JP5675518B2 - Composition and cross-linked product thereof - Google Patents
Composition and cross-linked product thereof Download PDFInfo
- Publication number
- JP5675518B2 JP5675518B2 JP2011151023A JP2011151023A JP5675518B2 JP 5675518 B2 JP5675518 B2 JP 5675518B2 JP 2011151023 A JP2011151023 A JP 2011151023A JP 2011151023 A JP2011151023 A JP 2011151023A JP 5675518 B2 JP5675518 B2 JP 5675518B2
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- JP
- Japan
- Prior art keywords
- composition
- polymer
- parts
- weight
- olefin
- 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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- 239000000203 mixture Substances 0.000 title claims description 128
- 229920000642 polymer Polymers 0.000 claims description 87
- 239000004711 α-olefin Substances 0.000 claims description 53
- 229920001577 copolymer Polymers 0.000 claims description 49
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- 239000005977 Ethylene Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 23
- 239000003431 cross linking reagent Substances 0.000 claims description 20
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 17
- 238000004132 cross linking Methods 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 16
- 238000005227 gel permeation chromatography Methods 0.000 claims description 6
- 239000003566 sealing material Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 description 47
- 239000005060 rubber Substances 0.000 description 46
- 238000004073 vulcanization Methods 0.000 description 18
- 239000000470 constituent Substances 0.000 description 16
- 238000004519 manufacturing process Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 16
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 14
- 150000004291 polyenes Chemical class 0.000 description 14
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- 229910052717 sulfur Inorganic materials 0.000 description 13
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- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 9
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 6
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- 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
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
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- 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-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
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
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- 239000006229 carbon black Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 238000009864 tensile test Methods 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 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 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical class ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- 239000004566 building material Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
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- 239000002904 solvent Substances 0.000 description 3
- 229960002447 thiram Drugs 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 241001441571 Hiodontidae Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000000748 compression moulding 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
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 235000014113 dietary fatty acids Nutrition 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- AUZONCFQVSMFAP-UHFFFAOYSA-N disulfiram Chemical compound CCN(CC)C(=S)SSC(=S)N(CC)CC AUZONCFQVSMFAP-UHFFFAOYSA-N 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
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- 239000006260 foam Substances 0.000 description 2
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical class ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
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- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
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- QMJRCSGCBNGINH-UHFFFAOYSA-N (2-butylphenyl) carbamodithioate;zinc Chemical compound [Zn].CCCCC1=CC=CC=C1SC(N)=S QMJRCSGCBNGINH-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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- RIPYNJLMMFGZSX-UHFFFAOYSA-N (5-benzoylperoxy-2,5-dimethylhexan-2-yl) benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(C)(C)CCC(C)(C)OOC(=O)C1=CC=CC=C1 RIPYNJLMMFGZSX-UHFFFAOYSA-N 0.000 description 1
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 1
- JSCFNQDWXBNVBP-UHFFFAOYSA-N 1,2-diphenylguanidine;phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O.C=1C=CC=CC=1N=C(N)NC1=CC=CC=C1 JSCFNQDWXBNVBP-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
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- PPWUTZVGSFPZOC-UHFFFAOYSA-N 1-methyl-2,3,3a,4-tetrahydro-1h-indene Chemical compound C1C=CC=C2C(C)CCC21 PPWUTZVGSFPZOC-UHFFFAOYSA-N 0.000 description 1
- CWJHMZONBMHMEI-UHFFFAOYSA-N 1-tert-butylperoxy-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1 CWJHMZONBMHMEI-UHFFFAOYSA-N 0.000 description 1
- FEEIOCGOXYNQIM-UHFFFAOYSA-N 2,3-di(propan-2-ylidene)bicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=C(C)C)C2=C(C)C FEEIOCGOXYNQIM-UHFFFAOYSA-N 0.000 description 1
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- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 description 1
- JDICEKWSLNPYSN-UHFFFAOYSA-N 2-(2,4-dinitrophenyl)-1,3-benzothiazole-4-thiol Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC=C1C1=NC2=C(S)C=CC=C2S1 JDICEKWSLNPYSN-UHFFFAOYSA-N 0.000 description 1
- IOHAVGDJBFVWGE-UHFFFAOYSA-N 2-ethylidene-3-propan-2-ylidenebicyclo[2.2.1]hept-5-ene Chemical compound C1C2C=CC1C(=CC)C2=C(C)C IOHAVGDJBFVWGE-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- OHNGXGZSKWCLQG-UHFFFAOYSA-N 2-tert-butylperoxyhexane Chemical compound CCCCC(C)OOC(C)(C)C OHNGXGZSKWCLQG-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- CPGFMWPQXUXQRX-UHFFFAOYSA-N 3-amino-3-(4-fluorophenyl)propanoic acid Chemical compound OC(=O)CC(N)C1=CC=C(F)C=C1 CPGFMWPQXUXQRX-UHFFFAOYSA-N 0.000 description 1
- AHZPYLAZRVPKIB-UHFFFAOYSA-N 4,5-dimethylhexa-1,4-diene Chemical compound CC(C)=C(C)CC=C AHZPYLAZRVPKIB-UHFFFAOYSA-N 0.000 description 1
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- HBPSHRBTXIZBDI-UHFFFAOYSA-N 4-ethylidene-8-methylnona-1,7-diene Chemical compound C=CCC(=CC)CCC=C(C)C HBPSHRBTXIZBDI-UHFFFAOYSA-N 0.000 description 1
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- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
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- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- LSFHOMLKNVLGCM-UHFFFAOYSA-N C(N)(S)=S.C(C)[Zn]C1=CC=CC=C1 Chemical compound C(N)(S)=S.C(C)[Zn]C1=CC=CC=C1 LSFHOMLKNVLGCM-UHFFFAOYSA-N 0.000 description 1
- ASLGGNXEWMBPBX-UHFFFAOYSA-M C(N)([S-])=S.C[Se+]C Chemical compound C(N)([S-])=S.C[Se+]C ASLGGNXEWMBPBX-UHFFFAOYSA-M 0.000 description 1
- XBRLOEZZLGIQLK-UHFFFAOYSA-N ClCC1C(C2C=CC1C2)C(=C)C.C(=C)=C2C1C=CC(C2)C1 Chemical compound ClCC1C(C2C=CC1C2)C(=C)C.C(=C)=C2C1C=CC(C2)C1 XBRLOEZZLGIQLK-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- 239000004166 Lanolin Substances 0.000 description 1
- HXKCUQDTMDYZJD-UHFFFAOYSA-N Methyl selenac Chemical compound CN(C)C(=S)S[Se](SC(=S)N(C)C)(SC(=S)N(C)C)SC(=S)N(C)C HXKCUQDTMDYZJD-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
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- 241000282320 Panthera leo Species 0.000 description 1
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Description
本発明は、成形加工性に優れ、かつ架橋した場合に優れたゴム弾性や形状記憶性を有するゴム組成物に関する。 The present invention relates to a rubber composition that has excellent processability and has excellent rubber elasticity and shape memory when crosslinked.
エチレン・α-オレフィン共重合体ゴムやエチレン・α-オレフィン・非共役ポリエン共重合体ゴム（ＥＰＤＭ）は、主鎖に不飽和結合を持たないため、共役ジエン系のゴムと比較して耐候性、耐熱性および耐オゾン性に優れる。 Ethylene / α-olefin copolymer rubber and ethylene / α-olefin / non-conjugated polyene copolymer rubber (EPDM) have no unsaturated bond in the main chain, so they have better weather resistance than conjugated diene rubbers. Excellent in heat resistance and ozone resistance.
これらの特性を利用して、これらの共重合体ゴムを含むゴム組成物、該ゴム組成物の架橋体、および該組成物の発泡体は、自動車工業部品、工業用ゴム製品、電気絶縁材、土木建材用品およびゴム引布などのゴム製品に広く用いられている。その中でもホース類やチューブ状の製品では、Ｓ字形状やＬ字形状、またはそれらが組み合わさって、三次元的に折り曲げられた製品が多く、最近では自動車のコンパクト化もあって、さらにその複雑さが増している。 Utilizing these characteristics, a rubber composition containing these copolymer rubbers, a crosslinked product of the rubber composition, and a foamed product of the composition are used for automobile industrial parts, industrial rubber products, electrical insulating materials, Widely used in civil engineering materials and rubber products such as rubberized fabric. Among these, hoses and tube-shaped products are often S-shaped, L-shaped, or a combination of them, and are three-dimensionally folded. Recently, automobiles have become more compact and more complicated. Is increasing.
現在、それら製品は、まず未加硫ゴムを押出機にて単層またはブレード入りの三層構造のホースを成形し、その後に、目的形状をしたマンドレル（円棒）をホース中空部に挿入し、スチーム缶または空気加硫槽で加硫と腑形（形状腑形）を同時に行い製造されている。しかしながら、この手法では生産効率が悪く、製品不良も多いことから、形状記憶性を有するゴム素材へのニーズが多いに高まっている。 Currently, these products are made by first forming unvulcanized rubber into a single-layer or braided three-layer hose using an extruder, and then inserting a mandrel with a desired shape into the hose hollow. It is manufactured by simultaneously performing vulcanization and bowl shape (shape bowl shape) in a steam can or an air vulcanization tank. However, since this method has poor production efficiency and many product defects, there is a growing need for rubber materials having shape memory properties.
形状記憶性ゴムとして、エチレン・α-オレフィン・非共役ポリエン共重合体ゴム（ＥＰＤＭ）に、平均分散粒子径０．１〜２０μｍのポリオレフィン樹脂がミクロ分散されているＥＰＤＭ／樹脂アロイが提案され、良好な形状記憶性、ゴム弾性を示すことが報告されている（例えば、特許文献１を参照）。 As a shape memory rubber, an EPDM / resin alloy in which a polyolefin resin having an average dispersed particle diameter of 0.1 to 20 μm is microdispersed in ethylene / α-olefin / non-conjugated polyene copolymer rubber (EPDM) is proposed, It has been reported that it exhibits good shape memory properties and rubber elasticity (see, for example, Patent Document 1).
特許文献１に記載のアロイを賦形したり、さらに充填材，伸展油，架橋剤などのいわゆるゴム用添加剤などをを配合することがあるが、アロイは、配合時の粘度が高くて扱いにくい場合があった。また、比較的高い温度で加熱することで配合時の粘度を低くしようとすると、例えば架橋剤を含有する場合にはある程度の架橋反応が進行してしまうなどして、賦形時の成形性にも影響がある場合があった。 The alloy described in Patent Document 1 may be shaped or may be further blended with so-called rubber additives such as fillers, extender oils, and cross-linking agents. It was sometimes difficult. In addition, when trying to reduce the viscosity at the time of blending by heating at a relatively high temperature, for example, when a crosslinking agent is contained, the crosslinking reaction proceeds to some extent, so that the moldability at the time of shaping is improved. There was also an impact.
本発明は、成型加工性に優れた組成物であって、その組成物の架橋体の形状記憶性およびゴム弾性に優れる組成物を提供することを目的とする。 An object of the present invention is to provide a composition excellent in molding processability, which is excellent in shape memory property and rubber elasticity of a crosslinked product of the composition.
本発明の第一は、以下に示す組成物に関する。
［１］エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）１００重量部と、以下の（i）〜（ii）を満たし、かつ炭素数３〜２０のα−オレフィンから選ばれる１種に由来する構成単位を主成分とする重合体（Ｂ）１５〜４０重量部と、を含む組成物；
（i）示差走査熱量計（ＤＳＣ）で測定した融点が１２５〜２４５℃、
（ii）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の数平均分子量（Ｍｎ）が１，０００〜１５，０００。
The first of the present invention relates to the composition shown below.
[1] One kind selected from ethylene / α-olefin / non-conjugated polyene copolymer (A) 100 parts by weight and the following (i) to (ii) and an α-olefin having 3 to 20 carbon atoms A composition containing 15 to 40 parts by weight of a polymer (B) whose main component is a structural unit derived from
(I) a melting point measured by a differential scanning calorimeter (DSC) of 125 to 245 ° C.,
(Ii) The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1,000 to 15,000.
［２］前記重合体（Ｂ）が、プロピレン由来の構成単位を主成分とするものであることを特徴とする、［１］に記載の組成物。
［３］前記重合体（Ｂ）における、前記炭素数３〜２０のα-オレフィン由来の構成単位の割合が、炭素数３〜２０のα-オレフィンから選ばれる１種に由来する構成単位とそれ以外の構成単位との合計１００モル％に対して５０モル％以上である、［１］または［２］に記載の組成物。
［４］前記重合体（Ｂ）の、（iii）密度勾配管法で測定した密度が８２０〜９２０ｋｇ／ｍ３である、［１］または［２］に記載の組成物。
[2] The composition according to [1], wherein the polymer (B) contains a propylene-derived structural unit as a main component.
[3] Constituent units derived from one type selected from α-olefins having 3 to 20 carbon atoms in which the proportion of the structural units derived from the α-olefins having 3 to 20 carbon atoms in the polymer (B) The composition according to [1] or [2], which is 50 mol% or more with respect to 100 mol% in total with other structural units.
