JP3607426B2 - Thermoplastic elastomer resin composition - Google Patents
Thermoplastic elastomer resin composition Download PDFInfo
- Publication number
- JP3607426B2 JP3607426B2 JP19432296A JP19432296A JP3607426B2 JP 3607426 B2 JP3607426 B2 JP 3607426B2 JP 19432296 A JP19432296 A JP 19432296A JP 19432296 A JP19432296 A JP 19432296A JP 3607426 B2 JP3607426 B2 JP 3607426B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- group
- weight
- mfr
- thermoplastic elastomer
- 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.)
- Expired - Lifetime
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 21
- 239000011342 resin composition Substances 0.000 title claims description 4
- 239000000203 mixture Substances 0.000 claims description 50
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 35
- 239000005977 Ethylene Substances 0.000 claims description 35
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 27
- 239000005060 rubber Substances 0.000 claims description 25
- 239000004711 α-olefin Substances 0.000 claims description 25
- 229920001971 elastomer Polymers 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 23
- 238000010828 elution Methods 0.000 claims description 22
- 229920001038 ethylene copolymer Polymers 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 20
- 238000004132 cross linking Methods 0.000 claims description 17
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 15
- 230000000737 periodic effect Effects 0.000 claims description 9
- 150000001923 cyclic compounds Chemical class 0.000 claims description 5
- 238000005194 fractionation Methods 0.000 claims description 5
- 150000003623 transition metal compounds Chemical class 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 description 28
- -1 polyethylene Polymers 0.000 description 21
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 20
- 239000000523 sample Substances 0.000 description 20
- 125000004432 carbon atom Chemical group C* 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000003921 oil Substances 0.000 description 13
- 235000019198 oils Nutrition 0.000 description 13
- 238000006116 polymerization reaction Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000003431 cross linking reagent Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- 229910052726 zirconium Inorganic materials 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 125000000753 cycloalkyl group Chemical group 0.000 description 7
- 239000003446 ligand Substances 0.000 description 7
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229920000092 linear low density polyethylene Polymers 0.000 description 6
- 239000004707 linear low-density polyethylene Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 125000003710 aryl alkyl group Chemical group 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000011088 calibration curve Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-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
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004342 Benzoyl peroxide Substances 0.000 description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- DKVSRPILOXOTTE-UHFFFAOYSA-L CCCO[Zr](Cl)(Cl)OCCC Chemical compound CCCO[Zr](Cl)(Cl)OCCC DKVSRPILOXOTTE-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000012774 insulation material Substances 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 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
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 125000005504 styryl group Chemical group 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- YGRHYJIWZFEDBT-UHFFFAOYSA-N tridecylaluminum Chemical compound CCCCCCCCCCCCC[Al] YGRHYJIWZFEDBT-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- GNUFQJQCEBFWDQ-UHFFFAOYSA-N (3,5-difluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC(F)=CC(F)=C1 GNUFQJQCEBFWDQ-UHFFFAOYSA-N 0.000 description 1
- RJUCIROUEDJQIB-GQCTYLIASA-N (6e)-octa-1,6-diene Chemical compound C\C=C\CCCC=C RJUCIROUEDJQIB-GQCTYLIASA-N 0.000 description 1
- KSJPEMPNAPZHCF-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-bis(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1CC(C)C KSJPEMPNAPZHCF-UHFFFAOYSA-N 0.000 description 1
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 description 1
- CVFPRCNHGYOETP-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-dipropylbenzene Chemical compound CCCC1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1CCC CVFPRCNHGYOETP-UHFFFAOYSA-N 0.000 description 1
- YPEOCTSXLWIZSO-UHFFFAOYSA-N 1,3-dimethylcyclopenta-1,3-diene Chemical compound CC1=CC(C)=CC1 YPEOCTSXLWIZSO-UHFFFAOYSA-N 0.000 description 1
- GKEUODMJRFDLJY-UHFFFAOYSA-N 1-Methylfluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C GKEUODMJRFDLJY-UHFFFAOYSA-N 0.000 description 1
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 description 1
- QMRIOEQPJDFOPT-UHFFFAOYSA-N 1-methylcyclohepta-1,3,5-triene Chemical compound CC1=CC=CC=CC1 QMRIOEQPJDFOPT-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- LZYHSPJFFHXHPW-UHFFFAOYSA-N 1H-inden-1-ylsilane Chemical compound C1=CC=C2C([SiH3])C=CC2=C1 LZYHSPJFFHXHPW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- DKLQZDIAQKGVTA-UHFFFAOYSA-N 4,7-dimethyl-1h-indene Chemical compound CC1=CC=C(C)C2=C1CC=C2 DKLQZDIAQKGVTA-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- IRAWLGHJHQBREM-UHFFFAOYSA-N 7-Methylinden Natural products CC1=CC=CC2=C1C=CC2 IRAWLGHJHQBREM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- RQDMEYLMEMRZME-UHFFFAOYSA-N C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 Chemical compound C=1C=CC=CC=1C[Zr]CC1=CC=CC=C1 RQDMEYLMEMRZME-UHFFFAOYSA-N 0.000 description 1
- AWHIZLGSPNLJRO-UHFFFAOYSA-M CCCCO[Zr](Cl)(OCCCC)OCCCC Chemical compound CCCCO[Zr](Cl)(OCCCC)OCCCC AWHIZLGSPNLJRO-UHFFFAOYSA-M 0.000 description 1
- MLOQZZUGWOLMCU-UHFFFAOYSA-N CC[Zr](CC)(CC)CC Chemical compound CC[Zr](CC)(CC)CC MLOQZZUGWOLMCU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910017970 MgO-SiO2 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910020413 SiO2—MgO Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 235000010724 Wisteria floribunda Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- JDOPTLDATIMJDC-UHFFFAOYSA-N [Zr+2].CCC[O-].CCC[O-] Chemical compound [Zr+2].CCC[O-].CCC[O-] JDOPTLDATIMJDC-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- CKEGKURXFKLBDX-UHFFFAOYSA-N butan-1-ol;hafnium Chemical compound [Hf].CCCCO.CCCCO.CCCCO.CCCCO CKEGKURXFKLBDX-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- NIOLTQNBOYMEQK-UHFFFAOYSA-N butan-1-olate;zirconium(2+) Chemical compound [Zr+2].CCCC[O-].CCCC[O-] NIOLTQNBOYMEQK-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- DWHYOXYJRGUQEP-UHFFFAOYSA-N carbanide zirconium(4+) Chemical compound [CH3-].[CH3-].[CH3-].[CH3-].[Zr+4] DWHYOXYJRGUQEP-UHFFFAOYSA-N 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- 238000012937 correction Methods 0.000 description 1
