JP5972200B2 - Thermoplastic elastomer composition, molded article using the same, and use - Google Patents
Thermoplastic elastomer composition, molded article using the same, and use Download PDFInfo
- Publication number
- JP5972200B2 JP5972200B2 JP2013055695A JP2013055695A JP5972200B2 JP 5972200 B2 JP5972200 B2 JP 5972200B2 JP 2013055695 A JP2013055695 A JP 2013055695A JP 2013055695 A JP2013055695 A JP 2013055695A JP 5972200 B2 JP5972200 B2 JP 5972200B2
- Authority
- JP
- Japan
- Prior art keywords
- olefin
- thermoplastic elastomer
- propylene
- parts
- elastomer composition
- 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.)
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- 229920002725 thermoplastic elastomer Polymers 0.000 title claims description 80
- 239000000203 mixture Substances 0.000 title claims description 76
- 239000004711 α-olefin Substances 0.000 claims description 85
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 77
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 77
- 229920001971 elastomer Polymers 0.000 claims description 65
- 239000005060 rubber Substances 0.000 claims description 62
- 229920005604 random copolymer Polymers 0.000 claims description 60
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 52
- 239000005977 Ethylene Substances 0.000 claims description 52
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 37
- 150000001336 alkenes Chemical class 0.000 claims description 35
- 238000002844 melting Methods 0.000 claims description 30
- 229920001577 copolymer Polymers 0.000 claims description 29
- 230000008018 melting Effects 0.000 claims description 29
- 229920000098 polyolefin Polymers 0.000 claims description 27
- 238000004132 cross linking Methods 0.000 claims description 24
- 239000004088 foaming agent Substances 0.000 claims description 10
- 238000005187 foaming Methods 0.000 claims description 9
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 8
- 239000004902 Softening Agent Substances 0.000 claims description 8
- 239000004566 building material Substances 0.000 claims description 6
- 229920006285 olefinic elastomer Polymers 0.000 claims description 6
- 239000006260 foam Substances 0.000 claims description 4
- 229920005672 polyolefin resin Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 description 24
- -1 polypropylene Polymers 0.000 description 24
- 229920001155 polypropylene Polymers 0.000 description 18
- 238000000465 moulding Methods 0.000 description 16
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 14
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 12
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000010734 process oil Substances 0.000 description 10
- 238000011156 evaluation Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 150000001451 organic peroxides Chemical class 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 239000002667 nucleating agent Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 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 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 229920001038 ethylene copolymer Polymers 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 4
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 229940087101 dibenzylidene sorbitol Drugs 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 150000004291 polyenes Chemical class 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 3
- FMZUHGYZWYNSOA-VVBFYGJXSA-N (1r)-1-[(4r,4ar,8as)-2,6-diphenyl-4,4a,8,8a-tetrahydro-[1,3]dioxino[5,4-d][1,3]dioxin-4-yl]ethane-1,2-diol Chemical compound C([C@@H]1OC(O[C@@H]([C@@H]1O1)[C@H](O)CO)C=2C=CC=CC=2)OC1C1=CC=CC=C1 FMZUHGYZWYNSOA-VVBFYGJXSA-N 0.000 description 3
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 3
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 3
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 3
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 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 3
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000806 elastomer Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 239000002480 mineral oil Substances 0.000 description 3
- 235000010446 mineral oil Nutrition 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 229920001195 polyisoprene Polymers 0.000 description 3
- 229920001384 propylene homopolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000454 talc Substances 0.000 description 3
- 229910052623 talc Inorganic materials 0.000 description 3
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 3
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- GRWZFPFQSHTXHM-UHFFFAOYSA-N 11-methyldodec-1-ene Chemical compound CC(C)CCCCCCCCC=C GRWZFPFQSHTXHM-UHFFFAOYSA-N 0.000 description 2
- LPWUGKDQSNKUOQ-UHFFFAOYSA-N 12-ethyltetradec-1-ene Chemical compound CCC(CC)CCCCCCCCCC=C LPWUGKDQSNKUOQ-UHFFFAOYSA-N 0.000 description 2
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 2
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 2
- QNJMAPUHMGDDBE-UHFFFAOYSA-N 9-methyldec-1-ene Chemical compound CC(C)CCCCCCC=C QNJMAPUHMGDDBE-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004156 Azodicarbonamide Substances 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 229920002367 Polyisobutene Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 2
- 235000019399 azodicarbonamide Nutrition 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 229920000092 linear low density polyethylene Polymers 0.000 description 2
- 239000004707 linear low-density polyethylene Substances 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000010687 lubricating oil Substances 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012748 slip agent Substances 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- MYOQALXKVOJACM-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy pentaneperoxoate Chemical compound CCCCC(=O)OOOC(C)(C)C MYOQALXKVOJACM-UHFFFAOYSA-N 0.000 description 1
- OXYKVVLTXXXVRT-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzenecarboperoxoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1 OXYKVVLTXXXVRT-UHFFFAOYSA-N 0.000 description 1
- SFTGRPFSYZGXQW-GQCTYLIASA-N (4e)-3-methylhexa-1,4-diene Chemical compound C\C=C\C(C)C=C SFTGRPFSYZGXQW-GQCTYLIASA-N 0.000 description 1
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- 239000010665 pine oil Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
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- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
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- 238000003825 pressing Methods 0.000 description 1
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- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 1
- 229960003656 ricinoleic acid Drugs 0.000 description 1
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- UNSYHJWOORERTF-UHFFFAOYSA-J sodium dicarboxyoxyalumanyl hydrogen carbonate hydrogen carbonate Chemical compound [Na+].[Al+3].OC([O-])=O.OC([O-])=O.OC([O-])=O.OC([O-])=O UNSYHJWOORERTF-UHFFFAOYSA-J 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
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- 239000003381 stabilizer Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- HSVFKFNNMLUVEY-UHFFFAOYSA-N sulfuryl diazide Chemical compound [N-]=[N+]=NS(=O)(=O)N=[N+]=[N-] HSVFKFNNMLUVEY-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- 150000005671 trienes Chemical class 0.000 description 1
- 229940070710 valerate Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940098697 zinc laurate Drugs 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は熱可塑性エラストマー組成物、それを用いた成形体、および用途に関する。 The present invention relates to a thermoplastic elastomer composition, a molded body using the same, and a use.
熱可塑性エラストマーは、軽量でリサイクルが容易であることから、省エネルギー、省資源タイプのエラストマーとして、特に加硫ゴムの代替として自動車部品、工業機械部品、電気・電子部品、建材等に広く使用されている。 Thermoplastic elastomers are lightweight and easy to recycle, so they are widely used as energy- and resource-saving elastomers, especially in automobile parts, industrial machine parts, electrical / electronic parts, building materials, etc. as an alternative to vulcanized rubber. Yes.
中でも、ポリオレフィン系熱可塑性エラストマーは、エチレン・プロピレン・非共役ジエン共重合体(EPDM)とポリプロピレンなどの結晶性ポリオレフィンを原料としていることから、他の熱可塑性エラストマーに比べて、比重が軽く、耐熱老化性、耐候性などの耐久性に優れているが、用途によっては更なる改良が求められている。 Above all, polyolefin-based thermoplastic elastomers are made from crystalline polyolefins such as ethylene / propylene / non-conjugated diene copolymer (EPDM) and polypropylene, so they have a lighter specific gravity and heat resistance than other thermoplastic elastomers. Although it is excellent in durability such as aging and weather resistance, further improvements are required depending on applications.
例えば、結晶性ポリオレフィン樹脂、および、エチレン、炭素数3〜20のα−オレフィン及び非共役ポリエンからなるエチレン・α−オレフィン・非共役ポリエン共重合体ゴムに、第三成分としてポリイソブチレン、ブチルゴム及びプロピレン含量が50モル%以上のプロピレン・エチレン共重合体ゴムから選ばれる少なくとも1つのゴムを加えて、成形品の外観を改良する方法(特許文献1:特開2001−11248号公報)、ポリオレフィン樹脂、およびエチレン−α−オレフィン共重合ゴム及び/またはエチレン−α−オレフィン・非共役ポリエン共重合ゴムに、第三成分として、プロピレン・エチレン共重合体及び/またはプロピレン・1−ブテン共重合体を加えて、スタンピング成形性などを改良する方法(特許文献2:特開2001−171439号公報)、あるいは、オレフィン系共重合体ゴムおよびポリプロピレン系樹脂に、第三成分として、プロピレン・エチレン共重合体を含むプロピレン・エチレンブロック共重合体を加えて、目ヤニの発生を抑制する方法(特許文献3:特開2006−36813号公報)など、第三成分として、プロピレン・エチレン共重合体を加える方法が提案されている。 For example, a crystalline polyolefin resin and ethylene / α-olefin / nonconjugated polyene copolymer rubber composed of ethylene, an α-olefin having 3 to 20 carbon atoms and a nonconjugated polyene, and polyisobutylene, butyl rubber and A method for improving the appearance of a molded product by adding at least one rubber selected from propylene / ethylene copolymer rubber having a propylene content of 50 mol% or more (Patent Document 1: Japanese Patent Application Laid-Open No. 2001-11248), polyolefin resin , And ethylene-α-olefin copolymer rubber and / or ethylene-α-olefin / non-conjugated polyene copolymer rubber with propylene / ethylene copolymer and / or propylene / 1-butene copolymer as a third component. In addition, a method for improving stamping moldability (Patent Document 2: JP-A-2 01-171439), or a propylene / ethylene block copolymer containing a propylene / ethylene copolymer as a third component to an olefin copolymer rubber and a polypropylene resin, A method of adding a propylene / ethylene copolymer as a third component, such as a suppressing method (Patent Document 3: Japanese Patent Application Laid-Open No. 2006-36813), has been proposed.
しかしながら、単に、特許文献1〜3に具体的に示されているプロピレン含有量が50〜60モル%のプロピレン・エチレン共重合体を用いても、目ヤニの発生は十分には抑制されず得られる成形品の外観不良の要因となり、伸びや強度といった機械物性も良好ではない。 However, even if a propylene / ethylene copolymer having a propylene content of 50 to 60 mol% specifically shown in Patent Documents 1 to 3 is used, the occurrence of eye cracks cannot be sufficiently suppressed. As a result, the mechanical properties such as elongation and strength are not good.
本発明は、押出成形時に目ヤニの発生を抑制でき、しかも、得られる成形品の外観が優れ、かつ機械物性も良好な成形品を得るに好適な熱可塑性エラストマー組成物を得ることを目的とする。 It is an object of the present invention to obtain a thermoplastic elastomer composition suitable for obtaining a molded product that can suppress the occurrence of eye cracks during extrusion molding and that has an excellent appearance and good mechanical properties. To do.
本発明は、オレフィン系ゴム(A)、融点(Tm)が70〜200℃の範囲にあるオレフィン系樹脂(B)および、下記(1)〜(3)を満たすプロピレン・α−オレフィンランダム共重合体(C)を含む混合物を動的架橋して、オレフィン系ゴム(A)の少なくとも一部を架橋してなる熱可塑性エラストマー組成物に係る。
(1)プロピレン含量が70モル%以上90モル%未満。
(2)重量平均分子量Mwと数平均分子量Mnの比Mw/Mnが3.5以下。
(3)融点(Tm)が70℃未満。
The present invention relates to an olefin rubber (A), an olefin resin (B) having a melting point (Tm) in the range of 70 to 200 ° C., and a propylene / α-olefin random copolymer satisfying the following (1) to (3) The present invention relates to a thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing the coalesced (C) and crosslinking at least a part of the olefin rubber (A).
(1) Propylene content is 70 mol% or more and less than 90 mol%.
(2) The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 3.5 or less.
(3) Melting point (Tm) is less than 70 ° C.
本発明の熱可塑性エラストマー組成物は、押出成形時に目ヤニの発生を抑制でき、しかも得られる成形は外観などの意匠性、機械的強度に優れるので、自動車用部品、土木・建材用品、電気・電子用品あるいは衛生用品などの種々の成形品に好適である。 The thermoplastic elastomer composition of the present invention can suppress the occurrence of spears at the time of extrusion molding, and the molding obtained is excellent in design such as appearance and mechanical strength, so that it can be used for automobile parts, civil engineering / building materials, It is suitable for various molded products such as electronic products and sanitary products.
<オレフィン系ゴム(A)>
本発明の熱可塑性エラストマー組成物の原料となる成分の一つであるオレフィン系ゴム(A)は、エチレン、プロピレン、1−ブテン、イソブテン、などのオレフィンの(共)重合体であり、具体的には、例えば、ポリイソブチレン、エチレン−α−オレフィン系共重合体ゴムが挙げられる。
これらオレフィン系ゴム(A)の中でも、エチレン・α−オレフィン・非共役ジエン共重合体ゴム(A1)およびエチレン−α−オレフィン共重合体ゴム(A2)が好ましい。
<Olefin rubber (A)>
The olefin-based rubber (A), which is one of the components used as the raw material of the thermoplastic elastomer composition of the present invention, is a (co) polymer of olefins such as ethylene, propylene, 1-butene, and isobutene. Examples include polyisobutylene and ethylene-α-olefin copolymer rubber.
