polyethylene at the outlet of the extruder became 10% by mass. The liquid mixture obtained by extrusion was spun through a spinneret having a hole diameter of 1.0 mm. The discharge speed was 1.0 m / min. Next, the spun fiber was brought into contact with liquid paraffin at 120 ° C. for 1 minute through a 3 cm air gap, and then cooled to room temperature and wound up. The winding speed was 5 m / min.
Next, liquid paraffin was extracted from the obtained fiber with hexane and dried at 40 ° C. for 1 hour.
The dried fiber was heated in a thermostat so that the yarn temperature became 50 ° C., and pre-drawn 2.0 times. Next, the fiber was heated in a thermostat so that the yarn temperature became 120 ° C., and the fiber was primarily drawn 15 times to obtain a drawn yarn. Next, the drawn yarn was heated in a thermostat so that the yarn temperature became 140 ° C., secondarily drawn 5 times, and cooled to 25 ° C. at a rate of 10 ° C./min to obtain a polyethylene fiber.
得られたポリエチレン繊維の物性を、上述した方法により測定した。測定結果を下記表１に示す。 The physical properties of the obtained polyethylene fiber were measured by the methods described above. The measurement results are shown in Table 1 below.
〔実施例２〕
原料として、ポリエチレン粒子［Ｃ］を使用し、押出機出口のポリエチレンの濃度を９質量％になるように流動パラフィンを液添設備により導入したこと以外は、実施例１と同様にして、ポリエチレン繊維を得た。
[Example 2]
A polyethylene fiber was prepared in the same manner as in Example 1 except that polyethylene particles [C] were used as a raw material, and liquid paraffin was introduced by a liquid addition facility so that the concentration of polyethylene at the outlet of the extruder was 9% by mass. I got
〔実施例３〕
原料として、ポリエチレン粒子［Ｄ］を使用し、押出機出口のポリエチレンの濃度を８質量％になるように流動パラフィンを液添設備により導入したこと以外は、実施例１と同様にして、ポリエチレン繊維を得た。
[Example 3]
A polyethylene fiber was prepared in the same manner as in Example 1, except that polyethylene particles [D] were used as a raw material, and liquid paraffin was introduced by a liquid addition facility so that the concentration of polyethylene at the outlet of the extruder was 8% by mass. I got
〔実施例４〕
スラリー溶液の濃度を８質量％に調製し、押出機の中段から流動パラフィンを導入しなかったこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Example 4]
A polyethylene fiber was obtained in the same manner as in Example 3, except that the concentration of the slurry solution was adjusted to 8% by mass, and liquid paraffin was not introduced from the middle stage of the extruder.
〔実施例５〕
紡糸後、１２０℃の流動パラフィンに接触させずに、室温まで急冷させたこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Example 5]
After spinning, a polyethylene fiber was obtained in the same manner as in Example 3, except that the fiber was rapidly cooled to room temperature without contact with liquid paraffin at 120 ° C.
〔実施例６〕
プレ延伸において、延伸倍率を３倍にしたこと、１次延伸において、延伸倍率を１０倍にしたこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Example 6]
In the pre-stretching, a polyethylene fiber was obtained in the same manner as in Example 3, except that the stretching ratio was set to 3 times in the primary stretching.
〔実施例７〕
プレ延伸において、延伸倍率を１．５倍にしたこと、１次延伸において、延伸倍率を２０倍にしたこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Example 7]
In the pre-stretching, a polyethylene fiber was obtained in the same manner as in Example 3, except that the stretching ratio was 1.5 times in the primary stretching, and the stretching ratio was 20 times in the primary stretching.
〔実施例８〕
原料として、ポリエチレン粒子［Ｈ］を使用したこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
Example 8
A polyethylene fiber was obtained in the same manner as in Example 3, except that polyethylene particles [H] were used as a raw material.
〔実施例９〕
１４０℃で延伸した後に２５℃まで５０℃／分で冷却したこと以外は、実施例７と同様にして、ポリエチレン繊維を得た。
[Example 9]
A polyethylene fiber was obtained in the same manner as in Example 7, except that the fiber was drawn at 140 ° C and then cooled to 25 ° C at 50 ° C / min.
〔実施例１０〕
プレ延伸をしなかったこと、１次延伸において、延伸倍率を３０倍にしたこと以外は、実施例７と同様にして、ポリエチレン繊維を得た。
[Example 10]
A polyethylene fiber was obtained in the same manner as in Example 7, except that the pre-stretching was not performed, and that the stretching ratio was 30 times in the primary stretching.
〔実施例１１〕
原料として、ポリエチレン粒子［Ｉ］を使用したこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Example 11]
A polyethylene fiber was obtained in the same manner as in Example 3, except that polyethylene particles [I] were used as a raw material.
