JP4929666B2 - Rubber composition and vulcanized rubber - Google Patents
Rubber composition and vulcanized rubberInfo
- Publication number
- JP4929666B2 JP4929666B2 JP2005292603A JP2005292603A JP4929666B2 JP 4929666 B2 JP4929666 B2 JP 4929666B2 JP 2005292603 A JP2005292603 A JP 2005292603A JP 2005292603 A JP2005292603 A JP 2005292603A JP 4929666 B2 JP4929666 B2 JP 4929666B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylene
- copolymer
- olefin
- rubber
- rubber composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229920001971 elastomer Polymers 0.000 title claims description 76
- 239000005060 rubber Substances 0.000 title claims description 76
- 239000000203 mixture Substances 0.000 title claims description 49
- 239000004636 vulcanized rubber Substances 0.000 title claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 48
- 239000005977 Ethylene Substances 0.000 claims description 48
- 239000004711 α-olefin Substances 0.000 claims description 42
- 229920001577 copolymer Polymers 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 24
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 10
- 238000005259 measurement Methods 0.000 claims description 10
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 4
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 4
- 239000003365 glass fiber Substances 0.000 claims description 4
- 238000002955 isolation Methods 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- 239000000454 talc Substances 0.000 claims description 4
- 229910052623 talc Inorganic materials 0.000 claims 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 claims description 4
- 239000003921 oil Substances 0.000 description 24
- 235000019198 oils Nutrition 0.000 description 24
- 229920000642 polymer Polymers 0.000 description 14
- 239000010734 process oil Substances 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000003068 static effect Effects 0.000 description 7
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 6
- -1 ethylene, ethylene Chemical group 0.000 description 6
- 150000004291 polyenes Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 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 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 150000004996 alkyl benzenes Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910052570 clay Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 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
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 2
- VSQLAQKFRFTMNS-UHFFFAOYSA-N 5-methylhexa-1,4-diene Chemical compound CC(C)=CCC=C VSQLAQKFRFTMNS-UHFFFAOYSA-N 0.000 description 2
- UCKITPBQPGXDHV-UHFFFAOYSA-N 7-methylocta-1,6-diene Chemical compound CC(C)=CCCCC=C UCKITPBQPGXDHV-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 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
- 235000014113 dietary fatty acids Nutrition 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
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 229930195729 fatty acid Natural products 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229920003049 isoprene rubber Polymers 0.000 description 2
- 229920005684 linear copolymer Polymers 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical compound ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- DNZZPKYSGRTNGK-PQZOIKATSA-N (1z,4z)-cycloocta-1,4-diene Chemical compound C1C\C=C/C\C=C/C1 DNZZPKYSGRTNGK-PQZOIKATSA-N 0.000 description 1
- YHHHHJCAVQSFMJ-FNORWQNLSA-N (3e)-deca-1,3-diene Chemical compound CCCCCC\C=C\C=C YHHHHJCAVQSFMJ-FNORWQNLSA-N 0.000 description 1
- JBVMSEMQJGGOFR-FNORWQNLSA-N (4e)-4-methylhexa-1,4-diene Chemical compound C\C=C(/C)CC=C JBVMSEMQJGGOFR-FNORWQNLSA-N 0.000 description 1
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- 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
- JAEZSIYNWDWMMN-UHFFFAOYSA-N 1,1,3-trimethylthiourea Chemical compound CNC(=S)N(C)C JAEZSIYNWDWMMN-UHFFFAOYSA-N 0.000 description 1
- VOSLXTGMYNYCPW-UHFFFAOYSA-N 1,10-Undecadiene Chemical compound C=CCCCCCCCC=C VOSLXTGMYNYCPW-UHFFFAOYSA-N 0.000 description 1
- BPHFKBMQSYYNGQ-UHFFFAOYSA-N 1,12-Tridecadiene Chemical compound C=CCCCCCCCCCC=C BPHFKBMQSYYNGQ-UHFFFAOYSA-N 0.000 description 1
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-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
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- KPAPHODVWOVUJL-UHFFFAOYSA-N 1-benzofuran;1h-indene Chemical compound C1=CC=C2CC=CC2=C1.C1=CC=C2OC=CC2=C1 KPAPHODVWOVUJL-UHFFFAOYSA-N 0.000 description 1
- AKUNSTOMHUXJOZ-UHFFFAOYSA-N 1-hydroperoxybutane Chemical compound CCCCOO AKUNSTOMHUXJOZ-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 1
- 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
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 1
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 description 1
- BDCLTORUANJIBT-UHFFFAOYSA-N 3-butylperoxy-1,1,5-trimethylcyclohexane Chemical group CCCCOOC1CC(C)CC(C)(C)C1 BDCLTORUANJIBT-UHFFFAOYSA-N 0.000 description 1
- MHKLKWCYGIBEQF-UHFFFAOYSA-N 4-(1,3-benzothiazol-2-ylsulfanyl)morpholine Chemical compound C1COCCN1SC1=NC2=CC=CC=C2S1 MHKLKWCYGIBEQF-UHFFFAOYSA-N 0.000 description 1
- HLBZWYXLQJQBKU-UHFFFAOYSA-N 4-(morpholin-4-yldisulfanyl)morpholine Chemical compound C1COCCN1SSN1CCOCC1 HLBZWYXLQJQBKU-UHFFFAOYSA-N 0.000 description 1
- NBOCQTNZUPTTEI-UHFFFAOYSA-N 4-[4-(hydrazinesulfonyl)phenoxy]benzenesulfonohydrazide Chemical compound C1=CC(S(=O)(=O)NN)=CC=C1OC1=CC=C(S(=O)(=O)NN)C=C1 NBOCQTNZUPTTEI-UHFFFAOYSA-N 0.000 description 1
- RMTZWXLMKQEBRG-UHFFFAOYSA-N 4-ethylidene-6,7-dimethylocta-1,6-diene Chemical compound C=CCC(=CC)CC(C)=C(C)C RMTZWXLMKQEBRG-UHFFFAOYSA-N 0.000 description 1
- OLBNUAAKBZOEAZ-UHFFFAOYSA-N 4-ethylidene-7-methylnona-1,6-diene Chemical compound CCC(C)=CCC(=CC)CC=C OLBNUAAKBZOEAZ-UHFFFAOYSA-N 0.000 description 1
- FCRAPARCDIBORN-UHFFFAOYSA-N 4-ethylidene-7-methylocta-1,6-diene Chemical compound C=CCC(=CC)CC=C(C)C FCRAPARCDIBORN-UHFFFAOYSA-N 0.000 description 1
- NRLFFJGFLKJBFL-UHFFFAOYSA-N 4-ethylideneocta-1,6-diene Chemical compound CC=CCC(=CC)CC=C NRLFFJGFLKJBFL-UHFFFAOYSA-N 0.000 description 1
- FYZHLRMYDRUDES-UHFFFAOYSA-N 5,7-dimethylocta-1,6-diene Chemical compound CC(C)=CC(C)CCC=C FYZHLRMYDRUDES-UHFFFAOYSA-N 0.000 description 1
- CBNXGQUIJRGZRX-UHFFFAOYSA-N 5-[4-fluoro-3-(trifluoromethyl)phenyl]furan-2-carbaldehyde Chemical compound C1=C(C(F)(F)F)C(F)=CC=C1C1=CC=C(C=O)O1 CBNXGQUIJRGZRX-UHFFFAOYSA-N 0.000 description 1
- OJVSJOBJBMTKIW-UHFFFAOYSA-N 5-methylhepta-1,5-diene Chemical compound CC=C(C)CCC=C OJVSJOBJBMTKIW-UHFFFAOYSA-N 0.000 description 1
- WKWWISMSTOFOGJ-UHFFFAOYSA-N 5-propylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=CCC)CC1C=C2 WKWWISMSTOFOGJ-UHFFFAOYSA-N 0.000 description 1
- KUFDSEQTHICIIF-UHFFFAOYSA-N 6-methylhepta-1,5-diene Chemical compound CC(C)=CCCC=C KUFDSEQTHICIIF-UHFFFAOYSA-N 0.000 description 1
- DHBQJICESILRNK-UHFFFAOYSA-N 6-methylocta-1,6-diene Chemical compound CC=C(C)CCCC=C DHBQJICESILRNK-UHFFFAOYSA-N 0.000 description 1
- IFKFMPUNGADJML-UHFFFAOYSA-N 7-ethyl-4-ethylidenenona-1,6-diene Chemical compound CCC(CC)=CCC(=CC)CC=C IFKFMPUNGADJML-UHFFFAOYSA-N 0.000 description 1
- XGJONQYTWPCPRL-UHFFFAOYSA-N 7-methylnona-1,7-diene Chemical compound CC=C(C)CCCCC=C XGJONQYTWPCPRL-UHFFFAOYSA-N 0.000 description 1
- PWENCKJTWWADRJ-UHFFFAOYSA-N 9-methyldeca-1,8-diene Chemical compound CC(C)=CCCCCCC=C PWENCKJTWWADRJ-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004156 Azodicarbonamide Substances 0.000 description 1
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Description
本発明は、ゴム組成物及びそのゴム組成物を加硫した加硫ゴムに関し、特に、加硫することにより強度、防振特性のバランスに優れた加硫ゴムとなるゴム組成物及びその加硫ゴムに関する。 TECHNICAL FIELD The present invention relates to a rubber composition and a vulcanized rubber obtained by vulcanizing the rubber composition, and in particular, a rubber composition that becomes a vulcanized rubber having an excellent balance of strength and vibration-proof characteristics by vulcanization and the vulcanization thereof. Related to rubber.