Among these olefin rubbers (A), ethylene / α-olefin / non-conjugated diene copolymer rubber (A1) and ethylene-α-olefin copolymer rubber (A2) are preferable.
<エチレン・α−オレフィン・非共役ジエン共重合体ゴム(A1)
本発明に係るエチレン・α−オレフィン・非共役ジエン共重合体ゴム(A1)は、エチレン、炭素原子数3〜20のα−オレフィンおよび非共役ポリエンからなるゴムである。
<Ethylene / α-olefin / non-conjugated diene copolymer rubber (A1)
The ethylene / α-olefin / non-conjugated diene copolymer rubber (A1) according to the present invention is a rubber composed of ethylene, an α-olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
本発明に係るエチレン・α−オレフィン・非共役ジエン共重合体ゴム(A1)を構成する炭素原子数3〜20のα−オレフィンとしては、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−ヘプテン、1−オクテン、1−ノネン、1−デセン、1−ウンデセン、1−ドデセン、1−トリデセン、1−テトラデセン、1−ペンタデセン、1−ヘキサデセン、1−ヘプタデセン、1−ノナデセン、1−エイコセン、9−メチル−1−デセン、11−メチル−1−ドデセン、12−エチル−1−テトラデセンなどが挙げられる。中でも、プロピレン、1−ブテン、4−メチル−1−ペンテン、1−ヘキセン、1−オクテンが好ましく、とりわけプロピレンが好ましい。これらα−オレフィンは、単独で、または2種以上を組合わせて用いてもよい。 Specific examples of the α-olefin having 3 to 20 carbon atoms constituting the ethylene / α-olefin / non-conjugated diene copolymer rubber (A1) according to the present invention include propylene, 1-butene and 4-methyl. -1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1 -Heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like. Among these, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.
本発明に係るエチレン・α−オレフィン・非共役ジエン共重合体ゴム(A1)を構成する非共役ポリエンとしては、具体的には、1,4−ヘキサジエン、3−メチル−1,4−ヘキサジエン、4−メチル−1,4−ヘキサジエン、5−メチル−1,4−ヘキサジエン、4,5−ジメチル−1,4−ヘキサジエン、7−メチル−1,6−オクタジエン、8−メチル−4−エチリデン−1,7−ノナジエン、4−エチリデン−1,7−ウンデカジエン等の鎖状非共役ジエン;
メチルテトラヒドロインデン、5−エチリデン−2−ノルボルネン、5−メチレン−2−ノルボルネン、5−イソプロピリデン−2−ノルボルネン、5−ビニリデン−2−ノルボルネン、6−クロロメチル−5−イソプロペニル−2−ノルボルネン、5−ビニル−2−ノルボルネン、5−イソプロペニル−2−ノルボルネン、5−イソブテニル−2−ノルボルネン、シクロペンタジエン、ノルボルナジエン等の環状非共役ジエン;
2,3−ジイソプロピリデン−5−ノルボルネン、2−エチリデン−3−イソプロピリデン−5−ノルボルネン、2−プロペニル−2,2−ノルボルナジエン、4−エチリデン−8−メチル−1,7−ナノジエン等のトリエンなどが挙げられ、これら非共役ジエンは単独でも、2種類以上でも使用することができる。これら非共役ジエンの中でも、5−エチリデン−2−ノルボルネン(ENB)、5−ビニル−2−ノルボルネン(VNB)が好ましい。
Specific examples of the non-conjugated polyene constituting the ethylene / α-olefin / non-conjugated diene copolymer rubber (A1) according to the present invention include 1,4-hexadiene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4,5-dimethyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 8-methyl-4-ethylidene- Chain non-conjugated dienes such as 1,7-nonadiene, 4-ethylidene-1,7-undecadiene;
Methyltetrahydroindene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 5-vinylidene-2-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene Cyclic nonconjugated dienes such as 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene, norbornadiene;
2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8-methyl-1,7-nanodiene, etc. A triene etc. are mentioned, These nonconjugated dienes can be used individually or in mixture of 2 or more types. Among these non-conjugated dienes, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) are preferable.
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体ゴム(A1)は、通常、(a)エチレンから導かれる単位と、(b)炭素数3〜20のα−オレフィンから導かれる単位とを、50/50〜95/5、好ましくは60/40〜80/20、さらに好ましくは65/35〜75/25[(a)/(b)]のモル比の範囲にある。 The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) according to the present invention is usually (a) a unit derived from ethylene and (b) a unit derived from an α-olefin having 3 to 20 carbon atoms. Are in the range of a molar ratio of 50/50 to 95/5, preferably 60/40 to 80/20, more preferably 65/35 to 75/25 [(a) / (b)].
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体ゴム(A1)は、通常、非共役ポリエン成分量の一指標であるヨウ素価が1〜50、好ましくは5〜40、さらに好ましくは10〜30の範囲にある。また、非共役ジエン量の全成分量は、通常、(A1)成分中の2〜20質量%の範囲にある。 The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) according to the present invention usually has an iodine value of 1 to 50, preferably 5 to 40, more preferably an index of the amount of the non-conjugated polyene component. It is in the range of 10-30. In addition, the total amount of the non-conjugated diene is usually in the range of 2 to 20% by mass in the component (A1).
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体ゴム(A1)は、通常、135℃、デカリン溶媒中で測定される極限粘度[η]が1〜10dl/g、好ましくは1.5〜8dl/gの範囲にある。 The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) according to the present invention usually has an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. of 1 to 10 dl / g, preferably 1. It is in the range of 5-8 dl / g.
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体(A1)は、その製造の際に軟化剤好ましくは鉱物油系軟化剤を配合した、いわゆる油展ゴムであってもよい。鉱物油系軟化剤としては、従来公知の鉱物油系軟化剤たとえばパラフィン系プロセスオイルなどが挙げられる。 The ethylene / α-olefin / non-conjugated polyene copolymer (A1) according to the present invention may be a so-called oil-extended rubber in which a softening agent, preferably a mineral oil softening agent, is blended in the production. Examples of the mineral oil softener include conventionally known mineral oil softeners such as paraffin process oil.
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体ゴム(A1)のムーニー粘度[ML1+4(100℃)]は、通常、10〜250、好ましくは30〜150の範囲にある。 The Mooney viscosity [ML 1 + 4 (100 ° C.)] of the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) according to the present invention is usually in the range of 10 to 250, preferably 30 to 150. .
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体ゴム(A1)は、単独で、あるいは二種以上のエチレン・α−オレフィン・非共役ポリエン共重合体ゴムを用いてもよい。
本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体ゴム(A1)は、従来公知の方法により製造することができる。
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) according to the present invention may be used alone or in combination of two or more kinds of ethylene / α-olefin / non-conjugated polyene copolymer rubber.
The ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) according to the present invention can be produced by a conventionally known method.
<エチレン・α−オレフィン共重合体ゴム(A2)
本発明に係るエチレン・α−オレフィン共重合体ゴム(A2)を構成するα−オレフィンは、前記本発明に係るエチレン・α−オレフィン・非共役ポリエン共重合体ゴム(A1)を構成するα−オレフィンと同様である。
<Ethylene / α-olefin copolymer rubber (A2)
The α-olefin composing the ethylene / α-olefin copolymer rubber (A2) according to the present invention is the α− composing the ethylene / α-olefin / non-conjugated polyene copolymer rubber (A1) according to the present invention. Similar to olefins.
本発明に係るエチレン・α−オレフィン共重合体ゴム(A2)は、通常、エチレンから誘導される構成単位含量(エチレン含有量)を50モル%以上、好ましくは50〜90モル%、さらに好ましくは60〜85モル%、炭素原子数3〜20のα−オレフィンから誘導される構成単位含量(α−オレフィン含有量)を50モル%以下、好ましくは50〜10モル%、より好ましくは40〜15モル%〔エチレン含有量+α−オレフィン含有量=100モル%〕を含む。 The ethylene / α-olefin copolymer rubber (A2) according to the present invention usually has a structural unit content (ethylene content) derived from ethylene of 50 mol% or more, preferably 50 to 90 mol%, more preferably The constituent unit content (α-olefin content) derived from 60 to 85 mol% and an α-olefin having 3 to 20 carbon atoms is 50 mol% or less, preferably 50 to 10 mol%, more preferably 40 to 15 Mol% [ethylene content + α-olefin content = 100 mol%].
<オレフィン系重合体(B)>
本発明の熱可塑性エラストマー組成物の原料となる成分の一つであるオレフィン系重合体(B)は、エチレン、プロピレン、1−ブテン、1−ペンテン、1−ヘキセン、4−メチル−1−ペンテン、1−オクテン、1−デセンなどのα−オレフィンの単独重合体、あるいは二種以上のα−オレフィンで、通常、主たるα−オレフィンの含有量が90モル%以上の共重合体であり、融点(Tm)が70〜200℃、好ましくは80〜170℃の範囲にある。
<Olefin polymer (B)>
The olefin polymer (B) which is one of the components used as the raw material of the thermoplastic elastomer composition of the present invention is ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene. , 1-octene, 1-decene and other α-olefin homopolymers, or two or more α-olefins, usually a copolymer having a main α-olefin content of 90 mol% or more, melting point (Tm) is in the range of 70 to 200 ° C, preferably 80 to 170 ° C.
本発明に係るオレフィン系重合体(B)は、通常、実質的に主鎖に不飽和結合を有していない。
本発明に係るオレフィン系重合体(B)は、単独で、あるいは二種以上のオレフィン系重合体を用いてもよい。
これらオレフィン系重合体(B)の中でも、プロピレン系重合体(B1)、エチレン系重合体(B2)が好ましい。
The olefin polymer (B) according to the present invention usually has substantially no unsaturated bond in the main chain.
The olefin polymer (B) according to the present invention may be used alone or in combination of two or more olefin polymers.
Among these olefin polymers (B), a propylene polymer (B1) and an ethylene polymer (B2) are preferable.
<プロピレン系重合体(B1)>
本発明に係るプロピレン系重合体(B1)は、プロピレンの単独重合体、あるいは、プロピレンと通常、10モル%以下の炭素数2〜10のα−オレフィン、例えば、エチレン、1−ブテン、1−ペンテン、4−メチル−1−ペンテンなどとのランダム共重合体、あるいは、プロピレンの単独重合体と非晶性あるいは低結晶性のプロピレン・エチレンランダム共重合体とのブロック共重合体であり、通常、融点が120〜170℃、好ましくは145〜165℃の範囲にある。
<Propylene-based polymer (B1)>
The propylene polymer (B1) according to the present invention is a homopolymer of propylene, or propylene and usually an α-olefin having 2 to 10 carbon atoms of 10 mol% or less, such as ethylene, 1-butene, 1- Random copolymer with pentene, 4-methyl-1-pentene, or block copolymer of propylene homopolymer and amorphous or low crystalline propylene / ethylene random copolymer The melting point is in the range of 120 to 170 ° C, preferably 145 to 165 ° C.
本発明に係るプロピレン系重合体(B1)は、通常、ポリプロピレン樹脂として、製造・販売されている。
本発明に係るプロピレン系重合体(B1)は、立体構造としては、アイソタクチック構造が好ましいが、シンジオタクチック構造のものやこれらの構造の混ざったもの、あるいは、一部アタクチック構造を含むものも用いることができる。
The propylene polymer (B1) according to the present invention is usually produced and sold as a polypropylene resin.
The propylene-based polymer (B1) according to the present invention preferably has an isotactic structure as a steric structure, but a syndiotactic structure, a mixture of these structures, or a part containing an atactic structure. Can also be used.
本発明に係るプロピレン系重合体(B1)は、通常、メルトフローレート(MFR:JIS K6758に従い、温度230℃、荷重21.18Nで測定)が0.05〜100g/10分、好ましくは0.1〜50g/10分の範囲にある。
本発明に係るプロピレン系重合体(B1)は、種々公知の重合方法によって重合される。
The propylene polymer (B1) according to the present invention usually has a melt flow rate (measured in accordance with MFR: JIS K6758 at a temperature of 230 ° C. and a load of 21.18 N) of 0.05 to 100 g / 10 min, preferably 0.8. It is in the range of 1-50 g / 10 minutes.
The propylene polymer (B1) according to the present invention is polymerized by various known polymerization methods.