- CHVJITGCYZJHLR-UHFFFAOYSA-N cyclohepta-1,3,5-triene Chemical compound C1C=CC=CC=C1 CHVJITGCYZJHLR-UHFFFAOYSA-N 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
- AIRILDQHJRAOBJ-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylsilane Chemical compound [SiH3]C1C=CC=C1 AIRILDQHJRAOBJ-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- KZLUHGRPVSRSHI-UHFFFAOYSA-N dimethylmagnesium Chemical compound C[Mg]C KZLUHGRPVSRSHI-UHFFFAOYSA-N 0.000 description 1
- AXAZMDOAUQTMOW-UHFFFAOYSA-N dimethylzinc Chemical compound C[Zn]C AXAZMDOAUQTMOW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- RMBPEFMHABBEKP-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2C3=C[CH]C=CC3=CC2=C1 RMBPEFMHABBEKP-UHFFFAOYSA-N 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- CCERQOYLJJULMD-UHFFFAOYSA-M magnesium;carbanide;chloride Chemical compound [CH3-].[Mg+2].[Cl-] CCERQOYLJJULMD-UHFFFAOYSA-M 0.000 description 1
- DLPASUVGCQPFFO-UHFFFAOYSA-N magnesium;ethane Chemical compound [Mg+2].[CH2-]C.[CH2-]C DLPASUVGCQPFFO-UHFFFAOYSA-N 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- QSLMQGXOMLSFAW-UHFFFAOYSA-N methanidylbenzene;zirconium(4+) Chemical compound [Zr+4].[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1.[CH2-]C1=CC=CC=C1 QSLMQGXOMLSFAW-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
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- 229920000636 poly(norbornene) polymer Polymers 0.000 description 1
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- 229920000915 polyvinyl chloride Polymers 0.000 description 1
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- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
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Description
【０００１】
【発明の属する技術分野】
本発明は、柔軟性に富み、流動性、引張特性、衝撃強度、耐熱性、耐油性に優れ、繰り返し疲労にも耐える熱可塑性エラストマー組成物に関する。さらに詳しくは、特定のエチレン（共）重合体とエチレン・αーオレフィン共重合体ゴムを含む熱可塑性エラストマー組成物に関する。
【０００２】
【従来の技術】
ポリオレフィン系熱可塑性エラストマーには、ポリエチレンやポリプロピレンなどの結晶性ポリオレフィンをハードセグメントに、エチレンープロピレン共重合体ゴム（ＥＰＲ）やエチレンープロピレンー非共役ジエン共重合体ゴム（ＥＰＤＭ）などの非晶性共重合体ゴムをソフトセグメントにそれぞれを用いたブレンド物、またはこれらブレンド物を部分架橋させた組成物が知られている。またこれらを直接多段重合により製造する方法も知られている。そして、これらの各セグメントの割合を変えることで柔軟性に富むものから、剛性のあるものまで、各種のグレードの製品が製造されている。
柔軟性グレードは、ゴム的な材料として、自動車部品、家電、土木建築、日用雑貨類などの用途に幅広く応用できることから非常に注目されている。このような柔軟性グレードを製造する場合には、ゴム的な柔軟性を付与するために、ソフトセグメント（ＥＰＲやＥＰＤＭなど）の割合を多くし、ハードセグメント（ポリエチレンやポリプロピレンなど）の割合を少なくする必要がある。
しかしながら、ＥＰＲやＥＰＤＭのようなソフトセグメントは引張強度が弱く、耐熱性、耐油性、流動性などが悪いことから、このようなソフトセグメントを多く含む柔軟性のある熱可塑性エラストマーは、やはり上記のような欠点を持つため、各種用途に利用することができない。これらの問題を改良するためにハードセグメントの割合を増すと、柔軟性が失われ、柔軟性熱可塑性エラストマーとしての特徴が失われる。
これらの問題点を解決するためハードセグメントにチグラー触媒による超低密度の線状ポリエチレンを混合することも行われている（例えば特開昭６１−２３３０３２号）。しかし超低密度の線状ポリエチレンでは高分岐度低分子量成分が多く内容物への溶出が多くなり、べとついたり、繰り返し変形に対する耐久性や機械的特性がなお十分に得られないなどこれらの組成物は必ずしも十分満足のいく改良がなされていなかった。
【０００３】
【発明が解決しようとする課題】
本発明の目的は、これらの要求を満たすことにあり、特に柔軟性に富み、流動性、引張特性、衝撃強度、耐熱性、耐油性に優れ、べたつきが少なく、また繰り返し変形に対し耐久性の良好な、熱可塑性エラストマー組成物を提供することにある。
【０００４】
【課題を解決するための手段】
本発明者らは、上記目的に沿って鋭意検討を重ねた結果、分子量分布は狭いにもかかわらず、比較的広い組成分布を持ち、なおかつ低分子量成分および非晶質部分の含有量の少ない新規なエチレン（共）重合体（Ａ）をハードセグメントとして用いるにより、上記目的を達成するに至った。
【０００５】
すなわち、本発明の第１は、
（Ａ）少なくとも共役二重結合を持つ有機環状化合物および周期律表第ＩＶ族の遷移金属化合物を含む触媒の存在下に、エチレンを単独重合あるいはエチレンとαーオレフィンを共重合することにより得られ、下記（ａ）〜（ｆ）を満足するエチレン（共）重合体１０〜９０重量％
（ａ）密度 ０．８６〜０．９６ｇ／ｃｍ３
（ｂ）メルトフローレート（ＭＦＲ） ０．０１〜１００ｇ／１０ｍｉｎ
（ｃ）分子量分布（Ｍｗ／Ｍｎ） １．５〜４．５
（ｄ）組成分布パラメーターＣｂ １．０８〜２．００
（ｅ）２５℃におけるオルソジクロロベンゼン（ＯＤＣＢ）可溶分の量
Ｘ（重量％）と密度ｄおよびＭＦＲが次の関係を満足する
イ）ｄ−０．００８ ×ｌｏｇＭＦＲ≧０．９３の場合
Ｘ＜２．０
ロ）ｄ−０．００８×ｌｏｇＭＦＲ＜０．９３の場合
Ｘ＜９．８ ×１０３ ×（０．９３００ −ｄ ＋０．００８ ×ｌｏｇ ＭＦＲ）２＋２．０（式１）
（ｆ）連続昇温溶出分別法（ＴＲＥＦ）による溶出温度−溶出量曲線のピークが複数である、および
（Ｂ）エチレン・αーオレフィン共重合体ゴム９０〜１０重量％からなることを特徴とする熱可塑性エラストマー組成物である。
本発明の第２は
前記本発明第１に記載の（Ａ）エチレン（共）重合体１０〜９０重量％および（Ｂ）エチレン・αーオレフィン共重合体ゴム９０〜１０重量％からなる組成物を部分架橋させて得られることを特徴とした熱可塑性エラストマー樹脂組成物である。
【０００６】
以下、本発明をさらに詳細に説明する。
本発明の（Ａ）エチレン（共）重合体はエチレン単独重合体、あるいはエチレンと炭素数３〜２０のα−オレフィンより選ばれた一種以上との共重合体を含むものである。この炭素数３〜２０のα−オレフィンとしては、好ましくは炭素数３〜１２のものであり、具体的にはプロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテン、１−デセン、１−ドデセンなどが挙げられる。また、これらのαーオレフインの含有量は、合計で通常３０モル％以下、好ましくは２０モル％以下の範囲で選択されることが望ましい。
【０００７】
本発明の（Ａ）エチレン（共）重合体の密度（ａ）はその用途の要求特性によって異なるが、０．８６〜０．９６ｇ／ｃｍ３ の範囲である。例えば、耐熱性や剛性を特に要求される用途では密度が０．９２ｇ／ｃｍ３ 以上のものが好ましく用いられ、柔軟性や、耐衝撃性を特に要求される用途では０．９２ｇ／ｃｍ３ 以下のものが好ましく用いられる。なお一般的には好ましくは０．８７〜０．９３ｇ／ｃｍ３ 、より好ましくは０．８７〜０．９１ｇ／ｃｍ３ の範囲である。密度が０．８６ｇ／ｃｍ３ 未満では剛性、耐熱性が劣り、組成物の表面にべたつきが発生し不具合を生じる。０．９６ｇ／ｃｍ３ を超えると柔軟性、耐衝撃性、引張強度などの機械的強度が低下し望ましくない。
【０００８】
本発明の（Ａ）エチレン（共）重合体のＭＦＲ（ｂ）は０．０１〜１００ｇ／１０ｍｉｎ 、好ましくは０．１〜５０ｇ／１０ｍｉｎの範囲にあることが望ましい。なおＭＦＲが０．０１ｇ／１０ｍｉｎ未満では組成物のＭＦＲが低すぎて流動性が悪くなり、成形加工性が悪くなる。１００ｇ／１０ｍｉｎ を超えると耐衝撃性、引張強度などの機械的強度が低下する。
【０００９】
本発明の（Ａ）エチレン（共）重合体の分子量分布Ｍｗ／Ｍｎ（ｃ）の算出方法は、ゲルパーミエイションクロマトグラフィー（ＧＰＣ）により重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）を求め、この比Ｍｗ／Ｍｎを求めるものである。
本発明のエチレン・αーオレフイン共重合体のＭｗ／Ｍｎは１．５〜４．５であり、好ましくは１．５〜３．５、より好ましくは２．０〜３．０、さらに好ましくは２．２〜２．９の範囲にあることが望ましい。Ｍｗ／Ｍｎが１．５未満では成形加工性が劣り、４．５を超えると耐衝撃性が劣ったり、べたつきが生じたりする。
【００１０】
本発明の（Ａ）エチレン（共）重合体の組成分布パラメーターＣｂ（ｄ）は１．０８〜２．００の範囲、好ましくは１．１０〜１．８０、さらに好ましくは１．１２〜１．７０の範囲である。Ｃｂ値が２．００を超えると、耐衝撃性、引張特性、繰り返し変形に対する耐久性、耐環境応力劣化性の悪化や、成形品のべたつき、熱収縮が大きくなる恐れがある。また共重合体においてはＣｂ値が１．０８未満では耐熱性が低下する恐れがある。
【００１１】
本発明のエチレン（共）重合体の組成分布パラメーターＣｂ（ｄ）の測定法は下記の通りである。
【００１２】
試料に耐熱安定剤を加え、ＯＤＣＢに試料濃度が０．２重量％となるように１３５℃で加熱溶解する。この加熱溶液を、けい藻土（セライト５４５）を充填したカラムに移送し充満後０．１℃／ｍｉｎ で２５℃まで冷却し、試料をセライト表面に析出沈着する。次に、このカラムにＯＤＣＢを一定流量で流しながら、カラム温度を５℃きざみに１２０℃まで段階的に昇温しながら、各温度において、試料を溶解した溶液を採取する。この溶液を冷却後メタノールで試料を再沈後、ろ過、乾燥し、各溶出温度における試料を得る。この分別された試料の重量分率および分岐度（炭素数１０００個あたりの分岐数）を測定する。分岐度の測定は１３ＣーＮＭＲにより求める。
【００１３】
このような方法で３０℃から９０℃で採取した各フラクションについては次のような、分岐度の補正を行う。すなわち、溶出温度に対して測定した分岐度をプロットし、相関関係を最小自乗法で直線に近似し、検量線を作成する。この近似の相関係数は十分大きい。この検量線により求めた値を各フラクションの分岐度とする。なお、溶出温度９５℃以上で採取したフラクションについては溶出温度と分岐度に必ずしも直線関係が成立しないのでこの補正は行わない。
【００１４】
次にそれぞれのフラクションの重量分率ｗｉ を、溶出温度５℃当たりの分岐度ｂｉ の変化量（ｂｉ ーｂｉ−１ ）で割って相対濃度ｃｉ を求め、分岐度に対して相対濃度をプロットし、組成分布曲線を得る。この組成分布曲線を一定の幅で分割し、次式より組成分布パラメーターＣｂを算出する。
【数１】
【００１５】
なお、エチレン（共）重合体の組成分布を記述する方法は多くの提案がなされている。例えば特開昭６０ー８８０１６号では、試料を溶剤分別して得た各分別試料の分岐数に対して、累積重量分率が特定の分布（対数正規分布）をすると仮定して数値処理を行い、重量平均分岐度（Ｃｗ）と数平均分岐度（Ｃｎ）の比を求めている。この近似計算は、試料の分岐数と累積重量分率が対数正規分布からずれると精度が下がり、市販のＬＬＤＰＥについて測定を行うと相関係数Ｒ２ はかなり低く、値の精度は充分でない。このＣｗ／Ｃｎと本発明のＣｂとは、定義および測定方法が異なる。
【００１６】
本発明の（Ａ）エチレン（共）重合体の、２５℃におけるＯＤＣＢ可溶分量Ｘ（ｅ）は、エチレン（共）重合体に含まれる高分岐度成分および低分子量成分の割合を示すものであり、耐熱性の低下や成形品表面のベタツキの原因をなるため少ないことが望ましい。ＯＤＣＢ可溶分の量は、共重合体全体のα−オレフィンの含有量および平均分子量、すなわち密度とＭＦＲに影響される。従って、前記ＯＤＣＢ可溶分の量Ｘ（重量％）は密度ｄとＭＦＲの関係が、ｄ−０．００８ ×ｌｏｇＭＦＲ≧０．９３を満たす場合は２重量％未満、好ましくは１重量％未満、さらに好ましくは０．５重量％未満であることが望ましい。