[4] The composition according to [1] or [2], wherein the density of the polymer (B) measured by (iii) density gradient tube method is 820 to 920 kg / m 3 .
［５］さらに充填材を含有していることを特徴とする、［１］〜［４］のいずれかに記載の組成物。
［６］さらに可塑剤を含有していることを特徴とする、［１］〜［５］のいずれかに記載の組成物。
［７］さらに架橋剤を含有していることを特徴とする、［１］〜［６］のいずれかに記載の組成物。
[5] The composition according to any one of [1] to [4], further comprising a filler.
[6] The composition according to any one of [1] to [5], further comprising a plasticizer.
[7] The composition according to any one of [1] to [6], further comprising a crosslinking agent.
本発明の第二は、以下に示す架橋体などに関する。
［８］前記［１］〜［７］に記載の組成物を架橋してなることを特徴とする架橋体。
［９］前記［８］に記載の架橋体からなる自動車用ウェザーストリップ、グロメット、ホース、またはシール材。
The second of the present invention relates to the following crosslinked bodies and the like.
[8] A crosslinked product obtained by crosslinking the composition according to [1] to [7].
[9] A weather strip, a grommet, a hose, or a sealing material for automobiles comprising the crosslinked product according to [8].
本発明によれば、成型加工性に優れ、かつ架橋した際に良好な形状記憶性及びゴム弾性を示すゴム組成物を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the rubber composition which is excellent in molding processability, and shows favorable shape memory property and rubber elasticity when bridge | crosslinking can be provided.
（Ａ）エチレン・α−オレフィン・非共役ポリエン共重合体
本発明の組成物は、エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）を含む。エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）は、エチレンから導かれる構成単位と、炭素数３以上（好ましくは３〜２０）のα-オレフィンから導かれる構成単位と、非共役ポリエンから導かれる構成単位と、を含む共重合体であり、通常はランダム共重合体である。
(A) Ethylene / α-olefin / non-conjugated polyene copolymer The composition of the present invention contains an ethylene / α-olefin / non-conjugated polyene copolymer (A). The ethylene / α-olefin / non-conjugated polyene copolymer (A) comprises a structural unit derived from ethylene, a structural unit derived from an α-olefin having 3 or more carbon atoms (preferably 3 to 20), and a non-conjugated polyene. And is a random copolymer.
エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）におけるα-オレフィンの具体例には、プロピレン、１-ブテン、４-メチルペンテン-１、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-メチルデセン-１、１１-メチルドデセン-１および１２-エチルテトラデセン-１などが含まれる。なかでも、プロピレン、１-ブテン、４-メチルペンテン-１、１-ヘキセンおよび１-オクテンが好ましく、特に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種以上組み合わせて用いられる。 Specific examples of the α-olefin in the ethylene / α-olefin / non-conjugated polyene copolymer (A) include propylene, 1-butene, 4-methylpentene-1, 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-methyldecene-1, 11-methyldodecene-1, 12-ethyltetradecene-1, and the like are included. Of these, propylene, 1-butene, 4-methylpentene-1, 1-hexene and 1-octene are preferable, and propylene is particularly preferable. These α-olefins are used alone or in combination of two or more.
エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）における非共役ポリエンの具体例には、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-ノナジエンおよび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および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-ノナジエン等のトリエンなどが挙げられる。なかでも、５-エチリデン-２-ノルボルネンおよび５-ビニル-２-ノルボルネンが好ましい。これらの非共役ポリエンは、単独で、または２種類以上組み合わせて用いられる。 Specific examples of the nonconjugated polyene in the ethylene / α-olefin / nonconjugated polyene copolymer (A) include 1,4-hexadiene, 3-methyl-1,4-hexadiene, and 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-1,7-nonadiene and 4-ethylidene Linear unconjugated dienes such as 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, 5-vinyl-2-norbornene, 5-isopropenyl-2-norbornene, 5-isobutenyl-2-norbornene, cyclopentadiene And cyclic non-conjugated dienes such as norbornadiene; 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,2-norbornadiene, 4-ethylidene-8- And trienes such as methyl-1,7-nonadiene. Of these, 5-ethylidene-2-norbornene and 5-vinyl-2-norbornene are preferable. These non-conjugated polyenes are used alone or in combination of two or more.
エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）における、エチレン（ａ）に由来する構造単位と、α-オレフィン（ｂ）に由来する構造単位とのモル比［（ａ）／（ｂ）］は、特に制限はないが通常５０／５０〜９０／１０、好ましくは５５／４５〜８５／１５である。エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）のヨウ素価は、特に制限はないが通常１〜４０、好ましくは２〜３５、より好ましくは３〜３０である。 In the ethylene / α-olefin / non-conjugated polyene copolymer (A), the molar ratio of the structural unit derived from ethylene (a) and the structural unit derived from α-olefin (b) [(a) / (b )] Is not particularly limited, but is usually 50/50 to 90/10, preferably 55/45 to 85/15. The iodine value of the ethylene / α-olefin / non-conjugated polyene copolymer (A) is not particularly limited, but is usually 1 to 40, preferably 2 to 35, and more preferably 3 to 30.
エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）の極限粘度〔η〕は特に制限されないが、通常、１３５℃、デカリン中で測定される極限粘度〔η〕は、通常、１．０〜５．０ｄｌ／ｇ、好ましくは１．０〜４．０ｄｌ／ｇである。 The intrinsic viscosity [η] of the ethylene / α-olefin / non-conjugated polyene copolymer (A) is not particularly limited, but the intrinsic viscosity [η] measured in decalin at 135 ° C. is usually 1.0. It is -5.0 dl / g, Preferably it is 1.0-4.0 dl / g.
エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）の具体例には、エチレン・プロピレン・５-エチリデン-２-ノルボルネンランダム共重合体、エチレン・プロピレン・５-エチリデン-２-ノルボルネン・５-ビニル-２-ノルボルネンランダム共重合体などが含まれる。 Specific examples of the ethylene / α-olefin / non-conjugated polyene copolymer (A) include ethylene / propylene / 5-ethylidene-2-norbornene random copolymer, ethylene / propylene / 5-ethylidene-2-norbornene / 5 -Vinyl-2-norbornene random copolymer is included.
上記のような共重合体（Ａ）は、例えば「新ポリマー製造プロセス（（株）工業調査会発行、ｐ３６５−ｐ３８０ （１９９４年） 第１２章 ＥＰＤＭ」に記載されている方法により製造することができるがこれに限定されるものではない。 The copolymer (A) as described above can be produced, for example, by the method described in “New polymer production process (issued by Industrial Research Council, p365-p380 (1994) Chapter 12 EPDM)”. Yes, but not limited to this.
（Ｂ）炭素数３〜２０のα-オレフィン由来の構成単位から選ばれる１種を主成分とする重合体
本発明の組成物は、炭素数３〜２０のα-オレフィン由来の構成単位から選ばれる１種を主成分とする重合体（Ｂ）を含む。
(B) A polymer mainly composed of one type selected from structural units derived from α-olefins having 3 to 20 carbon atoms The composition of the present invention is selected from structural units derived from α-olefins having 3 to 20 carbon atoms. The polymer (B) which has 1 type as a main component is included.
重合体（Ｂ）における当該１種の炭素数３〜２０のα-オレフィンは、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-メチルデセン-１、１１-メチルドデセン-１および１２-エチルテトラデセン-１から選ばれることが好ましい。 The one kind of C3-C20 α-olefin in the polymer (B) is specifically propylene, 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-pentadecene, 1-hexadecene, 1-heptadecene, 1-nonadecene, 1-eicocene, 9-methyldecene- It is preferably selected from 1,11-methyldodecene-1 and 12-ethyltetradecene-1.
重合体（Ｂ）とは、炭素数３〜２０のα-オレフィン由来から選ばれる１種に由来する構成単位（主成分の構成単位）と、当該１種のα-オレフィン以外の構成単位との合計を１００モル％とした場合に、当該炭素数３〜２０のα-オレフィンから選ばれる１種に由来する構成単位が、５０モル％以上である重合体のことをいう。 The polymer (B) is a structural unit derived from one type selected from α-olefins having 3 to 20 carbon atoms (a structural unit of the main component) and a structural unit other than the one type of α-olefin. When the total is defined as 100 mol%, it means a polymer in which the structural unit derived from one kind selected from the α-olefin having 3 to 20 carbon atoms is 50 mol% or more.
この場合において、主成分の構成単位以外の構成単位は、炭素数２〜２０のα-オレフィン由来の構成単位であって、主成分の構成単位以外のものであることが好ましい。主成分の構成単位以外の構成単位の例には、エチレンおよび上記した炭素数３〜２０のα-オレフィンが含まれる。 In this case, the constituent unit other than the constituent unit of the main component is a constituent unit derived from an α-olefin having 2 to 20 carbon atoms, and is preferably other than the constituent unit of the main component. Examples of the structural unit other than the structural unit of the main component include ethylene and the above-mentioned α-olefin having 3 to 20 carbon atoms.
重合体（Ｂ）に主成分の構成単位以外の構成単位が存在する場合には、その合計量は、主成分の構成単位と、それ以外の構成単位との合計を１００モル％とした場合に、通常５０モル％以下、好ましくは４９モル％以下であり、下限は０モル％を超える値であれば制限はないが、例えば０．０１モル％である。 When a constituent unit other than the constituent unit of the main component is present in the polymer (B), the total amount is when the sum of the constituent unit of the main component and the other constituent unit is 100 mol%. Usually, it is 50 mol% or less, preferably 49 mol% or less, and the lower limit is not limited as long as it is a value exceeding 0 mol%, for example, 0.01 mol%.
重合体（Ｂ）に主成分の構成単位以外の構成単位が存在する場合において、主成分の構成単位は、主成分の構成単位と、それ以外の構成単位との合計を１００モル％とした場合に、通常５０モル％以上、好ましくは５１モル％以上であり、上限は１００モル％未満であれば特に制限はないが、例えば９９．９９モル％である。 In the case where a constituent unit other than the constituent unit of the main component exists in the polymer (B), the constituent unit of the main component is 100 mol% in total of the constituent unit of the main component and the other constituent units. The upper limit is usually 50 mol% or more, preferably 51 mol% or more, and the upper limit is not particularly limited as long as it is less than 100 mol%, for example, 99.99 mol%.
重合体（Ｂ）は、耐熱性の点から、プロピレンが主成分である重合体または４-メチル-１-ペンテンが主成分である重合体であることが好ましく、特に好ましくはプロピレンが主成分である重合体である。重合体（Ｂ）は、プロピレンが主成分である重合体のなかでも、プロピレン単独重合体、プロピレンとエチレンとの共重合体、プロピレンと炭素原子数４〜２０のα-オレフィンから選ばれる少なくとも１種のオレフィンとの共重合体がより好ましい。 From the viewpoint of heat resistance, the polymer (B) is preferably a polymer containing propylene as a main component or a polymer containing 4-methyl-1-pentene as a main component, and particularly preferably propylene as a main component. It is a polymer. The polymer (B) is at least one selected from a propylene homopolymer, a copolymer of propylene and ethylene, and propylene and an α-olefin having 4 to 20 carbon atoms, among polymers mainly composed of propylene. More preferred are copolymers with seed olefins.
さらに、重合体（Ｂ）は、以下の（i）〜（ii）を満たす。 Furthermore, the polymer (B) satisfies the following (i) to (ii).
重合体（Ｂ）の、（i）示差走査熱量計（ＤＳＣ）で測定した融点が１２５〜２４５℃である。例えばプロピレン構成単位を５０モル％以上の割合で有する重合体の場合は、好ましい融点は１２５℃〜１７０℃、より好ましくは１３０〜１６５℃であり、特に好ましくは１４０〜１６５℃である。上記範囲の融点を有する重合体（Ｂ）と、共重合体（Ａ）とを含む組成物の架橋体（例えば加硫体）は、比較的高い温度で応力を受けた後も、ゴム弾性が保持されやすい。 The melting point of the polymer (B) measured by (i) a differential scanning calorimeter (DSC) is 125 to 245 ° C. For example, in the case of a polymer having a propylene structural unit in a proportion of 50 mol% or more, the preferable melting point is 125 ° C to 170 ° C, more preferably 130 to 165 ° C, and particularly preferably 140 to 165 ° C. The crosslinked product (eg, vulcanized product) of the composition containing the polymer (B) having the melting point in the above range and the copolymer (A) has rubber elasticity even after being subjected to stress at a relatively high temperature. Easy to hold.