〔比較例１〕
プレ延伸をしなかったこと、１次延伸において、延伸倍率を３０倍にしたこと、１４０℃で延伸した後に２５℃まで５０℃／分で冷却したこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Comparative Example 1]
In the same manner as in Example 3, except that pre-stretching was not performed, the primary stretching was performed at a stretching magnification of 30 times, and the film was stretched at 140 ° C. and then cooled to 25 ° C. at 50 ° C./min. A polyethylene fiber was obtained.
〔比較例２〕
プレ延伸において、恒温槽の温度を２５℃にしたこと、１４０℃で延伸した後に２５℃まで５０℃／分で冷却したこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Comparative Example 2]
In the pre-stretching, a polyethylene fiber was obtained in the same manner as in Example 3, except that the temperature of the thermostat was set to 25 ° C., and after stretching at 140 ° C., the temperature was cooled to 25 ° C. at 50 ° C./min.
〔比較例３〕
プレ延伸において、延伸倍率を１．２倍にしたこと、１次延伸において、延伸倍率を２５倍にしたこと、１４０℃で延伸した後に２５℃まで５０℃／分で冷却したこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Comparative Example 3]
In the pre-stretching, except that the stretching ratio was 1.2 times, in the first stretching, the stretching ratio was 25 times, and after stretching at 140 ° C., it was cooled to 25 ° C. at 50 ° C./min. A polyethylene fiber was obtained in the same manner as in Example 3.
〔比較例４〕
原料として、ポリエチレン粒子［Ｅ］を使用したこと、１４０℃で延伸した後に２５℃まで５０℃／分で冷却したこと以外は、実施例３と同様にして、ポリエチレン繊維を得た。
[Comparative Example 4]
A polyethylene fiber was obtained in the same manner as in Example 3, except that polyethylene particles [E] were used as a raw material, and that the film was drawn at 140 ° C and then cooled to 25 ° C at 50 ° C / min.
〔比較例５〕
原料として、ポリエチレン粒子［Ｅ］を使用したこと、１４０℃で延伸した後に２５℃まで１０℃／分で冷却したこと以外は、比較例１と同様にして、ポリエチレン繊維を得た。
[Comparative Example 5]
A polyethylene fiber was obtained in the same manner as in Comparative Example 1, except that polyethylene particles [E] were used as a raw material, and that the fiber was drawn at 140 ° C and then cooled to 25 ° C at 10 ° C / min.
本実施形態のポリエチレン繊維は、種々の用途に使用でき、特に限定されないが、例えば、ロープ、ネット、釣り糸、手袋、布地、積層体の用途に使用できる。特に、係留ロープ、ヨットロープ、釣り糸、漁網として好適に利用できる。 The polyethylene fiber of the present embodiment can be used for various applications, and is not particularly limited. For example, it can be used for ropes, nets, fishing lines, gloves, fabrics, and laminates. In particular, it can be suitably used as a mooring rope, a yacht rope, a fishing line, and a fishing net.
Claims (11)
Ｍ（ｔ）＝αｅｘｐ（−（１／２）（ｔ／Ｔα）2）ｓｉｎｂｔ／ｂｔ＋βｅｘｐ（−（１／Ｗａ）（ｔ／Ｔβ）Wa）＋γｅｘｐ（−ｔ／Ｔγ） 式１
α：成分（α）の組成分率（％）
Ｔα：成分（α）の緩和時間（ｍｓｅｃ）
β：成分（β）の組成分率（％）
Ｔβ：成分（β）の緩和時間（ｍｓｅｃ）
γ：成分（γ）の組成分率（％）
Ｔγ：成分（γ）の緩和時間（ｍｓｅｃ）
ｔ：観測時間（ｍｓｅｃ）
Ｗａ：形状係数（１＜Ｗａ＜２）
ｂ：形状係数（０．１＜ｂ＜０．２） By fitting the free induction decay (M (t)) of the polyethylene fiber at 90 ° C. measured by the solid echo method of pulsed nuclear magnetic resonance (NMR) using the following equation 1, the component having the lowest mobility ( α), the intermediate motility component (β) and the most motility component (γ), when the three components are approximated, the composition fraction of the most motility component (γ) is 1% or more and 10% Polyethylene fiber, wherein the relaxation time of the component (γ) having the highest mobility is 100 μs or more and 1000 μs or less.