また、ｄとＭＦＲの関係が、ｄ−０．００８ ×ｌｏｇＭＦＲ＜０．９３を満たす場合はＸ＜９．８ ×１０３ ×（０．９３００ ーｄ ＋０．００８ ×ｌｏｇ ＭＦＲ）２＋２．０の関係を満足し、好ましくはＸ＜７．４ ×１０３ ×（０．９３００ ーｄ ＋０．００８ ×ｌｏｇ ＭＦＲ）２＋１．０、さらに好ましくはＸ＜５．６ ×１０３ ×（０．９３００ ーｄ ＋０．００８ ×ｌｏｇ ＭＦＲ）２＋０．５の範囲であることが望ましい。
密度、ＭＦＲとＯＤＣＢ可溶分の量が上記の関係を満たすことは、共重合体全体に含まれているα−オレフィンが遍在していないことを示している。
【００１７】
なお、前記の２５℃におけるＯＤＣＢ可溶分量Ｘは、下記の方法により測定する。
すなわち試料０．５ｇを２０ｍｌのＯＤＣＢに加え１３５℃で２時間加熱し、試料を完全に溶解した後、２５℃まで冷却する。この溶液を２５℃で一晩放置後、テフロン製フィルターでろ過してろ液を採取する。試料溶液であるろ液を赤外分光器によりメチレンの非対称伸縮振動の波数２９２５ｃｍ−１付近の吸収ピーク強度を測定し、あらかじめ作成した検量線によりろ液中の試料濃度を算出する。この値より、２５℃におけるＯＤＣＢ可溶分を求める。
【００１８】
本発明のエチレン（共）重合体は連続昇温溶出分別法（ＴＲＥＦ）により求めた溶出温度ー溶出量曲線において、ピークが複数個ある（ｆ）必要があり、さらにその高温側のピークが８５℃から１００℃の間に存在することが特に好ましい。このピークが存在することにより、融点が高くなりまた結晶化度が上昇し成形体の耐熱性および剛性が向上する。図１に本発明の共重合体の溶出温度ー溶出量曲線を示した。図２にはいわゆる市販のメタロセン触媒による共重合体の溶出温度ー溶出量曲線であり両者は顕著に異なる。
【００１９】
本発明にかかわるＴＲＥＦの測定方法は下記の通りである。試料に耐熱安定剤を加え、ＯＤＣＢに試料濃度０．０５重量％となるように１３５℃で加熱溶解する。この加熱溶液５ｍｌを、ガラスビーズを充填したカラムに注入した後、０．１℃／ｍｉｎの冷却速度で２５℃まで冷却し、試料をガラスビーズ表面に沈着する。次に、このカラムにＯＤＣＢを一定流量で流しながら、カラム温度を５０℃／ｈｒの一定速度で昇温し、各温度において溶液に溶解可能な試料を順次溶出させる。この際、溶剤中の試料濃度はメチレンの非対称伸縮振動の波数２９２５ｃｍ−１に対する吸収を赤外検出器で連続的に検出される。この濃度から、溶出温度ー溶出量曲線を得ることができる。
ＴＲＥＦ分析は極少量の試料で、温度変化に対する溶出速度の変化を連続的に分析出来るため、分別法では検出出来ない比較的細かいピークの検出が可能である。
【００２０】
本発明の（Ａ）エチレン（共）重合体の製造は、少なくとも共役二重結合を持つ有機環状化合物および周期律表第ＩＶ族の遷移金属化合物を含む触媒の存在下に、エチレン単独あるいはエチレンと炭素数３〜２０のαーオレフィンを（共）重合させることによって行われる。特に以下の（１）周期律表第ＩＶ族の遷移金属化合物と（３）共役二重結合を持つ有機環状化合物に以下に示す触媒成分（２）および（４）を相互に接触することによって得られる触媒で（共）重合することが望ましい。
すなわち、（１）：一般式Ｍｅ１ Ｒ１ ｐ Ｒ２ ｑ （ＯＲ３ ）ｒ Ｘ１ ４−ｐ−ｑ−ｒ で表される周期律表第ＩＶ族の遷移金属化合物（式中Ｍｅ１ はジルコニウム、チタン、ハフニウムを示し、Ｒ１ およびＲ３ は個別に炭素数１〜２４の炭化水素基またはトリアルキルシリル基、Ｒ２ は２，４−ペンタンジオナト配位子またはその誘導体あるいはジベンゾイルメタナト配位子、ベンゾイルアセトナト配位子などの誘導体を示す、Ｘ１ はハロゲン原子を示し、ｐ、ｑおよびｒはそれぞれ０≦ｐ≦４、０≦ｑ≦４、０≦ｒ≦４、０≦ｐ＋ｑ＋ｒ≦４の範囲を満たす整数である）、（２）：一般式Ｍｅ２ Ｒ４ ｍ （ＯＲ５ ）ｎ Ｘ２ ｚ−ｍ−ｎ で表される化合物（式中Ｍｅ２ は周期律表第Ｉ 〜ＩＩＩ 族元素、Ｒ４ およびＲ５ は各々炭素数１〜２４の炭化水素基、Ｘ２ はハロゲン原子または水素原子（ただし、Ｘ２ が水素原子の場合はＭｅ２ は周期律表第ＩＩＩ族元素の場合に限る）を示し、ｚはＭｅ２ の価数を示し、ｍおよびｎは各々０≦ｍ≦ｚ、０≦ｎ≦ｚ、かつ０≦ｍ＋ｎ≦ｚの範囲を満たす整数である）、（３）：共役二重結合を持つ有機環状化合物、および（４）：Ａｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウム化合物および／またはホウ素化合物を相互に接触させて得られる触媒である。
【００２１】
上記触媒成分（１）の一般式Ｍｅ１ Ｒ１ ｐ Ｒ２ ｑ （ＯＲ３ ）ｒ Ｘ１ ４−ｐ−ｑ−ｒで表される化合物の式中Ｍｅ１ はジルコニウム、チタン、ハフニウムを示す。これらの遷移金属の種類は限定されるものではなく、複数を用いることもできるが、共重合体の耐候性の優れるジルコニウムが含まれることが特に好ましい。Ｒ１ およびＲ３ はそれぞれ炭素数１〜２４の炭化水素基で、好ましくは炭素数１〜１２、さらに好ましくは１〜８であり、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基などのアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基、キシリル基、メシチル基、インデニル基、ナフチル基などのアリール基；ベンジル基、トリチル基、フェネチル基、スチリル基、ベンズヒドリル基、フェニルブチル基、ネオフイル基などのアラルキル基などが挙げられる。これらは分岐があってもよい。Ｒ２ は２，４ーペンタンジオナト配位子またはその誘導体（ＣＨ３ ＣＯＣＨＣＯＣＨ３ ）、あるいはジベンゾイルメタナト配位子、ベンゾイルアセトナト配位子などの誘導体を示す。Ｘ１ はフッ素、ヨウ素、塩素および臭素などのハロゲン原子を示し、ｐ、ｑおよびｒはそれぞれ０≦ｐ≦４、０≦ｑ≦４、０≦ｒ≦４、０≦ｐ＋ｑ＋ｒ≦４の範囲である。
【００２２】
上記触媒成分（１）一般式で示される化合物の例としては、テトラメチルジルコニウム、テトラエチルジルコニウム、テトラベンジルジルコニウム、テトラプロポキシジルコニウム、トリプロポキシモノクロロジルコニウム、ジプロポキシジクロロジルコニウム、テトラブトキシジルコニウム、トリブトキシモノクロロジルコニウム、ジブトキシジクロロジルコニウム、テトラブトキシチタン、テトラブトキシハフニウムなどが挙げられ、また、前記２，４−ペンタンジオナト配位子またはその誘導体等の具体例には、テトラ（２，４−ペンタンジオナト）ジルコニウム、トリ（２，４−ペンタンジオナト）クロライドジルコニウム、ジ（２，４−ペンタンジオナト）ジエトキサイドジルコニウム、ジ（２，４−ペンタンジオナト）ジ−ｎ−プロポキサイドジルコニウム、ジ（２，４−ペンタンジオナト）ジ−ｎ−ブトキサイドジルコニウム、ジ（２，４−ペンタンジオナト）ジベンジルジルコニウム、ジ（２，４−ペンタンジオナト）ジネオフイルジルコニウム、テトラ（ジベンゾイルメタナート）ジルコニウム、ジ（ジベンゾイルメタナート）ジエトキサイドジルコニウム、ジ（ジベンゾイルメタナート）ジ−ｎ−プロポキサイドジルコニウム、ジ（ベンゾイルアセトナート）ジエトキサイドジルコニウム、ジ（ジベンゾイルアセトナート）ジ−ｎ−プロポキサイドジルコニウム等があげられ、これらを２種以上混合して用いても差し支えない。
【００２３】
上記触媒成分（２）の一般式Ｍｅ２ Ｒ４ ｍ （ＯＲ５ ）ｎ Ｘ２ ｚ−ｍ−ｎ で表される化合物の式中Ｍｅ２ は周期律表第Ｉ 〜ＩＩＩ 族元素を示し、リチウム、ナトリウム、カリウム、マグネシウム、カルシウム、亜鉛、ホウ素、アルミニウムなどである。Ｒ４ およびＲ５ は各々炭素数１〜２４の炭化水素基、好ましくは炭素数１〜１２、さらに好ましくは１〜８の炭化水素基であり、具体的にはメチル基、エチル基、プロピル基、イソプロピル基、ブチル基などのアルキル基；ビニル基、アリル基などのアルケニル基；フェニル基、トリル基、キシリル基、メシチル基、インデニル基、ナフチル基などのアリール基；ベンジル基、トリチル基、フェネチル基、スチリル基、ベンズヒドリル基、フェニルブチル基、ネオフイル基などのアラルキル基などが挙げられる。これらは分岐があってもよい。Ｘ２ はフッ素、ヨウ素、塩素および臭素のハロゲン原子または水素原子を示すものである。ただし、Ｘ２ が水素原子の場合はＭｅ２ はホウ素、アルミニウムなどに例示される周期律表第ＩＩＩ 族元素の場合に限るものである。また、ｚはＭｅ２ の価数を示し、ｍおよびｎは各々０≦ｍ≦ｚ、０≦ｎ≦ｚの範囲を満たす整数であり、かつ、０≦ｍ＋ｎ≦ｚである。
【００２４】
上記触媒成分（２）の一般式で示される化合物の例としては、メチルリチウム、エチルリチウムなどの有機リチウム化合物；ジメチルマグネシウム、ジエチルマグネシウム、メチルマグネシウムクロライド、エチルマグネシウムクロライドなどの有機マグネシウム化合物；ジメチル亜鉛、ジエチル亜鉛などの有機亜鉛化合物；トリメチルボロン、トリエチルボロンなどの有機ボロン化合物；トリメチルアルミニウム、トリエチルアルミニウム、トリプロピルアルミニウム、トリイソブチルアルミニウム、トリヘキシルアルミニウム、トリデシルアルミニウム、ジエチルアルミニウムクロライド、エチルアルミニウムジクロライド、エチルアルミニウムセスキクロライド、ジエチルアルミニウムエトキサイド、ジエチルアルミニウムハイドライドなどの有機アルミニウム化合物等が挙げられる。
【００２５】
上記触媒成分（３）の共役二重結合を持つ有機環状化合物としては、環状で共役である二重結合を２個以上、好ましくは２〜４個、さらに好ましくは２〜３個有する環を１個または２個以上もち、全炭素数が４〜２４、好ましくは４〜１２である環状炭化水素化合物；前記環状炭化水素化合物が部分的に１〜６個の炭化水素残基（典型的には、炭素数１〜１２のアルキル基またはアラルキル基）で置換された環状炭化水素化合物；共役である二重結合を２個以上、好ましくは２〜４個、さらに好ましくは２〜３個有する環を１個または２個以上もち、全炭素数が４〜２４、好ましくは４〜１２である環状炭化水素基を有する有機ケイ素化合物；前記環状炭化水素基が部分的に１〜６個の炭化水素残基またはアルカリ金属塩（ナトリウムまたはリチウム塩）で置換された有機ケイ素化合物が含まれる。特に好ましくは分子中のいずれかにシクロペンタジエン構造をもつものが望ましい。
【００２６】
上記の好適な化合物としては、シクロペンタジエン、インデン、アズレンまたはこれらのアルキル、アリール、アラルキル、アルコキシまたはアリールオキシ誘導体などが挙げられる。また、これらの化合物がアルキレン基（その炭素数は通常２〜８、好ましくは２〜３）を介して結合（架橋）した化合物も好適に用いられる。
【００２７】
環状炭化水素基を有する有機ケイ素化合物は、下記一般式で表示することができる。
ＡＬ ＳｉＲ６ ４−Ｌ
ここで、Ａはシクロペンタジエニル基、置換シクロペンタジエニル基、インデニル基、置換インデニル基で例示される前記環状水素基を示し、Ｒ６ はメチル基、エチル基、プロピル基、イソプロピル基、ブチル基などのアルキル基；メトキシ基、エトキシ基、プロポキシ基、ブトキシ基などのアルコキシ基；フェニル基などのアリール基；フェノキシ基などのアリールオキシ基；ベンジル基などのアラルキル基で示され、炭素数１〜２４、好ましくは１〜１２の炭化水素残基または水素を示し、Ｌは１≦Ｌ≦４、好ましくは１≦Ｌ≦３である。
【００２８】
上記成分（３）の有機環状炭化水素化合物の具体例としては、シクロペンタジエン、メチルシクロペンタジエン、エチルシクロペンタジエン、１，３ージメチルシクロペンタジエン、インデン、４ーメチルー１ーインデン、４，７ージメチルインデン、シクロヘプタトリエン、メチルシクロヘプタトリエン、シクロオクタテトラエン、アズレン、フルオレン、メチルフルオレンのような炭素数５〜２４のシクロポリエンまたは置換シクロポリエン、モノシクロペンタジエニルシラン、ビスシクロペンタジエニルシラン、トリスシクロペンタジエニルシラン、モノインデニルシラン、ビスインデニルシラン、トリスインデニルシラン等が挙げられる。
【００２９】
触媒成分（４）のＡｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウム化合物は、アルキルアルミニウム化合物と水とを反応させることにより得られる通常アルミノキサンと称される変性有機アルミニウムが好ましく、これは分子中に通常１〜１００個、好ましくは１〜５０個のＡｌ−Ｏ−Ａｌ結合を含有する。また、変性有機アルミニウム化合物は線状でも環状でもいずれでもよい。
【００３０】
有機アルミニウムと水との反応は通常不活性炭化水素中で行われる。該不活性炭化水素としては、ペンタン、ヘキサン、ヘプタン、シクロヘキサン、ベンゼン、トルエン、キシレン等の脂肪族、脂環族または芳香族炭化水素が好ましい。
水と有機アルミニウム化合物との反応比（水／Ａｌモル比）は通常０．２５／１〜１．２／１、好ましくは０．５／１〜１／１であることが望ましい。
【００３１】
ホウ素化合物の具体的な例としては、テトラ（ペンタフルオロフェニル）ホウ酸トリエチルアンモニウム（トリエチルアンモニウムテトラ（ペンタフルオロフェニル）ボレート）、テトラ（ペンタフルオロフェニル）ホウ酸ジメチルアニリニウム（ジメチルアニリニウムテトラ（ペンタフルオロフェニル）ボレート）、ブチルアンモニウムテトラ（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ−ジメチルアニリニウムテトラ（ペンタフルオロフェニル）ボレート、Ｎ，Ｎ−ジメチルアニリニウムテトラ（３，５−ジフルオロフェニル）ボレートなどが挙げられる。
【００３２】
また、本発明では上記触媒成分（１）〜（４）を相互に接触させることにより得られる触媒を、無機物担体および／または粒子状ポリマー担体（５）に担持させて重合反応に用いることもできる。成分（５）の無機物担体は、本発明の触媒を調製する段階において、本来の形状を保持している限り、粉末状、粒状、フレーク状、箔状、繊維状などいずれの形状であっても差し支えないが、いずれの形状であっても、最大長は通常５〜２００μｍ、好ましくは１０〜１００μｍの範囲のものが適している。また、無機物担体は多孔性であることが好ましく、通常、その表面積は５０〜１０００ｍ２ ／ｇ、細孔容積は０．０５〜３ｃｍ３ ／ｇの範囲にある。
本発明の無機物担体としては、炭素質物、金属、金属酸化物、金属塩化物、金属炭酸塩またはこれらの混合物が使用可能であり、これらは通常２００〜９００℃で空気中または窒素、アルゴンなどの不活性ガス中で焼成して用いられる。