エチレン・α−オレフィン・共役ジエン共重合ゴムやエチレン・α−オレフィン共重合ゴムは、自動車用ゴム材料、建材用ゴム材料、ゴムベルト・ゴムローラー材、防振用ゴム材、熱可塑性エラストマー改質材、チューブ、ホース、一般ゴム製品などの幅広い用途に用いられている。 Ethylene / α-olefin / conjugated diene copolymer rubber and ethylene / α-olefin copolymer rubber are automotive rubber materials, rubber materials for building materials, rubber belts / rubber roller materials, rubber materials for vibration isolation, and thermoplastic elastomer modifiers. Used in a wide range of applications such as tubes, hoses, and general rubber products.
一方、自動車用に用いられる防振ゴムとして、改良されたエチレン・α−オレフィン・非共役ジエン共重合ゴムの加硫物が種々提案されている（特許文献１〜３参照）。 On the other hand, various improved vulcanizates of ethylene / α-olefin / non-conjugated diene copolymer rubber have been proposed as vibration-proof rubbers used for automobiles (see Patent Documents 1 to 3).
例えば、特許文献１には、ロール加工性に優れ、且つ加硫後には耐疲労性が良好であるゴム組成物を提供することを目的として、７０℃のキシレン中で測定した極限粘度〔η〕が３ｄｌ／ｇ以上であるエチレン・α−オレフィン・非共役ジエン共重合体からなる高分子量共重合体と、７０℃のキシレン中で測定した極限粘度〔η〕が０．７〜１ｄｌ／ｇであるエチレン・α−オレフィン・非共役ジエン共重合体からなる低分子量共重合体とを含有し、バイモーダルな分子量分布を有するゴム組成物が開示されている。 For example, Patent Document 1 discloses an intrinsic viscosity [η] measured in xylene at 70 ° C. for the purpose of providing a rubber composition having excellent roll processability and good fatigue resistance after vulcanization. A high molecular weight copolymer composed of an ethylene / α-olefin / non-conjugated diene copolymer having a viscosity of 3 dl / g or more, and an intrinsic viscosity [η] measured in xylene at 70 ° C. of 0.7-1 dl / g A rubber composition containing a low molecular weight copolymer composed of an ethylene / α-olefin / non-conjugated diene copolymer and having a bimodal molecular weight distribution is disclosed.
特許文献２には、優れた耐熱老化性を有し、且つ耐動的疲労性と耐へたり性が共に有利に高められ得る耐熱防振ゴム用ゴム組成物を提供することを目的とし、ポリマー分子量が２０万以上、ポリマー粘度（ＭＬ1+4：１２１℃）が１２０以上のエチレン−プロピレン−ジエン三元共重合体を用い、パーオキサイド並びにコエージェント（架橋助剤）を配合した耐熱防振ゴム用ゴム組成物が開示されている。 Patent Document 2 aims to provide a rubber composition for heat-resistant and vibration-proof rubber having excellent heat aging resistance and capable of advantageously enhancing both dynamic fatigue resistance and sag resistance. Is a heat and vibration-proof rubber using an ethylene-propylene-diene terpolymer having a polymer viscosity (ML 1 + 4 : 121 ° C.) of 120 or more and a peroxide and a coagent (crosslinking aid). A rubber composition is disclosed.
特許文献３には、耐久性及び耐動的疲労性が改良された加硫ゴムを提供することを目的として、７０℃のキシレン中で測定した極限粘度〔η〕が３ｄｌ／ｇ以上のエチレン・α−オレフィン・非共役ジエン共重合体ゴムに、二重結合の７０％以上を水素添加した液状ジエン系ポリマーを含有する加硫ゴムが開示されている。 Patent Document 3 discloses that ethylene / α having an intrinsic viscosity [η] measured in xylene at 70 ° C. of 3 dl / g or more for the purpose of providing a vulcanized rubber having improved durability and dynamic fatigue resistance. A vulcanized rubber containing a liquid diene polymer obtained by hydrogenating 70% or more of double bonds to an olefin / non-conjugated diene copolymer rubber is disclosed.
本発明は、防振特性及び耐熱性のバランスに優れた加硫ゴムを与えるゴム組成物及びその加硫ゴム、特に防振材として好適に用いることができる加硫ゴムを提供することを目的とする。 An object of the present invention is to provide a rubber composition that provides a vulcanized rubber having an excellent balance between vibration-proofing properties and heat resistance, and a vulcanized rubber that can be suitably used as a vulcanized rubber, particularly as a vibration-proofing material. To do.
本発明者は、上記目的に対応すべく研究を行った結果、分子量が高く、且つ分岐の少ないエチレン・α−オレフィン・非共役ポリエン共重合体及び／又はエチレン・α−オレフィン共重合体を用いることにより、強度、伸びなどのゴムとして求められる特性と防振特性のバランスに優れた加硫ゴムとすることができることを見出した。本発明は、この知見に基づくものであり、以下のゴム組成物及び加硫ゴムを提供するものである。 As a result of research conducted to meet the above-mentioned object, the inventor uses an ethylene / α-olefin / non-conjugated polyene copolymer and / or an ethylene / α-olefin copolymer having a high molecular weight and few branches. Thus, it has been found that a vulcanized rubber having an excellent balance between properties required for rubber such as strength and elongation and vibration-proof properties can be obtained. The present invention is based on this finding and provides the following rubber composition and vulcanized rubber.