M (t) = αexp (− (１ ／) (t / Tα) 2 ) sinbt / bt + βexp (− (1 / Wa) (t / Tβ) Wa ) + γexp (−t / Tγ) Formula 1
α: composition ratio of component (α) (%)
Tα: relaxation time (msec) of component (α)
β: Composition fraction of component (β) (%)
Tβ: relaxation time of component (β) (msec)
γ: composition ratio (%) of component (γ)
Tγ: relaxation time (msec) of component (γ)
t: Observation time (msec)
Wa: shape factor (1 <Wa <2)
b: Shape factor (0.1 <b <0.2)
（ＤＳＣ測定条件）
（i）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（ii）１８０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（iii）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。 In a DSC curve of a second heating process (measurement condition (iii)) obtained by the following measurement conditions (i) to (iii) using a differential scanning calorimeter (DSC), an endothermic peak is in a range of 152 ° C or more. The polyethylene fiber according to claim 1 or 2, wherein no is detected.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(Ii) After holding at 180 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(Iii) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
（ＤＳＣ測定条件）
（I）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（II）５０℃で１分間保持後、１０℃／分の昇温速度で１４０℃まで昇温。
（III）１４０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（IV）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。 In the DSC curve of the heating process obtained under the following measurement conditions (I) using a differential scanning calorimeter (DSC), the heat of fusion (A) detected in the range of 160 ° C to 170 ° C and the DSC were used. In the DSC curve of the second heating process (measurement condition (IV)) obtained under the following measurement conditions (II) to (IV), the difference between the heat of fusion (B) detected in the range of 160 ° C to 170 ° C. The polyethylene fiber according to any one of claims 1 to 3, wherein the ratio (B) / (A) is 1 or more and 3 or less.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(II) After holding at 50 ° C. for 1 minute, the temperature was raised to 140 ° C. at a rate of 10 ° C./min.
(III) After holding at 140 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(IV) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
（ＤＳＣ測定条件）
（I）５０℃で１分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。
（II）５０℃で１分間保持後、１０℃／分の昇温速度で１４０℃まで昇温。
（III）１４０℃で５分間保持後、１０℃／分の降温速度で５０℃まで降温。
（IV）５０℃で５分間保持後、１０℃／分の昇温速度で１８０℃まで昇温。 In the DSC curve of the heating process obtained under the following measurement conditions (I) using a differential scanning calorimeter (DSC), the heat of fusion (A) detected in the range of 160 ° C to 170 ° C and the DSC were used. In the DSC curve of the second heating process (measurement condition (IV)) obtained under the following measurement conditions (II) to (IV), the difference between the heat of fusion (B) detected in the range of 160 ° C to 170 ° C. The polyethylene fiber according to claim 1, wherein the ratio (B) / (A) is 1.5 or more and 2.7 or less.
(DSC measurement conditions)
(I) After holding at 50 ° C. for 1 minute, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
(II) After holding at 50 ° C. for 1 minute, the temperature was raised to 140 ° C. at a rate of 10 ° C./min.
(III) After holding at 140 ° C. for 5 minutes, the temperature was lowered to 50 ° C. at a rate of 10 ° C./min.
(IV) After holding at 50 ° C. for 5 minutes, the temperature was raised to 180 ° C. at a rate of 10 ° C./min.
Ｍ（ｔ）＝αｅｘｐ（−（１／２）（ｔ／Ｔα）2）ｓｉｎｂｔ／ｂｔ＋βｅｘｐ（−（１／Ｗａ）（ｔ／Ｔβ）Wa）＋γｅｘｐ（−ｔ／Ｔγ） 式１
α：成分（α）の組成分率（％）
Ｔα：成分（α）の緩和時間（ｍｓｅｃ）
β：成分（β）の組成分率（％）
Ｔβ：成分（β）の緩和時間（ｍｓｅｃ）
γ：成分（γ）の組成分率（％）
Ｔγ：成分（γ）の緩和時間（ｍｓｅｃ）
ｔ：観測時間（ｍｓｅｃ）
Ｗａ：形状係数（１＜Ｗａ＜２）
ｂ：形状係数（０．１＜ｂ＜０．２） By fitting the free induction decay (M (t)) of the polyethylene fiber at 90 ° C. measured by the solid echo method of pulsed nuclear magnetic resonance (NMR) using the following equation 1, the component having the lowest mobility ( α), the intermediate motility component (β) and the most motility component (γ), when the three components are approximated, the composition fraction of the most motility component (γ) is 1% or more and 10% The use of polyethylene fibers in the ocean, wherein the relaxation time of the component (γ) having the highest mobility is 100 μs or more and 1000 μs or less.
M (t) = αexp (− (１ ／) (t / Tα) 2 ) sinbt / bt + βexp (− (1 / Wa) (t / Tβ) Wa ) + γexp (−t / Tγ) Formula 1
α: composition ratio of component (α) (%)
Tα: relaxation time (msec) of component (α)
β: Composition fraction of component (β) (%)
Tβ: relaxation time of component (β) (msec)
γ: composition ratio (%) of component (γ)
Tγ: relaxation time (msec) of component (γ)
t: Observation time (msec)
Wa: shape factor (1 <Wa <2)
b: Shape factor (0.1 <b <0.2)
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| WO2024076102A1 (en) * | 2022-10-07 | 2024-04-11 | 코오롱인더스트리 주식회사 | Polyethylene yarn having excellent thermal properties and method for manufacturing same |
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