重合体（Ｂ）の、（ii）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の数平均分子量（Ｍｎ）が、１×１０３〜１５×１０３、好ましくは３×１０３〜１４×１０３、より好ましくは５×１０３〜１３×１０３である。この範囲の数平均分子量を有する重合体（Ｂ）と、共重合体（Ａ）とを含む組成物の架橋体（加硫体）は、特にゴム弾性に優れる。この理由は定かではないが、この範囲の数平均分子量を有す重合体（Ｂ）は適度な粘度を有し、重合体（Ｂ）が共重合体（Ａ）中に適度に分散するため、架橋体において重合体（Ｂ）がゴム弾性を阻害しにくいと考えられる。 The number average molecular weight (Mn) in terms of polystyrene measured by (ii) gel permeation chromatography (GPC) of the polymer (B) is 1 × 10 3 to 15 × 10 3 , preferably 3 × 10 3 to 14. × 10 3, more preferably from 5 × 10 3 ~13 × 10 3 . The crosslinked body (vulcanized body) of the composition containing the polymer (B) having the number average molecular weight in this range and the copolymer (A) is particularly excellent in rubber elasticity. The reason for this is not clear, but the polymer (B) having a number average molecular weight in this range has an appropriate viscosity, and the polymer (B) is appropriately dispersed in the copolymer (A). It is considered that the polymer (B) hardly inhibits rubber elasticity in the crosslinked body.
重合体（Ｂ）は、さらに以下の（iii）及び（iv）から選ばれる１つ以上を満たすことが好ましい。 The polymer (B) preferably further satisfies at least one selected from the following (iii) and (iv).
重合体（Ｂ）の、（iii）密度勾配管法で測定した密度が８２０〜９２０ｋｇ／ｍ３である。特に、重合体（Ｂ）がプロピレンを主成分とする重合体である場合には、その密度は好ましくは８９０〜９２０ｋｇ／ｃｍ３である。 The density of the polymer (B) measured by (iii) density gradient tube method is 820 to 920 kg / m 3 . In particular, when the polymer (B) is a polymer containing propylene as a main component, the density is preferably 890 to 920 kg / cm 3 .
重合体（Ｂ）の、（iv）針入度が５ｄｍｍ以下であり、好ましくは３ｄｍｍ以下であり、より好ましくは１ｄｍｍ以下である。針入度は、２５℃において、JIS K2207に規格化された方法に従って測定すればよい。 The polymer (B) has (iv) penetration of 5 dmm or less, preferably 3 dmm or less, more preferably 1 dmm or less. The penetration may be measured at 25 ° C. according to a method standardized in JIS K2207.
本発明に用いる重合体（Ｂ）としては、従来公知の方法で製造したものを用いてもよく、例えば市販品を用いてもよい。 As a polymer (B) used for this invention, what was manufactured by the conventionally well-known method may be used, for example, a commercial item may be used.
〔その他の成分〕
本発明の組成物には、意図する架橋体の用途や性能に応じて、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）に、重合体（Ｂ）を溶融状態でミクロ分散させた樹脂とともに、一般にゴム製品の製造で用いられる各種公知の配合剤を配合してもよい。配合剤の例には、充てん剤、軟化剤、加硫助剤、老化防止剤、加工助剤、アルコキシシラン化合物、架橋剤、架橋助剤、活性剤、反応抑制剤、着色剤、分散剤、難燃剤、可塑剤、酸化防止剤、スコーチ防止剤、紫外線吸収剤、帯電防止剤、滑剤、防カビ剤、素練促進剤、粘着付与剤、分散染料や酸性染料を代表例とする各種染料、無機・有機顔料、界面活性剤、および塗料などの配合剤、また必要に応じて、発泡剤、発泡助剤などの発泡のための化合物、脱泡剤を、本発明の目的を損なわない範囲で適宜選定し、適切な配合量を配合することができる。
[Other ingredients]
In the composition of the present invention, the polymer (B) is microdispersed in a molten state in the ethylene / α-olefin / non-conjugated polyene random copolymer (A) according to the intended use and performance of the crosslinked product. Various known compounding agents generally used in the manufacture of rubber products may be blended together with the resin. Examples of compounding agents include fillers, softeners, vulcanization aids, anti-aging agents, processing aids, alkoxysilane compounds, cross-linking agents, cross-linking aids, activators, reaction inhibitors, colorants, dispersants, Flame retardants, plasticizers, antioxidants, scorch inhibitors, ultraviolet absorbers, antistatic agents, lubricants, fungicides, peptizers, tackifiers, various dyes such as disperse dyes and acid dyes as representative examples, Additives such as inorganic and organic pigments, surfactants, and paints, and if necessary, foaming compounds such as foaming agents and foaming aids, and defoaming agents are within a range that does not impair the purpose of the present invention. It can select suitably and can mix | blend an appropriate compounding quantity.
〔充てん剤〕
本発明の組成物に含まれうる充てん剤は、通常、合成ゴムの充てん剤として使用されている充てん剤である限り、特に限定はされない。充てん剤の例には、ＳＲＦ、ＧＰＦ、ＦＥＦ、ＭＡＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦ、ＦＴ、ＭＴ等のカーボンブラック、シリカ、活性化炭酸カルシウム、軽質炭酸カルシウム、重質炭酸カルシウム、微粉タルク、微粉ケイ酸、タルク、クレーなどや、これらの無機物の表面をシランカップリング剤等で処理したものを用いることができる。
[Filler]
The filler that can be contained in the composition of the present invention is not particularly limited as long as it is a filler that is usually used as a filler for synthetic rubber. Examples of fillers include SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, MT, etc. carbon black, silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine talc, fine powder silica Acids, talc, clay, etc., or those obtained by treating the surface of these inorganic substances with a silane coupling agent or the like can be used.
市販されているカーボンブラックの例には「旭＃５５Ｇ」、「旭＃５０ＨＧ」、「旭＃６０Ｇ」（商品名；旭カーボン株式会社製）、「シーストＶ」、「シーストＳＯ」（商品名；東海カーボン株式会社製）などを挙げることができる。 Examples of commercially available carbon black include “Asahi # 55G”, “Asahi # 50HG”, “Asahi # 60G” (trade name; manufactured by Asahi Carbon Co., Ltd.), “Seast V”, “Seast SO” (trade name) ; Manufactured by Tokai Carbon Co., Ltd.).
充てん剤の比表面積は、５〜１２０ｍ２／ｇであることが好ましい。組成物における充てん剤の含有量は、共重合体（Ａ）１００質量部に対し、例えば１〜２４０重量部、好ましくは５〜２００重量部、さらに好ましくは１０〜１００重量部の範囲でありうる。 The specific surface area of the filler is preferably 5 to 120 m 2 / g. The content of the filler in the composition may be in the range of, for example, 1 to 240 parts by weight, preferably 5 to 200 parts by weight, and more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the copolymer (A). .
〔軟化剤〕
本発明の組成物に含まれうる軟化剤は、通常ゴムに使用される軟化剤であればよい。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、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、ヤシ油等の脂肪油系軟化剤；トール油；サブ；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；石油樹脂、アタクチックポリプロピレン、クマロンインデン樹脂等の合成高分子物質などを挙げることができる。なかでも石油系軟化剤が好ましく用いられ、特にプロセスオイルが好ましく用いられる。
[Softener]
The softener that can be included in the composition of the present invention may be any softener that is usually used for rubber. Specifically, petroleum-based softeners such as process oil, lubricating oil, paraffin, liquid paraffin, petroleum asphalt, and petroleum jelly; coal-tar softeners such as coal tar and coal tar pitch; castor oil, linseed oil, rapeseed oil, Fat oil-based softeners such as coconut oil; tall oil; sub; waxes such as beeswax, carnauba wax and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, barium stearate, calcium stearate and zinc laurate; petroleum Examples thereof include synthetic polymer materials such as resin, atactic polypropylene, and coumarone indene resin. Of these, petroleum softeners are preferably used, and process oil is particularly preferably used.
組成物における軟化剤の含有量は、ゴム成形体の用途により適宜選択できるが、通常、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）１００重量部に対して、１質量部以上１５０質量部以下、好ましくは５質量部以上１３０重量部以下、より好ましくは１０質量部以上１００質量部以下である。 The content of the softening agent in the composition can be appropriately selected depending on the use of the rubber molded body, but is usually 1 part by mass or more with respect to 100 parts by weight of the ethylene / α-olefin / nonconjugated polyene random copolymer (A). 150 parts by mass or less, preferably 5 parts by mass or more and 130 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass or less.
架橋剤（Ｃ）
本発明の組成物には、エチレン・α−オレフィン・非共役ポリエンランダム共重合体（Ａ）と、特定の重合体（Ｂ）と、さらに架橋剤（Ｃ）が含まれていることが好ましい態様の一つである。つまり本発明の組成物は、通常、架橋体として用いられる。本発明の組成物に含まれる架橋剤の例には、イオウやイオウ化合物などの加硫剤や、有機過酸化物が含まれるが、なかでもイオウが好ましい。
Cross-linking agent (C)
The composition of the present invention preferably includes an ethylene / α-olefin / non-conjugated polyene random copolymer (A), a specific polymer (B), and a crosslinking agent (C). one of. That is, the composition of the present invention is usually used as a crosslinked product. Examples of the crosslinking agent contained in the composition of the present invention include vulcanizing agents such as sulfur and sulfur compounds, and organic peroxides. Among them, sulfur is preferable.
架橋剤としてのイオウの具体例には、粉末イオウ、沈降イオウ、コロイドイオウ、表面処理イオウ、不溶性イオウなどが含まれる。架橋剤としてのイオウ化合物の具体例には、塩化イオウ、二塩化イオウ、高分子多硫化物などが含まれる。 Specific examples of sulfur as a cross-linking agent include powdered sulfur, precipitated sulfur, colloidal sulfur, surface treated sulfur, insoluble sulfur and the like. Specific examples of the sulfur compound as the crosslinking agent include sulfur chloride, sulfur dichloride, and polymer polysulfide.
架橋剤としてのイオウ化合物とは、加硫温度で活性イオウを放出する化合物である。架橋剤としてのイオウ化合物の例には、モルフォリンジスルフィド、アルキルフェノ−ルジスルフィド、テトラメチルチウラムジスルフィド、ジペンタメチレンチウラムテトラスルフィド、ジメチルジチオカルバミン酸セレンなどが含まれる。 The sulfur compound as a crosslinking agent is a compound that releases active sulfur at the vulcanization temperature. Examples of the sulfur compound as the crosslinking agent include morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, dipentamethylenethiuram tetrasulfide, selenium dimethyldithiocarbamate and the like.
架橋剤としてのイオウやイオウ化合物は、１種または２種以上組み合わせて用いられる。 Sulfur or a sulfur compound as a crosslinking agent is used alone or in combination of two or more.
組成物における架橋剤としてのイオウおよびイオウ化合物の含有量は、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）１００重量部に対して、通常０．１〜１０重量部、好ましくは０．３〜５重量部でありうるが、要求される物性に応じて適宜最適量を決定することが望ましい。 The content of sulfur and a sulfur compound as a crosslinking agent in the composition is usually 0.1 to 10 parts by weight, preferably 100 parts by weight of ethylene / α-olefin / non-conjugated polyene random copolymer (A), preferably Although it may be 0.3-5 parts by weight, it is desirable to determine the optimum amount as appropriate according to the required physical properties.
架橋剤としてイオウまたはイオウ化合物を使用するときは、加硫促進剤を併用することが好ましい。 When sulfur or a sulfur compound is used as the crosslinking agent, it is preferable to use a vulcanization accelerator in combination.
加硫促進剤の具体例には、Ｎ-シクロヘキシル-２-ベンゾチアゾールスルフェンアミド、Ｎ-オキシジエチレン-２-ベンゾチアゾ−ルスルフェンアミド、Ｎ,Ｎ-ジイソプロピル-２-ベンゾチアゾ−ルスルフェンアミドなどのスルフェンアミド系化合物；２-メルカプトベンゾチアゾール、２-（２',４'-ジニトロフェニル）メルカプトベンゾチアゾール、２-（４'-モルホリノジチオ）ベンゾチアゾール、ジベンゾチアジルジスルフィド等のチアゾール系化合物；ジフェニルグアニジン、ジオルソトリルグアニジン、ジオルソニトリルグアニジン、オルソニトリルバイグアナイド、ジフェニルグアニジンフタレート等のグアニジン化合物；アセトアルデヒド-アニリン反応物、ブチルアルデヒド-アニリン縮合物、ヘキサメチレンテトラミン、アセトアルデヒドアンモニア等のアルデヒドアミンまたはアルデヒド-アンモニア系化合物；２-メルカプトイミダゾリン等のイミダゾリン系化合物；チオカルバニリド、ジエチルチオユリア、ジブチルチオユリア、トリメチルチオユリア、ジオルソトリルチオユリア等のチオユリア系化合物；テトラメチルチウラムモノスルフィド、テトラメチルチウラムジスルフィド、テトラエチルチウラムジスルフィド、テトラブチルチウラムジスルフィド、ペンタメチレンチウラムテトラスルフィド等のチウラム系化合物；ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジ-ｎ-ブチルジチオカルバミン酸亜鉛、エチルフェニルジチオカルバミン酸亜鉛、ブチルフェニルジチオカルバミン酸亜鉛、ジメチルジチオカルバミン酸ナトリウム、ジメチルジチオカルバミン酸セレン、ジメチルジチオカルバミン酸テルル等のジチオ酸塩系化合物；ジブチルキサントゲン酸亜鉛等のザンテート系化合物；亜鉛華（酸化亜鉛）などが含まれる。 Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole sulfenamide, N-oxydiethylene-2-benzothiazol sulfenamide, N, N-diisopropyl-2-benzothiazol sulfenamide, and the like. Sulfenamide compounds; 2-mercaptobenzothiazole, 2- (2 ′, 4′-dinitrophenyl) mercaptobenzothiazole, 2- (4′-morpholinodithio) benzothiazole, dibenzothiazyl disulfide and other thiazole compounds; Guanidine compounds such as diphenylguanidine, diorthotolylguanidine, diorthonitrile guanidine, orthonitrile biguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde Aldehyde amines such as deammonia or aldehyde-ammonia compounds; imidazoline compounds such as 2-mercaptoimidazoline; Thiuram compounds such as thiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide; zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc di-n-butyldithiocarbamate, ethylphenyl Zinc dithiocarbamate, zinc butylphenyl dithiocarbamate, sodium dimethyldithiocarbamate, dimethyl Selenium dithiocarbamate, dithio acid salt-based compounds such as dimethyl dithiocarbamate tellurium; dibutyl Ruki xanthate-based compounds such as Santo Gen zinc; zinc white (zinc oxide) and the like.