<エチレン系重合体(B2)>
本発明に係るエチレン系重合体(B2)は、エチレンの単独重合体、あるいは、エチレンと10モル%以下の炭素数2〜10のα−オレフィン、例えば、プロピレン、エチレン、1−ブテン、1−ペンテン、4−メチル−1−ペンテンなどとのランダム共重合体であり、通常、融点が80〜150℃、好ましくは90〜130℃の範囲にある。
<Ethylene polymer (B2)>
The ethylene-based polymer (B2) according to the present invention is an ethylene homopolymer, or an α-olefin having 2 to 10 carbon atoms and less than 10 mol%, such as propylene, ethylene, 1-butene, 1- It is a random copolymer with pentene, 4-methyl-1-pentene and the like, and usually has a melting point of 80 to 150 ° C, preferably 90 to 130 ° C.
本発明に係るエチレン系重合体(B2)は、通常、高圧法低密度ポリエチレン、線状低密度ポリエチレン、高密度ポリエチレンなどとして、製造・販売されている。
本発明に係るエチレン系重合体(B2)は、通常、メルトフローレート(MFR:JIS K6758に従い、温度190℃、荷重21.18Nで測定)が0.05〜100g/10分、好ましくは0.1〜50g/10分の範囲にある。
The ethylene polymer (B2) according to the present invention is usually produced and sold as a high-pressure method low-density polyethylene, linear low-density polyethylene, high-density polyethylene, or the like.
The ethylene-based polymer (B2) according to the present invention usually has a melt flow rate (measured according to MFR: JIS K6758 at a temperature of 190 ° C. and a load of 21.18 N) of 0.05 to 100 g / 10 minutes, preferably 0.8. It is in the range of 1-50 g / 10 minutes.
<プロピレン・α−オレフィンランダム共重合体(C)>
本発明の熱可塑性エラストマー組成物の原料となる成分の一つであるプロピレン・α−オレフィンランダム共重合体(C)は、プロピレンと炭素数2以上(但し、プロピレンは除く)のα−オレフィンとのランダム共重合体であって、下記(1)〜(3)を満たす共重合体である。
(1)プロピレンから導かれる単位を70モル%以上〜90モル%未満、好ましくは75〜88モル%、α−オレフィンから導かれる単位を11〜30モル%、好ましくは12〜25モル%〔プロピレン含有量+α−オレフィン含有量=100モル%〕の範囲、
(2)分子量分布〔重量平均分子量(Mw)/数平均分子量(Mn)〕が3.5以下、好ましくは3.0〜1.5の範囲、
(3)融点(Tm)が70℃未満、好ましくは60℃以下。
<Propylene / α-olefin random copolymer (C)>
The propylene / α-olefin random copolymer (C), which is one of the components used as the raw material of the thermoplastic elastomer composition of the present invention, is propylene and an α-olefin having 2 or more carbon atoms (excluding propylene). And a copolymer satisfying the following (1) to (3).
(1) Units derived from propylene are 70 mol% or more and less than 90 mol%, preferably 75 to 88 mol%, units derived from α-olefin are 11 to 30 mol%, preferably 12 to 25 mol% [propylene Content + α-olefin content = 100 mol%],
(2) Molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is 3.5 or less, preferably in the range of 3.0 to 1.5,
(3) Melting point (Tm) is less than 70 ° C, preferably 60 ° C or less.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)において、プロピレンと共重合されるα−オレフィンは、通常、炭素数2〜20のα−オレフィンであり、具体的には、エチレン、1−ブテン、4−メチル−1−ペンテン、1−ヘキセン、1−ヘプテン、1−オクテン、1−ノネン、1−デセン、1−ウンデセン、1−ドデセン、1−トリデセン、1−テトラデセン、1−ペンタデセン、1−ヘキサデセン、1−ヘプタデセン、1−ノナデセン、1−エイコセン、9−メチル−1−デセン、11−メチル−1−ドデセン、12−エチル−1−テトラデセンなどが挙げられる。中でも、プロピレン、1−ブテン、4−メチル−1−ペンテン、1−ヘキセン、1−オクテンが好ましく、とりわけ、エチレンが好ましい。これらα−オレフィンは、単独で、または2種以上を組合わせて用いてもよい。 In the propylene / α-olefin random copolymer (C) according to the present invention, the α-olefin copolymerized with propylene is usually an α-olefin having 2 to 20 carbon atoms, specifically, ethylene, 1-butene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1- Examples include pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. Among these, propylene, 1-butene, 4-methyl-1-pentene, 1-hexene and 1-octene are preferable, and ethylene is particularly preferable. These α-olefins may be used alone or in combination of two or more.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)は、通常、実質的に主鎖に不飽和結合を有していない。
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)の分子量分布〔重量平均分子量(Mw)/数平均分子量(Mn)〕は、GPCを用いて、オルトジクロロベンゼン溶媒を用いて、140℃で測定した値である。
The propylene / α-olefin random copolymer (C) according to the present invention usually has substantially no unsaturated bond in the main chain.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the propylene / α-olefin random copolymer (C) according to the present invention is 140 using GPC and an orthodichlorobenzene solvent. It is a value measured at ° C.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)において、融点(Tm)が70℃未満であるとは、融点(Tm)を有しない所謂非晶性の共重合体を含むことを意味する。具体的には、例えば、後述のDSCを用いた融点(Tm)の測定で、DSCの測定温度範囲である−100〜200℃の間で融解熱量(ΔH)が10J/g以上の融解ピークが観測されない共重合体をも含むことである。 In the propylene / α-olefin random copolymer (C) according to the present invention, the melting point (Tm) of less than 70 ° C. includes a so-called amorphous copolymer having no melting point (Tm). means. Specifically, for example, in the measurement of the melting point (Tm) using a DSC described later, a melting peak with a heat of fusion (ΔH) of 10 J / g or more is observed between −100 to 200 ° C., which is the DSC measurement temperature range. It also includes copolymers that are not observed.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)は、好ましくは、
共重合モノマー連鎖分布B値が0.95以上、より好ましくは0.95〜1.5、さらに好ましくは0.95〜1.3の範囲にある。
The propylene / α-olefin random copolymer (C) according to the present invention is preferably
The copolymerization monomer chain distribution B value is 0.95 or more, more preferably 0.95 to 1.5, and still more preferably 0.95 to 1.3.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)における共重合モノマー連鎖分布を示すパラメータであるB値は、コールマン等(B.D.Cole-man and T.G.Fox, J. Polym.Sci., Al,3183(1963) )により提案されており、以下のように定義される。 The B value, which is a parameter indicating the copolymer monomer chain distribution in the propylene / α-olefin random copolymer (C) according to the present invention, is determined by Coleman et al. (BDCole-man and TGFox, J. Polym. Sci., Al , 3183). (1963)) and is defined as follows:
B=P12/(2P1 ・P2 )
ここで、P1 、P2 はそれぞれ第1モノマーであるプロピレン含有量分率、第2モノマーであるα−オレフィン含有量分率であり、P12は全二分子連鎖中の(第1モノマー)−(第2モノマー)連鎖の割合である。
B = P 12 / (2P 1 · P 2 )
Here, P 1 and P 2 are the first monomer propylene content fraction and the second monomer α-olefin content fraction, respectively, and P 12 is the entire bimolecular chain (first monomer). -(Second monomer) The proportion of linkage.
なおこのB値は1のときベルヌーイ統計に従い、B<1のとき共重合体はブロック的であり、B>1のとき交互的であることを示す。
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)は、本発明に係るプロピレン系重合体(B1)との相溶性が良好となり、得られる熱可塑性エラストマー組成物は、充分な柔軟性、耐熱性、耐傷付性を発揮する傾向がある。
The B value is in accordance with Bernoulli statistics when 1, and the copolymer is block-like when B <1 and alternating when B> 1.
The propylene / α-olefin random copolymer (C) according to the present invention has good compatibility with the propylene-based polymer (B1) according to the present invention, and the resulting thermoplastic elastomer composition has sufficient flexibility. , Tend to exhibit heat resistance and scratch resistance.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)は、通常、メルトフローレート(MFR:温度230℃、荷重21.18Nで測定)が0.05〜100g/10分、好ましくは0.1〜50g/10分の範囲にある。 The propylene / α-olefin random copolymer (C) according to the present invention usually has a melt flow rate (MFR: measured at a temperature of 230 ° C. and a load of 21.18 N) of 0.05 to 100 g / 10 minutes, preferably 0. .1 to 50 g / 10 min.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)は、135℃、デカリン溶媒中で測定した極限粘度[η]が、通常、0.01〜10dl/g、好ましくは0.05〜10dl/gの範囲にある。本発明に係るプロピレン・エチレンランダム共重合体(C)の極限粘度[η]が、前記範囲内にあると、より、耐候性、耐オゾン性、耐熱老化性、低温特性、耐動的疲労性などの特性に優れた熱可塑性エラストマーを得ることができる。 The propylene / α-olefin random copolymer (C) according to the present invention has an intrinsic viscosity [η] measured in a decalin solvent at 135 ° C. is usually 0.01 to 10 dl / g, preferably 0.05 to It is in the range of 10 dl / g. When the intrinsic viscosity [η] of the propylene / ethylene random copolymer (C) according to the present invention is within the above range, the weather resistance, ozone resistance, heat aging resistance, low temperature characteristics, dynamic fatigue resistance, etc. A thermoplastic elastomer having excellent properties can be obtained.
本発明に係るプロピレン・α−オレフィンランダム共重合体(C)は、種々公知の製造方法、例えば、メタロセン触媒の存在下、プロピレンと炭素数2〜20のα−オレフィン(但し、プロピレンを除く)を共重合させることにより製造し得る。具体的には、特開2007−002266号公報に記載の製造方法を使用し得る。 The propylene / α-olefin random copolymer (C) according to the present invention can be produced by various known production methods, for example, propylene and an α-olefin having 2 to 20 carbon atoms (excluding propylene) in the presence of a metallocene catalyst. Can be produced by copolymerization. Specifically, the production method described in JP 2007-002266 A can be used.
また、本発明に係るプロピレン・α−オレフィンランダム共重合体(C)は、エクソン・モービル社から、Vistamaxx 6102、Vistamaxx 6202などの商品名で、ダウ・ケミカル社からVersify 2300、Versify 2400などの商品名で製造・販売されている。 Further, the propylene / α-olefin random copolymer (C) according to the present invention is a product name such as Vistamaxx 6102 and Vistamaxx 6202 from Exxon Mobil, and products such as Versify 2300 and Versify 2400 from Dow Chemical. Manufactured and sold by name.
<熱可塑性エラストマー組成物>
本発明の熱可塑性エラストマー組成物は、前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)を含む混合物(前駆体)を動的架橋して、前記オレフィン系ゴム(A)の少なくとも一部を架橋してなる熱可塑性エラストマー組成物である。
<Thermoplastic elastomer composition>
The thermoplastic elastomer composition of the present invention moves a mixture (precursor) containing the olefin rubber (A), the olefin polymer (B), and the propylene / α-olefin random copolymer (C). It is a thermoplastic elastomer composition obtained by subjecting at least a part of the olefinic rubber (A) to cross-linking.
本発明の熱可塑性エラストマー組成物は、好ましくは前記オレフィン系ゴム(A)100質量部に対して、前記オレフィン系重合体(B)10〜200質量部、より好ましくは20〜180質量部、前記プロピレン・α−オレフィンランダム共重合体(C)を1〜200質量部、より好ましくは10〜150質量部の範囲で含む混合物(前駆体)を動的架橋してなる。 The thermoplastic elastomer composition of the present invention is preferably 10 to 200 parts by mass of the olefin polymer (B), more preferably 20 to 180 parts by mass with respect to 100 parts by mass of the olefin rubber (A). It is obtained by dynamically crosslinking a mixture (precursor) containing 1 to 200 parts by mass, more preferably 10 to 150 parts by mass of the propylene / α-olefin random copolymer (C).
本発明の熱可塑性エラストマー組成物は、前記オレフィン系重合体(B)に加わえて、前記プロピレン・α−オレフィンランダム共重合体(C)を含むことにより、押出成形時に目ヤニの発生を抑制でき、しかも、得られる成形品の外観が優れ、かつ機械物性も良好な成形品を得るに好適な熱可塑性エラストマー組成物を得ることができる。 The thermoplastic elastomer composition of the present invention includes the propylene / α-olefin random copolymer (C) in addition to the olefin-based polymer (B), thereby suppressing generation of spears during extrusion molding. Moreover, it is possible to obtain a thermoplastic elastomer composition suitable for obtaining a molded product having an excellent appearance and good mechanical properties.
<前駆体>
本発明の熱可塑性エラストマー組成物を得るための、前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)を含む混合物(前駆体)には、前記成分に加え、架橋剤、架橋助剤、軟化剤などを加えることができる。
<Precursor>
A mixture (precursor) containing the olefin rubber (A), the olefin polymer (B), and the propylene / α-olefin random copolymer (C) for obtaining the thermoplastic elastomer composition of the present invention. In addition to the above components, a crosslinking agent, a crosslinking aid, a softening agent, and the like can be added.