【００３３】
該無機物担体に用いることができる好適な金属としては、鉄、アルミニウム、ニッケルなどが挙げられる。また、金属酸化物としては周期律表Ｉ〜ＶＩＩＩ族の単独酸化物または複合酸化物が挙げられ、具体的にはＳｉＯ２ 、Ａｌ２ Ｏ３ 、ＭｇＯ、ＣａＯ、Ｂ２ Ｏ３ 、ＴｉＯ２ 、ＺｒＯ２ 、Ｆｅ２ Ｏ３ 、ＳｉＯ２ ーＡｌ２ Ｏ３ 、Ａｌ２ Ｏ３ ーＭｇＯ、Ａｌ２ Ｏ３ ーＣａＯ、Ａｌ２ Ｏ３ ーＭｇＯーＣａＯ、Ａｌ２ Ｏ３ ーＭｇＯーＳｉＯ２ 、Ａｌ２ Ｏ３ ーＣｕＯ、Ａｌ２ Ｏ３ ーＦｅ２ Ｏ３ 、Ａｌ２ Ｏ３ ーＮｉＯ、ＳｉＯ２ ーＭｇＯなどが挙げられる。なお酸化物で表示した上記の式は分子式ではなく、組成のみを示すものである。つまり、本発明において用いられる複酸化物の構造および成分比率は、特に限定されるものではない。また、本発明において用いる金属酸化物は、少量の水分を吸着していても差し支えなく、少量の不純物を含有していても差し支えない。
【００３４】
金属塩化物としては、たとえばアルカリ金属、アルカリ土類金属の塩化物が好ましく、具体的にはＭｇＣｌ２ 、ＣａＣｌ２ などが特に好適である。金属炭酸塩としては、アルカリ金属、アルカリ土類金属の炭酸塩が好ましく、具体的には、炭酸マグネシウム、炭酸カルシウム、炭酸バリウムなどが挙げられる。炭素質物質としてはたとえばカーボンブラック、活性炭などが挙げられる。
以上の無機担体はいずれも本発明に好適に用いられることができるが、特に金属酸化物のシリカ、アルミナなどの使用が好ましい。
【００３５】
一方、粒子状ポリマー担体としては、触媒調製時および重合反応時において、溶融などせずに固体状を保つものである限り、熱可塑性樹脂、熱硬化性樹脂のいずれもが使用でき、その粒径は通常５〜２０００μｍ、好ましくは１０〜１００μｍの範囲のものが望ましい。これらのポリマー担体の分子量は、当該ポリマーが触媒調製時および重合反応時において固体状物質として存在できる程度であれば、特に限定されることはなく、低分子量のものから超高分子量のものまで任意に使用可能である。
具体的には、粒子状のエチレン重合体、エチレン・αーオレフィン共重合体、プロピレン重合体または共重合体、ポリ１ーブテンなどで代表される各種のポリオレフィン（好ましくは炭素数２〜１２）、ポリエステル、ポリアミド、ポリ塩化ビニル、ポリ（メタ）アクリル酸メチル、ポリスチレン、ポリノルボルネン、各種天然高分子およびこれらの混合物等が挙げられる。
【００３６】
上記無機物担体および／または粒子状ポリマー担体は、このまま使用することもできるが、好ましくは予備処理としてこれらの担体を有機アルミニウム化合物やＡｌ−Ｏ−Ａｌ結合を含む変性有機アルミニウム化合物などに接触処理させた後に成分（５）として用いることもできる。
【００３７】
本発明の（Ａ）エチレン（共）重合体は、気相法、スラリー法、溶液法等で製造され、一段重合法、多段重合法など特に限定されるものではない。
上記の方法で重合され、前記（ａ）〜（ｆ）を満足するエチレン（共）重合体（Ａ）を用いることにより、柔軟性、機械的強度、耐熱性のバランスがよく、また繰り返し使用に対する耐久性に優れた組成物となる。また、架橋剤を用いて部分架橋すると機械的強度の低下が少なく、耐熱性や耐油性が向上する。
【００３８】
本発明の（Ｂ）エチレン・αーオレフィン共重合体ゴムとは、エチレン・αーオレフィン共重合体ゴムまたはエチレンーαーオレフィンー非共役ジエン共重合体ゴムであり、これらの共重合体ゴムは非晶性の共重合体である。エチレン・αーオレフィン共重合体ゴム成分中のαーオレフィンとしてはプロピレン、１−ブテン、４−メチル−１−ペンテン、１−ヘキセン、１−オクテンなどが挙げられる。特に好ましくはプロピレンである。非共役ジエンとしては、１、４ーヘキサジエン、１、６ーオクタジエン、ジシクロペンタジエン、ビニルノルボルネン、エチリデンノルボルネンなどが挙げられる。好ましくは、１、４ーヘキサジエンやエチリデンノルボルネンである。
【００３９】
前記（Ｂ）エチレン・αーオレフィン共重合体ゴムのムーニー粘度（ＭＬ１＋４ 、１００℃）は１０〜９５程度のものが好ましい。エチレン・αーオレフィン共重合体ゴムのムーニー粘度が１０より小さいと、熱可塑性エラストマー組成物の引張強度が低下したり、表面がベタついたリして好ましくない。ムーニー粘度が９５を超えると熱可塑性エラストマー組成物の流動性が悪くなり好ましくない。
【００４０】
本発明の熱可塑性エラストマー組成物中に占めるエチレン（共）重合体（Ａ）（以下成分（Ａ）という）およびエチレン・αーオレフィン共重合体ゴム（Ｂ）（以下成分（Ｂ）という）の組成割合は、成分（Ａ）が１０〜９０重量％、好ましくは２５〜７５重量％、成分（Ｂ）が９０〜１０重量％、好ましくは７５〜２５重量％である。
成分（Ａ）が９０重量％を越えると柔軟性がなくなり、また１０重量％より少なくなると適度な剛性がなくなり、また引張強度が低下し、耐油性が悪くなり望ましくない。
【００４１】
本発明の熱可塑性エラストマーは特に耐熱性や耐油性を向上させて使用される場合は、部分架橋して用いられる。部分架橋とは、組成物の一部分を架橋するものであり、流動性を維持しながら、架橋剤を使用して部分架橋させるものである。
部分架橋物を製造する方法としては、任意の公知技術が使用できる。代表的な例は、上記組成物に架橋剤を添加して機械的な溶融混練を行う方法であり、一軸および二軸押出機、バンバリーミキサー、各種ニーダー、ロールなどを用いて部分架橋させることができる。溶融混練の温度は一般に３００℃以下であり、好ましくは使用する架橋剤の半減期が１分以下となる温度で、通常１００〜３００℃である。また、架橋剤を含浸等により混合した後、熱あるいは放射線によって部分架橋させてもよい。
【００４２】
架橋剤としては通常、有機過酸化物が用いられる。具体的には、２，５ージメチルー２，５ージ（ｔ−ブチルパーオキシ）ヘキサン、ジーｔ−ブチルパーオキシド、ジ（ｔ−ブチルパーオキシ）ジイソプロピルベンゼン、ジ（ｔ−ブチルパーオキシ）ジイソブチルベンゼン、ジクミルパーオキシド、ｔ−ブチルクミルパーオキシド、ｔ−ブチルパーオキシベンゾエート、１，１ービス（ｔ−ブチルパーオキシ）ー３，３，５ートリメチルパーオキシド、ベンゾイルパーオキシド、ｐ−クロルベンゾイルパーオキシドなどが挙げられる。また、架橋助剤を使用しても良い。具体的には液状ポリブタジエン、ジビニルベンゼン、エチレンジメタクリレート、ジアリルフタレートなどを挙げることができる。
架橋剤の使用量は樹脂成分に対して、０．００５〜３重量％、好ましくは０．０５〜１重量％である。架橋剤の使用量は架橋組成物に要求される性能によって決定されるので必ずしもこれらの数字に限定されるものではない。また、数種類の架橋剤や架橋助剤を目的によって併用してもよい。
このようにして部分架橋させて得られる本発明の熱可塑性エラストマー組成物を沸騰キシレンで５時間抽出して測定される沸騰キシレン不溶分率（ゲル分率）は、０．５〜６０重量％、好ましくは２〜５０重量％である。ゲル分率が０．５重量％より少ないと耐油性などが低下し、またゲル分率が６０重量％を超えると引張強度や伸びが低下し望ましくない。
【００４３】
本発明においては、本発明で意図する特性を本質的に損なわない範囲において、必要に応じてカーボンブラック、炭酸カルシウム、シリカ、金属繊維、炭素繊維などの各種フィラーや酸化防止剤、難燃剤、滑剤、帯電防止剤、防曇剤、顔料、紫外線吸収剤、分散剤などの公知の添加剤や、フィラーの分散を助け、柔軟性や弾性を増す目的でのパラフィン系、ナフテン系あるいは芳香族系の植物油等を必要に応じて配合してもよい。また、部分架橋を行う場合には、架橋の前後、ないし架橋時（特に溶融混練時）に上記添加剤を必要に応じて配合してもよい。
さらに本発明で意図する特性を本質的に損なわない範囲において、高密度ポリエチレン、低密度ポリエチレン、直鎖状低密度ポリエチレンなどの結晶性ポリオレフィン、天然ゴム、各種合成ゴム、スチレン系熱可塑性組成物などの各種樹脂やゴムを必要に応じて配合してもよい。
【００４４】
本発明の熱可塑性エラストマー組成物は射出成形、押出成形、中空成形、インフレーション成形、Ｔダイ成形等によって成形され、例えば自動車部品としてはバンパー、マッドガード、内装表皮材、家電製品としてはホース、パッキン等として用いられ、その他建築用ガスケット、遮音材料、文房具、日用雑貨類などに用いられる。また、部分架橋した組成物はこれらとほぼ同様の用途に用いられるが、中でも耐熱性や耐油性の要求される用途に用いられる。
【００４５】
【実施例】
次に実施例により本発明を更に詳しく説明するが、本発明はこれらによって限定されるものではない。
なお本実施例に用いた試験法は以下の通りである。
（物性試験方法）
ＭＦＲ ：ＪＩＳ Ｋ６７５８に準拠した。
引張試験 ：ＪＩＳ Ｋ６３０１に準拠した。３号ダンベルを用いて試験片を作り、５０ｍｍ／ 分の引張速度で測定した。引張破壊時における強度を引張強度とし、その際の伸び率を引張伸びとした。
永久伸び ：ＪＩＳ Ｋ６３０１に準拠した。３号ダンベルを用いて試験片を作り、試験片を１００％伸長した状態で１０分間保持し、急に収縮させ１０分間放置後の伸び率より求めた。
ビカット軟化点 ：プレス（２１０℃）により、厚さ３ｍｍの試料を作り、それを測定に用いた。加熱溶液中の試験片に垂直においた針状圧子を通じて１ｋｇの荷重を加えながら、５０℃／ ６０分の速度で伝熱媒体を昇温させ、針状圧子が１ｍｍ侵入したときの伝熱媒体の温度をビカット軟化点とした。
硬度 ：ＪＩＳ Ｋ６３０１に準じて試験片を作成し、Ａ型試験機を用いて測定した。
耐油性 ：ＪＩＳ Ｋ６３０１に準じて試験片を作成し、ＪＩＳ ３号油を用いて７０℃、２２時間の体積変化を求めた。
ゲル分率 ：熱プレス（１９０℃、５分）を用いて、厚さ２００μｍのシートを作成し、４０ｍｍ×２０ｍｍのシートを３枚切り取り、それらをそれぞれ１２０メッシュの金網製の袋に入れて、二重管式ソックスレー抽出器を用いて、沸騰キシレンで５時間抽出を行う。沸騰キシレン不溶分を取り出し、真空乾燥（８０℃、７時間）を行い、沸騰キシレン不溶分をゲル分率として求める。
【００４６】
（エチレン・αーオレフィン共重合体の重合）
固体触媒の調製
窒素下で電磁誘導撹拌機付き触媒調製器（Ｎｏ． １）に精製トルエンを加え、ついでジプロポキシジクロロジルコニウム（Ｚｒ（ＯＰｒ）２ Ｃｌ２ ）２８ｇおよびメチルシクロペンタジエン４８ｇを加え、０℃に系を保持しながらトリデシルアルミニウムを４５ｇを滴下し、滴下終了後、反応系を５０℃に保持して１６時間撹拌した。この溶液をＡ液とする。次に窒素下で別の撹拌器付き触媒調製器（Ｎｏ． ２）に精製トルエンを加え、前記Ａ溶液と、ついでメチルアルミノキサン６．４ｍｏｌのトルエン溶液を添加し反応させた。これをＢ液とする。
次に窒素下で撹拌器付き調製器（Ｎｏ． １）に精製トルエンを加え、ついであらかじめ４００℃で所定時間焼成処理したシリカ（富士デビソン社製、グレード＃９５２、表面積３００ｍ２ ／ｇ）１４００ｇを加えた後、前記Ｂ溶液の全量を添加し、室温で撹拌した。ついで窒素ブローにて溶媒を除去して流動性の良い固体触媒粉末を得た。これを触媒Ｃとする。
【００４７】
試料Ａ１、Ａ２の重合
連続式の流動床気相法重合装置を用い、重合温度７０℃、全圧２０ｋｇｆ／ｃｍ２ Ｇでエチレンと１−ブテンの共重合を行った。前記触媒Ｃを連続的に供給して重合を行ない、系内のガス組成を一定に保つため、各ガスを連続的に供給しながら重合を行った。なお、試料量が足りない場合はこれらの操作を繰り返して必要量を得た。
また、生成した共重合体の物性は以下の通りである。
試料Ｂ１、Ｂ２の重合
Ｂ１は三塩化バナジルーエチルアルミニウムセスキクロリド系触媒を用いて共重合させたエチレンープロピレン共重合体ゴムである。共重合ゴムのムーニー粘度（ＭＬ１＋４ 、１００℃）は７３であり、プロピレン含有量は２６重量％、密度は０．８６２ｇ／ｃｍ３ であった。
Ｂ２は三塩化バナジルーエチルアルミニウムセスキクロリド系触媒を用いて、エチレン、プロピレンおよびエチリデンノルボルネン（ＥＮＢ）を共重合させた共重合ゴムである。共重合ゴムのムーニー粘度（ＭＬ１＋４ 、１００℃）は９０であり、プロピレン含有量は２７重量％、密度は０．８６３ｇ／ｃｍ３ 、共重合体ゴム中のＥＮＢ含有量はヨウ素価に換算して１６であった。
【００４９】
（実施例１〜５）
本発明の効果を調べたもので、表１に示した成分を加えペレット化し、前記の方法で各種試験を行った。その結果を表１に併せて示した。
【００５０】
（比較例１）
実施例１のエチレン・１−ブテン共重合体の代わりに、エチレンと１−ブテンを通常のチグラー系触媒で共重合させてＭＦＲ：０．９ｇ／１０ｍｉｎ 、密度：０．９００ｇ／ｃｍ３ とした直鎖状低密度ポリエチレンＡ３を用いた以外は実施例１と同様に行った。結果を表１に示す．強度が弱く、永久のびが大きい。
（比較例２）
実施例２のエチレン・１−ブテン共重合体の代わりに、エチレンと１−ブテンを通常のチグラー系触媒で共重合させてＭＦＲ：０．９ｇ／１０ｍｉｎ 、密度：０．９００ｇ／ｃｍ３ とした直鎖状低密度ポリエチレンＡ３を用いた以外は実施例２と同様に行った。結果を表１に示す。永久伸びが大きい。
（比較例３）
実施例２のエチレン・１−ブテン共重合体の代わりに、エチレンと１−ブテンを通常のチグラー系触媒で共重合させてＭＦＲ：１．０ｇ／１０ｍｉｎ 、密度：０．９２０ｇ／ｃｍ３ とした直鎖状低密度ポリエチレンＡ４を用いた以外は実施例２と同様に行った。結果を表１に示す。引張伸びが小さいが、永久伸びが大きい。
（比較例４）
実施例２で使用したエチレン・１−ブテン共重合体単独の各種物性を表１に示した。柔軟性がなく、永久伸びも大きい。
（比較例５）
実施例２で使用したエチレンープロピレンーＥＮＢ共重合体ゴム単独の各種物性を表１に示した。強度が弱い。
【００５１】
（実施例６）
本発明の部分架橋したものの効果を調べたもので、表２に示した成分に架橋剤としてジ（ｔ−ブチルパーオキシ）ジプロピルベンゼンを０．１重量部、酸化防止剤としてイルガノックス１０１０（商品名、チバガイギー社製）０．１重量部、滑剤としてステアリン酸カルシウム０．１重量部（重量部はいずれも全重合体１００重量部に対する）をドライブレンドしたのち、２００℃に予熱したバンパリーミキサーに投入し、１０分間混練し、熱可塑性エラストマー組成物を得た。そして、前記の方法で各種試験を行った．その結果を表２に併せて示した。架橋剤を加えていない実施例２と比べるとゲル分率が多く、耐油性が優れている。
（比較例６）
実施例６のエチレン・１−ブテン共重合体の代わりに、エチレンと１−ブテンを通常のチグラー系触媒で共重合させてＭＦＲ：０．９ｇ／１０ｍｉｎ 、密度：０．９００ｇ／ｃｍ３ とした直鎖状低密度ポリエチレンＡ３を用いた以外は実施例６と同様に行った。結果を表２に示す。永久伸びが大きく、架橋による強度の低下が大きい。
【００５２】
【表１】