［１］ （Ａ）極限粘度［η］が４．５〜１０ｄｌ／ｇであり、［η］／［η］ｂｌａｎｋで表される分岐指数（ｇ）が０．７５以上であり、そのＧＰＣクロマトグラムにおいて、分子量１×１０ ５ 未満の低分子量領域の面積割合が４％以下となる共重合体である、エチレン・α−オレフィン共重合体及び／又はエチレン・α−オレフィン・非共役ポリエン共重合体；及び
（Ｂ）可塑化材料
を含有するゴム組成物。
（但し、［η］は、デカリンを用いて測定温度１３５℃でＪＩＳ Ｋ７３６７−３に準拠して測定して求めた極限粘度であり、［η］ｂｌａｎｋは、その極限粘度［η］のエチレン・α−オレフィン共重合体又はエチレン・α−オレフィン・非共役ポリエン共重合体と同一重量平均分子量（標準ポリスチレンを用いたＧＰＣ法により求めた）を有し、且つエチレン含量が７０モル％の直鎖エチレン・プロピレン共重合体の極限粘度である。）
[1] (A) The intrinsic viscosity [η] is 4.5 to 10 dl / g , the branching index (g) represented by [η] / [η] blank is 0.75 or more , and its GPC chromatography In ethylene, ethylene / α-olefin copolymer and / or ethylene / α-olefin / non-conjugated polyene copolymer is a copolymer in which the area ratio of the low molecular weight region having a molecular weight of less than 1 × 10 5 is 4% or less. And (B) a rubber composition containing a plasticizing material.
(However, [η] is the intrinsic viscosity determined by measuring in accordance with JIS K7367-3 at a measurement temperature of 135 ° C. using decalin, and [η] blank is the ethylene viscosity of the intrinsic viscosity [η]. A straight chain having the same weight average molecular weight (determined by GPC method using standard polystyrene) as the α-olefin copolymer or ethylene / α-olefin / non-conjugated polyene copolymer, and having an ethylene content of 70 mol% (This is the intrinsic viscosity of ethylene / propylene copolymer.)
［２］ 前記（Ａ）エチレン・α−オレフィン共重合体及び／又はエチレン・α−オレフィン・非共役ポリエン共重合体の合計１００質量部に対して、（Ｂ）可塑化材料を１０〜８０質量部含有する上記［１］に記載のゴム組成物。 [2] 10 to 80 parts by mass of (B) plasticized material with respect to 100 parts by mass in total of (A) ethylene / α-olefin copolymer and / or ethylene / α-olefin / non-conjugated polyene copolymer. The rubber composition as described in [1] above, which is contained in part.
［３］ 前記（Ａ）エチレン・α−オレフィン共重合体及び／又はエチレン・α−オレフィン・非共役ポリエン共重合体の合計１００質量部に対して、（Ｃ）フィラーを１〜１００質量部含有する上記［１］又は［２］に記載のゴム組成物。 [ 3 ] (A) 1-100 mass parts of (C) filler is contained with respect to a total of 100 mass parts of the (A) ethylene / α-olefin copolymer and / or ethylene / α-olefin / non-conjugated polyene copolymer. The rubber composition according to the above [1] or [2] .
［４］ 前記（Ｃ）フィラーが、シリカ、カーボンブラック、ガラスファイバー、マイカ、チタン酸カリウムウイスカー、タルク、クレー、硫酸バリウム、ガラスフレーク及びフッ素樹脂からなる群から選ばれる少なくとも１種である上記［３］に記載のゴム組成物。 [ 4 ] The above (C) filler is at least one selected from the group consisting of silica, carbon black, glass fiber, mica, potassium titanate whisker, talc, clay, barium sulfate, glass flakes and fluororesin. 3 ] The rubber composition as described in the above.
［５］ （Ｄ）加硫剤により、上記［１］〜［４］の何れかに記載のゴム組成物が加硫された加硫ゴム。 [ 5 ] (D) A vulcanized rubber obtained by vulcanizing the rubber composition according to any one of [1] to [ 4 ] with a vulcanizing agent.
［６］ 上記［５］に記載の防振用加硫ゴム。 [ 6 ] The anti-vibration vulcanized rubber according to [5 ] above.
本発明のゴム組成物は、加硫後の防振特性に優れ、防振材として好適に用いることができる。 The rubber composition of the present invention has excellent anti-vibration properties after vulcanization and can be suitably used as an anti-vibration material.
以下、本発明のゴム組成物、これを加硫した加硫ゴムについて具体例に基づき詳細に説明するが、本発明はこれらの具体例に限定されるものではない。 Hereinafter, although the rubber composition of this invention and the vulcanized rubber which vulcanized this are demonstrated in detail based on a specific example, this invention is not limited to these specific examples.
［ゴム組成物］
（Ａ）エチレン・α−オレフィン共重合体及び／又はエチレン・α−オレフィン・非共役ポリエン共重合体：
本発明に用いられるエチレン・α−オレフィン共重合体及び／又はエチレン・α−オレフィン・非共役ポリエン共重合体（以下、「（Ａ）成分」ともいう）は、極限粘度［η］が４．５〜１０ｄｌ／ｇであり、［η］／［η］ｂｌａｎｋで表される分岐指数（ｇ）が０．７５以上であり、そのＧＰＣクロマトグラムにおいて、分子量１×１０ ５ 未満の低分子量領域の面積割合が４％以下となる共重合体である。
[Rubber composition]
(A) Ethylene / α-olefin copolymer and / or ethylene / α-olefin / non-conjugated polyene copolymer:
The ethylene / α-olefin copolymer and / or the ethylene / α-olefin / non-conjugated polyene copolymer (hereinafter also referred to as “component (A)”) used in the present invention has an intrinsic viscosity [η] of 4. 5 to 10 dl / g , the branching index (g) represented by [η] / [η] blank is 0.75 or more , and in the GPC chromatogram thereof, a low molecular weight region having a molecular weight of less than 1 × 10 5 It is a copolymer having an area ratio of 4% or less .
本発明における極限粘度［η］は、デカリンを用いて測定温度１３５℃でＪＩＳ Ｋ７３６７−３に準拠して測定して求めた極限粘度である。本発明における分岐指数（ｇ）は［η］／［η］blankで表される値であり、［η］は、上述した極限粘度である。［η］blankは、［η］を測定したエチレン・α−オレフィン共重合体又はエチレン・α−オレフィン・非共役ジエン共重合体と同一重量平均分子量（ＧＰＣ法による標準ポリスチレン換算分子量）を有し、且つエチレン含量が７０モル％の直鎖エチレン・プロピレン共重合体の極限粘度である。なお、ＧＰＣ測定法は、温度１３５℃、Ｏ−ジクロルベンゼン溶媒、流速１ｍｌ／ｍｉｎ、という条件で測定して求めた値である。 The intrinsic viscosity [η] in the present invention is an intrinsic viscosity obtained by measuring in accordance with JIS K7367-3 at a measurement temperature of 135 ° C. using decalin. The branching index (g) in the present invention is a value represented by [η] / [η] blank , and [η] is the above-described intrinsic viscosity. [Η] blank has the same weight average molecular weight (standard polystyrene equivalent molecular weight by GPC method) as the ethylene / α-olefin copolymer or ethylene / α-olefin / non-conjugated diene copolymer measured for [η]. And the intrinsic viscosity of a linear ethylene / propylene copolymer having an ethylene content of 70 mol%. The GPC measurement method is a value obtained by measurement under conditions of a temperature of 135 ° C., an O-dichlorobenzene solvent, and a flow rate of 1 ml / min.
極限粘度［η］は、通常分子量に対応して大きくなるが、同じ分子量の重合体を比較すると直鎖状の重合体が最も大きい［η］を示し、重合体が分岐しているほど［η］が小さくなる。従って、同一重量平均分子量の直鎖状の共重合体の極限粘度［η］blankに対する［η］の比（［η］／［η］blank）は、最大で１であり、分岐度０、即ち直鎖状の共重合体であることを示し、この比（［η］／［η］blank）が小さいほど、共重合体の分岐度が大きいことを示す。 The intrinsic viscosity [η] usually increases corresponding to the molecular weight, but when comparing polymers having the same molecular weight, the linear polymer shows the largest [η], and the more the polymer is branched, the more [η ] Becomes smaller. Therefore, the ratio of [η] to the intrinsic viscosity [η] blank ([η] / [η] blank ) of the linear copolymer having the same weight average molecular weight is 1 at the maximum, and the degree of branching is 0. This indicates that the copolymer is a linear copolymer, and the smaller this ratio ([η] / [η] blank ), the greater the degree of branching of the copolymer.