〈架橋剤〉
本発明で用いられる架橋剤としては、たとえば有機過酸化物、イオウ、イオウ化合物、フェノール樹脂等のフェノール系加硫剤などが挙げられるが、中でも有機過酸化物が好ましく用いられる。
<Crosslinking agent>
Examples of the crosslinking agent used in the present invention include organic peroxides, sulfur, sulfur compounds, phenolic vulcanizing agents such as phenol resins, etc. Among them, organic peroxides are preferably used.
有機過酸化物としては、具体的には、ジクミルペルオキシド、ジ-tert-ブチルペルオキシド、2,5-ジメチル-2,5-ジ-(tert-ブチルペルオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(tert-ブチルペルオキシ)ヘキシン-3、1,3-ビス(tert-ブチルペルオキシイソプロピル)ベンゼン、1,1-ビス(tert-ブチルペルオキシ)-3,3,5-トリメチルシクロヘキサン、n-ブチル-4,4-ビス(tert-ブチルペルオキシ)バレレート、ベンゾイルペルオキシド、p-クロロベンゾイルペルオキシド、2,4-ジクロロベンゾイルペルオキシド、tert-ブチルペルオキシベンゾエート、tert-ブチルペルベンゾエート、tert-ブチルペルオキシイソプロピルカーボネート、ジアセチルペルオキシド、ラウロイルペルオキシド、tert-ブチルクミルペルオキシドなどが挙げられる。 Specific examples of organic peroxides include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 2,5-dimethyl-2. , 5-Di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n -Butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperbenzoate, tert-butylperoxyisopropyl Examples include carbonate, diacetyl peroxide, lauroyl peroxide, tert-butyl cumyl peroxide and the like.
中でも、臭気性、スコーチ安定性の点で2,5-ジメチル-2,5-ジ(tert-ブチルペルオキシ)ヘキサン、2,5-ジメチル-2,5-ジ(tert- ブチルペルオキシ)ヘキシン-3、1,3-ビス(tert-ブチルペルオキシイソプロピル)ベンゼン、1,1-ビス(tert-ブチルペルオキシ)-3,3,5-トリメチルシクロヘキサンおよびn-ブチル-4,4-ビス(tert-ブチルペルオキシ)バレレートが好ましく、中でも1,3-ビス(tert-ブチルペルオキシイソプロピル)ベンゼンが最も好ましい。 Among them, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 in terms of odor and scorch stability 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane and n-butyl-4,4-bis (tert-butylperoxy) ) Valerate is preferred, with 1,3-bis (tert-butylperoxyisopropyl) benzene being most preferred.
これら有機過酸化物は、前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)の合計量100質量部に対して、通常、0.01〜15質量部、好ましくは0.03〜12質量部の割合で用いられる。有機過酸化物を上記割合で用いると、オレフィン系ゴム(A)が少なくとも一部が架橋された熱可塑性エラストマー組成物が得られ、耐熱性、引張特性およびゴム弾性が十分な成形体が得られる。 These organic peroxides are usually based on 100 parts by mass of the total amount of the olefin rubber (A), the olefin polymer (B), and the propylene / α-olefin random copolymer (C). 0.01 to 15 parts by mass, preferably 0.03 to 12 parts by mass is used. When the organic peroxide is used in the above ratio, a thermoplastic elastomer composition in which the olefin rubber (A) is at least partially crosslinked is obtained, and a molded article having sufficient heat resistance, tensile properties and rubber elasticity is obtained. .
〈架橋助剤〉
本発明においては、前記有機過酸化物による架橋処理に際し、硫黄、p-キノンジオキシム、p,p'-ジベンゾイルキノンジオキシム、N-メチル-N,4- ジニトロソアニリン、ニトロベンゼン、ジフェニルグアニジン、トリメチロールプロパン-N,N'-m-フェニレンジマレイミド等の架橋助剤、あるいはジビニルベンゼン、トリアリルシアヌレート、エレチングリコールジメタクリレート、ジエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレート、アリルメタクリレート等の多官能性メタクリレートモノマー、ビニルブチラートまたはビニルステアレート等の多官能性ビニルモノマーからなる架橋助剤を添加してもよい。このような架橋助剤を添加することにより、前記オレフィン系ゴム(A)の均一かつ緩和な架橋反応が期待できる。特に、本発明においてはジビニルベンゼンを用いると、取扱い易さ、前記被処理物の主成分たる前記オレフィン系ゴム(A)、オレフィン系重合体(B)、およびプロピレン・α−オレフィンランダム共重合体(C)との相溶性が良好であり、かつ前記有機過酸化物の可溶化作用を有し、有機過酸化物の分散助剤として働くため、熱処理による架橋効果が均質で、流動性と物性のバランスのとれた熱可塑性エラストマー組成物が得られるため最も好ましい。
<Crosslinking aid>
In the present invention, during the crosslinking treatment with the organic peroxide, sulfur, p-quinonedioxime, p, p′-dibenzoylquinonedioxime, N-methyl-N, 4-dinitrosoaniline, nitrobenzene, diphenylguanidine , Crosslinking aids such as trimethylolpropane-N, N'-m-phenylenedimaleimide, or divinylbenzene, triallyl cyanurate, eletin glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate A crosslinking aid comprising a polyfunctional methacrylate monomer such as allyl methacrylate, or a polyfunctional vinyl monomer such as vinyl butyrate or vinyl stearate may be added. By adding such a crosslinking aid, uniform and mild crosslinking reaction of the olefin rubber (A) can be expected. In particular, when divinylbenzene is used in the present invention, it is easy to handle, the olefin rubber (A), the olefin polymer (B), and the propylene / α-olefin random copolymer as the main components of the object to be treated. Good compatibility with (C), solubilization of the organic peroxide, and works as a dispersion aid for the organic peroxide, so the crosslinking effect by heat treatment is homogeneous, fluidity and physical properties Is most preferable because a thermoplastic elastomer composition having a good balance can be obtained.
本発明に係る架橋助剤は、前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)の合計量100質量部に対して、通常、0.01〜15質量部、好ましくは0.03〜12質量部の割合で用いられる。 The crosslinking aid according to the present invention is based on 100 parts by mass of the total amount of the olefin rubber (A), the olefin polymer (B), and the propylene / α-olefin random copolymer (C). Usually, it is used in a proportion of 0.01 to 15 parts by mass, preferably 0.03 to 12 parts by mass.
〈軟化剤〉
本発明に係る前駆体には、動的架橋時に流動性や硬度の調整剤として軟化剤を添加しても良い。
<Softener>
A softener may be added to the precursor according to the present invention as a fluidity or hardness adjusting agent during dynamic crosslinking.
軟化剤は、予め前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、あるいは前記プロピレン・α−オレフィンランダム共重合体(C)に、前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)を混合時に、あるいは、混合物(前駆体)を動的架橋時に注入する方法により加ええる。その際、上記方法を単独で、あるいは上記方法を併用して添加してもよい。 The softening agent may be used in advance to the olefin rubber (A), the olefin polymer (B), or the propylene / α-olefin random copolymer (C). The blend (B) and the propylene / α-olefin random copolymer (C) can be added by mixing, or the mixture (precursor) can be added by a method of injecting during dynamic crosslinking. In that case, you may add the said method individually or in combination of the said method.
本発明に係る軟化剤としては、具体的には、プロセスオイル、潤滑油、パラフィン、流動パラフィン、ポリエチレンワックス、ポリプロピレンワックス、石油アスファルト、ワセリン等の石油系軟化剤;コールタール、コールタールピッチ等のコールタール系軟化剤;
ヒマシ油、アマニ油、ナタネ油、大豆油、椰子油等の脂肪油系軟化剤;トール油;サブ、(ファクチス);蜜ロウ、カルナウバロウ、ラノリン等のロウ類;リシノール酸、パルミチン酸、ステアリン酸、ステアリン酸バリウム、ステアリン酸カルシウム、ラウリン酸亜鉛等の脂肪酸および脂肪酸塩;ナフテン酸;パイン油、ロジンまたはその誘導体;テルペン樹脂、石油樹脂、クマロンインデン樹脂、アタクチックポリプロピレン等の合成高分子物質;ジオクチルフタレート、ジオクチルアジペート、ジオクチルセバケート等のエステル系軟化剤;マイクロクリスタリンワックス、液状ポリブタジエン、変性液状ポリブタジエン、液状ポリイソプレン、末端変性ポリイソプレン、水添末端変性ポリイソプレン、液状チオコール、炭化水素系合成潤滑油などが挙げられる。中でも、石油系軟化剤、特にプロセスオイルが好ましく用いられる。
Specific examples of the softener according to the present invention include petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, polyethylene wax, polypropylene wax, petroleum asphalt, and petroleum jelly; coal tar, coal tar pitch, and the like. Coal tar softener;
Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil; tall oil; sub, (factis); waxes such as beeswax, carnauba wax, lanolin; ricinoleic acid, palmitic acid, stearic acid Fatty acids and fatty acid salts such as barium stearate, calcium stearate, zinc laurate; naphthenic acid; pine oil, rosin or derivatives thereof; synthetic polymer substances such as terpene resin, petroleum resin, coumarone indene resin, atactic polypropylene; Ester softeners such as dioctyl phthalate, dioctyl adipate, dioctyl sebacate; microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid polyisoprene, terminal modified polyisoprene, hydrogenated terminal modified polyisoprene, liquid thiocol, hydrocarbon-based compounds Such as lubricating oil, and the like. Among these, petroleum softeners, particularly process oils are preferably used.
本発明に係る軟化剤を加える場合は、前記オレフィン系ゴム(A)100質量部に対して、通常、10〜200質量部、好ましくは15〜150質量部、更に好ましくは20〜80質量部の範囲で配合される。軟化剤を上記のような割合で用いると、得られる熱可塑性エラストマー組成物は成形時の流動性に優れ、得られる成形体の機械的物性を低下させることはない。本発明において、軟化剤の使用量が200質量部を超えると、得られる熱可塑性エラストマー組成物の耐熱性、耐熱老化性は低下する傾向にある。 When adding the softener which concerns on this invention, it is 10-200 mass parts normally with respect to 100 mass parts of said olefin rubber (A), Preferably it is 15-150 mass parts, More preferably, it is 20-80 mass parts. Formulated in a range. When the softening agent is used in the above ratio, the resulting thermoplastic elastomer composition has excellent fluidity during molding and does not deteriorate the mechanical properties of the resulting molded article. In this invention, when the usage-amount of a softening agent exceeds 200 mass parts, it exists in the tendency for the heat resistance of the thermoplastic elastomer composition obtained and heat aging resistance to fall.
〈その他添加剤〉
本発明の熱可塑性エラストマー組成物、あるいは前記前駆体には、必要に応じて、スリップ剤、核剤、充填剤、酸化防止剤、耐候安定剤、着色剤、発泡剤等の添加剤を、本発明の目的を損なわない範囲で配合することができる。
<Other additives>
If necessary, the thermoplastic elastomer composition of the present invention or the precursor may contain additives such as a slip agent, a nucleating agent, a filler, an antioxidant, a weathering stabilizer, a colorant, and a foaming agent. It can mix | blend in the range which does not impair the objective of invention.
上記核剤としては、非融解型および融解型の結晶化核剤が挙げられ、これらを単独でまたは2種以上組み合わせて用いることができる。非融解型の結晶化核剤としては、タルク、マイカ、シリカ、アルミニウムなどの無機物、臭素化ビフェニルエーテル、アルミニウムヒドロキシジ−p−tert−ブチルベンゾエート(TBBA)、有機リン酸塩、ロジン系結晶化核剤、置換トリエチレングリコールテレフタレートおよびTerylene&Nylon繊維などが挙げられ、特にヒドロキシ−ジ−p−tert−ブチル安息香酸アルミニウム、メチレンビス(2,4−ジ−tert−ブチルフェニル)リン酸ナトリウム塩、2,2'−メチレンビス(4,6−ジ−tert−ブチルフェニル)リン酸ナトリウム、ロジン系結晶化核剤が望ましい。融解型の結晶化核剤としては、ジベンジリデンソルビトール(DBS)、置換DBS、低級アルキルジベンジリデンソルビトール(PDTS)、などのソルビトール系の化合物が挙げられる。 Examples of the nucleating agent include non-melting type and melting type crystallization nucleating agents, and these can be used alone or in combination of two or more. Non-melting crystallization nucleating agents include inorganic substances such as talc, mica, silica, aluminum, brominated biphenyl ether, aluminum hydroxydi-p-tert-butylbenzoate (TBBA), organophosphate, rosin crystallization Nucleating agents, substituted triethylene glycol terephthalate and Terylene & Nylon fibers, etc., especially hydroxy-di-p-tert-butylbenzoic acid aluminum salt, methylenebis (2,4-di-tert-butylphenyl) phosphoric acid sodium salt, 2, 2'-methylenebis (4,6-di-tert-butylphenyl) phosphate, rosin-based crystallization nucleating agent is desirable. Examples of the melting crystallization nucleating agent include sorbitol-based compounds such as dibenzylidene sorbitol (DBS), substituted DBS, and lower alkyl dibenzylidene sorbitol (PDTS).