【表２】
【表３】
【表４】
【発明の効果】
分子量分布が狭く、組成分布が適度な広さを有する特定のエチレン（共）重合体およびエチレン・αーオレフィン共重合体ゴムを配合することにより柔軟性に富み、流動性、引張特性、衝撃強度、耐熱性、耐油性に優れ、ベタつきの少ない、繰り返し疲労にも耐える熱可塑性エラストマー組成物を提供することが可能となる。また、さらにこれらの組成物を部分架橋することにより、更に耐熱性と耐油性が向上した熱可塑性エラストマー組成物を提供できる。
本発明の熱可塑性エラストマー組成物は上記のような優れた特性を有していることから、バンパー、マッドガード、内装表皮材などの自動車部品、家電、各種パッキン、建築用ガスケット、遮音材料などの土木建築、文房具などの日用雑貨類などの用途に幅広く応用できる。
【図面の簡単な説明】
【図１】本発明で用いる共重合体のＴＲＥＦ曲線である。
【図２】メタロセン共重合体のＴＲＥＦ曲線である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a thermoplastic elastomer composition that is rich in flexibility, excellent in fluidity, tensile properties, impact strength, heat resistance, oil resistance, and resistant to repeated fatigue. More specifically, the present invention relates to a thermoplastic elastomer composition containing a specific ethylene (co) polymer and an ethylene / α-olefin copolymer rubber.
[0002]
[Prior art]
Polyolefin thermoplastic elastomers include amorphous polyolefins such as ethylene-propylene copolymer rubber (EPR) and ethylene-propylene-nonconjugated diene copolymer rubber (EPDM) with crystalline polyolefins such as polyethylene and polypropylene as hard segments. Known are blends obtained by using a copolymer copolymer rubber for each soft segment, or compositions obtained by partially crosslinking these blends. In addition, a method for producing them directly by multistage polymerization is also known. Various grades of products are manufactured, from those that are flexible to those that are rigid by changing the proportion of each segment.
The flexible grade is attracting a great deal of attention because it can be widely applied as a rubber material to automotive parts, home appliances, civil engineering and construction, daily necessities. When manufacturing such flexible grades, in order to give rubber-like flexibility, the proportion of soft segments (such as EPR and EPDM) is increased and the proportion of hard segments (such as polyethylene and polypropylene) is decreased. There is a need to.
However, since soft segments such as EPR and EPDM have low tensile strength and poor heat resistance, oil resistance, fluidity, etc., flexible thermoplastic elastomers containing many such soft segments are still Because of such disadvantages, it cannot be used for various purposes. Increasing the proportion of hard segments to ameliorate these problems loses flexibility and loses its characteristics as a flexible thermoplastic elastomer.
In order to solve these problems, ultra-low density linear polyethylene using a Ziegler catalyst is mixed with the hard segment (for example, JP-A-61-233032). However, ultra-low density linear polyethylene has a high degree of branching and low molecular weight components, and elution into the contents increases, resulting in stickiness, durability against repeated deformation and mechanical properties still not being sufficiently obtained. The composition has not necessarily been satisfactorily improved.
[0003]
[Problems to be solved by the invention]
The object of the present invention is to satisfy these requirements. Particularly, it is rich in flexibility, excellent in fluidity, tensile properties, impact strength, heat resistance and oil resistance, has little stickiness, and is durable against repeated deformation. The object is to provide a good thermoplastic elastomer composition.
[0004]
[Means for Solving the Problems]
As a result of intensive investigations in line with the above-mentioned purpose, the present inventors have a novel composition having a relatively wide composition distribution and a low content of low molecular weight components and an amorphous part even though the molecular weight distribution is narrow. By using an ethylene (co) polymer (A) as a hard segment, the above object was achieved.
[0005]
That is, the first of the present invention is
(A) It is obtained by homopolymerizing ethylene or copolymerizing ethylene and α-olefin in the presence of a catalyst containing an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table, 10 to 90% by weight of ethylene (co) polymer satisfying the following (a) to (f)
(A) Density 0.86-0.96 g / cm3
(B) Melt flow rate (MFR) 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) 1.5 to 4.5
(D) Composition distribution parameter Cb 1.08 to 2.00
(E) Amount of orthodichlorobenzene (ODCB) soluble at 25 ° C
X (wt%), density d, and MFR satisfy the following relationship:
A) When d−0.008 × logMFR ≧ 0.93
X <2.0
B) In the case of d−0.008 × log MFR <0.93
X <9.8 × 103× (0.9300 -d +0.008 × log MFR)2+2.0 (Formula 1)
(F) There are a plurality of peaks in the elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF), and
(B) A thermoplastic elastomer composition comprising 90 to 10% by weight of ethylene / α-olefin copolymer rubber.
The second aspect of the present invention is
It is obtained by partially crosslinking the composition comprising (A) 10 to 90% by weight of ethylene (co) polymer and (B) 90 to 10% by weight of ethylene / α-olefin copolymer rubber described in the first invention. This is a thermoplastic elastomer resin composition.
[0006]
Hereinafter, the present invention will be described in more detail.
The (A) ethylene (co) polymer of the present invention includes an ethylene homopolymer or a copolymer of ethylene and one or more selected from ethylene and an α-olefin having 3 to 20 carbon atoms. The α-olefin having 3 to 20 carbon atoms is preferably one having 3 to 12 carbon atoms, specifically, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene. , 1-decene, 1-dodecene and the like. In addition, the total content of these α-olefins is usually 30 mol% or less, preferably 20 mol% or less.
[0007]
The density (a) of the (A) ethylene (co) polymer of the present invention varies depending on the required characteristics of the application, but is 0.86 to 0.96 g / cm.3Range. For example, the density is 0.92 g / cm for applications that particularly require heat resistance and rigidity.3The above are preferably used, and 0.92 g / cm for applications that particularly require flexibility and impact resistance.3The following are preferably used. In general, preferably 0.87 to 0.93 g / cm.3, More preferably 0.87 to 0.91 g / cm3Range. Density is 0.86 g / cm3If it is less than that, the rigidity and heat resistance are inferior, and the surface of the composition becomes sticky and causes problems. 0.96 g / cm3Exceeding this is undesirable because mechanical strength such as flexibility, impact resistance, and tensile strength decreases.