（Ａ）成分は、［η］が４．５〜１０ｄｌ／ｇであり、且つ分岐指数（ｇ）が０．７５以上、即ち、分子量が高く、且つ分岐が少ないことにより、（Ａ）成分を含むゴム組成物を架橋すると耐熱性及び防振特性のバランスに優れた架橋ゴムとすることができる。 The component (A) has [η] of 4.5 to 10 dl / g and a branching index (g) of 0.75 or more, that is, a high molecular weight and few branches. When the rubber composition is cross-linked, a cross-linked rubber having an excellent balance between heat resistance and vibration-proof characteristics can be obtained.
（Ａ）成分の［η］は、強度及び静動比改良という観点から、４．０ｄｌ／ｇ以上であることが好ましい。４．５ｄｌ／ｇ以上であることがより好ましく、更に好ましくは５．０ｄｌ／ｇ以上である。一方、（Ａ）成分の［η］が大きすぎる、即ち、分子量が高すぎると共重合体の製造や加工が困難となる。従って、（Ａ）成分の［η］は、１１ｄｌ／ｇ以下であることが好ましく、１０ｄｌ／ｇ以下であることが更に好ましい。 [Η] of the component (A) is preferably 4.0 dl / g or more from the viewpoint of improvement in strength and static-dynamic ratio. More preferably, it is 4.5 dl / g or more, More preferably, it is 5.0 dl / g or more. On the other hand, if [η] of the component (A) is too large, that is, if the molecular weight is too high, it becomes difficult to produce or process the copolymer. Therefore, [η] of the component (A) is preferably 11 dl / g or less, and more preferably 10 dl / g or less.
（Ａ）成分の分岐指数（ｇ）は、静動比改良という観点から、０．７０以上であることが好ましい。より好ましくは、０．７５以上であり、更に好ましくは０．８０以上である。なお、（Ａ）成分の分岐指数（ｇ）の上限は、上述のように１である。 The branching index (g) of the component (A) is preferably 0.70 or more from the viewpoint of improving the static / dynamic ratio. More preferably, it is 0.75 or more, More preferably, it is 0.80 or more. The upper limit of the branching index (g) of the component (A) is 1 as described above.
（Ａ）成分の低分子量成分は極めて少ないことが好ましく、（Ａ）成分のＧＰＣクロマトグラムにおいて、分子量１×１０5未満の低分子量領域の（Ａ）成分全体に対する面積割合は４％以下であることが好ましく、より好ましくは３％以下である。即ち、ＧＰＣ測定により得られる（Ａ）成分の分子量分布を示すクロマトグラムにおいて、（Ａ）成分全体の分子量分布曲線の積分値（クロマトグラム上の（Ａ）成分全体のピーク面積に相当）に対する分子量１×１０5未満の部分（低分子量領域）の積分値（クロマトグラム上の分子量１×１０5未満の部分の面積に相当）の割合が４％以下であることが好ましく、３％以下であることがより好ましい。この低分子量領域の割合が５％を超えると、即ち低分子量成分が多くなりすぎると静動比が大きくなり、防振特性が悪化する。 It is preferable that the low molecular weight component of the component (A) is extremely small. In the GPC chromatogram of the component (A), the area ratio of the low molecular weight region having a molecular weight of less than 1 × 10 5 to the total component (A) is 4% or less. Preferably, it is 3% or less. That is, in the chromatogram showing the molecular weight distribution of the component (A) obtained by GPC measurement, the molecular weight relative to the integral value of the molecular weight distribution curve of the entire component (A) (corresponding to the peak area of the entire component (A) on the chromatogram). The ratio of the integrated value (corresponding to the area of the molecular weight less than 1 × 10 5 on the chromatogram) of the portion less than 1 × 10 5 (low molecular weight region) is preferably 4% or less, and 3% or less. It is more preferable. If the proportion of the low molecular weight region exceeds 5%, that is, if the amount of low molecular weight components is excessive, the static ratio increases and the vibration isolation characteristics deteriorate.
（Ａ）成分として用いられるエチレン・α−オレフィン共重合体におけるα−オレフィンは、炭素数３〜２０のα−オレフィンであることが好ましい。好ましいα−オレフィンとしては、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−ヘプテン、１−オクテン、１−デセンなどが挙げられ、この中でもプロピレン、１−ブテン、１−ヘキセン、１−オクテンが好ましく、特にプロピレンが好ましい。これらのα−オレフィンは、単独で又は２種以上を混合して使用することができる。エチレン成分含量は、全単量体成分中に、５０〜８０質量％であることが好ましく、更に好ましくは５４〜７５質量％である。エチレン成分含量が上記範囲内にあることにより、良好な防振性を示す。エチレン成分含量が８０質量％を超えると、温度依存性が悪化し、一方、５０質量％未満であると、強度及び耐熱性の悪化、共重合ゴムの生産性の低下、コストアップなどの不具合が生じ好ましくない。 The α-olefin in the ethylene / α-olefin copolymer used as the component (A) is preferably an α-olefin having 3 to 20 carbon atoms. Preferred α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene and the like, among which propylene, 1-butene, 1-hexene, 1 -Octene is preferred, especially propylene. These α-olefins can be used alone or in admixture of two or more. The ethylene component content is preferably 50 to 80% by mass, more preferably 54 to 75% by mass in the total monomer components. When the ethylene component content is within the above range, good vibration isolation is exhibited. If the ethylene component content exceeds 80% by mass, the temperature dependency deteriorates. On the other hand, if it is less than 50% by mass, the strength and heat resistance deteriorate, the productivity of the copolymer rubber decreases, and the cost increases. This is undesirable.
（Ａ）成分として用いられるエチレン・α−オレフィン・非共役ポリエン共重合体におけるα−オレフィンとしては、上述のエチレン・α−オレフィン共重合体におけるα−オレフィンと同様のものが挙げられ、同様のものが好ましい。エチレン成分含量は、全単量体成分中に、５０〜８０質量％であることが好ましく、特に好ましくは５４〜７５質量％である。エチレン成分含量が上記範囲内にあることにより、加硫ゴムのゴム的性質及び低温特性が適切なものとなる。エチレン成分含量が８０質量％を超えると、加硫ゴムの低温における圧縮永久歪が悪化し、一方、５０質量％未満であると、共重合ゴムの生産性の低下、コストアップなどの不具合が生じ好ましくない。 Examples of the α-olefin in the ethylene / α-olefin / non-conjugated polyene copolymer used as the component (A) include the same as the α-olefin in the ethylene / α-olefin copolymer described above. Those are preferred. The ethylene component content is preferably 50 to 80% by mass, particularly preferably 54 to 75% by mass, based on all monomer components. When the ethylene component content is within the above range, the rubber-like properties and low-temperature characteristics of the vulcanized rubber become appropriate. If the ethylene component content exceeds 80% by mass, the compression set at a low temperature of the vulcanized rubber deteriorates. On the other hand, if it is less than 50% by mass, problems such as a decrease in the productivity of the copolymer rubber and an increase in cost occur. It is not preferable.