上記スリップ剤としては、たとえば脂肪酸アミド、シリコーンオイル、グリセリン、ワックス、パラフィン系オイルなどが挙げられる。
上記充填剤としては、従来公知の充填剤、具体的には、カーボンブラック、クレー、タルク、炭酸カルシウム、カオリン、ケイソウ土、シリカ、アルミナ、グラファイト、ガラス繊維などが挙げられる。
Examples of the slip agent include fatty acid amide, silicone oil, glycerin, wax, and paraffinic oil.
Examples of the filler include conventionally known fillers, specifically, carbon black, clay, talc, calcium carbonate, kaolin, diatomaceous earth, silica, alumina, graphite, glass fiber, and the like.
(発泡剤)
発泡剤としては、例えば、重炭酸ナトリウムおよび炭酸ナトリウム、炭酸水素アンモニウム、炭酸アンモニウム、亜硝酸アンモニウムなどの無機系発泡剤;N,N'−ジニトロソペンタメチレンテトラミンおよびN,N'−ジニトロソテレフタルアミドなどのニトロソ化合物;アゾジカルボンアミドおよびアゾビスイソブチロニトリルなどのアゾ化合物;ベンゼンスルホニルヒドラジドおよび4,4'−オキシビス(ベンゼンスルホニルヒドラジド)などのヒドラジド化合物;カルシウムアジドおよび4,4'−ジフェニルジスルホニルアジドなどのアジド化合物などの有機発泡剤が挙げられる。また、市販品としては、例えば、セルマイクMB1023(商品名;三協化成社製)、ビニホールAC−2F(商品名;永和化成工業社製)、ビニホールAC#LQ(商品名;永和化成工業社製、アゾジカルボンアミド(略号ADCA))、ネオセルボンN#1000SW(商品名;永和化成工業社製、4,4'−オキシビス(ベンゼンスルホニルヒドラジド(略号OBSH))、セルラーD(商品名;永和化成工業社製、N,N'−ジニトロソペンタメチレンテトラミン(略号DPT))などが挙げられる。
発泡剤の配合量は、熱可塑性エラストマー組成物100質量部に対して、通常1〜70質量部、好ましくは3〜60質量部であることが、発泡ガス発生量の点で好ましい。
(Foaming agent)
Examples of the foaming agent include inorganic foaming agents such as sodium bicarbonate and sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite; N, N′-dinitrosopentamethylenetetramine and N, N′-dinitrosoterephthalamide Nitroso compounds such as; azo compounds such as azodicarbonamide and azobisisobutyronitrile; hydrazide compounds such as benzenesulfonyl hydrazide and 4,4′-oxybis (benzenesulfonyl hydrazide); calcium azide and 4,4′-diphenyldi Organic foaming agents such as azide compounds such as sulfonyl azide. As commercially available products, for example, Cellmic MB1023 (trade name; manufactured by Sankyo Kasei Co., Ltd.), Bini Hall AC-2F (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd.), Bini Hall AC # LQ (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd.) , Azodicarbonamide (abbreviation ADCA)), Neocerbon N # 1000SW (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., 4,4′-oxybis (benzenesulfonylhydrazide (abbreviation: OBSH)), Cellular D (trade name; Eiwa Kasei Kogyo Co., Ltd.) Manufactured, N, N′-dinitrosopentamethylenetetramine (abbreviation DPT)) and the like.
The blending amount of the foaming agent is usually 1 to 70 parts by weight, preferably 3 to 60 parts by weight, with respect to 100 parts by weight of the thermoplastic elastomer composition, in terms of the amount of foaming gas generated.
(発泡助剤)
本発明では、発泡剤に加えて、必要に応じて、発泡助剤を添加してもよい。発泡助剤は、発泡剤の分解温度の低下、分解促進または気泡の均一化などの作用を示す。
(Foaming aid)
In the present invention, in addition to the foaming agent, a foaming aid may be added as necessary. The foaming aid exhibits actions such as lowering the decomposition temperature of the foaming agent, promoting decomposition, or uniforming the bubbles.
発泡助剤としては、例えば、亜鉛、カルシウム、鉛、鉄およびバリウム等の金属化合物、サリチル酸、フタル酸、ステアリン酸、シュウ酸およびクエン酸などの有機酸またはその塩、タルク、硫酸バリウムおよびシリカ等の微粒無機粒子、尿素またはその誘導体などが挙げられる。また、クエン酸、シュウ酸、フマル酸、フタル酸、リンゴ酸、酒石酸、乳酸、シクロヘキサン1,2−ジカルボン酸、ショウノウ酸、エチレンジアミン四酢酸、トリエチレンテトラミン六酢酸およびニトリロ酸等の多価カルボン酸と、炭酸水素ナトリウム、炭酸水素ナトリウムアルミニウムおよび炭酸水素カリウム等の無機炭酸化合物との混合物や、これらの反応により生じる中間体、例えば、クエン酸二水素ナトリウム、シュウ酸カリウム等のポリカルボン酸の塩なども挙げられる。市販品としては、例えば、セルペーストK5(商品名;永和化成工業社製、尿素)およびFE−507(商品名;永和化成工業社製、重曹)などが挙げられる。 Examples of the foaming aid include metal compounds such as zinc, calcium, lead, iron and barium, organic acids such as salicylic acid, phthalic acid, stearic acid, oxalic acid and citric acid or salts thereof, talc, barium sulfate and silica. Fine inorganic particles, urea or a derivative thereof. Also, polyvalent carboxylic acids such as citric acid, oxalic acid, fumaric acid, phthalic acid, malic acid, tartaric acid, lactic acid, cyclohexane 1,2-dicarboxylic acid, camphoric acid, ethylenediaminetetraacetic acid, triethylenetetramine hexaacetic acid and nitrilolic acid And inorganic carbonate compounds such as sodium hydrogen carbonate, sodium aluminum hydrogen carbonate and potassium hydrogen carbonate, and intermediates produced by these reactions, for example, salts of polycarboxylic acids such as sodium dihydrogen citrate and potassium oxalate And so on. Examples of commercially available products include cell paste K5 (trade name; manufactured by Eiwa Kasei Kogyo Co., Ltd., urea) and FE-507 (trade name: manufactured by Eiwa Kasei Kogyo Co., Ltd., baking soda).
発泡助剤の配合量は、特に限定されないが、熱可塑性エラストマー組成物:100質量部に対して、通常0.1〜5質量部、好ましくは0.5〜4質量部である。
発泡剤または発泡助剤は、発泡成形体を成形する前にドライブレンドして、成形するときに分解するようにしてもよいし、予め、ペレットに溶融ブレンドしてもよい。
Although the compounding quantity of a foaming adjuvant is not specifically limited, It is 0.1-5 mass parts normally with respect to 100 mass parts of thermoplastic elastomer compositions: Preferably it is 0.5-4 mass parts.
The foaming agent or foaming aid may be dry blended before molding the foamed molded article and decomposed during molding, or may be melt blended into pellets in advance.
<熱可塑性エラストマー組成物の製造方法>
本発明の熱可塑性エラストマー組成物は、前記前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)、必要に応じて前記軟化剤など所定量含む混合物(前駆体)を動的架橋することにより得られる。動的架橋を行う際には、前記架橋剤の存在下、あるいは前記架橋剤と前記架橋助剤の存在下に、動的に熱処理するのがよい。
<Method for producing thermoplastic elastomer composition>
The thermoplastic elastomer composition of the present invention comprises the olefin rubber (A), the olefin polymer (B), the propylene / α-olefin random copolymer (C), and if necessary, the softener. It can be obtained by dynamically crosslinking a mixture (precursor) containing a predetermined amount. When dynamic crosslinking is performed, heat treatment is preferably performed dynamically in the presence of the crosslinking agent or in the presence of the crosslinking agent and the crosslinking aid.
ここに、「動的に熱処理する」とは、溶融状態で混練することをいう。
本発明における動的な熱処理は、非開放型の装置中で行なうことが好ましく、また窒素、炭酸ガス等の不活性ガス雰囲気下で行なうことが好ましい。熱処理の温度は、オレフィン系重合体(B)の融点から300℃の範囲であり、通常150〜270℃、好ましくは170℃〜250℃である。混練時間は、通常1〜20分間、好ましくは1〜10分間である。また、加えられる剪断力は、剪断速度で10〜50,000sec-1、好ましくは100〜10,000sec-1の範囲である。
Here, “dynamically heat-treating” means kneading in a molten state.
The dynamic heat treatment in the present invention is preferably performed in a non-open type apparatus, and is preferably performed in an inert gas atmosphere such as nitrogen or carbon dioxide. The temperature of heat processing is the range of 300 degreeC from melting | fusing point of an olefin type polymer (B), and is 150-270 degreeC normally, Preferably it is 170 degreeC-250 degreeC. The kneading time is usually 1 to 20 minutes, preferably 1 to 10 minutes. Further, the shear force applied is, 10~50,000Sec -1 shear rate, preferably in the range of 100~10,000sec -1.
混練装置としては、ミキシングロール、インテンシブミキサー(たとえばバンバリーミキサー、ニーダー)、一軸または二軸押出機等を用いることができるが、非開放型の装置が好ましい。 As a kneading apparatus, a mixing roll, an intensive mixer (for example, a Banbury mixer, a kneader), a uniaxial or biaxial extruder can be used, and a non-open type apparatus is preferable.
本発明によれば、上述した動的な熱処理によって、前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)を含み、前記オレフィン系ゴム(A)の少なくとも一部が架橋された熱可塑性エラストマー組成物が得られる。 According to the present invention, the olefin rubber (A), the olefin polymer (B), and the propylene / α-olefin random copolymer (C) are contained by the dynamic heat treatment described above, and the olefin A thermoplastic elastomer composition in which at least a part of the rubber (A) is crosslinked is obtained.
前記オレフィン系ゴム(A)、前記オレフィン系重合体(B)、および前記プロピレン・α−オレフィンランダム共重合体(C)を含む混合物(前駆体)を動的架橋して得られる熱可塑性エラストマー組成物で架橋される重合体は、主としてオレフィン系ゴム(A)である。 Thermoplastic elastomer composition obtained by dynamically crosslinking a mixture (precursor) containing the olefin rubber (A), the olefin polymer (B), and the propylene / α-olefin random copolymer (C). The polymer that is crosslinked with the product is mainly an olefin rubber (A).
<熱可塑性エラストマーの用途>
本発明の熱可塑性エラストマー組成物は、種々公知の成形方法、具体的には、例えば、押出成形、プレス成形、射出成形、カレンダー成形、中空成形等の各種の成形方法により、熱可塑性エラストマー成形体とすることができる。さらに、上記成形方法で得られたシートなど成形体を熱成形などで二次加工、あるいは、他の材料と積層して成形体とすることができる。
<Uses of thermoplastic elastomer>
The thermoplastic elastomer composition of the present invention can be produced by various known molding methods, specifically, by various molding methods such as extrusion molding, press molding, injection molding, calendar molding, and hollow molding. It can be. Furthermore, a molded body such as a sheet obtained by the above molding method can be formed into a molded body by secondary processing by thermoforming or the like, or laminated with other materials.
本発明に係る熱可塑性エラストマー成形体は特にその使用用途を限定されるものではないが、例えば、自動車用部品、土木・建材用品、電気・電子部品、衛生用品、フィルム・シート、発泡体など種々公知の用途に好適である。 The thermoplastic elastomer molded body according to the present invention is not particularly limited in its usage, but various examples such as automobile parts, civil engineering / building materials, electrical / electronic parts, sanitary goods, films / sheets, foams, etc. Suitable for known applications.
〈自動車部品〉
本発明の熱可塑性エラストマー成形体の使用し得る自動車部品としては、例えば、ウェザーストリップ、天井材、内装シート、バンパーモール、サイドモール、エアスポイラー、エアダクトホース、カップホルダー、サイドブレーキグリップ、シフトノブカバー、シート調整ツマミ、フラッパードアシール、ワイヤーハーネスグロメット、ラックアンドピニオンブーツ、サスペンションカバーブーツ、ガラスガイド、インナーベルトラインシール、ルーフガイド 、トランクリッドシール、モールデッドクォーターウィンドガスケット、コーナーモールディング、グラスエンキャプシュレーション、フードシール、グラスランチャンネル、セカンダリーシール、各種パッキン類、バンパー部品、ボディパネル、サイドシールド、グラスランチャンネル、インストルメントパネル表皮、ドア表皮、天井表皮、ウェザーストリップ材、ホース、ステアリングホイール、ブーツ、ワイヤーハーネスカバー、シートアジャスターカバー等を例示でき、中でも、本発明の熱可塑性エラストマー組成物は、押出成形時に目ヤニの発生を抑制でき、しかも、得られる成形品の外観が優れるので、押出成形で得られる成形品が、特に好ましい。
<Auto parts>
Examples of automobile parts that can be used for the thermoplastic elastomer molded body of the present invention include, for example, a weather strip, a ceiling material, an interior sheet, a bumper molding, a side molding, an air spoiler, an air duct hose, a cup holder, a side brake grip, a shift knob cover, Seat adjustment knob, flapper door seal, wire harness grommet, rack and pinion boot, suspension cover boot, glass guide, inner belt line seal, roof guide, trunk lid seal, molded quarter window gasket, corner molding, glass encapsulation, Food seal, glass run channel, secondary seal, various packings, bumper parts, body panel, side shield, glass launcher Can be exemplified, such as a tunnel, an instrument panel skin, a door skin, a ceiling skin, a weather strip material, a hose, a steering wheel, a boot, a wire harness cover, a seat adjuster cover, etc. Among them, the thermoplastic elastomer composition of the present invention is extruded. A molded product obtained by extrusion molding is particularly preferred because it can sometimes suppress the occurrence of eye cracks and has an excellent appearance of the molded product obtained.