組成物における加硫促進剤の含有量は、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）１００重量部に対して、通常０．１〜２０重量部、好ましくは０．２〜１０重量部の割合であるが、要求される物性に応じて適宜最適量を決定することが望ましい。 The content of the vulcanization accelerator in the composition is usually 0.1 to 20 parts by weight, preferably 0.2 to 100 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer (A). Although it is a ratio of 10 parts by weight, it is desirable to appropriately determine the optimum amount according to the required physical properties.
本発明の組成物に含まれる架橋剤は、有機過酸化物であってもよい。有機過酸化物としては、通常ゴムの過酸化物加硫に使用されるものであればよい。具体的には、ジクミルパーオキサイド、ジ-t-ブチルパーオキサイド、ジ-t-ブチルパーオキシ-３,３,５-トリメチルシクロヘキサン、t-ブチルヒドロパーオキサイド、t-ブチルクミルパーオキサイド、ベンゾイルパーオキサイド、２,５-ジメチル-２,５-ジ（ｔ-ブチルパーオキシン）ヘキシン-３、２,５-ジメチル-２,５- ジ（ベンゾイルパーオキシ）ヘキサン、２,５-ジメチル-２,５-モノ（ｔ-ブチルパーオキシ）-ヘキサン、α,α'-ビス（ｔ-ブチルパーオキシ-ｍ-イソプロピル）ベンゼンなどが挙げられる。なかでも、ジクミルパーオキサイド、ジ-t-ブチルパーオキサイド、ジ-t-ブチルパーオキシ-３,３,５-トリメチルシクロヘキサンが好ましく用いられる。これらの有機過酸化物は、１種または２種以上組み合わせて用いられる。 The crosslinking agent contained in the composition of the present invention may be an organic peroxide. Any organic peroxide may be used as long as it is usually used for rubber peroxide vulcanization. Specifically, dicumyl peroxide, di-t-butyl peroxide, di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butyl hydroperoxide, t-butylcumyl peroxide, benzoyl Peroxide, 2,5-dimethyl-2,5-di (t-butylperoxin) hexyne-3,2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2 , 5-mono (t-butylperoxy) -hexane, α, α′-bis (t-butylperoxy-m-isopropyl) benzene, and the like. Of these, dicumyl peroxide, di-t-butyl peroxide, and di-t-butylperoxy-3,3,5-trimethylcyclohexane are preferably used. These organic peroxides are used alone or in combination of two or more.
組成物における有機過酸化物の含有量は、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）１００ｇに対して、通常０．０００３〜０．０５モル、好ましくは０．００１〜０．０３モルの範囲であるが、要求される物性に応じて適宜最適量を決定することが望ましい。 The content of the organic peroxide in the composition is usually 0.0003 to 0.05 mol, preferably 0.001 to 0, per 100 g of the ethylene / α-olefin / non-conjugated polyene random copolymer (A). Although it is in the range of 0.03 mol, it is desirable to determine the optimum amount as appropriate according to the required physical properties.
架橋剤として有機過酸化物を使用するときは、架橋助剤を併用することが好ましい。架橋助剤の具体例には、イオウ；ｐ-キノンジオキシム等のキノンジオキシム系化合物；ポリエチレングリコールジメタクリレート等のメタクリレート系化合物；ジアリルフタレート、トリアリルシアヌレート等のアリル系化合物；その他マレイミド系化合物；ジビニルベンゼンなどが含まれる。 When using an organic peroxide as a crosslinking agent, it is preferable to use a crosslinking aid in combination. Specific examples of crosslinking aids include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; other maleimides Compound; divinylbenzene and the like are included.
組成物における架橋助剤の含有量は、有機過酸化物１モルに対して、０．５〜２モル、好ましくは、およそ等モルである。 The content of the crosslinking aid in the composition is 0.5 to 2 mol, preferably about equimolar to 1 mol of the organic peroxide.
〔老化防止剤〕
本発明の組成物には老化防止剤が含まれていてもよい。老化防止剤を使用すれば、本発明の組成物およびその架橋体の材料寿命を長くすることが可能である。このことは、通常のゴムの場合と同様である。老化防止剤の例には、特開平９−３０９９８６に記載のものを挙げることができる。老化防止剤は、単独あるいは２種以上の組み合わせて用いることができる。組成物における老化防止剤の含有量は、共重合体（Ａ）１００重量部に対して、通常０．１〜５重量部、好ましくは０．５〜３重量部の割合である。
[Anti-aging agent]
The composition of the present invention may contain an antiaging agent. If an anti-aging agent is used, it is possible to lengthen the material life of the composition of the present invention and its crosslinked product. This is the same as in the case of ordinary rubber. Examples of the anti-aging agent include those described in JP-A-9-309986. Antiaging agents can be used alone or in combination of two or more. Content of anti-aging agent in a composition is 0.1-5 weight part normally with respect to 100 weight part of copolymers (A), Preferably it is a ratio of 0.5-3 weight part.
〔加工助剤〕
本発明の組成物には加工助剤が含まれていてもよい。加工助剤としては、通常のゴム加工に使用される加工助剤を使用することができる。加工助剤の例には、特開平９−３０９９８６の［００６１］に記載のものを挙げることができる。組成物における加工助剤の含有量は、通常、共重合体（Ａ）１００重量部に対して、約１０重量部以下、好ましくは約１〜５重量部の割合である。
[Processing aid]
The composition of the present invention may contain a processing aid. As processing aids, processing aids used in normal rubber processing can be used. Examples of processing aids include those described in [0061] of JP-A-9-309986. The content of the processing aid in the composition is usually about 10 parts by weight or less, preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the copolymer (A).
〔発泡剤および発泡助剤〕
本発明の組成物には、通常ゴムに使用される発泡剤および発泡助剤を含みうる。発泡剤および発泡助剤を配合した組成物を成形し、発泡させ、そして架橋（加硫）させることで、発泡体からなる架橋体を得ることができる。発泡剤の例には、特開平９−３０９９８６の［００６６］に記載のものを挙げることができる。組成物における発泡剤の含有量は、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）１００重量部に対して、０．５〜３０重量部、好ましくは１〜２０重量部の割合である。
[Foaming agent and foaming aid]
The composition of the present invention may contain a foaming agent and a foaming aid that are commonly used for rubber. A composition containing a foaming agent and a foaming aid is molded, foamed, and cross-linked (vulcanized) to obtain a cross-linked product made of a foam. Examples of the foaming agent include those described in [0066] of JP-A-9-309986. The foaming agent content in the composition is 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer (A). It is.
本発明の組成物には、必要に応じて発泡助剤を添加してもよい。発泡剤と併用される発泡助剤は、発泡剤の分解温度の低下、分解促進、気泡の均一化などの作用をする。発泡助剤の例には、特開平９−３０９９８６に記載のものを挙げることができる。これらの発泡助剤は、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）１００重量部に対して、０．０１〜１０重量部、好ましくは０．１〜５重量部の割合でありうるが、要求される物性値に応じて適宜最適量を決定することが望ましい。 You may add a foaming adjuvant to the composition of this invention as needed. The foaming aid used in combination with the foaming agent acts to lower the decomposition temperature of the foaming agent, promote decomposition, and make the bubbles uniform. Examples of foaming aids include those described in JP-A-9-309986. These foaming assistants are 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer (A). Although it is possible, it is desirable to appropriately determine the optimum amount according to the required physical property value.
〔脱泡剤〕
本発明の組成物には、脱泡剤が含まれていてもよい。組成物を架橋（加硫）するときに、内包する水分により気泡ができたり、発泡度が異なったりすることがあるので、脱泡剤を添加することでこれらを防止する。脱泡剤の具体暦には、酸化カルシウムが含まれる。
[Defoaming agent]
The composition of the present invention may contain a defoaming agent. When the composition is crosslinked (vulcanized), bubbles may be formed due to the moisture contained therein, and the degree of foaming may be different. Therefore, these are prevented by adding a defoaming agent. The calendar of the defoamer includes calcium oxide.
組成物における脱泡剤の含有量は、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）１００重量部に対して、通常２０重量部以下、好ましくは１０重量部以下の割合でありうるが、要求される物性値に応じて適宜最適量を決定することが望ましい。 The content of the defoaming agent in the composition is usually 20 parts by weight or less, preferably 10 parts by weight or less with respect to 100 parts by weight of the ethylene / α-olefin / non-conjugated polyene random copolymer (A). However, it is desirable to appropriately determine the optimum amount according to the required physical property value.
〔その他の樹脂〕
本発明の組成物には、本発明の目的を損なわない範囲内でその他の樹脂を含んでいてもよい。その他の樹脂の例には、エチレン・α-オレフィン共重合体樹脂が含まれる。エチレン・α-オレフィン共重合体樹脂は、エチレンから導かれる単位と、炭素数３以上、好ましくは３〜２０のα−オレフィンから導かれる単位とを含む共重合体樹脂である。
[Other resins]
The composition of the present invention may contain other resins as long as the object of the present invention is not impaired. Examples of other resins include ethylene / α-olefin copolymer resins. The ethylene / α-olefin copolymer resin is a copolymer resin containing a unit derived from ethylene and a unit derived from an α-olefin having 3 or more carbon atoms, preferably 3 to 20 carbon atoms.
［組成物］
本発明の組成物において、重合体（Ｂ）の含有量は、エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）１００質量部に対して、通常は１５〜４０質量部であり、好ましくは１５〜３５質量部であり、より好ましくは１５〜３０質量部であり、特に好ましくは１５〜２５質量部である。共重合体（Ａ）と重合体（Ｂ）とを、好適な比率で含む本発明の組成物は、その粘度が過剰に高まらずに加工性に優れる。加工性が優れているとは、組成物を混練しやすいことなどを言う。
[Composition]
In the composition of the present invention, the content of the polymer (B) is usually 15 to 40 parts by mass with respect to 100 parts by mass of the ethylene / α-olefin / non-conjugated polyene copolymer (A), preferably Is 15 to 35 parts by mass, more preferably 15 to 30 parts by mass, and particularly preferably 15 to 25 parts by mass. The composition of the present invention containing the copolymer (A) and the polymer (B) in a suitable ratio is excellent in processability without excessively increasing the viscosity. Excellent workability means that the composition is easily kneaded.
また、共重合体（Ａ）と重合体（Ｂ）とを、好適な比率で含む本発明の組成物は、その架橋体の形状記憶性が高く、かつゴム弾性に優れる。形状記憶性とは、加熱条件下で応力が印加された状態での形状が、冷却して応力を開放しても保持されやすく（形状固定性）、かつ、再加熱すると元の形状に戻りやすいこと（形状回復性）をいう。ゴム弾性に優れるとは、永久圧縮歪み（％）の値が小さいことを意味する。 Moreover, the composition of this invention containing a copolymer (A) and a polymer (B) in a suitable ratio has high shape memory property of the crosslinked body, and is excellent in rubber elasticity. Shape memory property means that the shape in the state where stress is applied under heating conditions can be easily retained even after cooling to release the stress (shape fixability), and it can easily return to its original shape when reheated. (Shape recovery). “Excellent rubber elasticity” means that the value of permanent compression strain (%) is small.
共重合体（Ａ）のようなエラストマーに、重合体（Ｂ）のような低分子量成分を含む組成物の架橋体は、通常、ゴム弾性などが低下することがある。しかし、驚くべきことに、共重合体（Ａ）に適量の重合体（Ｂ）を配合した組成物は、優れた加工性を有しつつ、その架橋体は、形状記憶性に優れながら、かつゴム弾性にも特異的に優れる組成物が得られる。架橋体のゴム弾性を高めるには、重合体（Ａ）１００質量部あたり、１５〜２５質量部の重合体（Ｂ）を含むことが好ましい。 In a crosslinked product of a composition containing a low molecular weight component such as the polymer (B) in an elastomer such as the copolymer (A), rubber elasticity or the like may usually be lowered. Surprisingly, however, the composition in which an appropriate amount of the polymer (B) is blended with the copolymer (A) has excellent processability, while the crosslinked product has excellent shape memory property, and A composition that is also excellent in rubber elasticity is obtained. In order to increase the rubber elasticity of the crosslinked product, it is preferable to contain 15 to 25 parts by mass of the polymer (B) per 100 parts by mass of the polymer (A).