エチレン・α−オレフィン・非共役ポリエン共重合体における非共役ポリエンとしては、例えば、５−エチリデン−２−ノルボルネン、ジシクロペンタジエン、５−プロピリデン−２−ノルボルネン、５−ビニル−２−ノルボルネン、２，５−ノルボルナジエン、１，４−シクロヘキサジエン、１，４−シクロオクタジエン、１，５−シクロオクタジエンなどの環状ポリエン、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、５−メチル−１，５−ヘプタジエン、６−メチル−１，５−ヘプタジエン、６−メチル−１，６−オクタジエン、７−メチル−１，６−オクタジエン、５，７−ジメチル−１，６−オクタジエン、７−メチル−１，７−ノナジエン、８−メチル−１，７−ノナジエン、８−メチル−１，８−デカジエン、９−メチル−１，８−デカジエン、４−エチリデン−１，６−オクタジエン、７−メチル−４−エチリデン−１，６−オクタジエン、７−メチル−４−エチリデン−１，６−ノナジエン、７−エチル−４−エチリデン−１，６−ノナジエン、６，７−ジメチル−４−エチリデン−１，６−オクタジエン、６，７−ジメチル−４−エチリデン−１，６−ノナジエンなどの炭素数が６〜１５の内部不飽和結合を有する鎖状ポリエン、１，５−ヘキサジエン、１，６−ヘプタジエン、１，７−オクタジエン、１，８−ノナジエン、１，９−デカジエン、１，１０−ウンデカジエン、１，１１−ドデカジエン、１，１２−トリデカジエン、１，１３−テトラデカジエンなどのα，ω−ジエンが挙げられる。この中でも５−エチリデン−２−ノルボルネン、ジシクロペンタジエン、５−ビニル−２−ノルボルネン、７−メチル−１，６−オクタジエン、５−メチル−１，４−ヘキサジエンが好ましく、特に５−エチリデン−２−ノルボルネンが好ましい。これら非共役ポリエンは、単独で又は２種以上を混合して使用することができる。 Examples of the non-conjugated polyene in the ethylene / α-olefin / non-conjugated polyene copolymer include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5-vinyl-2-norbornene, 2 , 5-norbornadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene and other cyclic polyenes, 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5- Methyl-1,4-hexadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 6-methyl-1,6-octadiene, 7-methyl-1,6-octadiene, 5, 7-dimethyl-1,6-octadiene, 7-methyl-1,7-nonadiene, 8-methyl-1,7-nonadiene 8-methyl-1,8-decadiene, 9-methyl-1,8-decadiene, 4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl-4- Ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1, A chain polyene having an internal unsaturated bond having 6 to 15 carbon atoms, such as 6-nonadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9- Examples include α, ω-dienes such as decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, and 1,13-tetradecadiene. Among these, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene and 5-methyl-1,4-hexadiene are preferable, and 5-ethylidene-2 is particularly preferable. -Norbornene is preferred. These non-conjugated polyenes can be used alone or in admixture of two or more.
非共役ポリエンは、共重合体のヨウ素価が０〜４０、特に０〜３０の範囲となるように共重合体中に含まれることが好ましい。このヨウ素価は、非共役ポリエン成分の含有量の目安であり、ヨウ素価が４０を超えると、混練りの際、ゲル化を起こしやすくなり、押出しなどの成形工程でブツ発生などのトラブルが発生しやすくなる。 The non-conjugated polyene is preferably contained in the copolymer so that the iodine value of the copolymer is in the range of 0 to 40, particularly 0 to 30. This iodine value is a measure of the content of the non-conjugated polyene component. If the iodine value exceeds 40, gelation is likely to occur during kneading, and troubles such as blistering occur in molding processes such as extrusion. It becomes easy to do.
（Ａ）成分の重量平均分子量は、通常、８０万〜３００万、好ましくは１００万〜２００万、数平均分子量は、通常、３０万〜１２０万、好ましくは４０万〜１００万であり、分子量分布を示すＱ値（Ｍｗ／Ｍｎ）は、通常、１．７〜３．５、好ましくは１．７〜３．０である。 The weight average molecular weight of the component (A) is usually 800,000 to 3,000,000, preferably 1,000,000 to 2,000,000, and the number average molecular weight is usually 300,000 to 1,200,000, preferably 400,000 to 1,000,000. The Q value (Mw / Mn) indicating the distribution is usually 1.7 to 3.5, preferably 1.7 to 3.0.
（Ａ）成分は、気相重合法、溶液重合法、スラリー重合法などの適宜の方法により製造することができる。これらの重合操作は、バッチ式でも連続式でも実施することができる。上記溶液重合法あるいはスラリー重合法においては、反応媒体として、通常、不活性炭化水素が使用される。このような不活性炭化水素溶媒としては、例えばｎ−ペンタン、ｎ−ヘキサン、ｎ−ヘプタン、ｎ−オクタン、ｎ−デカン、ｎ−ドデカンなどの脂肪族炭化水素類；シクロヘキサン、メチルシクロヘキサンなどの脂環族炭化水素類；ベンゼン、トルエン、キシレンなどの芳香族炭化水素類などが挙げられる。これらの炭化水素溶媒は、単独で又は２種以上を混合して用いることもできる。また、原料モノマーを炭化水素溶媒として利用することもできる。 The component (A) can be produced by an appropriate method such as a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. These polymerization operations can be carried out either batchwise or continuously. In the solution polymerization method or slurry polymerization method, an inert hydrocarbon is usually used as a reaction medium. Examples of such inert hydrocarbon solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane, n-decane, and n-dodecane; fats such as cyclohexane and methylcyclohexane. Cyclic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene. These hydrocarbon solvents can be used alone or in admixture of two or more. Moreover, a raw material monomer can also be utilized as a hydrocarbon solvent.
（Ａ）成分を製造する際に用いられる重合触媒としては、例えばＶ、Ｔｉ、Ｚｒ及びＨｆから選ばれる遷移金属の化合物と有機金属化合物とからなるオレフィン重合触媒を挙げることができる。上記遷移金属の化合物及び有機金属化合物は、それぞれ単独で又は２種以上を混合して使用することができる。このようなオレフィン重合触媒の特に好ましい例としては、メタロセン化合物と有機アルミニウム化合物又は該メタロセン化合物と反応してイオン性錯体を形成するイオン性化合物とからなるメタロセン系触媒、又はバナジウム化合物と有機アルミニウム化合物とからなるチーグラー・ナッタ系触媒を挙げることができる。なお、（Ａ）成分の製造の際に、分子量調整剤として、水素ガスが用いられることがある。水素ガスの使用量は、触媒種、触媒量、重合温度、重合圧力などの重合条件、及び重合スケール、撹拌状態、チャージ方法などの重合プロセスによっても異なるが、例えばチーグラー・ナッタ系触媒を用いた溶液重合では、全単量体成分に対し、通常、０．０１〜２０ｐｐｍ、好ましくは０．１〜１０ｐｐｍである。 As a polymerization catalyst used when manufacturing (A) component, the olefin polymerization catalyst which consists of the compound of the transition metal chosen from V, Ti, Zr, and Hf and an organometallic compound can be mentioned, for example. These transition metal compounds and organometallic compounds can be used alone or in admixture of two or more. Particularly preferred examples of such an olefin polymerization catalyst include a metallocene catalyst comprising a metallocene compound and an organoaluminum compound or an ionic compound that reacts with the metallocene compound to form an ionic complex, or a vanadium compound and an organoaluminum compound. A Ziegler-Natta catalyst consisting of In the production of the component (A), hydrogen gas may be used as a molecular weight regulator. The amount of hydrogen gas used varies depending on the polymerization conditions such as catalyst type, catalyst amount, polymerization temperature, polymerization pressure, and the polymerization process such as polymerization scale, stirring state, and charging method. For example, a Ziegler-Natta catalyst was used. In solution polymerization, it is 0.01-20 ppm normally with respect to all the monomer components, Preferably it is 0.1-10 ppm.