〈土木・建材用品〉
本発明の熱可塑性エラストマー成形体の使用し得る土木・建材用品としては、例えば、地盤改良用シート、上水板、騒音防止壁等の土木資材や建材、土木・建築用各種ガスケットおよびシート、止水材、目地材、建築用窓枠などを例示できき、中でも、本発明の熱可塑性エラストマー組成物は、押出成形時に目ヤニの発生を抑制でき、しかも、得られる成形品の外観が優れるので、押出成形で得られる成形品が、特に好ましい。
<Civil engineering / building materials>
Civil engineering / building materials that can be used for the thermoplastic elastomer molded body of the present invention include, for example, ground improvement sheets, waterworks, noise prevention walls and other civil engineering materials and construction materials, civil engineering / architectural gaskets and sheets, Water materials, joint materials, architectural window frames, etc. can be exemplified. Among them, the thermoplastic elastomer composition of the present invention can suppress the occurrence of spears at the time of extrusion molding, and the appearance of the obtained molded product is excellent. A molded product obtained by extrusion molding is particularly preferable.
〈電気・電子部品〉
本発明の熱可塑性エラストマー成形体の使用し得る電気・電子部品としては、例えば、電線被覆材、コネクター、キャップ、プラグ等の電気・電子部品などを例示でき、中でも、本発明の熱可塑性エラストマー組成物は、押出成形時に目ヤニの発生を抑制でき、しかも、得られる成形品の外観が優れるので、押出成形で得られる成形品が、特に好ましい。
<Electric / electronic parts>
Examples of the electric / electronic parts that can be used in the thermoplastic elastomer molded article of the present invention include electric / electronic parts such as wire coating materials, connectors, caps, plugs, etc., among others, the thermoplastic elastomer composition of the present invention. Since the product can suppress the occurrence of glazing at the time of extrusion molding and the appearance of the obtained molded product is excellent, a molded product obtained by extrusion molding is particularly preferred.
〈衛生用品〉
本発明の熱可塑性エラストマー成形体の使用し得る衛生用品としては、例えば、生理用品、使い捨ておむつ、歯ブラシ用グリップ等の衛生用品などを例示でき、中でも、本発明の熱可塑性エラストマー組成物は、押出成形時に目ヤニの発生を抑制でき、しかも、得られる成形品の外観が優れるので、押出成形で得られる成形品が、特に好ましい。
<Hygiene products>
Examples of sanitary products that can be used for the thermoplastic elastomer molded article of the present invention include sanitary products such as sanitary products, disposable diapers, and grips for toothbrushes. Among them, the thermoplastic elastomer composition of the present invention is extruded. A molded product obtained by extrusion molding is particularly preferred because generation of eyes can be suppressed during molding and the appearance of the obtained molded product is excellent.
〈フィルム・シート〉
本発明の熱可塑性エラストマー成形体の使用し得るフィルム・シートとしては、例えば、輸液バッグ、医療容器、自動車内外装材、飲料ボトル、衣装ケース、食品包材、食品容器、レトルト容器、パイプ、透明基板、シーラントなどを例示でき、中でも、本発明の熱可塑性エラストマー組成物は、押出成形時に目ヤニの発生を抑制でき、しかも、得られる成形品の外観が優れるので、押出成形で得られる成形品が、特に好ましい。
<Film / Sheet>
Examples of films and sheets that can be used for the thermoplastic elastomer molded article of the present invention include, for example, infusion bags, medical containers, automotive interior and exterior materials, beverage bottles, clothing cases, food packaging materials, food containers, retort containers, pipes, transparent Examples include substrates, sealants, etc. Among them, the thermoplastic elastomer composition of the present invention can suppress generation of cracks during extrusion molding, and the appearance of the resulting molded product is excellent, so that the molded product obtained by extrusion molding Is particularly preferred.
〈発泡体〉
本発明の熱可塑性エラストマー成形体の使用し得る発泡体としては、例えば、自動車内装表皮材、ウェザーストリップスポンジ、ボディパネル、ステアリングホイール、サイドシールドなどを例示できる。
<Foam>
Examples of the foam that can be used in the thermoplastic elastomer molded body of the present invention include an automobile interior skin material, a weather strip sponge, a body panel, a steering wheel, and a side shield.
〈その他〉
本発明の熱可塑性エラストマー成形体の使用し得るその他用途としては、例えば、靴底、サンダル等の履物;水泳用フィン、水中眼鏡、ゴルフクラブグリップ、野球バットグリップ等のレジャー用品、ガスケット、防水布、ベルト、ガーデンホース、階段用滑り止めテープ、物流用パレットの滑り止めテープなどを例示できる。
本発明の熱可塑性エラストマー成形体の使用し得る用途として、上記用途に限らず、種々の用途に使用し得る。
<Others>
Other uses that can be used for the thermoplastic elastomer molded article of the present invention include, for example, footwear such as shoe soles and sandals; leisure goods such as swimming fins, underwater glasses, golf club grips, baseball bat grips, gaskets, and waterproof cloths. Belts, garden hoses, anti-slip tapes for stairs, non-slip tapes for logistics pallets, and the like.
The use of the thermoplastic elastomer molded article of the present invention is not limited to the above uses, and can be used for various uses.
以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。
実施例および比較例で用いた重合体および添加剤などを以下に示す。
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all.
The polymers and additives used in Examples and Comparative Examples are shown below.
(1)オレフィン系ゴム(A)
(1−1)エチレン・プロピレン・ENB共重合体ゴム(A1−1)
商品名 三井EPT 3072EPM(商標)、三井化学社製、エチレン含量:76モル%、ムーニー粘度ML(1+4)125℃:51、ヨウ素価:11.5、油展量(パラフィン系プロセスオイル):40PHR。
(1) Olefin rubber (A)
(1-1) Ethylene / propylene / ENB copolymer rubber (A1-1)
Product name Mitsui EPT 3072 EPM (trademark), manufactured by Mitsui Chemicals, ethylene content: 76 mol%, Mooney viscosity ML (1 + 4) 125 ° C: 51, iodine value: 11.5, oil extended amount (paraffinic process oil) : 40 PHR.
(1−2)エチレン・プロピレン・ENB共重合体ゴム(A1−2)
商品名 三井EPT 3052EPM(商標)、三井化学社製、エチレン含量:76モル%、MFR:2.7g/10分(230℃、荷重5kg)、ヨウ素価11.5、プロピレン単独重合体(商品名 プライムポリプロ E−200GPプライムポリマー社製)含有量:33PHR、油展量:(パラフィン系プロセスオイル)62PHR。
(1-2) Ethylene / propylene / ENB copolymer rubber (A1-2)
Trade name: Mitsui EPT 3052 EPM (trademark), manufactured by Mitsui Chemicals, ethylene content: 76 mol%, MFR: 2.7 g / 10 min (230 ° C., load 5 kg), iodine value 11.5, propylene homopolymer (trade name) Prime Polypro E-200GP Prime Polymer Co., Ltd.) Content: 33 PHR, Oil extended amount: (paraffinic process oil) 62 PHR.
(1−3)エチレン・プロピレン・ENB共重合体ゴム(A1−3)
三井EPT 3092PM(商標)、エチレン含量:77.0モル%、ムーニー粘度ML(1+4)125℃:61、ヨウ素価:9.8。
(1-3) Ethylene / propylene / ENB copolymer rubber (A1-3)
Mitsui EPT 3092PM (trademark), ethylene content: 77.0 mol%, Mooney viscosity ML (1 + 4) 125 ° C: 61, iodine value: 9.8.
(2)オレフィン系重合体(B)
(2−1)プロピレン単独重合体(B1−1)
商品名 プライムポリプロ J105G、プライムポリマー社製、MFR(230℃、荷重21.18N):9.0g/10分、融点:162℃。
(2) Olefin polymer (B)
(2-1) Propylene homopolymer (B1-1)
Product name Prime Polypro J105G, manufactured by Prime Polymer Co., Ltd., MFR (230 ° C., load 21.18 N): 9.0 g / 10 min, melting point: 162 ° C.
(2−2)プロピレンブロック共重合体(B1−2)
商品名 EL-Pro P740J(商標)、SCG CHEMICALS社製(タイ)、MFR(230℃、荷重21.18N):27g/10分、融点:160℃。
(2-2) Propylene block copolymer (B1-2)
Product name EL-Pro P740J (trademark), manufactured by SCG CHEMICALS (Thailand), MFR (230 ° C., load 21.18 N): 27 g / 10 min, melting point: 160 ° C.
(2−3)直鎖状低密度ポリエチレン(B2−1)
商品名 ウルトゼックス20200J、プライムポリマー社製、MFR(190℃、荷重21.18N):8.5g/10分、密度:918kg/m3、融点:120℃、ビカット軟化点:94℃。
(2-3) Linear low density polyethylene (B2-1)
Trade name: Ultrazex 20200J, manufactured by Prime Polymer Co., Ltd., MFR (190 ° C., load 21.18 N): 8.5 g / 10 min, density: 918 kg / m 3 , melting point: 120 ° C., Vicat softening point: 94 ° C.
(2−4)メタロセン直鎖状低密度ポリエチレン(B2−2)
商品名 エボリューSP0540、プライムポリマー製、MFR(190℃、荷重21.18N):3.8g/10分、密度:903kg/m3、融点:98℃、ビカット軟化点:83℃。
(2-4) Metallocene linear low density polyethylene (B2-2)
Product name Evolue SP0540, made of prime polymer, MFR (190 ° C., load 21.18 N): 3.8 g / 10 min, density: 903 kg / m 3 , melting point: 98 ° C., Vicat softening point: 83 ° C.
(3)プロピレン・α−オレフィンランダム共重合体(C)
(3−1)プロピレン・エチレンランダム共重合体(C1)
商品名 Vistamaxx 6102、エクソン・モービル社製、エチレン含有量:21.4モル%、Mw/Mn:2.1、B値:1.02、MFR(230℃、荷重21.18N):3.0g/10分、密度:863kg/m3。
(3) Propylene / α-olefin random copolymer (C)
(3-1) Propylene / ethylene random copolymer (C1)
Product name Vistamaxx 6102, manufactured by Exxon Mobil, ethylene content: 21.4 mol%, Mw / Mn: 2.1, B value: 1.02, MFR (230 ° C., load 21.18 N): 3.0 g / 10 minutes, density: 863 kg / m 3 .
(3−2)プロピレン・エチレンランダム共重合体(C2)
商品名 Vistamaxx 6202 エクソン・モービル社製、エチレン含有量:20.1モル%、Mw/Mn:2.9、MFR(230℃、荷重21.18N):20g/10分、密度:861kg/m3。
(3-2) Propylene / ethylene random copolymer (C2)
Product name Vistamaxx 6202 manufactured by ExxonMobil, ethylene content: 20.1 mol%, Mw / Mn: 2.9, MFR (230 ° C., load 21.18 N): 20 g / 10 min, density: 861 kg / m 3 .
(3−3)プロピレン・エチレンランダム共重合体(C3)
商品名 Versify 2300 ダウ・ケミカル社、エチレン含有量:13.5モル%、Mw/Mn:2.2、MFR(230℃、荷重21.18N):2.0g/10分、密度:866kg/m3。
(3-3) Propylene / ethylene random copolymer (C3)
Product name Versify 2300 Dow Chemical Company, ethylene content: 13.5 mol%, Mw / Mn: 2.2, MFR (230 ° C., load 21.18 N): 2.0 g / 10 min, density: 866 kg / m 3 .
(4)プロピレン・エチレンランダム共重合体(D)
(4−1)エチレン・プロピレンランダム共重合体(D1)
商品名 タフマーS4020 三井化学社製、エチレン含有量:34.0モル%、Mw/Mn:5.4、MFR(230℃、荷重21.18N):2.0g/10分、密度:860kg/m3。
(4) Propylene / ethylene random copolymer (D)
(4-1) Ethylene / propylene random copolymer (D1)
Product name Toughmer S4020, manufactured by Mitsui Chemicals, ethylene content: 34.0 mol%, Mw / Mn: 5.4, MFR (230 ° C., load 21.18 N): 2.0 g / 10 min, density: 860 kg / m 3 .