[0008]
The MFR (b) of the (A) ethylene (co) polymer of the present invention is 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min. In addition, when MFR is less than 0.01 g / 10min, MFR of a composition is too low, fluidity | liquidity will worsen, and moldability will worsen. When it exceeds 100 g / 10 min, mechanical strength such as impact resistance and tensile strength is lowered.
[0009]
The calculation method of molecular weight distribution Mw / Mn (c) of (A) ethylene (co) polymer of the present invention is the weight average molecular weight (Mw) and number average molecular weight (Mn) determined by gel permeation chromatography (GPC). The ratio Mw / Mn is obtained.
The Mw / Mn of the ethylene / α-olefin copolymer of the present invention is 1.5 to 4.5, preferably 1.5 to 3.5, more preferably 2.0 to 3.0, and even more preferably 2. Desirably, it is in the range of 2 to 2.9. If Mw / Mn is less than 1.5, the moldability is inferior, and if it exceeds 4.5, the impact resistance is inferior or stickiness occurs.
[0010]
The composition distribution parameter Cb (d) of the (A) ethylene (co) polymer of the present invention is in the range of 1.08 to 2.00, preferably 1.10 to 1.80, more preferably 1.12 to 1. The range is 70. If the Cb value exceeds 2.00, impact resistance, tensile characteristics, durability against repeated deformation, deterioration of environmental stress resistance, stickiness of the molded product, and thermal shrinkage may increase. In the copolymer, if the Cb value is less than 1.08, the heat resistance may be lowered.
[0011]
The method for measuring the composition distribution parameter Cb (d) of the ethylene (co) polymer of the present invention is as follows.
[0012]
A heat-resistant stabilizer is added to the sample and dissolved in ODCB by heating at 135 ° C. so that the sample concentration becomes 0.2% by weight. This heated solution is transferred to a column filled with diatomaceous earth (Celite 545), and after filling, cooled to 25 ° C. at 0.1 ° C./min to deposit the sample on the celite surface. Next, a solution in which the sample is dissolved is collected at each temperature while ODCB is allowed to flow through the column at a constant flow rate and the column temperature is raised stepwise to 120 ° C. in steps of 5 ° C. After cooling this solution, the sample is reprecipitated with methanol, filtered and dried to obtain samples at each elution temperature. The weight fraction and the degree of branching (number of branches per 1000 carbon atoms) of the sorted sample are measured. The degree of branching is determined by 13C-NMR.
[0013]
For each fraction collected at 30 ° C. to 90 ° C. by such a method, the degree of branching is corrected as follows. That is, the degree of branching measured against the elution temperature is plotted, the correlation is approximated to a straight line by the method of least squares, and a calibration curve is created. This approximate correlation coefficient is sufficiently large. The value obtained from this calibration curve is taken as the degree of branching of each fraction. For the fraction collected at an elution temperature of 95 ° C. or higher, the linear relationship is not necessarily established between the elution temperature and the degree of branching, so this correction is not performed.
[0014]
Next, the weight fraction w of each fractioniThe degree of branching per elution temperature of 5 ° C.iChange amount (bi-Bi-1) Divided by relative concentration ciAnd plot the relative concentration against the degree of branching to obtain a composition distribution curve. This composition distribution curve is divided by a certain width, and the composition distribution parameter Cb is calculated from the following equation.
[Expression 1]
[0015]
Many proposals have been made for a method for describing the composition distribution of an ethylene (co) polymer. For example, in Japanese Patent Laid-Open No. 60-88016, numerical processing is performed on the assumption that the cumulative weight fraction has a specific distribution (logarithmic normal distribution) with respect to the number of branches of each fractionated sample obtained by solvent fractionation of the sample. The ratio of the weight average branching degree (Cw) and the number average branching degree (Cn) is obtained. This approximate calculation is less accurate when the number of sample branches and the cumulative weight fraction deviate from the logarithmic normal distribution, and the correlation coefficient R2 is considerably low when measurements are performed on commercially available LLDPE, and the accuracy of the values is not sufficient. The definition and measurement method of Cw / Cn and Cb of the present invention are different.
[0016]
The ODCB soluble amount X (e) of the ethylene (co) polymer of the present invention at 25 ° C. indicates the ratio of the high branching component and the low molecular weight component contained in the ethylene (co) polymer. It is desirable that the amount is small because it causes a decrease in heat resistance and stickiness of the surface of the molded product. The amount of ODCB solubles is affected by the α-olefin content and average molecular weight of the entire copolymer, ie density and MFR. Therefore, the amount X (% by weight) of the ODCB-soluble component is less than 2% by weight, preferably less than 1% by weight when the relationship between density d and MFR satisfies d−0.008 × log MFR ≧ 0.93. More preferably, it is less than 0.5% by weight.
Further, when the relationship between d and MFR satisfies d−0.008 × log MFR <0.93, X <9.8 × 103× (0.9300 -d +0.008 × log MFR)2+2.0, preferably X <7.4 × 103× (0.9300 -d +0.008 × log MFR)2+1.0, more preferably X <5.6 × 103× (0.9300 -d +0.008 × log MFR)2A range of +0.5 is desirable.
The fact that the density, MFR and ODCB soluble content satisfy the above relationship indicates that the α-olefin contained in the entire copolymer is not ubiquitous.
[0017]
The ODCB soluble amount X at 25 ° C. is measured by the following method.
That is, 0.5 g of the sample is added to 20 ml of ODCB and heated at 135 ° C. for 2 hours to completely dissolve the sample, and then cooled to 25 ° C. The solution is allowed to stand at 25 ° C. overnight and then filtered through a Teflon filter to collect the filtrate. The filtrate, which is a sample solution, was subjected to an asymmetric stretching vibration wave number of methylene of 2925 cm using an infrared spectrometer.-1The absorption peak intensity in the vicinity is measured, and the sample concentration in the filtrate is calculated using a calibration curve prepared in advance. From this value, the ODCB soluble content at 25 ° C. is determined.
[0018]
The ethylene (co) polymer of the present invention needs to have a plurality of peaks (f) in the elution temperature-elution amount curve determined by the continuous temperature rising elution fractionation method (TREF), and the peak on the higher temperature side is 85. It is particularly preferred that it is present between 0 ° C and 100 ° C. The presence of this peak increases the melting point, increases the crystallinity, and improves the heat resistance and rigidity of the molded body. FIG. 1 shows an elution temperature-elution amount curve of the copolymer of the present invention. FIG. 2 is an elution temperature-elution amount curve of a copolymer by a so-called commercially available metallocene catalyst, and both are remarkably different.
[0019]
The method for measuring TREF according to the present invention is as follows. A heat-resistant stabilizer is added to the sample, and dissolved in ODCB by heating at 135 ° C. to a sample concentration of 0.05% by weight. After 5 ml of this heated solution is injected into a column filled with glass beads, it is cooled to 25 ° C. at a cooling rate of 0.1 ° C./min, and the sample is deposited on the surface of the glass beads. Next, while flowing ODCB through this column at a constant flow rate, the column temperature is raised at a constant rate of 50 ° C./hr, and samples that can be dissolved in the solution are sequentially eluted at each temperature. At this time, the sample concentration in the solvent was 2925 cm, the wave number of asymmetric stretching vibration of methylene.-1Is continuously detected by an infrared detector. From this concentration, an elution temperature-elution amount curve can be obtained.
TREF analysis is a very small amount of sample, and since it is possible to continuously analyze changes in elution rate with respect to temperature changes, relatively fine peaks that cannot be detected by the fractionation method can be detected.
[0020]
In the production of the (A) ethylene (co) polymer of the present invention, at least in the presence of a catalyst containing an organic cyclic compound having a conjugated double bond and a group IV transition metal compound, ethylene alone or ethylene and This is carried out by (co) polymerizing an α-olefin having 3 to 20 carbon atoms. In particular, the catalyst components (2) and (4) shown below are brought into contact with the following (1) a transition metal compound of Group IV of the periodic table and (3) an organic cyclic compound having a conjugated double bond. It is desirable to (co) polymerize with the resulting catalyst.
That is, (1): General formula Me1R1 pR2 q(OR3)rX1 4-pqrA transition metal compound of Group IV of the periodic table (wherein Me1Represents zirconium, titanium, hafnium, R1And R3Individually represent a hydrocarbon group having 1 to 24 carbon atoms or a trialkylsilyl group, R2Represents a derivative such as a 2,4-pentanedionate ligand or a derivative thereof, or a dibenzoylmethanato ligand or a benzoylacetonate ligand, X1Represents a halogen atom, and p, q, and r are integers satisfying the ranges of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4, and 0 ≦ p + q + r ≦ 4), (2): General Formula Me2R4 m(OR5)nX2 z-mnA compound represented by the formula:2Is a group I-III element of the periodic table, R4And R5Are each a hydrocarbon group having 1 to 24 carbon atoms, X2Is a halogen atom or a hydrogen atom (however, X2Me is a hydrogen atom2Is limited to a group III element in the periodic table), z is Me2M and n are integers satisfying the ranges of 0 ≦ m ≦ z, 0 ≦ n ≦ z, and 0 ≦ m + n ≦ z), (3): an organic ring having a conjugated double bond Compound (4): A catalyst obtained by bringing a modified organoaluminum compound and / or boron compound containing an Al—O—Al bond into contact with each other.
[0021]
General formula Me of the catalyst component (1)1R1 pR2 q(OR3)rX1 4-pqrIn the formula of the compound represented by1Represents zirconium, titanium and hafnium. The type of these transition metals is not limited, and a plurality of transition metals can be used, but it is particularly preferable that zirconium having excellent weather resistance of the copolymer is included. R1And R3Are each a hydrocarbon group having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. Alkyl group; alkenyl group such as vinyl group and allyl group; aryl group such as phenyl group, tolyl group, xylyl group, mesityl group, indenyl group and naphthyl group; benzyl group, trityl group, phenethyl group, styryl group, benzhydryl group, Examples thereof include aralkyl groups such as phenylbutyl group and neofoyl group. These may be branched. R2Is a 2,4-pentanedionato ligand or its derivative (CH3COCHCOCH3Or a derivative such as a dibenzoylmethanato ligand or a benzoylacetonato ligand. X1Represents a halogen atom such as fluorine, iodine, chlorine and bromine, and p, q and r are in a range of 0 ≦ p ≦ 4, 0 ≦ q ≦ 4, 0 ≦ r ≦ 4 and 0 ≦ p + q + r ≦ 4, respectively.
[0022]
Examples of the compound represented by the above general formula (1) are tetramethylzirconium, tetraethylzirconium, tetrabenzylzirconium, tetrapropoxyzirconium, tripropoxymonochlorozirconium, dipropoxydichlorozirconium, tetrabutoxyzirconium, tributoxymonochlorozirconium. , Dibutoxydichlorozirconium, tetrabutoxytitanium, tetrabutoxyhafnium and the like, and specific examples of the 2,4-pentanedionate ligand or derivatives thereof include tetra (2,4-pentanedionato ) Zirconium, tri (2,4-pentanedionato) chloride zirconium, di (2,4-pentanedionato) diethoxide zirconium, di (2,4-pentandedionato) di-n- Lopoxide zirconium, di (2,4-pentanedionato) di-n-butoxide zirconium, di (2,4-pentanedionato) dibenzylzirconium, di (2,4-pentandedionato) dineo Zirconium, tetra (dibenzoylmethanato) zirconium, di (dibenzoylmethanato) diethoxide zirconium, di (dibenzoylmethanato) di-n-propoxidezirconium, di (benzoylacetonato) diethoxide zirconium , Di (dibenzoylacetonate) di-n-propoxide zirconium and the like, and a mixture of two or more of these may be used.