（Ｂ）可塑化材料：
本発明のゴム組成物は、（Ｂ）可塑化材料（以下、「（Ｂ）成分」ともいう）を含有する。可塑化材料を含有することにより、加工性が向上する。可塑化材料としては、伸展油、液状ポリマー、軟化剤等が挙げられる。軟化剤としてはプロセスオイル、潤滑油、パラフィン、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、ヤシ油等の樹脂油系軟化材、密ロウ、カルナウバロウ、ラノリン等のロウ類、リシノール酸、バルチミン酸、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及び脂肪酸塩、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が挙げられる。
(B) Plasticized material:
The rubber composition of the present invention contains (B) a plasticized material (hereinafter also referred to as “component (B)”). By containing a plasticizing material, processability is improved. Examples of the plasticizing material include an extending oil, a liquid polymer, and a softening agent. Softeners include process oils, lubricating oils, petroleum softeners such as paraffin and petrolatum, coal tar softeners such as coal tar and coal tar pitch, and resin oils such as castor oil, linseed oil, rapeseed oil and coconut oil. Softening materials, waxes such as beeswax, carnauba wax, lanolin, synthetic polymers such as fatty acids and fatty acid salts such as ricinoleic acid, bartimic acid, barium stearate, calcium stearate, zinc laurate, atactic polypropylene, coumarone indene resin Examples include substances.
伸展油として、鉱物油としてはアロマティック系伸展油、ナフテン系伸展油、パラフィン系伸展油が挙げられる。また、合成油としてはアルキルベンゼン系オイルが挙げられる。 As the extending oil, the mineral oil includes aromatic extending oil, naphthenic extending oil, and paraffin extending oil. Synthetic oils include alkylbenzene oils.
アロマティック系伸展油としては、出光興産社製の、ダイアナプロセスオイルＡＣ−１２，ＡＣ４６０，ＡＨ−１６，ＡＨ−５８、エクソンモービル社製の、モービルゾールＫ，同２２，同１３０、日鉱共石社製の、共石プロセスＸ５０，Ｘ１００，Ｘ１４０、シェル化学社製の、レゾックスＮｏ．３、デュートレックス７２９ＵＫ、新日本石油社〔旧日本石油社〕製の、コウモレックス２００，３００，５００，７００、エクソンモービル社製の、エッソプロセスオイル１１０，同１２０、新日本石油社〔旧三菱石油社〕製の、三菱３４ヘビープロセス油、三菱４４ヘビープロセス油、三菱３８ヘビープロセス油、三菱３９ヘビープロセス油などが挙げられる。 Aromatic extension oils include: Diana Process Oil AC-12, AC460, AH-16, AH-58, manufactured by Idemitsu Kosan Co., Ltd., Mobilsol K, 22, 22, 130 manufactured by ExxonMobil Corporation, and Nikko Kyoishi. Kyoishi Process X50, X100, X140, manufactured by Shell Inc., Resox No. 3. Deutrex 729UK, manufactured by Nippon Oil Co., Ltd. (former Nippon Oil Co., Ltd.), Komolex 200, 300, 500, 700, manufactured by ExxonMobil Co., Ltd., Esso Process Oil 110, 120, Nippon Oil Corporation (former Mitsubishi) Petroleum Company] Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 Heavy Process Oil, Mitsubishi 39 Heavy Process Oil, and the like.
ナフテン系伸展油としては、出光興産社製の、ダイアナプロセスオイルＮＳ−２４，ＮＳ−１００，ＮＭ−２６，ＮＭ−２８０，ＮＰ−２４、エクソンモービル社製のナプレックス３８、富士興産社製の、フッコールＦＬＥＸ＃１０６０Ｎ，＃１１５０Ｎ，＃１４００Ｎ，＃２０４０Ｎ，＃２０５０Ｎ、日鉱共石社製の、共石プロセスＲ２５，Ｒ５０，Ｒ２００，Ｒ１０００、シェル化学社製の、シェルフレックス３７１ＪＹ，同３７１Ｎ，同４５１，同Ｎ−４０，同２２，同２２Ｒ，同３２Ｒ，同１００Ｒ，同１００Ｓ，同１００ＳＡ，同２２０ＲＳ，同２２０Ｓ，同２６０，同３２０Ｒ，同６８０、新日本石油社〔旧日本石油社〕製のコウモレックス２号プロセスオイル、エクソンモービル社製の、エッソプロセスオイルＬ−２，同７６５、新日本石油社〔旧三菱石油社〕製の三菱２０ライトプロセス油などが挙げられる。 As naphthenic extension oils, Diana Process Oil NS-24, NS-100, NM-26, NM-280, NP-24 manufactured by Idemitsu Kosan Co., Ltd., Naplex 38 manufactured by ExxonMobil Co., Ltd., manufactured by Fuji Kosan Co., Ltd. , Fukkor FLEX # 1060N, # 1150N, # 1400N, # 2040N, # 2050N, Kyoishi Process R25, R50, R200, R1000 manufactured by Nikko Kyoishi Co., Ltd., Shelf Rex 371JY, 371N manufactured by Shell Chemical Co. 451, N-40, 22, 22R, 32R, 100R, 100S, 100S, 100SA, 220RS, 220S, 260, 320R, 680, Nippon Oil Corporation (former Nippon Oil Company) Komolex No. 2 process oil made by ExxonMobil Corp., Esso process oil L-2, 76 , Such as Nippon Oil Corporation [former Mitsubishi Oil Co.] manufactured by Mitsubishi 20 light process oil and the like.
パラフィン系伸展油としては、出光興産社製の、ダイアナプロセスオイルＰＷ−９０，ＰＷ−３８０，ＰＳ−３２，ＰＳ−９０，ＰＳ−４３０、富士興産社製の、フッコールプロセスＰ−１００，Ｐ−２００，Ｐ−３００，Ｐ４００，Ｐ−５００、日鉱共石社製の、共石プロセスＰ−２００，Ｐ−３００，Ｐ−５００，共石ＥＰＴ７５０，同１０００，共石プロセスＳ９０、シェル化学社製の、ルブレックス２６，同１００，同４６０、エクソンモービル社製の、エッソプロセスオイル８１５，同８４５，同Ｂ−１、エクソンモービル社製のナプレックス３２、新日本石油社〔旧三菱石油社〕製の三菱１０ライトプロセス油などが挙げられる。 As the paraffinic extension oil, Diana Process Oil PW-90, PW-380, PS-32, PS-90, PS-430 manufactured by Idemitsu Kosan Co., Ltd., Fukkor Process P-100, P manufactured by Fuji Kosan Co., Ltd. are used. -200, P-300, P400, P-500, manufactured by Nikko Kyoishi Co., Ltd., Kyoishi Process P-200, P-300, P-500, Kyoishi EPT750, 1000, Kyoishi Process S90, Shell Chemical Co., Ltd. Manufactured by Lebrex 26, 100, 460, ExxonMobil, Esso Process Oil 815, 845, B-1, ExxonMobil Naplex 32, Nippon Oil Corporation (former Mitsubishi Oil Corporation) ] Mitsubishi 10 light process oil, etc.
アルキルベンゼン系オイルはプロピレンのテトラマーとベンゼンとの反応、又はｎ−パラフィンの脱水素化反応により得られるｎ−オレフィンとベンゼンとの反応によって製造される炭化水素系オイルであり、モノアルキルベンゼン、ジアルキルベンゼン、トリアルキルベンゼン、ジフェニルアルカン等のアルキルベンゼン類を含有する合成オイルである。 The alkylbenzene oil is a hydrocarbon oil produced by the reaction of propylene tetramer and benzene, or the reaction of n-olefin and benzene obtained by dehydrogenation reaction of n-paraffin, and includes monoalkylbenzene, dialkylbenzene, It is a synthetic oil containing alkylbenzenes such as trialkylbenzene and diphenylalkane.
液状ポリマーは、常温で液状のポリマーであり、ポリブテン、液状ポリブタジエン及びその水添物、液状ＥＢＭ、液状ＥＰＭ、液状ＥＰＤＭ等が挙げられる。この中でもポリブテンが好ましい。 The liquid polymer is a liquid polymer at normal temperature, and examples thereof include polybutene, liquid polybutadiene and hydrogenated products thereof, liquid EBM, liquid EPM, and liquid EPDM. Of these, polybutene is preferred.