(4−2)エチレン・プロピレンランダム共重合体(D2)
商品名 タフマーS4030 三井化学社製、エチレン含有量:40.0モル%、Mw/Mn:5.3、B値:0.91、MFR(230℃、荷重21.18N):0.4g/10分、密度:860kg/m3。
(4-2) Ethylene / propylene random copolymer (D2)
Product name TAFMER S4030, manufactured by Mitsui Chemicals, ethylene content: 40.0 mol%, Mw / Mn: 5.3, B value: 0.91, MFR (230 ° C., load 21.18 N): 0.4 g / 10 Min, density: 860 kg / m 3 .
(5)エチレン・α−オレフィンランダム共重合体(E)
(5−1)エチレン・1−ブテンランダム共重合体(E1)
商品名 タフマーA0550S(商標)、三井化学社製、密度:861kg/m3、MFR(230℃、荷重21.18N):0.9g/10分。
(5) Ethylene / α-olefin random copolymer (E)
(5-1) Ethylene / 1-butene random copolymer (E1)
Trade name Toughmer A0550S (trademark), manufactured by Mitsui Chemicals, density: 861 kg / m 3 , MFR (230 ° C., load 21.18 N): 0.9 g / 10 min.
(5−2)エチレン・プロピレンランダム共重合体(E2)
商品名 タフマーP0775(商標)、三井化学社製、密度:867kg/m3、MFR(230℃、荷重21.18N):0.6g/10分。
(5-2) Ethylene / propylene random copolymer (E2)
Product name TAFMER P0775 (trademark), manufactured by Mitsui Chemicals, density: 867 kg / m 3 , MFR (230 ° C., load 21.18 N): 0.6 g / 10 min.
(6)ブチルゴム
商品名:IIR065、エクソンモービルケミカル社製、不飽和度:0.8モル%、ムーニー粘度ML(1+8)125℃:32。
(6) Butyl rubber Product name: IIR065, manufactured by ExxonMobil Chemical Co., Ltd., degree of unsaturation: 0.8 mol%, Mooney viscosity ML (1 + 8) 125 ° C .: 32.
(7)軟化剤
パラフィン系プロセスオイル:出光興産製、商品名 ダイアナプロセス PW−100
(7) Softener Paraffinic process oil: Idemitsu Kosan Co., Ltd., trade name Diana Process PW-100
(8)架橋剤
日本油脂株式会社製、2,5-ジメチルー2,5-ビス(t-ブチルパーオキシ)ヘキサン。
(8) Crosslinking agent 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane manufactured by Nippon Oil & Fats Co., Ltd.
(9)架橋助剤
新日鐵化学株式会社製、商品名DVB−810、ジビニルベンゼン混合物。
(9) Crosslinking aid: Nippon Steel Chemical Co., Ltd., trade name DVB-810, divinylbenzene mixture.
(10)酸化防止剤
商品名 IRGANOX1010、BASF社製、ペンタエリスリトールテトラキス[3,−(3,5−ジ−tert−ブチル−4−ヒドロキシフェニル)プロピオネート]。
(10) Antioxidant Trade name IRGANOX 1010, manufactured by BASF, pentaerythritol tetrakis [3,-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate].
(11)紫外線吸収剤
商品名 Tinuvin326、BASF社製、2-(5-クロロ-2-ベンゾトリアゾリル)-6-tert-ブチル-p-クレゾール。
(11) Ultraviolet absorber Product name Tinuvin 326, manufactured by BASF, 2- (5-chloro-2-benzotriazolyl) -6-tert-butyl-p-cresol.
(12)滑剤
(12−1)オレイン酸アミド
商品名 アーモスリップCP、ライオン株式会社製、
(12) Lubricant (12-1) Oleic acid amide Product name Armoslip CP, manufactured by Lion Corporation,
(12−2)ステアリン酸カルシウム
ステアリン酸カルシウム 日本油脂株式会社製
実施例および比較例で得られた熱可塑性エラストマー組成物の物性は以下の方法で測定した。
(12-2) Calcium stearate Calcium stearate Nippon Oil & Fat Co., Ltd. The physical properties of the thermoplastic elastomer compositions obtained in Examples and Comparative Examples were measured by the following methods.
(1)硬度
熱可塑性エラストマー組成物の硬度は、JIS K6253に準拠して、ショアーA硬度を測定した。
ショアーA硬度は、熱可塑性エラストマー組成物を用いて、プレス成形機により厚さ2mmのシートを作製し、A型測定器を用い、押針接触後直ちに目盛りを読み取った。
(1) Hardness The hardness of the thermoplastic elastomer composition was measured by Shore A hardness according to JIS K6253.
For Shore A hardness, a 2 mm thick sheet was prepared by a press molding machine using the thermoplastic elastomer composition, and the scale was read immediately after contact with the pressing needle using an A-type measuring instrument.
(2)破断点応力・伸び
JIS K6251に準拠して、引張試験を下記の条件で行ない、破断時の引張強度と伸びを測定した。
(2) Breaking point stress / elongation According to JIS K6251, a tensile test was performed under the following conditions, and the tensile strength and elongation at break were measured.
(試験条件)プレス成形機により厚さ2mmのシートを作製し、当該シートからJIS3号試験片を打ち抜き、引張試験機(東洋精機製作所社製 ストログラフAE)を用いて引張速度500mm/分の条件で引張試験を行なった。 (Test conditions) A sheet having a thickness of 2 mm was prepared by a press molding machine, a JIS No. 3 test piece was punched from the sheet, and a tensile tester (Strograph AE manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used. A tensile test was performed.
(3)目ヤニ量
熱可塑性エラストマー組成物を、スクリュー径50mm、L/Dが31、圧縮比が3.1のフルフライト型スクリューを有する1軸押出機と、それに取り付けた開口部22mm×2mmのダイスを用いて、前記押出機の導入部からダイス出口まで160から200℃のグラジエント昇温により、テープ状の熱可塑性エラストマー組成物からなる成形品を12kg/hで10分間押出した後、ダイスに付着した目ヤニ、さらには成形品に付着した目ヤニを秤量した。
(3) Eye amount The thermoplastic elastomer composition is a single screw extruder having a full flight type screw having a screw diameter of 50 mm, an L / D of 31, and a compression ratio of 3.1, and an opening 22 mm × 2 mm attached thereto. The molded article made of the tape-shaped thermoplastic elastomer composition was extruded at 12 kg / h for 10 minutes by a gradient temperature increase from 160 to 200 ° C. from the introduction part of the extruder to the die outlet. The eye spear adhering to the mold and the eye spear adhering to the molded product were weighed.
(4)成形品の外観
熱可塑性エラストマー組成物を、スクリュー径50mm、L/Dが31、圧縮比が3.1のフルフライト型スクリューを有する1軸押出機と、それに取り付けた開口部33mm×1mmのダイスを用いて、前記押出機の導入部からダイス出口まで160から200℃のグラジエント昇温により、テープ状の熱可塑性エラストマー組成物からなる成形品を8kg/hで10分間押出した後、得られたテープ状の成形品の外観を以下の基準で評価した。
レベル1:成形品の形状が不安定である。
レベル2:成形品の表面に凹凸が多数ある。
レベル3:成形品の表面に少し凹凸がある。
レベル4:成形品の表面がほぼ平滑である。
レベル5:成形品の表面が平滑である。
また、テープ状シート(ブツの評価方法)
(4) Appearance of molded product A thermoplastic elastomer composition, a single-screw extruder having a full flight type screw having a screw diameter of 50 mm, an L / D of 31, and a compression ratio of 3.1, and an opening 33 mm × attached thereto After extruding a molded article made of a tape-like thermoplastic elastomer composition at 8 kg / h for 10 minutes, using a 1 mm die, with a gradient temperature increase from 160 to 200 ° C. from the introduction part of the extruder to the die outlet, The appearance of the obtained tape-shaped molded product was evaluated according to the following criteria.
Level 1: The shape of the molded product is unstable.
Level 2: There are many irregularities on the surface of the molded product.
Level 3: There is a slight unevenness on the surface of the molded product.
Level 4: The surface of the molded product is almost smooth.
Level 5: The surface of the molded product is smooth.
In addition, tape-like sheet (evaluation method)
(5)融点(Tm)
重合体の融点(Tm)は、示差走査熱量計(DSC)としてセイコーインストルメント社製のRDC220を用い、重合体試料約5mgを精秤し、JIS K 7121に準拠し、窒素ガス流入量:50ml/分の条件下で、−100℃から加熱速度:100℃/分で230℃まで昇温して試料を一旦融解させた後、230℃に10分間維持し、冷却速度:10℃/分で−150℃まで降温して結晶化させた後、再度、加熱速度:10℃/分で230℃まで昇温して熱融解曲線を得、得られた熱融解曲線から、融解熱量(ΔH)が10J/g以上の融解ピークで最大吸収ピークを融点(Tm)とした。また、上記測定温度範囲で、融解熱量(ΔH)が10J/g以上の融解ピークが観測されない場合は、融点が観測されない、とした。
(5) Melting point (Tm)
The melting point (Tm) of the polymer is a differential scanning calorimeter (DSC) using an RDC220 manufactured by Seiko Instruments Inc., approximately 5 mg of a polymer sample is precisely weighed, and in accordance with JIS K 7121, nitrogen gas inflow: 50 ml The sample was heated from -100 ° C. to 230 ° C. at a heating rate of 100 ° C./min under the conditions of / min for 1 minute, then maintained at 230 ° C. for 10 minutes, and at a cooling rate of 10 ° C./min. After cooling to −150 ° C. for crystallization, the temperature was increased again to 230 ° C. at a heating rate of 10 ° C./min to obtain a heat melting curve. From the obtained heat melting curve, the heat of fusion (ΔH) was The maximum absorption peak was the melting point (Tm) at a melting peak of 10 J / g or more. Further, in the measurement temperature range, when no melting peak with a heat of fusion (ΔH) of 10 J / g or more was observed, no melting point was observed.
〔実施例1〕
オレフィン系ゴム(A)としてA1−1を83.3質量部〔A1−1:83.3質量部に対して、オレフィン系ゴム(A)成分量:59.5質量部、および、パラフィン系プロセスオイル量:23.8質量部含有〕、A1−2を78.9質量部〔A1−2:78.9質量部に対して、オレフィン系ゴム(A)成分量:40.5質量部、パラフィン系プロセスオイル:25.1質量部、および、ポリプロピレン:13.4質量部含有〕《オレフィン系ゴムの総量:100質量部》を用い、オレフィン系重合体(B)として、B1−1をオレフィン系ゴム成分の総量:100質量部に対して35.1質量部、プロピレン・α−オレフィンランダム共重合体(C)としてC1をオレフィン系ゴム成分の総量:100質量部に対して21.9質量部、更に、オレフィン系ゴム成分の総量:100質量部に対して、架橋剤として過酸化物(日本油脂株式会社製、2,5-ジメチルー2,5-ビス(t-ブチルパーオキシ)ヘキサン)を0.93質量部、架橋助剤としてジビニルベンゼン(新日鐵化学株式会社製、商品名DVB−810)を0.37質量部、軟化剤(パラフィン系プロセスオイル:出光興産製、商品名 ダイアナプロセス PW−100)を0.56質量部、酸化防止剤としてフェノール系酸化防止剤(日本チバガイギー(株)製、イルガノックス1010)を0.44質量部、紫外線吸収剤としてベンゾトリアゾール系(日本チバガイギー(株)製、チヌビン326)を0.22質量部、および、滑剤として脂肪酸アミド系(ライオン(株)製、アーモスリップCP)を0.22質量部をヘンシェルミキサーで十分混合し、押出機(神戸製鋼(株)製、KTX−46)を用いて、シリンダー温度、C1:120℃、C2〜C3:140℃、C4:150℃、C5:180℃、C6:200℃、C7〜C14:230℃、ダイス温度:200℃、スクリュー回転数400rpm、押出量:50kg/hr、シリンダー9の位置よりパラフィン系プロセスオイル(出光興産製、商品名 ダイアナプロセス PW−100)をオレフィン系ゴム(A)の総量:100質量部に対して30.7質量部を液添注入しながら溶融混練を行い、熱可塑性エラストマー組成物のペレットを得た。
得られた熱可塑性エラストマー組成物を用いて、前記方法に従って評価し、表1に示す。
[Example 1]
As the olefin rubber (A), A1-1 is 83.3 parts by mass [A1-1: 83.3 parts by mass, the amount of the olefin rubber (A) component: 59.5 parts by mass, and a paraffin process. Oil amount: 23.8 parts by mass], A1-2 of 78.9 parts by mass [A1-2: 78.9 parts by mass, olefinic rubber (A) component amount: 40.5 parts by mass, paraffin System process oil: 25.1 parts by mass and polypropylene: 13.4 parts by mass] << Total amount of olefinic rubber: 100 parts by mass >> Using B1-1 as the olefin polymer (B) Total amount of rubber component: 35.1 parts by mass with respect to 100 parts by mass, C1 as propylene / α-olefin random copolymer (C): Total amount of olefinic rubber component: 21.9 parts by mass with respect to 100 parts by mass , In addition, a peroxide (2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, manufactured by Nippon Oil & Fats Co., Ltd.) as a crosslinking agent with respect to 100 parts by mass of the total amount of the olefin rubber component is 0. .93 parts by mass, 0.37 parts by mass of divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd., trade name DVB-810) as a crosslinking aid, softener (paraffinic process oil: Idemitsu Kosan, trade name Diana Process PW -100) 0.56 parts by mass, phenolic antioxidant (manufactured by Ciba Geigy Japan Ltd., Irganox 1010) as an antioxidant, 0.44 parts by mass, and benzotriazole type (Nippon Ciba Geigy Co., Ltd.) as an ultraviolet absorber. ), 0.22 parts by mass of TINUVIN 326) and 0.22 parts by mass of fatty acid amide (Lion Corporation, Armoslip CP) as a lubricant. Mix well with a mixer and use an extruder (KTX-46, manufactured by Kobe Steel Co., Ltd.), cylinder temperature, C1: 120 ° C, C2 to C3: 140 ° C, C4: 150 ° C, C5: 180 ° C, C6. : 200 ° C., C7 to C14: 230 ° C., die temperature: 200 ° C., screw rotation speed 400 rpm, extrusion rate: 50 kg / hr, paraffin-based process oil (made by Idemitsu Kosan Co., Ltd., trade name Diana Process PW-100) The total amount of olefin rubber (A) was melt kneaded while liquid-injecting 30.7 parts by mass with respect to 100 parts by mass to obtain pellets of a thermoplastic elastomer composition.