[0023]
General formula Me of the catalyst component (2)2R4 m(OR5)nX2 z-mnIn the formula of the compound represented by2Represents Group I to III elements of the Periodic Table, such as lithium, sodium, potassium, magnesium, calcium, zinc, boron, and aluminum. R4And R5Are each a hydrocarbon group having 1 to 24 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and butyl. Alkyl groups such as vinyl groups; alkenyl groups such as vinyl groups and allyl groups; aryl groups such as phenyl groups, tolyl groups, xylyl groups, mesityl groups, indenyl groups, naphthyl groups; benzyl groups, trityl groups, phenethyl groups, styryl groups, Examples thereof include aralkyl groups such as a benzhydryl group, a phenylbutyl group and a neofoyl group. These may be branched. X2Represents a halogen atom or a hydrogen atom of fluorine, iodine, chlorine and bromine. However, X2Me is a hydrogen atom2Is limited to the group III elements of the periodic table exemplified by boron, aluminum and the like. Z is Me2M and n are integers satisfying the ranges of 0 ≦ m ≦ z and 0 ≦ n ≦ z, respectively, and 0 ≦ m + n ≦ z.
[0024]
Examples of the compound represented by the general formula of the catalyst component (2) include organic lithium compounds such as methyl lithium and ethyl lithium; organic magnesium compounds such as dimethyl magnesium, diethyl magnesium, methyl magnesium chloride, and ethyl magnesium chloride; dimethyl zinc Organic zinc compounds such as diethylzinc; organoboron compounds such as trimethylboron and triethylboron; trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, tridecylaluminum, diethylaluminum chloride, ethylaluminum dichloride, Ethyl aluminum sesquichloride, diethyl aluminum ethoxide, diethyl aluminum hydride And organic aluminum compounds such as.
[0025]
As the organic cyclic compound having a conjugated double bond of the catalyst component (3), 1 ring having 2 or more, preferably 2 to 4 and more preferably 2 to 3 cyclic double-conjugated double bonds. A cyclic hydrocarbon compound having 1 or 2 carbon atoms and a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon compound is partially composed of 1 to 6 hydrocarbon residues (typically , A cyclic hydrocarbon compound substituted with an alkyl group or aralkyl group having 1 to 12 carbon atoms; a ring having 2 or more, preferably 2 to 4, more preferably 2 to 3 conjugated double bonds An organosilicon compound having a cyclic hydrocarbon group having 1 or 2 or more and a total carbon number of 4 to 24, preferably 4 to 12; the cyclic hydrocarbon group partially has 1 to 6 hydrocarbon residues Group or alkali metal salt (sodium or Organosilicon compounds substituted with lithium salt) is included. Particularly preferred is one having a cyclopentadiene structure in any of the molecules.
[0026]
Suitable examples of the compound include cyclopentadiene, indene, azulene, or alkyl, aryl, aralkyl, alkoxy or aryloxy derivatives thereof. Moreover, the compound which these compounds couple | bonded (bridge | crosslinked) via the alkylene group (The carbon number is 2-8 normally, Preferably 2-3) is also used suitably.
[0027]
The organosilicon compound having a cyclic hydrocarbon group can be represented by the following general formula.
ALSiR6 4-L
Here, A represents the cyclic hydrogen group exemplified by a cyclopentadienyl group, a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group, and R6Is an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group or a butyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; an aryl group such as a phenyl group; an aryloxy group such as a phenoxy group A hydrocarbon residue or hydrogen having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, represented by an aralkyl group such as a benzyl group, and L is 1 ≦ L ≦ 4, preferably 1 ≦ L ≦ 3.
[0028]
Specific examples of the organic cyclic hydrocarbon compound of the component (3) include cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene, 1,3-dimethylcyclopentadiene, indene, 4-methyl-1-indene, 4,7-dimethylindene, Cyclopolyene having 5 to 24 carbon atoms such as cycloheptatriene, methylcycloheptatriene, cyclooctatetraene, azulene, fluorene, methylfluorene or substituted cyclopolyene, monocyclopentadienylsilane, biscyclopentadienylsilane, Examples include triscyclopentadienylsilane, monoindenylsilane, bisindenylsilane, and trisindenylsilane.
[0029]
The modified organoaluminum compound containing the Al—O—Al bond of the catalyst component (4) is preferably a modified organoaluminum usually called aluminoxane obtained by reacting an alkylaluminum compound with water, and this is in the molecule. Usually, it contains 1 to 100, preferably 1 to 50 Al—O—Al bonds. The modified organoaluminum compound may be linear or cyclic.
[0030]
The reaction between organoaluminum and water is usually carried out in an inert hydrocarbon. As the inert hydrocarbon, aliphatic, alicyclic or aromatic hydrocarbons such as pentane, hexane, heptane, cyclohexane, benzene, toluene and xylene are preferable.
The reaction ratio (water / Al molar ratio) between water and the organoaluminum compound is usually 0.25 / 1 to 1.2 / 1, preferably 0.5 / 1 to 1/1.
[0031]
Specific examples of boron compounds include triethylammonium tetra (pentafluorophenyl) borate (triethylammonium tetra (pentafluorophenyl) borate), dimethylanilinium tetra (pentafluorophenyl) borate (dimethylanilinium tetra (penta Fluorophenyl) borate), butylammonium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (pentafluorophenyl) borate, N, N-dimethylanilinium tetra (3,5-difluorophenyl) borate, etc. Can be mentioned.
[0032]
In the present invention, the catalyst obtained by bringing the catalyst components (1) to (4) into contact with each other can be supported on an inorganic carrier and / or a particulate polymer carrier (5) and used for the polymerization reaction. . As long as the inorganic carrier of component (5) retains its original shape in the stage of preparing the catalyst of the present invention, it may be any shape such as powder, granule, flake, foil, and fiber. However, in any shape, the maximum length is usually in the range of 5 to 200 μm, preferably 10 to 100 μm. The inorganic carrier is preferably porous, and usually has a surface area of 50 to 1000 m.2/ G, pore volume is 0.05-3 cm3/ G.
As the inorganic carrier of the present invention, carbonaceous materials, metals, metal oxides, metal chlorides, metal carbonates or mixtures thereof can be used. These are usually in the air at 200 to 900 ° C. or in the form of nitrogen, argon or the like. Used by firing in an inert gas.
[0033]
Suitable metals that can be used for the inorganic carrier include iron, aluminum, nickel and the like. In addition, examples of the metal oxide include single oxides or composite oxides of groups I to VIII of the periodic table.2, Al2O3, MgO, CaO, B2O3TiO2, ZrO2, Fe2O3, SiO2-Al2O3, Al2O3-MgO, Al2O3-CaO, Al2O3-MgO-CaO, Al2O3-MgO-SiO2, Al2O3-CuO, Al2O3-Fe2O3, Al2O3-NiO, SiO2-MgO etc. are mentioned. In addition, said formula represented with the oxide shows not a molecular formula but only a composition. That is, the structure and component ratio of the double oxide used in the present invention are not particularly limited. In addition, the metal oxide used in the present invention may adsorb a small amount of moisture or may contain a small amount of impurities.
[0034]
As the metal chloride, for example, an alkali metal or alkaline earth metal chloride is preferable, and specifically, MgCl.2, CaCl2Etc. are particularly suitable. As the metal carbonate, carbonates of alkali metals and alkaline earth metals are preferable, and specific examples include magnesium carbonate, calcium carbonate, barium carbonate and the like. Examples of the carbonaceous material include carbon black and activated carbon.
Any of the above inorganic carriers can be suitably used in the present invention, but the use of metal oxides such as silica and alumina is particularly preferred.
[0035]
On the other hand, as the particulate polymer carrier, any one of a thermoplastic resin and a thermosetting resin can be used as long as it is kept in a solid state without melting during the catalyst preparation and the polymerization reaction. Is usually in the range of 5 to 2000 μm, preferably 10 to 100 μm. The molecular weight of these polymer carriers is not particularly limited as long as the polymer can be present as a solid substance at the time of catalyst preparation and polymerization reaction, and can be arbitrarily selected from low molecular weight to ultra high molecular weight. Can be used.
Specifically, various polyolefins (preferably having 2 to 12 carbon atoms) represented by particulate ethylene polymer, ethylene / α-olefin copolymer, propylene polymer or copolymer, poly-1-butene, polyester, and the like , Polyamide, polyvinyl chloride, poly (meth) acrylate methyl, polystyrene, polynorbornene, various natural polymers, and mixtures thereof.
[0036]
The inorganic carrier and / or the particulate polymer carrier can be used as they are, but preferably, as a pretreatment, these carriers are contacted with an organoaluminum compound or a modified organoaluminum compound containing an Al—O—Al bond. After that, it can also be used as component (5).
[0037]
The (A) ethylene (co) polymer of the present invention is produced by a gas phase method, a slurry method, a solution method or the like, and is not particularly limited, such as a one-stage polymerization method or a multi-stage polymerization method.
By using the ethylene (co) polymer (A) that is polymerized by the above method and satisfies the above (a) to (f), the balance of flexibility, mechanical strength, and heat resistance is good, and for repeated use. It becomes a composition excellent in durability. Moreover, when partially crosslinked using a crosslinking agent, there is little decrease in mechanical strength, and heat resistance and oil resistance are improved.
[0038]
The (B) ethylene / α-olefin copolymer rubber of the present invention is an ethylene / α-olefin copolymer rubber or an ethylene / α-olefin / non-conjugated diene copolymer rubber, and these copolymer rubbers are amorphous. It is a copolymer. Examples of the α-olefin in the ethylene / α-olefin copolymer rubber component include propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene. Particularly preferred is propylene. Non-conjugated dienes include 1,4-hexadiene, 1,6-octadiene, dicyclopentadiene, vinyl norbornene, ethylidene norbornene and the like. Preferred are 1,4-hexadiene and ethylidene norbornene.
[0039]
(B) Mooney viscosity (ML) of ethylene / α-olefin copolymer rubber1 + 4, 100 ° C.) is preferably about 10 to 95. When the Mooney viscosity of the ethylene / α-olefin copolymer rubber is less than 10, it is not preferable because the tensile strength of the thermoplastic elastomer composition is lowered or the surface is sticky. If the Mooney viscosity exceeds 95, the fluidity of the thermoplastic elastomer composition deteriorates, which is not preferable.
[0040]
Composition of ethylene (co) polymer (A) (hereinafter referred to as component (A)) and ethylene / α-olefin copolymer rubber (B) (hereinafter referred to as component (B)) in the thermoplastic elastomer composition of the present invention The proportion of the component (A) is 10 to 90% by weight, preferably 25 to 75% by weight, and the component (B) is 90 to 10% by weight, preferably 75 to 25% by weight.
When the component (A) exceeds 90% by weight, the flexibility is lost, and when it is less than 10% by weight, the appropriate rigidity is lost, the tensile strength is lowered, and the oil resistance is deteriorated.
[0041]
The thermoplastic elastomer of the present invention is used by partially crosslinking, particularly when it is used with improved heat resistance and oil resistance. Partial cross-linking refers to cross-linking a part of the composition, and partial cross-linking using a cross-linking agent while maintaining fluidity.
Any known technique can be used as a method for producing the partially crosslinked product. A typical example is a method of adding a cross-linking agent to the above composition and performing mechanical melt-kneading, and partially cross-linking using a single and twin screw extruder, a Banbury mixer, various kneaders, rolls and the like. it can. The temperature of melt kneading is generally 300 ° C. or lower, preferably 100 to 300 ° C., usually at a temperature at which the half-life of the crosslinking agent used is 1 minute or shorter. Further, after mixing the crosslinking agent by impregnation or the like, it may be partially crosslinked by heat or radiation.
[0042]
As the cross-linking agent, an organic peroxide is usually used. Specifically, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, di-t-butyl peroxide, di (t-butylperoxy) diisopropylbenzene, di (t-butylperoxy) diisobutyl Benzene, dicumyl peroxide, t-butyl cumyl peroxide, t-butyl peroxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl peroxide, benzoyl peroxide, p-chloro Examples include benzoyl peroxide. Moreover, you may use a crosslinking adjuvant. Specific examples include liquid polybutadiene, divinylbenzene, ethylene dimethacrylate, diallyl phthalate, and the like.
The amount of the crosslinking agent used is 0.005 to 3% by weight, preferably 0.05 to 1% by weight, based on the resin component. Since the usage-amount of a crosslinking agent is determined by the performance requested | required of a crosslinking composition, it is not necessarily limited to these numbers. Several kinds of crosslinking agents and crosslinking assistants may be used in combination depending on the purpose.