（Ｂ）可塑化材料は２種類以上を複合して使用してもよく、その総配合量は、（Ａ）成分１００質量部に対して１０〜８０質量部であることが好ましく、１０〜６０質量部であることが更に好ましく、１０〜５０質量部であることが特に好ましい。可塑化材料の配合量が１０質量部未満では、可塑化材料の添加による加工性改良効果が十分に得られず、８０質量部を超えると強度低下となる。 (B) Two or more kinds of plasticizing materials may be used in combination, and the total blending amount is preferably 10 to 80 parts by mass with respect to 100 parts by mass of component (A). It is more preferable that it is a mass part, and it is especially preferable that it is 10-50 mass parts. When the blending amount of the plasticizing material is less than 10 parts by mass, the effect of improving the workability due to the addition of the plasticizing material cannot be sufficiently obtained, and when it exceeds 80 parts by mass, the strength is lowered.
（Ｃ）フィラー：
本発明のゴム組成物は、（Ｃ）フィラー（以下、「（Ｃ）成分」ともいう）を含有することが好ましい。フィラーを含有することにより、強度が向上する。好ましいフィラーとしては、シリカ、カーボンブラック、ガラスファイバー、ガラス粉末、ガラスビーズ、マイカ、炭酸カルシウム、チタン酸カリウムウイスカー、タルク、クレー、硫酸バリウム、ガラスフレーク及びフッ素樹脂などを挙げることができ、この中でもシリカ、カーボンブラック、ガラスファイバー、マイカ、チタン酸カリウムウイスカー、タルク、クレー、硫酸バリウム、ガラスフレーク及びフッ素樹脂が好ましい。更にシリカ及びカーボンブラックが好ましく、特にシリカを含むことが好ましく、シリカとカーボンブラックとの両者を含むことがより好ましい。シリカは、静動比の点から好ましく、カーボンブラックは、ゴム組成物及び加硫ゴムの強度の点から好ましい。シリカには湿式法ホワイトカーボン、乾式法ホワイトカーボン、コロイダルシリカ等の種類があり、何れも使用できるが、なかでも含水ケイ酸を主成分とする湿式法ホワイトカーボンが好ましい。カーボンブラックには、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、グラファイト等が挙げられる。いずれも使用することができるが、なかでもファーネスブラックが好ましく、具体例としてはＳＲＦ、ＧＰＦ、ＦＥＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦ、ＭＴなどが好ましい。
(C) Filler:
The rubber composition of the present invention preferably contains (C) filler (hereinafter also referred to as “component (C)”). By containing the filler, the strength is improved. Preferred fillers include silica, carbon black, glass fiber, glass powder, glass beads, mica, calcium carbonate, potassium titanate whisker, talc, clay, barium sulfate, glass flakes and fluororesin, among these. Silica, carbon black, glass fiber, mica, potassium titanate whisker, talc, clay, barium sulfate, glass flakes and fluororesin are preferred. Further, silica and carbon black are preferable, particularly silica is preferably included, and both silica and carbon black are more preferably included. Silica is preferred from the standpoint of static ratio, and carbon black is preferred from the standpoint of the strength of the rubber composition and vulcanized rubber. There are various types of silica such as wet method white carbon, dry method white carbon, colloidal silica, etc., and any of them can be used. Among them, wet method white carbon mainly containing hydrous silicic acid is preferable. Examples of carbon black include furnace black, acetylene black, thermal black, channel black, and graphite. Any of them can be used, among which furnace black is preferable, and specific examples include SRF, GPF, FEF, HAF, ISAF, SAF, and MT.
（Ｃ）フィラーの配合量は用途によって異なるが、（Ａ）成分１００質量部に対し、１〜１００質量部であることが好ましく、１０〜７０質量部であることが更に好ましく、１０〜６０質量部であることが特に好ましい。フィラーの配合量が１質量部未満では、フィラーの添加による強度向上の効果が十分に得られず、１００質量部を超えるとゴム組成物の粘度が上がり過ぎ、混練り、成形加工が困難となる。 (C) Although the compounding quantity of a filler changes with uses, it is preferable that it is 1-100 mass parts with respect to 100 mass parts of (A) component, It is more preferable that it is 10-70 mass parts, 10-60 masses Part is particularly preferred. When the blending amount of the filler is less than 1 part by mass, the effect of improving the strength due to the addition of the filler cannot be sufficiently obtained, and when it exceeds 100 parts by mass, the viscosity of the rubber composition is excessively increased and kneading and molding are difficult. .
（Ｄ）加硫剤：
本発明のゴム組成物は、（Ｄ）加硫剤（以下、「（Ｄ）成分」ともいう）を配合して加硫することにより加硫ゴムとすることにより、耐熱性、防振特性のバランスに優れた加硫ゴムとすることができる。
(D) Vulcanizing agent:
The rubber composition of the present invention has heat resistance and vibration-proof characteristics by blending (D) a vulcanizing agent (hereinafter also referred to as “component (D)”) and vulcanizing to obtain a vulcanized rubber. A vulcanized rubber having an excellent balance can be obtained.
加硫剤としては、有機化酸化物系加硫剤及びイオウ系加硫剤を挙げることができ、これらの少なくとも１種を含むことが好ましく、両者を含むことが更に好ましい。有機過酸化物系加硫剤としては、ジクミルペルオキシド、２、５−ジメチル−２、５−ジ（第三ブチルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジ（ベンゾイルペルオキシ）ヘキサン、２，５−ジメチル−２，５−ジメチル−２，５−ジ（第三ブチルペルオキシ）ヘキシン−３、ジ第三ブチルペルオキシド、ジ第三ブチルオキシ−３，３，５−トリメチルシクロヘキサン、第三ブチルヒドロペルオキシドなどを挙げることができ、この中でもジクミルペルオキシド、ジ第三ブチルペルオキシド、ジ第三ブチルペルオキシ−３，３，５−トリメチルシクロヘキサンが好ましい。イオウ系加硫剤としては、イオウ、塩化イオウ、二塩化イオウ、モルホリンジスルフィド、アルキルフェノールジスルフィド、テトラメチルチウラムジスルフィド、ジメチルジチオカルバミン酸セレンなどを挙げることができ、この中でもイオウが好ましい。 Examples of the vulcanizing agent include organic oxide-based vulcanizing agents and sulfur-based vulcanizing agents, preferably including at least one of these, and more preferably including both. Examples of organic peroxide vulcanizing agents include dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, and 2,5-dimethyl-2,5-di (benzoylperoxy) hexane. 2,5-dimethyl-2,5-dimethyl-2,5-di (tertiarybutylperoxy) hexyne-3, ditertiarybutylperoxide, ditertiarybutyloxy-3,3,5-trimethylcyclohexane, third Examples thereof include butyl hydroperoxide, among which dicumyl peroxide, ditertiary butyl peroxide, and ditertiary butylperoxy-3,3,5-trimethylcyclohexane are preferable. Examples of the sulfur vulcanizing agent include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate, and sulfur is preferred.
イオウ系加硫剤は、（Ａ）成分１００質量部に対して、通常、０．１〜１０質量部、好ましくは０．１〜６質量部の割合で使用される。また、有機過酸化物系加硫剤は、（Ａ）成分１００質量部に対して、通常、０．１〜１５質量部、好ましくは０．２〜１０質量部の割合で使用される。また、イオウ系加硫剤を使用するときは、必要に応じて、加硫促進剤、加硫助剤が併用される。 The sulfur-based vulcanizing agent is usually used at a ratio of 0.1 to 10 parts by mass, preferably 0.1 to 6 parts by mass with respect to 100 parts by mass of the component (A). Moreover, an organic peroxide type | system | group vulcanizing agent is 0.1-15 mass parts normally with respect to 100 mass parts of (A) component, Preferably it is used in the ratio of 0.2-10 mass parts. Moreover, when using a sulfur type vulcanizing agent, a vulcanization accelerator and a vulcanization auxiliary are used in combination as necessary.