共重合体（Ａ）に適量の重合体（Ｂ）を配合した組成物が、特異的にゴム弾性に優れる理由は限定されないものの、重合体（Ｂ）が組成物の架橋反応に及ぼす影響にいくらか関連があるのではないかと考える。つまり、本発明の組成物において、重合体（Ｂ）は通常は共重合体（Ａ）に適度に分散しており、共重合体（Ａ）の運動性を高めているとも考えられる。 Although the reason why the composition in which an appropriate amount of the polymer (B) is blended with the copolymer (A) is specifically excellent in rubber elasticity is not limited, there is some influence on the influence of the polymer (B) on the crosslinking reaction of the composition. I think that there is a connection. That is, in the composition of the present invention, the polymer (B) is usually dispersed in the copolymer (A) appropriately, and it is considered that the mobility of the copolymer (A) is enhanced.
そのため、組成物における重合体（Ｂ）の含有量が少量であると、組成物の流動性が低下し、架橋反応時の共重合体（Ａ）の運動性も低下する。架橋反応時の共重合体（Ａ）の運動性が低下すると、架橋体の架橋密度が小さくなり、ゴム弾性が発現しにくいと考えられる。 Therefore, when the content of the polymer (B) in the composition is small, the fluidity of the composition is lowered, and the mobility of the copolymer (A) during the crosslinking reaction is also lowered. If the mobility of the copolymer (A) during the crosslinking reaction is lowered, it is considered that the crosslinking density of the crosslinked body is reduced and rubber elasticity is hardly exhibited.
一方、組成物における重合体（Ｂ）の含有量が多過ぎると、重合体（Ｂ）が共重合体（Ａ）中にミクロ分散できずに、いわば凝集状態となる。そのため、架橋体のゴム弾性が発現しにくいとも考えられる。 On the other hand, when there is too much content of the polymer (B) in a composition, a polymer (B) cannot be micro-dispersed in a copolymer (A), and will be in an aggregate state. For this reason, it is considered that the rubber elasticity of the crosslinked body is hardly exhibited.
ところが、１００質量部の共重合体（Ａ）に対して、なかでも、重合体（Ｂ）を１５〜２５質量部含む組成物は、共重合体（Ａ）中での重合体（Ｂ）の分散性がよく、組成物の架橋反応時には、共重合体（Ａ）の運動性が高まり、架橋体の架橋密度がより高くなり、特異な現象を示すのではないかと考える。 However, the composition containing 15 to 25 parts by mass of the polymer (B) with respect to 100 parts by mass of the copolymer (A) is a polymer (B) in the copolymer (A). It is considered that the dispersibility is good and the mobility of the copolymer (A) is increased during the crosslinking reaction of the composition, the crosslinking density of the crosslinked body is increased, and a unique phenomenon is exhibited.
また本発明の組成物の架橋体は、低分子量の重合体（Ｂ）の代わりに高分子量の重合体を含む組成物の架橋体よりも、引っ張り試験における破断時強度が高く、破断伸び率も高い。 Further, the crosslinked product of the composition of the present invention has higher strength at break in the tensile test than the crosslinked product of the composition containing a high molecular weight polymer instead of the low molecular weight polymer (B), and the elongation at break is also high. high.
〔組成物の製造方法〕
本発明の組成物は、エチレン・α-オレフィン・非共役ポリエンランダム共重合体（Ａ）と重合体（Ｂ）と、必要に応じて架橋剤、充てん剤、軟化剤などの一般にゴム製品の製造で用いられる各種公知の配合剤を、一般的なゴム配合物の製造方法によって調製することができる。
[Production Method of Composition]
The composition of the present invention is generally used for the production of rubber products such as ethylene / α-olefin / non-conjugated polyene random copolymer (A) and polymer (B) and, if necessary, a crosslinking agent, a filler, and a softening agent. Various known compounding agents used in the above can be prepared by a general method for producing a rubber compound.
特に、本発明の組成物は、低分子量（１×１０３〜１５×１０３）の重合体（Ｂ）を含むため、製造時の原料組成物の粘度が比較的小さく、混練装置への負荷が小さいため製造しやすい。 In particular, since the composition of the present invention contains a polymer (B) having a low molecular weight (1 × 10 3 to 15 × 10 3 ), the viscosity of the raw material composition at the time of production is relatively small and the load on the kneading apparatus It is easy to manufacture because it is small.
本発明の組成物の製造方法の一例を以下に示す。まず、エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）と重合体（Ｂ）とを混合する。混合は、例えば二軸押出機やバンバリーミキサー、ニーダー、インターミックスのようなインターナルミキサー（密閉式混合機）類などにより行えばよい。それにより、エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）中に、重合体（Ｂ）を溶融状態で分散させる。 An example of the manufacturing method of the composition of this invention is shown below. First, the ethylene / α-olefin / non-conjugated polyene copolymer (A) and the polymer (B) are mixed. The mixing may be performed by, for example, a twin screw extruder, a Banbury mixer, a kneader, an internal mixer (closed mixer) such as an intermix, or the like. Thereby, the polymer (B) is dispersed in a molten state in the ethylene / α-olefin / non-conjugated polyene copolymer (A).
次いで、充てん材、必要に応じて、軟化剤（油展用）、加工助剤、加硫促進剤などの添加剤を、バンバリーミキサー、ニーダー、インターミックスのようなインターナルミキサー（密閉式混合機）類により、１２０〜２５０℃（重合体（Ｂ）の融点以上の温度）で混練する。例えば、重合体（Ｂ）がプロピレン由来の構成単位を５０モル％以上含む重合体である場合には、好ましくは１２０〜１７０℃で２〜２０分間混練する。 Next, fillers, if necessary, additives such as softeners (for oil expansion), processing aids, vulcanization accelerators, internal mixers such as Banbury mixers, kneaders and intermixes (closed mixers) And kneading at 120 to 250 ° C. (temperature higher than the melting point of the polymer (B)). For example, when the polymer (B) is a polymer containing 50 mol% or more of a structural unit derived from propylene, it is preferably kneaded at 120 to 170 ° C. for 2 to 20 minutes.
次いで、オープンロールのようなロール類、あるいはニーダーを使用して、混練物の温度を重合体（Ｂ）の融点以上の温度でせん断を加え、せん断を加えながら重合体（Ｂ）の融点以下まで冷却してブレンド物を得る。 Next, using a roll such as an open roll or a kneader, the kneaded product is sheared at a temperature equal to or higher than the melting point of the polymer (B), and the shearing is applied until the melting point of the polymer (B) or lower is reached. Cool to obtain a blend.
得られたブレンド物に、必要に応じて、軟化剤、架橋剤（加硫剤、たとえばイオウ）、加硫促進剤、発泡剤、架橋剤等の添加剤を、オープンロールのようなロール類あるいはニーダーを使用して混合する。さらに必要に応じて、加硫促進剤、架橋助剤、発泡助剤、脱法剤を追加混合し、ロール温度４０〜８０℃で５〜３０分間混練した後、分出しすることにより、本発明の組成物を調製することができる。 If necessary, an additive such as a softening agent, a crosslinking agent (vulcanizing agent such as sulfur), a vulcanization accelerator, a foaming agent, a crosslinking agent, or the like, such as an open roll, Mix using a kneader. Furthermore, if necessary, a vulcanization accelerator, a crosslinking aid, a foaming aid, and a desiccant are additionally mixed, kneaded at a roll temperature of 40 to 80 ° C. for 5 to 30 minutes, and then dispensed. A composition can be prepared.
本発明の組成物は、低分子量の重合体（Ｂ）を用いていることから、共重合体（Ａ）と重合体（Ｂ）とその他の成分とを、任意の順序で混練装置に添加して組成物を製造することもできる。さらには、共重合体（Ａ）と重合体（Ｂ）とその他の成分とを、全て一括して最初から投入して組成物を製造することもできる。共重合体（Ａ）と重合体（Ｂ）とをあらかじめ混練して、共重合体（Ａ）と重合体（Ｂ）とからなる組成物を調製しておき、さらにその他の成分を添加する態様も好ましい一態様である。 Since the composition of the present invention uses the low molecular weight polymer (B), the copolymer (A), the polymer (B) and other components are added to the kneading apparatus in any order. The composition can also be manufactured. Furthermore, the copolymer (A), the polymer (B), and other components can be added all at once from the beginning to produce a composition. A mode in which the copolymer (A) and the polymer (B) are previously kneaded to prepare a composition comprising the copolymer (A) and the polymer (B), and other components are added. Is also a preferred embodiment.
本発明の組成物を製造するにあたっては、重合体（Ｂ）を用いているため、製造の際の混練トルクが低く製造が容易であり、しかも（Ｂ）が（Ａ）に比較的良く分散する。本発明の組成物は、未架橋の状態でも用いることが可能であるが、次に示すように、架橋体として用いた場合には、その効果をよく発揮する。 In producing the composition of the present invention, since the polymer (B) is used, the kneading torque during the production is low and the production is easy, and (B) is relatively well dispersed in (A). . The composition of the present invention can be used even in an uncrosslinked state, but when used as a crosslinked product, the effect is well exhibited as shown below.
〔架橋体およびその製造方法〕
本発明の架橋体は、本発明の組成物を架橋（例えば加硫）してなり、ポリオレフィン樹脂がミクロ分散して形成されることから、優れた機械特性とゴム弾性とをあわせもつ。そのため、通常のエチレン・α-オレフィン・非共役ポリエンランダム共重合体の使用用途である自動車部品、家電関連部品、土木・建材関連部品、雑貨ならびに日用品をはじめ種々の用途に適用することができる。
[Crosslinked product and production method thereof]
The crosslinked product of the present invention is formed by crosslinking (for example, vulcanizing) the composition of the present invention, and is formed by microdispersing the polyolefin resin, and thus has excellent mechanical properties and rubber elasticity. Therefore, it can be applied to various uses including automobile parts, home appliance-related parts, civil engineering / building material-related parts, miscellaneous goods and daily necessities, which are ordinary uses of ethylene / α-olefin / non-conjugated polyene random copolymers.
このような用途としては、具体的には、自動車用ウェザーストリップ、例えばドアウェザーストリップ、トランクウェザーストリップ、ラゲージウェザーストリップ、ルーフサイドレールウェザーストリップ、スライドドアウェザーストリップ、ベンチレータウェザーストリップ、スライディングループパネルウェザーストリップ、フロントウインドウェザーストリップ、リヤウインドウェザーストリップ、クォーターウインドウェザーストリップ、ロックピラーウェザーストリップ、ドアガラスアウナーウェザーストリップ、ドアガラスインナーウェザーストリップ、ダムウインドシールド、グラスランチャネル、ドアミラー用ブラケット、シールヘッドランプ、シールカウルトップ；自動車用ホース、例えばブレーキホース、ラジエーターホース、ヒーターホース、エアークリーナーホース；送水用ホース；ガス用ホース；建材シール部品、例えばガスケット、エアータイト、目地材、戸当たり部； 家電シール部品；自動車用カップ・シール材、例えばマスタシリンダーピストンカップ、ホイールシリンダーピストンカップ等が挙げられる。 Examples of such applications include automotive weather strips, such as door weather strips, trunk weather strips, luggage weather strips, roof side rail weather strips, sliding door weather strips, ventilator weather strips, sliding loop panel weather strips. , Front window weather strip, rear window weather strip, quarter window weather strip, lock pillar weather strip, door glass outer weather strip, door glass inner weather strip, dam windshield, glass run channel, bracket for door mirror, seal headlamp, seal Cowl top; automotive hoses such as brake hoses, radiators Hose, heater hose, air cleaner hose; water supply hose; gas hose; building material seal parts such as gaskets, air tights, joint materials, door stops; home appliance seal parts; automotive cups and seal materials such as master cylinder piston cups And wheel cylinder piston cups.
本発明の架橋体（加硫である場合には、ゴム成形体）は、物性上の特性を損なわない範囲であれば、発泡成形体であってもよい。発泡成形体の用途として、具体的には、ドアスポンジ用スポンジ、オープニングトリム用スポンジ、フードシール用スポンジ、トランクシール用スポンジ等のウェザーストリップ用スポンジ材；断熱スポンジ、ダムラバー等高発泡スポンジ材などが挙げられる。 The crosslinked product of the present invention (in the case of vulcanization, a rubber molded product) may be a foamed molded product as long as it does not impair physical properties. Specific applications of foam moldings include weather sponges such as door sponges, opening trim sponges, hood seal sponges, trunk seal sponges, etc .; high foam sponge materials such as heat insulation sponges and dam rubbers. Can be mentioned.