Using the obtained thermoplastic elastomer composition, it was evaluated according to the above-mentioned method and shown in Table 1.
〔実施例2〕
実施例1で用いたプロピレン・α−オレフィンランダム共重合体(C)に替えて、プロピレン・α−オレフィンランダム共重合体(C)として、C3を用いる以外は実施例1と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
[Example 2]
In place of the propylene / α-olefin random copolymer (C) used in Example 1, C3 was used as the propylene / α-olefin random copolymer (C), except that C3 was used. A plastic elastomer was obtained. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
〔比較例1〕
実施例1で用いたプロピレン・α−オレフィンランダム共重合体(C)に替えて、エチレン・プロピレンランダム共重合体としてD2を用いる以外は実施例1と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
[Comparative Example 1]
A thermoplastic elastomer was obtained in the same manner as in Example 1 except that D2 was used as the ethylene / propylene random copolymer instead of the propylene / α-olefin random copolymer (C) used in Example 1. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
〔実施例3〕
オレフィン系ゴム(A)としてA1−3を100質量部、オレフィン系重合体(B)としてB1−1、B1−2、およびB2−1をA1−3:100質量部に対して、各々12,9質量部、65.7質量部、および77.1質量部〔オレフィン系重合体(B)の総量:155.7質量部〕、プロピレン・α−オレフィンランダム共重合体(C)としてC1をA1−3:100質量部に対して、30質量部、更に、A1−3:100質量部に対して、架橋剤として過酸化物(日本油脂株式会社製、2,5-ジメチルー2,5-ビス(t-ブチルパーオキシ)ヘキサン)を1.21質量部、架橋助剤としてジビニルベンゼン(新日鐵化学株式会社製、商品名DVB−810)を0.49質量部、軟化剤(パラフィン系プロセスオイル:出光興産製、商品名 ダイアナプロセス PW−100)を0.73質量部、酸化防止剤としてフェノール系酸化防止剤(日本チバガイギー(株)製、イルガノックス1010)を0.57質量部、紫外線吸収剤としてベンゾトリアゾール系(日本チバガイギー(株)製、チヌビン326)を0.29質量部をヘンシェルミキサーで十分混合し、押出機(神戸製鋼(株)製、KTX−46)を用いて、シリンダー温度、C1:120℃、C2〜C3:140℃、C4:150℃、C5:180℃、C6:200℃、C7〜C14:230℃、ダイス温度:200℃、スクリュー回転数400rpm、押出量:50kg/hr、シリンダー9の位置よりパラフィン系プロセスオイル(出光興産製、商品名 ダイアナプロセス PW−100)をA1−3:100質量部に対して11.4質量部を液添注入しながら溶融混練を行い、熱可塑性エラストマー組成物のペレットを得た。
得られた熱可塑性エラストマー組成物を用いて、前記方法に従って評価し、表1に示す。
Example 3
100 parts by mass of A1-3 as the olefin rubber (A), and B1-1, B1-2, and B2-1 as the olefin polymer (B) are respectively 12, 9 parts by mass, 65.7 parts by mass, and 77.1 parts by mass (total amount of olefin polymer (B): 155.7 parts by mass), C1 as A1 as a propylene / α-olefin random copolymer (C) -3: 100 parts by weight, 30 parts by weight, and A1-3: 100 parts by weight as a crosslinking agent (Nippon Yushi Co., Ltd., 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane) is 1.21 parts by mass, divinylbenzene (manufactured by Nippon Steel Chemical Co., Ltd., trade name DVB-810) is used as a crosslinking aid, 0.49 parts by mass, and a softening agent (paraffinic process). Oil: Made by Idemitsu Kosan, trade name Diana Process PW-100) 0.73 parts by mass, phenolic antioxidant (Nihon Ciba Geigy Co., Ltd., Irganox 1010) 0.57 parts by mass as an antioxidant, and benzotriazole type (Nippon Ciba Geigy) as an ultraviolet absorber. Co., Ltd., Tinuvin 326) 0.29 parts by mass was sufficiently mixed with a Henschel mixer, and using an extruder (KTX-46, KTX-46), cylinder temperature, C1: 120 ° C., C 2 − C3: 140 ° C., C4: 150 ° C., C5: 180 ° C., C6: 200 ° C., C7 to C14: 230 ° C., die temperature: 200 ° C., screw rotation speed 400 rpm, extrusion amount: 50 kg / hr, from the position of the cylinder 9 Paraffin-based process oil (trade name, Diana Process PW-100, manufactured by Idemitsu Kosan Co., Ltd.) is 1 to 1 part by mass of A1-3: 100. Was melt-kneaded with Eki添 injected .4 parts by weight to obtain pellets of the thermoplastic elastomer composition.
Using the obtained thermoplastic elastomer composition, it was evaluated according to the above-mentioned method and shown in Table 1.
〔実施例4〕
実施例4で用いたプロピレン・α−オレフィンランダム共重合体(C)に替えて、プロピレン・α−オレフィンランダム共重合体(C)として、C3を用いる以外は実施例4と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
Example 4
Instead of the propylene / α-olefin random copolymer (C) used in Example 4, the procedure is the same as in Example 4 except that C3 is used as the propylene / α-olefin random copolymer (C). A plastic elastomer was obtained. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
〔比較例2〕
実施例3で用いたプロピレン・α−オレフィンランダム共重合体(C)に替えて、エチレン・プロピレンランダム共重合体としてD2を用い、且つ、配合剤の量を表1に示す量で用いる以外は実施例3と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
[Comparative Example 2]
Instead of the propylene / α-olefin random copolymer (C) used in Example 3, D2 was used as the ethylene / propylene random copolymer, and the amount of the compounding agent was used in the amounts shown in Table 1. It carried out similarly to Example 3 and obtained the thermoplastic elastomer. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
〔実施例5〕
実施例3で用いたオレフィン系重合体(B)に替えて、B1−2:13.9質量部、およびB2−2:47.8質量部からなるオレフィン系重合体(B)、プロピレン・α−オレフィンランダム共重合体(C)に替えて、C1:80.0質量部、および、C2:36.1質量部からなるプロピレン・α−オレフィンランダム共重合体(C)を用い、且つ、配合剤の量を表1に示す量で用いる以外は実施例3と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
Example 5
Instead of the olefin polymer (B) used in Example 3, the olefin polymer (B) consisting of B1-2: 13.9 parts by mass and B2-2: 47.8 parts by mass, propylene / α -In place of the olefin random copolymer (C), a propylene / α-olefin random copolymer (C) composed of C1: 80.0 parts by mass and C2: 36.1 parts by mass was used and blended A thermoplastic elastomer was obtained in the same manner as in Example 3 except that the amount of the agent was used in the amount shown in Table 1. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
〔比較例3〕
実施例3で用いたオレフィン系重合体(B)に替えて、B1−2:25.0質量部、およびB2−2:47.8質量部からなるオレフィン系重合体(B)、プロピレン・α−オレフィンランダム共重合体(C)に替えて、エチレン・プロピレンランダム共重合体としてD1を80.0質量部、および、ブチルゴムを25.0質量部とし、且つ、配合剤の量を表1に示す量で用いる以外は実施例3と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
[Comparative Example 3]
Instead of the olefin polymer (B) used in Example 3, B1-2: 25.0 parts by mass, and B2-2: 47.8 parts by mass, the olefin polymer (B), propylene / α -Instead of the olefin random copolymer (C), the ethylene / propylene random copolymer has a D1 of 80.0 parts by mass, a butyl rubber of 25.0 parts by mass, and the amounts of the compounding agents are shown in Table 1. A thermoplastic elastomer was obtained in the same manner as in Example 3 except that the amount shown was used. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
〔参考例1〕
実施例3で用いたプロピレン・α−オレフィンランダム共重合体(C)に替えて、エチレン・1−ブテンランダム共重合体としてE1を用いる以外は実施例3と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
[Reference Example 1]
A thermoplastic elastomer was obtained in the same manner as in Example 3 except that E1 was used as the ethylene / 1-butene random copolymer instead of the propylene / α-olefin random copolymer (C) used in Example 3. It was. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
〔参考例2〕
実施例3で用いたプロピレン・α−オレフィンランダム共重合体(C)に替えて、エチレン・プロピレンランダム共重合体としてE2を用いる以外は実施例3と同様に行い、熱可塑性エラストマーを得た。得られた熱可塑性エラストマー組成物の評価結果を表1に示す。
[Reference Example 2]
A thermoplastic elastomer was obtained in the same manner as in Example 3 except that E2 was used as the ethylene / propylene random copolymer instead of the propylene / α-olefin random copolymer (C) used in Example 3. The evaluation results of the obtained thermoplastic elastomer composition are shown in Table 1.
Claims (12)
融点(Tm)が70〜200℃の範囲にあるオレフィン系樹脂(B)および、
下記(1)〜(3)を満たすプロピレン・エチレンランダム共重合体(C)を含む混合物を動的架橋して、オレフィン系ゴム(A)の少なくとも一部を架橋してなる熱可塑性エラストマー組成物。
(1)プロピレン含量が70モル%以上90モル%未満。
(2)重量平均分子量Mwと数平均分子量Mnの比Mw/Mnが3.5以下。
(3)融点(Tm)が70℃未満または融点(Tm)が観測されない。 Olefin rubber (A),
An olefin resin (B) having a melting point (Tm) in the range of 70 to 200 ° C., and
A thermoplastic elastomer composition obtained by dynamically crosslinking a mixture containing a propylene / ethylene random copolymer (C) satisfying the following (1) to (3) and crosslinking at least a part of the olefin rubber (A). .
(1) Propylene content is 70 mol% or more and less than 90 mol%.
(2) The ratio Mw / Mn of the weight average molecular weight Mw and the number average molecular weight Mn is 3.5 or less.
(3) The melting point (Tm) is less than 70 ° C. or the melting point (Tm) is not observed.
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WO2018125391A1 (en) | 2016-12-29 | 2018-07-05 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizates for foaming applications |
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JP5165183B2 (en) * | 2004-07-22 | 2013-03-21 | 三菱化学株式会社 | Olefin-based thermoplastic elastomer composition and method for producing the same |
JP4816023B2 (en) * | 2005-03-16 | 2011-11-16 | 住友化学株式会社 | Method for producing thermoplastic elastomer composition and method for producing foamed thermoplastic elastomer composition |
EP2169003B1 (en) * | 2007-06-14 | 2014-05-07 | Mitsui Chemicals, Inc. | Thermoplastic elastomer composition |
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WO2018125391A1 (en) | 2016-12-29 | 2018-07-05 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizates for foaming applications |
US10508184B2 (en) | 2016-12-29 | 2019-12-17 | Exxonmobil Chemical Patents Inc. | Foaming agent masterbatches for foaming thermoplastic vulcanizates |
US11192992B2 (en) | 2016-12-29 | 2021-12-07 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizates for foaming applications |
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