The boiling xylene insoluble fraction (gel fraction) measured by extracting the thermoplastic elastomer composition of the present invention obtained by partial crosslinking in this way with boiling xylene for 5 hours is 0.5 to 60% by weight, Preferably it is 2 to 50 weight%. When the gel fraction is less than 0.5% by weight, oil resistance and the like are lowered, and when the gel fraction is more than 60% by weight, the tensile strength and elongation are lowered, which is not desirable.
[0043]
In the present invention, various fillers such as carbon black, calcium carbonate, silica, metal fibers, carbon fibers, antioxidants, flame retardants, lubricants, etc., as long as the characteristics intended in the present invention are not essentially impaired. , Known additives such as antistatic agents, antifogging agents, pigments, UV absorbers, dispersants, and paraffinic, naphthenic or aromatics for the purpose of helping to disperse fillers and increase flexibility and elasticity. You may mix | blend vegetable oil etc. as needed. When performing partial cross-linking, the above additives may be blended as necessary before and after cross-linking or during cross-linking (particularly during melt kneading).
Furthermore, in a range that does not substantially impair the properties intended in the present invention, crystalline polyolefins such as high-density polyethylene, low-density polyethylene, and linear low-density polyethylene, natural rubber, various synthetic rubbers, styrenic thermoplastic compositions, etc. These various resins and rubbers may be blended as necessary.
[0044]
The thermoplastic elastomer composition of the present invention is molded by injection molding, extrusion molding, hollow molding, inflation molding, T-die molding, etc., for example, bumpers, mud guards, interior skin materials for automobile parts, hoses, packings, etc. for home appliances. It is used for other construction gaskets, sound insulation materials, stationery, daily miscellaneous goods and the like. Further, the partially crosslinked composition is used for almost the same applications as these, but is used for applications requiring heat resistance and oil resistance.
[0045]
【Example】
EXAMPLES Next, although an Example demonstrates this invention in more detail, this invention is not limited by these.
The test methods used in this example are as follows.
(Physical property test method)
MFR: Conforms to JIS K6758.
Tensile test: compliant with JIS K6301. Test pieces were made using a No. 3 dumbbell and measured at a tensile speed of 50 mm / min. The strength at the time of tensile fracture was defined as tensile strength, and the elongation at that time was defined as tensile elongation.
Permanent elongation: Conforms to JIS K6301. A test piece was prepared using a No. 3 dumbbell, and the test piece was held for 10 minutes in a state where it was stretched 100%, rapidly contracted, and obtained from the elongation after standing for 10 minutes.
Vicat softening point: A sample having a thickness of 3 mm was prepared by pressing (210 ° C.) and used for measurement. While applying a 1 kg load through a needle-shaped indenter placed perpendicular to the test piece in the heated solution, the temperature of the heat transfer medium was increased at a rate of 50 ° C./60 minutes, and when the needle-shaped indenter entered 1 mm, The temperature was defined as the Vicat softening point.
Hardness: A test piece was prepared according to JIS K6301 and measured using an A type testing machine.
Oil resistance: A test piece was prepared according to JIS K6301 and the volume change at 70 ° C. for 22 hours was determined using JIS No. 3 oil.
Gel fraction: Using a hot press (190 ° C., 5 minutes), create a sheet having a thickness of 200 μm, cut out three 40 mm × 20 mm sheets, put them in a 120 mesh wire mesh bag, Extraction with boiling xylene for 5 hours using a double tube Soxhlet extractor. The boiling xylene insoluble matter is taken out, vacuum dried (80 ° C., 7 hours), and the boiling xylene insoluble matter is determined as a gel fraction.
[0046]
(Polymerization of ethylene / α-olefin copolymer)
Preparation of solid catalyst
Purified toluene was added to a catalyst preparation apparatus (No. 1) with an electromagnetic induction stirrer under nitrogen, and then dipropoxydichlorozirconium (Zr (OPr)2Cl2) 28 g and 48 g of methylcyclopentadiene were added, 45 g of tridecylaluminum was added dropwise while maintaining the system at 0 ° C., and after completion of the addition, the reaction system was maintained at 50 ° C. and stirred for 16 hours. Let this solution be A liquid. Next, purified toluene was added to another catalyst preparation device with a stirrer (No. 2) under nitrogen, and the solution A and then a toluene solution of methylaluminoxane 6.4 mol were added and reacted. This is B liquid.
Next, purified toluene was added to a preparator equipped with a stirrer (No. 1) under nitrogen, and then pre-treated for a predetermined time at 400 ° C. for silica (made by Fuji Devison, Grade # 952, surface area 300 m).2/ G) After adding 1400 g, the whole amount of the solution B was added and stirred at room temperature. Subsequently, the solvent was removed by nitrogen blowing to obtain a solid catalyst powder having good fluidity. This is referred to as catalyst C.
[0047]
Polymerization of samples A1 and A2
Using a continuous fluidized bed gas phase polymerization apparatus,
The physical properties of the produced copolymer are as follows.
Polymerization of samples B1 and B2
B1 is an ethylene-propylene copolymer rubber copolymerized using vanadyl trichloride aluminum aluminum sesquichloride catalyst. Mooney viscosity of copolymer rubber (ML1 + 4, 100 ° C.) is 73, the propylene content is 26% by weight, and the density is 0.862 g / cm.3Met.
B2 is a copolymer rubber obtained by copolymerizing ethylene, propylene and ethylidene norbornene (ENB) using a vanadyl triethylaluminum sesquichloride-based catalyst. Mooney viscosity of copolymer rubber (ML1 + 4, 100 ° C.) is 90, propylene content is 27 wt%, density is 0.863 g / cm3The ENB content in the copolymer rubber was 16 in terms of iodine value.
[0049]
(Examples 1-5)
The effects of the present invention were examined. The components shown in Table 1 were added to form pellets, and various tests were performed by the above-described methods. The results are also shown in Table 1.
[0050]
(Comparative Example 1)
Instead of the ethylene / 1-butene copolymer of Example 1, ethylene and 1-butene were copolymerized with an ordinary Ziegler-based catalyst to obtain MFR: 0.9 g / 10 min, density: 0.900 g / cm.3The same procedure as in Example 1 was conducted except that the linear low density polyethylene A3 was used. The results are shown in Table 1. The strength is weak and the permanent spread is large.
(Comparative Example 2)
Instead of the ethylene / 1-butene copolymer of Example 2, ethylene and 1-butene were copolymerized with a normal Ziegler-based catalyst to obtain MFR: 0.9 g / 10 min, density: 0.900 g / cm.3The same procedure as in Example 2 was performed except that the linear low density polyethylene A3 was used. The results are shown in Table 1. The permanent elongation is large.
(Comparative Example 3)
Instead of the ethylene / 1-butene copolymer of Example 2, ethylene and 1-butene were copolymerized with a normal Ziegler-based catalyst to obtain MFR: 1.0 g / 10 min, density: 0.920 g / cm.3The same procedure as in Example 2 was conducted except that the linear low density polyethylene A4 was used. The results are shown in Table 1. Although the tensile elongation is small, the permanent elongation is large.
(Comparative Example 4)
Various physical properties of the ethylene / 1-butene copolymer used in Example 2 are shown in Table 1. There is no flexibility and the permanent elongation is large.
(Comparative Example 5)
Various physical properties of the ethylene-propylene-ENB copolymer rubber used alone in Example 2 are shown in Table 1. The strength is weak.
[0051]
(Example 6)
The effect of the partially cross-linked product of the present invention was examined. In the components shown in Table 2, 0.1 part by weight of di (t-butylperoxy) dipropylbenzene as a cross-linking agent and Irganox 1010 (as an anti-oxidant) (Product name, manufactured by Ciba Geigy) 0.1 parts by weight and 0.1 parts by weight of calcium stearate as a lubricant (all parts are 100 parts by weight of the total polymer), and then pre-heated to 200 ° C. And kneaded for 10 minutes to obtain a thermoplastic elastomer composition. Various tests were conducted by the method described above. The results are also shown in Table 2. Compared to Example 2 in which no cross-linking agent was added, the gel fraction was high and the oil resistance was excellent.
(Comparative Example 6)
Instead of the ethylene / 1-butene copolymer of Example 6, ethylene and 1-butene were copolymerized with a normal Ziegler-based catalyst to obtain MFR: 0.9 g / 10 min, density: 0.900 g / cm.3The same procedure as in Example 6 was conducted except that the linear low density polyethylene A3 was used. The results are shown in Table 2. The permanent elongation is large, and the strength is greatly reduced by crosslinking.
[0052]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
【The invention's effect】
By blending specific ethylene (co) polymer and ethylene / α-olefin copolymer rubber with narrow molecular weight distribution and moderate composition distribution, it is rich in flexibility, fluidity, tensile properties, impact strength, It is possible to provide a thermoplastic elastomer composition that is excellent in heat resistance and oil resistance, has less stickiness, and can withstand repeated fatigue. Further, by partially cross-linking these compositions, a thermoplastic elastomer composition having further improved heat resistance and oil resistance can be provided.
Since the thermoplastic elastomer composition of the present invention has the above-mentioned excellent characteristics, it is a civil engineering such as automobile parts such as bumpers, mudguards, interior skin materials, home appliances, various packings, gaskets for construction, and sound insulation materials. It can be widely applied to daily goods such as architecture and stationery.
[Brief description of the drawings]
FIG. 1 is a TREF curve of a copolymer used in the present invention.
FIG. 2 is a TREF curve of a metallocene copolymer.
Claims (2)
（ａ）密度 ０．８６〜０．９６ｇ／ｃｍ３
（ｂ）メルトフローレート（ＭＦＲ） ０．０１〜１００ｇ／１０ｍｉｎ
（ｃ）分子量分布（Ｍｗ／Ｍｎ） １．５〜４．５
（ｄ）組成分布パラメーターＣｂ １．０８〜２．００
（ｅ）２５℃におけるオルソジクロロベンゼン（ＯＤＣＢ）可溶分の量
Ｘ（重量％）と密度ｄおよびＭＦＲが
イ）ｄ−０．００８ ×ｌｏｇＭＦＲ≧０．９３の場合
Ｘ＜２．０
ロ）ｄ−０．００８ ×ｌｏｇＭＦＲ＜０．９３の場合
Ｘ＜９．８ ×１０３ ×（０．９３００ −ｄ ＋０．００８ ×ｌｏｇ ＭＦＲ）２＋２．０（式１）
（ｆ）連続昇温溶出分別法（ＴＲＥＦ）による溶出温度ー溶出量曲線のピークが複数である、および
（Ｂ）エチレン・αーオレフィン共重合体ゴム９０〜１０重量％
からなることを特徴とする熱可塑性エラストマー樹脂組成物。(A) It is obtained by homopolymerizing ethylene or copolymerizing ethylene and α-olefin in the presence of a catalyst containing an organic cyclic compound having at least a conjugated double bond and a transition metal compound of Group IV of the periodic table, 10 to 90% by weight of ethylene (co) polymer satisfying the following (a) to (f)
(A) Density 0.86 to 0.96 g / cm 3
(B) Melt flow rate (MFR) 0.01-100 g / 10 min
(C) Molecular weight distribution (Mw / Mn) 1.5 to 4.5
(D) Composition distribution parameter Cb 1.08 to 2.00
(E) The amount X (wt%) of the orthodichlorobenzene (ODCB) soluble component at 25 ° C. and the density d and MFR a) d−0.008 × log MFR ≧ 0.93 X <2.0
B) In the case of d−0.008 × log MFR <0.93, X <9.8 × 10 3 × (0.9300 −d + 0.008 × log MFR) 2 +2.0 (Formula 1)
(F) Multiple peaks of elution temperature-elution amount curve by continuous temperature rising elution fractionation method (TREF), and (B) ethylene / α-olefin copolymer rubber 90-10% by weight
A thermoplastic elastomer resin composition comprising:
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| JP19432296A JP3607426B2 (en) | 1996-07-24 | 1996-07-24 | Thermoplastic elastomer resin composition |
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| JP19432296A JP3607426B2 (en) | 1996-07-24 | 1996-07-24 | Thermoplastic elastomer resin composition |
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