本発明の架橋体は、特に形状記憶性が求められる、シボなどの模様を有していてもよいフィルム、シートまたはチューブ状の熱収縮性成形体として、また各種シール材、グロメット類、衣服のギャザー類、異形パイプの接続などの用途、さらには、自動車用ラジエーターホース等のジョイントホース、グラスランチャンネル、ウェザーストリップスポンジなどの自動車用部品の用途などに広く利用することができる。
本発明の架橋体は、特にグロメット、ホース、シール材または自動車用ウエザーストリップに好適に用いられる。
The crosslinked product of the present invention is a film, sheet or tube-like heat-shrinkable molded product that may have a pattern such as a texture, in which shape memory properties are particularly required, and various sealing materials, grommets, and clothing. It can be widely used for applications such as gathers, connection of irregularly shaped pipes, and for automotive parts such as joint hoses such as radiator hoses for automobiles, glass run channels, and weatherstrip sponges.
The cross-linked product of the present invention is particularly suitably used for grommets, hoses, sealing materials or automobile weather strips.
〔架橋体の製造方法〕
本発明の組成物を架橋体（ゴム成形体）とするには、未架橋（未加硫）の組成物を調製し、次に、この未架橋の組成物を所望の形状に成形した後に、架橋（加硫）反応すればよい。
[Method for producing crosslinked product]
In order to make the composition of the present invention into a crosslinked product (rubber molded product), after preparing an uncrosslinked (unvulcanized) composition, and then molding the uncrosslinked composition into a desired shape, A crosslinking (vulcanization) reaction may be performed.
未架橋（未加硫）のゴム組成物は、種々の成形法により成形し、成形体を構成する組成物を架橋（加硫）することができる。特に、圧縮成形、押出し成形、射出成形などの型成形により成形し、成形物を構成する組成物を架橋（加硫）する場合にその特性を発揮しやすい。 An uncrosslinked (unvulcanized) rubber composition can be molded by various molding methods to crosslink (vulcanize) the composition constituting the molded body. In particular, when molding is performed by molding such as compression molding, extrusion molding, injection molding or the like, and the composition constituting the molded product is crosslinked (vulcanized), the characteristics are easily exhibited.
圧縮成形の場合には、予め秤量した未架橋（未加硫）の組成物を型に入れ、型を閉じた後１２０〜２７０℃の温度で、３０秒〜１２０分加熱することにより、目的とする架橋体（加硫ゴム成形体）が得られる。 In the case of compression molding, an uncrosslinked (unvulcanized) composition weighed in advance is put into a mold, and after closing the mold, it is heated at a temperature of 120 to 270 ° C. for 30 seconds to 120 minutes. A crosslinked product (vulcanized rubber molded product) is obtained.
押出し成形の場合には、リボン状あるいはペレット状の未架橋（未加硫）の組成物を、所望の形状の口金をセットした押出し機に供給する。次いで、所望の形状に調製された組成物を、１５０℃〜３５０℃の温度に設定された加硫槽中に連続的に供給し、３０秒〜２０分間加熱することにより、目的とする架橋体（ゴム成形体）が得られる。 In the case of extrusion molding, a ribbon-shaped or pellet-shaped uncrosslinked (unvulcanized) composition is supplied to an extruder in which a die having a desired shape is set. Next, the composition prepared in a desired shape is continuously supplied into a vulcanization tank set at a temperature of 150 ° C. to 350 ° C., and heated for 30 seconds to 20 minutes, whereby the desired crosslinked body is obtained. (Rubber molding) is obtained.
射出成形の場合、リボン状あるいはペレット状の未架橋（未加硫）の組成物を、スクリューにより予め設定した量だけポットに供給する。引き続き予備加熱された組成物を、プランジャーにより金型内に１〜２０秒で送り込む。組成物を射出した後、１２０〜２７０℃の温度で、３０秒〜１２０分加熱することにより、目的とする架橋体（ゴム成形体）が得られる。 In the case of injection molding, a ribbon-shaped or pellet-shaped uncrosslinked (unvulcanized) composition is supplied to the pot by a predetermined amount by a screw. Subsequently, the preheated composition is fed into the mold by a plunger in 1 to 20 seconds. After injecting the composition, the target crosslinked product (rubber molded product) is obtained by heating at a temperature of 120 to 270 ° C. for 30 seconds to 120 minutes.
次に本発明について実施例を示してさらに詳細に説明するが、本発明はこれらによって限定されるものではない。 EXAMPLES Next, although an Example is shown and this invention is demonstrated further in detail, this invention is not limited by these.
エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）の各物性を、以下の通り測定および評価した。 Each physical property of the ethylene / α-olefin / non-conjugated polyene copolymer (A) was measured and evaluated as follows.
（１）エチレン含量：１３ＣＮＭＲにより測定した。具体的には、日本電子製ＪＮＭ−ＥＣＸ４００Ｐ型核磁気共鳴装置を用い、試料２０ｍｇをＮＭＲサンプル管（５ｍｍφ）中で重水素化o-ジクロロベンゼン約０．５ｍｌに完全に溶解させた後、１２０℃にて積算回数は１万回以上の条件で測定した。
（２）ムーニー粘度（ＭＬ）：ムーニー粘度計（島津製作所社製ＳＭＶ２０２型）を用いて、１２５℃におけるムーニー粘度を測定した。
（３）極限粘度[η]：試料約２０ｍｇを、デカリン１５ｍｌに溶解し、１３５℃のオイルバス中で比粘度ηspを測定した。このデカリン溶液にデカリン溶媒を５ｍｌ追加して希釈後、同様にして比粘度ηspを測定する。この希釈操作をさらに２回繰り返し、濃度（Ｃ）を０に外挿した時のηsp／Ｃの値を極限粘度として求めた（下式参照）。
［η］＝ｌｉｍ（ηsp／Ｃ） （Ｃ→０）
（４）ヨウ素価：ＪＩＳＫ００７０に従って測定した。
(1) Ethylene content: measured by 13 CNMR. Specifically, using a JNM-ECX400P nuclear magnetic resonance apparatus manufactured by JEOL, 20 mg of a sample was completely dissolved in about 0.5 ml of deuterated o-dichlorobenzene in an NMR sample tube (5 mmφ), and then 120 The number of integrations was measured at 10,000 ° C. under conditions of 10,000 times or more.
(2) Mooney viscosity (ML): Mooney viscosity at 125 ° C. was measured using a Mooney viscometer (SMV202 type, manufactured by Shimadzu Corporation).
(3) Intrinsic viscosity [η]: About 20 mg of a sample was dissolved in 15 ml of decalin, and the specific viscosity η sp was measured in an oil bath at 135 ° C. After adding 5 ml of decalin solvent to this decalin solution for dilution, the specific viscosity η sp is measured in the same manner. This dilution operation was further repeated twice, and the value of η sp / C when the concentration (C) was extrapolated to 0 was determined as the intrinsic viscosity (see the following formula).
[Η] = lim (η sp / C) (C → 0)
(4) Iodine value: measured according to JISK0070.
炭素数３〜２０のα−オレフィンから選ばれる１種に由来する構成単位を主成分とする重合体（Ｂ）の各物性を、以下の通り評価した。
（５）組成：１３ＣＮＭＲにより測定した。具体的には（１）エチレン含量と同じ条件で測定を行った。
（６）数平均分子量（Ｍｎ）：ゲル浸透クロマトグラフＡｌｌｉａｎｃｅ ＧＰＣ２０００型（Ｗａｔｅｒｓ社）を使用し、カラムにはＴＳＫｇｅｌカラム（東ソー社製）×４（それぞれ７．５ｍｍＩ.Ｄ.×３０ｃｍ，東ソー社）を使用し、移動相にはo-ジクロロベンゼン（和光純薬 特級試薬）を使用した。測定は、カラム温度１４０℃、移動相流速１．０ｍＬ／ｍｉｎの条件下で実施し、検出には示差屈折計を用いた。分子量校正にはポリスチレンを用いた。
（７）融点：示差走査型熱量計（ＤＳＣ）〔ＤＳＣ−２０（セイコー電子工業社製）〕を用いて測定した。まず、測定試料を５００℃／分の昇温速度で一旦２００℃まで昇温して、５分間保持した後、直ちに室温まで２０℃／分の降温速度で−２０℃まで降温した。この試料約１０ｍｇを−２０℃から２００℃の温度範囲で、昇温速度１０℃／分の条件でＤＳＣ測定した。この最後の昇温過程における測定結果から得られたカーブの吸熱ピークを示す温度を融点とした。なお、重合体（Ｂ）の吸熱ピークが２つ以上存在する場合には、ピークを示す温度のうち、最も低温のものピーク温度を融点とした。
（８）密度：ＪＩＳＫ７１１２のＤ法（密度勾配管法）に従って測定した。
（９）針入度（２５度）：ＪＩＳＫ２２０７に記載されている試験方法に従って測定した。
Each physical property of the polymer (B) whose main component is a structural unit derived from one type selected from α-olefins having 3 to 20 carbon atoms was evaluated as follows.
(5) Composition: Measured by 13 CNMR. Specifically, the measurement was performed under the same conditions as (1) ethylene content.
(6) Number average molecular weight (Mn): Gel permeation chromatograph Alliance GPC2000 type (Waters) is used, and TSKgel column (manufactured by Tosoh Corp.) × 4 (7.5 mm ID × 30 cm, Tosoh Corp., respectively) ) And o-dichlorobenzene (Wako Pure Chemicals special grade reagent) was used as the mobile phase. The measurement was performed under conditions of a column temperature of 140 ° C. and a mobile phase flow rate of 1.0 mL / min, and a differential refractometer was used for detection. Polystyrene was used for molecular weight calibration.
(7) Melting point: Measured using a differential scanning calorimeter (DSC) [DSC-20 (manufactured by Seiko Electronics Industry)]. First, the measurement sample was once heated to 200 ° C. at a temperature rising rate of 500 ° C./min, held for 5 minutes, and immediately cooled to −20 ° C. at a temperature lowering rate of 20 ° C./min. About 10 mg of this sample was subjected to DSC measurement in the temperature range from −20 ° C. to 200 ° C. under the temperature rising rate of 10 ° C./min. The temperature showing the endothermic peak of the curve obtained from the measurement result in the final temperature raising process was defined as the melting point. When two or more endothermic peaks of the polymer (B) exist, the lowest peak temperature among the temperatures showing the peaks was taken as the melting point.
(8) Density: Measured according to D method (density gradient tube method) of JISK7112.
(9) Penetration (25 degrees): Measured according to the test method described in JISK2207.
未架橋の組成物の物性；
（１０）ムーニー粘度（ＭＬ）：上記（２）と同じ方法で測定した。
（１１）最低粘度（Ｖｍ）およびスコーチ時間（ｔ５）：ムーニー粘度計（島津製作所社製ＳＭＶ２０２型）を用いて、１２５℃におけるムーニー粘度の変化を測定した。そして測定開始以降の最低のムーニー粘度を最低粘度Ｖｍとし、さらにその最低粘度Ｖｍより５パーセント上昇するまでの時間を求め、これをスコーチ時間ｔ５（ｍｉｎ.）とした。
Physical properties of the uncrosslinked composition;
(10) Mooney viscosity (ML): Measured by the same method as in (2) above.
(11) Minimum viscosity (Vm) and scorch time (t5): Changes in Mooney viscosity at 125 ° C. were measured using a Mooney viscometer (SMV202 type manufactured by Shimadzu Corporation). Then, the lowest Mooney viscosity after the start of the measurement was defined as the minimum viscosity Vm, and the time required to increase by 5 percent from the minimum viscosity Vm was determined, and this was defined as the scorch time t5 (min.).
架橋体の物性；
（１２）硬さ試験（ＨＡ）：加硫成形体の平らな部分を重ねて１２ｍｍとし、ＪＩＳ Ｋ６２５３に従い硬度（ＪＩＳ−Ａ）を測定した。
（１３）引張り試験：加硫成形体をＪＩＳ Ｋ６２５１に従い、測定温度２３℃、引張速度５００ｍｍ／分の条件で引張試験を行い、破断時強度（ＴＢ）および破断伸び（ＥＢ）を測定した。
（１４）圧縮永久歪試験：ＪＩＳ Ｋ６２５０の６．５の要領で加硫成形体からサンプルを抜き取り、ＪＩＳ Ｋ６２６２（１９９７）に従って、７０℃×２２時間、および７０℃×９６時間処理後の圧縮永久歪を測定した。
（１５）形状記憶試験：厚み２ｍｍシートからＪＩＳ３号ダンベルの形状にサンプルを打ち抜き、２ｃｍ標線（Ｌ１）を引き、１００％伸長を与え（このときの標線間隔をＬ２とする）、２００℃オーブンに１０分間放置した。室温で３０分間冷却後、応力を開放し、３０分後に標線間隔（Ｌ３）を測定した。形状固定性は、以下の式で算出した。
形状固定性（％）＝１００＊（Ｌ３−Ｌ１）／（Ｌ２−Ｌ１）
そして再び２００℃オーブンに１０分間放置した。室温で３０分間冷却後、応力を開放し、３０分後に標線間隔（Ｌ４）を測定した。形状回復性は、以下の式で算出した。
形状回復性（％）＝１００＊（Ｌ３−Ｌ４）／（Ｌ３−Ｌ１）
Physical properties of the crosslinked product;
(12) Hardness test (HA): The flat part of the vulcanized molded body was overlapped to 12 mm, and the hardness (JIS-A) was measured according to JIS K6253.
(13) Tensile test: The vulcanized molded body was subjected to a tensile test in accordance with JIS K6251 under conditions of a measurement temperature of 23 ° C. and a tensile speed of 500 mm / min to measure strength at break (TB) and elongation at break (EB).
(14) Compression set test: A sample was extracted from the vulcanized molded article in accordance with 6.5 of JIS K6250, and subjected to compression permanent after 70 ° C. × 22 hours and 70 ° C. × 96 hours treatment according to JIS K6262 (1997). Strain was measured.
(15) Shape memory test: A sample was punched from a 2 mm thick sheet into a JIS No. 3 dumbbell shape, a 2 cm marked line (L1) was drawn, and 100% elongation was given (the marked line interval at this time is L2), 200 ° C. Left in oven for 10 minutes. After cooling at room temperature for 30 minutes, the stress was released, and after 30 minutes, the marked line interval (L3) was measured. The shape fixability was calculated by the following formula.
Shape fixability (%) = 100 * (L3-L1) / (L2-L1)
Then, it was again left in a 200 ° C. oven for 10 minutes. After cooling at room temperature for 30 minutes, the stress was released, and after 30 minutes, the marked line interval (L4) was measured. The shape recoverability was calculated by the following formula.
Shape recovery (%) = 100 * (L3-L4) / (L3-L1)
［製造例１］
＜エチレン・プロピレン・非共役ポリエン共重合体（Ａ）の製造＞
攪拌翼を備えた容量１５Ｌの重合器を用いて、連続的にエチレン、プロピレン、５-エチリデン-２-ノルボルネン（ＥＮＢ）および５-ビニル-２-ノルボルネン（ＶＮＢ）の四元共重合反応を行った。重合器上部から重合溶媒としてヘキサンを毎時５Ｌの速度で連続的に供給し、一方、重合器下部から重合器中の重合液が常に５リットルとなるように連続的に重合液を抜き出した。触媒として、ＶＯＣｌ3、Ａｌ（Ｃ２Ｈ５）１．５Ｃｌ１．５を使用した。すなわちＶＯＣｌ３は重合器中のバナジウム原子濃度が０．５５ｍｍｏｌ／Ｌとなるように、またＡｌ（Ｃ２Ｈ５）１．５Ｃｌ１．５は重合器中のアルミニウム原子濃度が３．３ｍｍｏｌ／Ｌとなるように重合器中に連続的に供給した。
[Production Example 1]
<Production of ethylene / propylene / non-conjugated polyene copolymer (A)>
A quaternary copolymerization reaction of ethylene, propylene, 5-ethylidene-2-norbornene (ENB) and 5-vinyl-2-norbornene (VNB) was continuously performed using a 15 L polymerization vessel equipped with a stirring blade. It was. Hexane was continuously supplied as a polymerization solvent from the upper part of the polymerization vessel at a rate of 5 L / hour, while the polymerization solution was continuously withdrawn from the lower part of the polymerization vessel so that the polymerization solution in the polymerization vessel was always 5 liters. As the catalyst, VOCl 3 , Al (C 2 H 5 ) 1.5 Cl 1.5 was used. That is, VOCl 3 has a vanadium atom concentration of 0.55 mmol / L in the polymerization vessel, and Al (C 2 H 5 ) 1.5 Cl 1.5 has an aluminum atom concentration of 3.3 mmol / L in the polymerization vessel. L was continuously fed into the polymerization vessel.
モノマーのエチレンは１７０Ｌ／ｈ、およびプロピレンは３７５Ｌ／ｈの速度で連続供給した。またＥＮＢおよびＶＮＢは重合器中の濃度がそれぞれ７．５ｇ／Ｌ、０．３９ｇ／Ｌとなるように連続供給した。分子量調整剤としては水素を使用し、これを重合器ガス相の水素濃度が３．１モル％となるように供給した。共重合反応は重合圧力を０．７ＭＰａに保ちながら、重合器外部ジャケットに冷却水を循環させることにより、４０℃の温度で行った。 Monomer ethylene was continuously fed at a rate of 170 L / h and propylene at a rate of 375 L / h. ENB and VNB were continuously fed so that the concentrations in the polymerization vessel were 7.5 g / L and 0.39 g / L, respectively. Hydrogen was used as the molecular weight regulator, and this was supplied so that the hydrogen concentration in the polymerizer gas phase was 3.1 mol%. The copolymerization reaction was performed at a temperature of 40 ° C. by circulating cooling water through the outer jacket of the polymerization vessel while maintaining the polymerization pressure at 0.7 MPa.
このような反応により、エチレンとプロピレンとＥＮＢとＶＮＢからなる共重合体が均一に溶解した溶液を得た。重合器下部から抜き出した重合液中に少量のメタノールを添加して重合反応を停止させ、スチームストリッピング処理にて重合体を溶媒から分離した後、８０℃で一昼夜減圧乾燥した。以上の操作でエチレン、プロピレン、ＥＮＢおよびＶＮＢからなる共重合体が毎時２６５ｇの速度で得られた。 By such a reaction, a solution in which a copolymer composed of ethylene, propylene, ENB, and VNB was uniformly dissolved was obtained. A small amount of methanol was added to the polymerization solution extracted from the lower part of the polymerization vessel to stop the polymerization reaction. The polymer was separated from the solvent by a steam stripping treatment, and then dried under reduced pressure at 80 ° C. overnight. By the above operation, a copolymer composed of ethylene, propylene, ENB and VNB was obtained at a rate of 265 g per hour.
得られたエチレン・プロピレン・非共役ポリエン共重合体（Ａ）の各物性を以下に示す。
エチレン含量５４．３ｗｔ％、ＥＮＢ含量８．４ｗｔ％、ＶＮＢ含量０．４ｗｔ％
ＭＬ１＋４（１２５℃）７８
[η] ２．８ｄｌ／ｇ
ヨウ素価 ２３．７
The physical properties of the obtained ethylene / propylene / non-conjugated polyene copolymer (A) are shown below.
Ethylene content 54.3 wt%, ENB content 8.4 wt%, VNB content 0.4 wt%
ML1 + 4 (125 ° C.) 78
[η] 2.8 dl / g
Iodine number 23.7
〔実施例１〕
エチレン・α-オレフィン・非共役ポリエン共重合体（Ａ）成分として、製造例１で得た共重合体１００重量部を用意した。また、（Ｂ）成分として、プロピレン由来の構成単位を全構成単位の５０モル％以上の割合で有する重合体〔商品名：ハイワックスＴＭＮＰ５００三井化学（株）製、ＤＳＣによる融解ピーク温度１５３／１６１℃、数平均分子量（Ｍｎ）（７，３６０）、密度９０５ｋｇ／ｍ３、針入度＜１ｄｍｍ〕２０重量部を用意した。用意した（Ａ）成分と（Ｂ）成分とを、ＭＩＸＴＲＯＮ ＢＢ ＭＩＸＥＲ（神戸製鋼所社製、ＢＢ−４型、容積２．９５Ｌ、ローター４ＷＨ）に入れ、約１６５℃で５分間混練した。その後、ミキサーから排出し、自然に冷却した。
[Example 1]
As an ethylene / α-olefin / non-conjugated polyene copolymer (A) component, 100 parts by weight of the copolymer obtained in Production Example 1 was prepared. In addition, as the component (B), a polymer having propylene-derived structural units in a proportion of 50 mol% or more of the total structural units [trade name: High Wax TM NP500, manufactured by Mitsui Chemicals, Inc., DSC melting peak temperature 153 / 161 ° C., number average molecular weight (Mn) (7,360), density 905 kg / m 3 , penetration <1 dmm] 20 parts by weight were prepared. The prepared component (A) and component (B) were placed in MIXTRON BB MIXER (Kobe Steel, BB-4, volume 2.95 L, rotor 4WH) and kneaded at about 165 ° C. for 5 minutes. Then, it discharged from the mixer and cooled naturally.
得られた組成物に対して、加硫促進助剤として亜鉛華（商品名；ＭＥＴＡ−Ｚ １０２、井上石灰工業株式会社製）を５重量部、加工助剤としてステアリン酸を２重量部、活性剤（商品名；アーカード ２ＨＴ−Ｆ、ライオン・アクゾ株式会社製）を２重量部、充てん剤としてカーボンブラック（商品名；旭＃５０Ｇ、旭カーボン株式会社製）を９０重量部、軟化剤としてプロセスオイル（商品名；ダイアナプロセスオイル ＰＷ-３８０、出光興産株式会社製）を７０重量部混練した。混練条件は、ローター回転数が５０ｒｐｍ、フローティングウェイト圧力が３ｋｇ／ｃｍ２、混練時間が５分間で行った。 For the obtained composition, 5 parts by weight of zinc white (trade name; META-Z 102, manufactured by Inoue Lime Industry Co., Ltd.) as a vulcanization accelerating aid, 2 parts by weight of stearic acid as a processing aid, active 2 parts by weight of agent (trade name; ARCARD 2HT-F, manufactured by Lion Akzo Co., Ltd.), 90 parts by weight of carbon black (trade name; Asahi # 50G, manufactured by Asahi Carbon Co., Ltd.) as a filler, process as a softener 70 parts by weight of oil (trade name; Diana Process Oil PW-380, manufactured by Idemitsu Kosan Co., Ltd.) was kneaded. The kneading conditions were a rotor rotation speed of 50 rpm, a floating weight pressure of 3 kg / cm 2 , and a kneading time of 5 minutes.
次いで、上記配合物が温度５０℃となったことを確認した後、６インチロールを用いて上記配合物に加硫剤としてイオウを１重量部、加硫促進剤として「ノクセラー ＭＤＢ−Ｐ」（商品名；大内新興化学工業株式会社製）を０．５重量部、加硫促進剤として「ノクセラー ＴＢＴ」（商品名；大内新興化学工業株式会社製）を０．５重量部、加硫促進剤として「サンセラーＢＺ」（商品名；三新化学工業株式会社製）を１重量部、加硫促進剤として「サンセラー２２−Ｃ」（商品名；三新化学工業株式会社製）を１重量部、脱泡剤として「ＶＥＳＴＡ−ＢＳ」（商品名；井上石灰工業株式会社製）を６重量部混練した。 Next, after confirming that the temperature of the blend became 50 ° C., 1 part by weight of sulfur as a vulcanizing agent and “Noxeller MDB-P” (as a vulcanization accelerator) were added to the blend using a 6-inch roll. Product name: 0.5 part by weight of Ouchi Shinsei Chemical Co., Ltd.), 0.5 part by weight of “Noxeller TBT” (trade name: Ouchi Shinsei Chemical Co., Ltd.) as a vulcanization accelerator 1 part by weight of "Sunseller BZ" (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.) as an accelerator, and 1 part by weight of "Sunseller 22-C" (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.) as a vulcanization accelerator 6 parts by weight of “VESTA-BS” (trade name; manufactured by Inoue Lime Industry Co., Ltd.) as a defoaming agent.
混練条件は、ロール温度を前ロール／後ロール＝５０℃／５０℃、ロール回転数を前ロール／後ロール＝１３ｒｐｍ／１１．５ｒｐｍ、ロール間隙を２．５ｍｍとして混練時間８分間で分出して、未架橋（未加硫）の組成物を得た。組成物の各物性を測定し、結果を表１に示した。 The kneading conditions are as follows: roll temperature is front roll / rear roll = 50 ° C./50° C., roll rotation speed is front roll / rear roll = 13 rpm / 11.5 rpm, roll gap is 2.5 mm, and kneading time is 8 minutes. An uncrosslinked (unvulcanized) composition was obtained. The physical properties of the composition were measured, and the results are shown in Table 1.
次に、この配合物からプレス成形機を用いて１７０℃で１０分間加硫を行って、厚み２ｍｍのゴムシートを調製した。また、圧縮永久歪試験用のゴムブロックは、１７０℃で１５分間加硫して調製した。得られた架橋体（加硫物）について、引張り試験、硬さ試験、圧縮永久歪試験、形状記憶試験を上記方法にて行った。結果を表１に示す。 Next, the compound was vulcanized at 170 ° C. for 10 minutes using a press molding machine to prepare a rubber sheet having a thickness of 2 mm. A rubber block for compression set test was prepared by vulcanization at 170 ° C. for 15 minutes. The obtained crosslinked product (vulcanized product) was subjected to a tensile test, a hardness test, a compression set test, and a shape memory test by the above methods. The results are shown in Table 1.
〔実施例２〕
（Ｂ）成分として、プロピレン由来の構成単位を全構成単位の５０モル％以上の割合で有する重合体〔商品名：ハイワックスＴＭＮＰ５０５ 三井化学（株）製、ＤＳＣによる融解ピーク温度１４３／１５１℃、数平均分子量（Ｍｎ）（８，４３０）、密度９０３ｋｇ／ｍ3、針入硬度＜１ｄｍｍ〕を２０重量部用意した。（Ｂ）成分を変更すること以外は実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。
[Example 2]
(B) As a component, a polymer having propylene-derived structural units in a proportion of 50 mol% or more of all structural units [trade name: High Wax TM NP505, manufactured by Mitsui Chemicals, Inc., DSC melting peak temperature 143/151 ° C. 20 parts by weight of a number average molecular weight (Mn) (8,430), a density of 903 kg / m 3 , and a penetration hardness <1 dmm] were prepared. (B) Except having changed a component, it obtained the composition and its crosslinked body (vulcanizate) in the same procedure as Example 1, and performed various evaluations. The results are shown in Table 1.
〔実施例３〕
（Ｂ）成分として、プロピレン由来の構成単位を全構成単位の５０モル％以上の割合で有する重合体〔商品名：ハイワックスＴＭＮＰ５０６ 三井化学（株）製、ＤＳＣによる融解ピーク温度１２８／１３８℃、数平均分子量（Ｍｎ）（１０，０５０）、密度８９７ｋｇ／ｍ3、針入硬度＜１ｄｍｍ〕を２０重量部用意した。（Ｂ）成分を変更すること以外は、実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。
Example 3
(B) As a component, a polymer having a propylene-derived structural unit in a proportion of 50 mol% or more of all structural units [trade name: High Wax TM NP506, manufactured by Mitsui Chemicals, Inc., melting peak temperature by DSC 128/138 ° C. 20 parts by weight of a number average molecular weight (Mn) (10,050), a density of 897 kg / m 3 , and a penetration hardness <1 dmm] were prepared. (B) Except having changed a component, in the same procedure as Example 1, the composition and its crosslinked body (vulcanizate) were obtained, and various evaluation was performed. The results are shown in Table 1.
〔実施例４〕
（Ｂ）成分として、プロピレン由来の構成単位を全構成単位の５０モル％以上の割合で有する重合体〔商品名：ハイワックスＴＭＮＰ０５５ 三井化学（株）製、ＤＳＣによる融解ピーク温度１３６／１４５℃、数平均分子量（Ｍｎ）（３，７９０）、密度９００ｋｇ／ｍ3、針入硬度１ｄｍｍ〕を２０重量部用意した。（Ｂ）成分を変更すること以外は、実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。
Example 4
(B) As a component, a polymer having propylene-derived constituent units in a proportion of 50 mol% or more of all constituent units [trade name: High Wax TM NP055, Mitsui Chemicals, Inc., DSC melting peak temperature 136/145 ° C. , Number average molecular weight (Mn) (3,790), density 900 kg / m 3 , penetration hardness 1 dmm] was prepared in an amount of 20 parts by weight. (B) Except having changed a component, in the same procedure as Example 1, the composition and its crosslinked body (vulcanizate) were obtained, and various evaluation was performed. The results are shown in Table 1.
〔実施例５〕
（Ｂ）成分として、プロピレン由来の構成単位を全構成単位の５０モル％以上の割合で有する重合体〔商品名：ハイワックスＴＭＮＰ５０５ 三井化学（株）製、ＤＳＣによる融解ピーク温度１４３／１５１℃、数平均分子量（Ｍｎ）（８，４３０）、密度９０３ｋｇ／ｍ3、針入硬度＜１ｄｍｍ〕を３０重量部用意した。（Ｂ）成分を変更すること以外は、実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。
Example 5
(B) As a component, a polymer having propylene-derived structural units in a proportion of 50 mol% or more of all structural units [trade name: High Wax TM NP505, manufactured by Mitsui Chemicals, Inc., DSC melting peak temperature 143/151 ° C. 30 parts by weight of a number average molecular weight (Mn) (8,430), a density of 903 kg / m 3 , and a penetration hardness <1 dmm] were prepared. (B) Except having changed a component, in the same procedure as Example 1, the composition and its crosslinked body (vulcanizate) were obtained, and various evaluation was performed. The results are shown in Table 1.
〔比較例１〕
実施例１における（Ｂ）成分の代わりに、高分子量ポリプロピレンとして（ii）プロピレンホモポリマー（ＰＰ）〔商品名：プライムポリプロ（登録商標）Ｊ１０５Ｇ 株式会社プライムポリマー社製、２３０℃、２．１６ｋｇ荷重で測定したＭＦＲが９．０、密度９００Ｋｇ／ｍ３〕を用意した。そして、実施例１における（Ａ）成分と、（ii）成分とを以下の方法でアロイ化した。
[Comparative Example 1]
(Ii) Propylene homopolymer (PP) [trade name: Prime Polypro (registered trademark) J105G, manufactured by Prime Polymer Co., Ltd., 230 ° C., 2.16 kg load, instead of the component (B) in Example 1 as high molecular weight polypropylene The MFR measured in step 9.0 was 9.0, and the density was 900 kg / m 3 ]. And (A) component in Example 1 and (ii) component were alloyed with the following method.
製造例１で得た（Ａ）成分１００重量部と、（ii）ＰＰ２０重量部とを、ＭＩＸＴＲＯＮ ＢＢ ＭＩＸＥＲ（神戸製鋼所社製、ＢＢ−４型、容積２．９５Ｌ、ローター４ＷＨ）に入れ、ＰＰの融点以上の温度（約１７０℃）で５分間混練し、（Ａ）成分に（ii）ＰＰを均一に分散させた。その後、ミキサーから排出し、自然に冷却することで（Ａ）成分／ＰＰのアロイ（iii）を調製した。 100 parts by weight of component (A) obtained in Production Example 1 and (ii) 20 parts by weight of PP are put into MIXTRON BB MIXER (Kobe Steel Works, BB-4, volume 2.95 L, rotor 4WH). The mixture was kneaded for 5 minutes at a temperature equal to or higher than the melting point of PP (about 170 ° C.), and (ii) PP was uniformly dispersed in component (A). Then, it discharged | emitted from the mixer and prepared the alloy (iii) of (A) component / PP by cooling naturally.
調製したアロイ（iii）を用いた以外は、実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。 Except for using the prepared alloy (iii), the composition and its crosslinked product (vulcanized product) were obtained in the same procedure as in Example 1, and various evaluations were performed. The results are shown in Table 1.
〔比較例２〕
（Ｂ）成分としてポリエチレンワックス〔商品名：エクセレックス（登録商標）３０２００Ｂ 三井化学（株）製、ＤＳＣにより測定した融点１０２℃、数平均分子量（Ｍｎ）３，９６０、密度９１３ｋｇ／ｍ３、針入硬度６ｄｍｍ〕を２０重量部用意した。（Ｂ）成分を変更すること以外は、実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。
[Comparative Example 2]
(B) Polyethylene wax as a component [trade name: EXELEX (registered trademark) 30200B, manufactured by Mitsui Chemicals, Inc., melting point 102 ° C. measured by DSC, number average molecular weight (Mn) 3,960, density 913 kg / m 3 , needle 20 parts by weight were prepared. (B) Except having changed a component, in the same procedure as Example 1, the composition and its crosslinked body (vulcanizate) were obtained, and various evaluation was performed. The results are shown in Table 1.
〔比較例３〕
（Ｂ）成分を用いないこと以外は、実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。
[Comparative Example 3]
(B) Except not using a component, in the same procedure as Example 1, the composition and its crosslinked body (vulcanizate) were obtained, and various evaluation was performed. The results are shown in Table 1.
〔比較例４〕
（Ｂ）成分としてプロピレン単独重合体〔商品名：ハイワックスＴＭＮＰ５００ 三井化学（株）製、ＤＳＣによる融解ピーク温度１５３／１６１℃、数平均分子量（Ｍｎ）７，３６０、密度９０５ｋｇ／ｍ３、針入硬度＜１ｄｍｍ〕を１０重量部、および充てん剤としてカーボンブラック（商品名；旭＃５０Ｇ、旭カーボン株式会社製）を１０５重量部用意した。（Ｂ）成分と充てん剤の添加量を変更すること以外は、実施例１と同様の手順で、組成物およびその架橋体（加硫物）を得て、各種評価を行った。結果を表１に示す。
[Comparative Example 4]
(B) as propylene homopolymer [trade name: High Wax TM NP500, manufactured by Mitsui Chemicals, Inc., melting peak temperature 153/161 ° C. by DSC, number average molecular weight (Mn) 7,360, density 905 kg / m 3 , 10 parts by weight of penetration hardness <1 dmm] and 105 parts by weight of carbon black (trade name; Asahi # 50G, manufactured by Asahi Carbon Co., Ltd.) as a filler were prepared. (B) Except changing the addition amount of a component and a filler, the composition and its crosslinked body (vulcanized material) were obtained in the same procedure as Example 1, and various evaluation was performed. The results are shown in Table 1.
各実施例と比較例３との比較から分かるように、ＥＰＤＭに重合体（Ｂ）を配合した組成物の架橋体は、形状記憶性（形状固定性および形状回復性）に優れていることがわかる。また、各実施例と比較例２との比較から分かるように、ＥＰＤＭにポリエチレンワックスを配合した組成物の架橋体よりも、ＥＰＤＭに重合体（Ｂ）を配合した組成物の架橋体の方が、形状記憶性（形状固定性および形状回復性）に優れていることがわかる。 As can be seen from the comparison between each Example and Comparative Example 3, the crosslinked product of the composition in which the polymer (B) is blended with EPDM is excellent in shape memory property (shape fixability and shape recoverability). Recognize. Further, as can be seen from the comparison between each Example and Comparative Example 2, the crosslinked body of the composition in which the polymer (B) is blended with EPDM is more than the crosslinked body of the composition in which the polyethylene wax is blended with EPDM. It can be seen that the shape memory property (shape fixability and shape recoverability) is excellent.
各実施例と比較例１との比較から分かるように、ＥＰＤＭに重合体（Ｂ）を配合した組成物（実施例１〜５）は、ＥＰＤＭとポリプロピレンのアロイを含む組成物（比較例１）よりも、Ｖｍで代表される粘度が低く、成形や混練がしやすいことがわかる。 As can be seen from the comparison between each Example and Comparative Example 1, the composition (Examples 1 to 5) in which the polymer (B) is blended with EPDM is a composition containing an alloy of EPDM and polypropylene (Comparative Example 1). It can be seen that the viscosity represented by Vm is low, and molding and kneading are easy.
実施例１〜３と比較例１との比較から分かるように、ＥＰＤＭに重合体（Ｂ）を配合した組成物の架橋体は、ＥＰＤＭとポリプロピレンのアロイを含む組成物の架橋体よりも、永久圧縮歪みの値（％）が低いことがわかる。また、実施例１〜３と比較すると、実施例４の組成物の架橋体は、永久圧縮歪みの値（％）がやや大きいが、これは重合体（Ｂ）の分子量や融点に関連があると考えられる。 As can be seen from the comparison between Examples 1 to 3 and Comparative Example 1, the crosslinked product of the composition in which the polymer (B) is blended with EPDM is more permanent than the crosslinked product of the composition containing an alloy of EPDM and polypropylene. It can be seen that the compression strain value (%) is low. Moreover, compared with Examples 1-3, the crosslinked body of the composition of Example 4 has a slightly large value (%) of permanent compression strain, which is related to the molecular weight and melting point of the polymer (B). it is conceivable that.
実施例１〜４と比較すると、実施例５の永久圧縮歪みの値（％）はやや大きいが、これは重合体（Ｂ）の配合量がやや多いためであると考えられる。また、実施例１〜４と比較すると、比較例４の形状記憶性（形状固定性および形状回復性）が劣るが、これは重合体（Ｂ）の配合量が少ないためであると考えられる。 Compared with Examples 1 to 4, the value (%) of permanent compression strain of Example 5 is slightly large, but this is considered to be because the blending amount of the polymer (B) is slightly large. Moreover, compared with Examples 1-4, although the shape memory property (shape fixability and shape recovery property) of the comparative example 4 is inferior, it is thought that this is because there are few compounding quantities of a polymer (B).
本発明の組成物は、形状記憶性やゴム弾性に優れる架橋体を提供することができる。そのため本発明の組成物は、自動車部品、家電関連部品、土木・建材関連部品、雑貨ならびに日用品をはじめ種々の用途の部材に適用することができる。 The composition of the present invention can provide a crosslinked product having excellent shape memory properties and rubber elasticity. Therefore, the composition of the present invention can be applied to members for various uses including automobile parts, home appliance-related parts, civil engineering / building material-related parts, sundries, and daily necessities.
Claims (12)
以下の（i）〜（ii）を満たし、かつ、炭素数３〜２０のα−オレフィンから選ばれる１種に由来する構成単位を主成分とする重合体（Ｂ）１５〜４０重量部と、を含む組成物；
（i）示差走査熱量計（ＤＳＣ）で測定した融点が１２５〜２４５℃、
（ii）ゲルパーミエーションクロマトグラフィー（ＧＰＣ）で測定したポリスチレン換算の数平均分子量（Ｍｎ）が１，０００〜１５，０００。 100 parts by weight of ethylene / α-olefin / non-conjugated polyene copolymer (A),
15-40 parts by weight of a polymer (B) satisfying the following (i) to (ii) and having as a main component a structural unit derived from one kind selected from α-olefins having 3 to 20 carbon atoms; A composition comprising:
(I) a melting point measured by a differential scanning calorimeter (DSC) of 125 to 245 ° C.,
(Ii) The polystyrene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) is 1,000 to 15,000.
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