加硫促進剤としては、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−ベンゾチアゾール−スルフェンアミド、Ｎ，Ｎ−ジイソプロピル−２−ベンゾチアゾールスルフェンアミド、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−（２，６−ジエチル−４−モルホリノチオ）ベンゾチアゾール、ジベンゾチアジル−ジスルフィド；ジフェニルグアニジン、トリフェニルグアニジン、ジオルソトリルグアニジン、オルソ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；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；２−メルカプトイミダゾリン；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；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、ジメチルジチオカルバミン酸亜鉛、ジエチル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、ジエチルジチオカルバミン酸テルル；ジブチルキサントゲン酸亜鉛などを挙げることができる。これら加硫促進剤は、（Ａ）成分１００質量部に対して、通常、０．１〜２０質量部、好ましくは０．２〜１０質量部の割合で使用される。 Examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazole-sulfenamide, N-oxydiethylene-2-benzothiazole-sulfenamide, N, N-diisopropyl-2-benzothiazole sulfenamide, 2- Mercaptobenzothiazole, 2- (2,4-dinitrophenyl) mercaptobenzothiazole, 2- (2,6-diethyl-4-morpholinothio) benzothiazole, dibenzothiazyl-disulfide; diphenylguanidine, triphenylguanidine, diortho Tolyl guanidine, orthotolyl biguanide, diphenyl guanidine phthalate; acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia; 2-mercaptoimidazo Thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide, pentamethylenethiuram tetrasulfide, dimethyldithiocarbamine Zinc oxide, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, tellurium diethyldithiocarbamate, zinc dibutylxanthate, etc. Can be mentioned. These vulcanization accelerators are usually used in a proportion of 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of component (A).
加硫助剤としては、酸化マグネシウム、酸化亜鉛などの金属酸化物を挙げることができるが、酸化亜鉛の使用が好ましい。これらの加硫助剤は、（Ａ）成分１００質量部に対して、通常、１〜２０質量部、好ましくは３〜１０質量部使用される。 Examples of the vulcanization aid include metal oxides such as magnesium oxide and zinc oxide, but use of zinc oxide is preferable. These vulcanization aids are usually used in an amount of 1 to 20 parts by weight, preferably 3 to 10 parts by weight, per 100 parts by weight of component (A).
また、有機過酸化物系加硫剤による加硫に際しては、イオウ、ｐ−キノンジオキシムなどのキノンジオキシム系、ポリエチレングリコールジメタクリレート、ジアリルフタレート、トリアリルシアヌレート、ジビニルベンゼンなどを架橋助剤として使用してもよい。この架橋助剤は、（Ａ）成分１００質量部に対し、通常、０．１〜２０質量部、好ましくは０．１〜１０質量部使用される。 In addition, when vulcanizing with an organic peroxide vulcanizing agent, crosslinking aids such as quinone dioxime such as sulfur and p-quinonedioxime, polyethylene glycol dimethacrylate, diallyl phthalate, triallyl cyanurate, divinylbenzene, etc. May be used as This crosslinking aid is usually used in an amount of 0.1 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of component (A).
発泡体を製造するときは、発泡剤が配合される。発泡剤としては、重炭酸ナトリウム、炭酸ナトリウム、重炭酸アンモニウム、炭酸アンモニウム、亜硝酸アンモニウム、Ｎ，Ｎ′−ジメチルＮ，Ｎ′−ジニトロンテレフタルアミド、Ｎ，Ｎ′−ジニトロソペンタメチレンテトラミン、アゾジカルボンアミド、アゾビスイソブチロニトリル、アゾシクロヘキシルニトリル、アゾジアミノネンゼン、バリウムアゾジカルボキシレート、ベンゼンスルホニルヒドラジド、トルエンスルホニルヒドラジド、Ｐ，Ｐ′−オキシビス（ベンゼンスルホニルヒドラジド）、ジフェニルスルホン−３，３′−ジスルホニルヒドラジド、カルシウムアジド、４，４′−ジフェニルジスルホニルアジドバラトルエンマルホニルアジドを挙げることができる。発泡剤は、（Ａ）成分１００質量部に対して、通常、０．５〜３０質量部、好ましくは１〜１５質量部の割合で配合される。また、必要に応じて、発泡剤と併用して、発泡助剤を使用しても差し支えない。 When manufacturing a foam, a foaming agent is mix | blended. Examples of blowing agents include sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite, N, N'-dimethyl N, N'-dinitrone terephthalamide, N, N'-dinitrosopentamethylenetetramine, azo Dicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminonene, barium azodicarboxylate, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, P, P'-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3, Mention may be made of 3'-disulfonylhydrazide, calcium azide, 4,4'-diphenyldisulfonyl azidobaratoluene malonyl azide. A foaming agent is normally mix | blended in the ratio of 0.5-30 mass parts with respect to 100 mass parts of (A) component, Preferably it is 1-15 mass parts. Further, if necessary, a foaming aid may be used in combination with a foaming agent.
また、ゴム成分として、本発明の目的の達成を損なわない範囲で、本発明の（Ａ）成分と共に他の種類のゴムを併用しても差し支えない。併用する好ましいゴムとしては、スチレンブタジエンゴム（ＳＢＲ）、ブタジエンゴム（ＢＲ）、アクリルニトリルブタジエンゴム（ＮＢＲ）、又はこれらの水添物、天然ゴム（ＮＲ）、イソプレンゴム（ＩＲ）等が挙げられる。 Further, as the rubber component, other types of rubbers may be used in combination with the component (A) of the present invention as long as the achievement of the object of the present invention is not impaired. Preferred rubbers used in combination include styrene butadiene rubber (SBR), butadiene rubber (BR), acrylonitrile butadiene rubber (NBR), or hydrogenated products thereof, natural rubber (NR), isoprene rubber (IR) and the like. .
（Ａ）〜（Ｄ）成分及びその他の添加剤は、従来から公知の混練機を用いてこれらの成分を混練することによりゴム組成物を調製することができる。即ち、上記の配合成分を、オープンロールミル、バンバリーミキサー、ニーダーなどを用い混練してゴム組成物とすることができる。この場合、溶融混練温度は、通常、３０〜２００℃、好ましくは６０〜１８０℃である。なお、（Ｂ）成分である可塑化材料の添加方法としては、（Ａ）成分の重合溶液に可塑化材料を添加し、溶液状態で混合する方法でもよい。この方法は、操作上、（Ａ）成分と（Ｂ）成分とを混合する過程を省略することができ、両者の混合均一性に優れる点から好ましい。 Components (A) to (D) and other additives can be prepared by kneading these components using a conventionally known kneader. That is, the above compounding components can be kneaded using an open roll mill, a Banbury mixer, a kneader, or the like to obtain a rubber composition. In this case, the melt kneading temperature is usually 30 to 200 ° C, preferably 60 to 180 ° C. In addition, as a method for adding the plasticizing material as the component (B), a method of adding the plasticizing material to the polymerization solution of the component (A) and mixing in a solution state may be used. This method is preferable from the viewpoint that, in operation, the process of mixing the component (A) and the component (B) can be omitted, and the mixing uniformity of both is excellent.
その後、ゴム組成物を押出機や金型により所望の形状に成形後、高周波加熱装置、エアーオーブン、ＰＣＭ、ＬＣＭなどの加熱装置により、加硫して加硫ゴム製品を得ることができる。また、それ自体公知の加硫装置を用いて、金型内で、成形、加硫させる方法で加硫ゴム製品を製造してもよい。加硫ゴム製品の製造は、加硫方法、配合、用途により大幅に異なるが、例えばプレス加硫の場合、加硫条件としては、加熱温度は好ましくは１４０〜２００℃、加熱時間が１〜６０分程度である。 Thereafter, the rubber composition is molded into a desired shape by an extruder or a mold, and then vulcanized by a heating device such as a high-frequency heating device, an air oven, PCM, or LCM to obtain a vulcanized rubber product. Moreover, you may manufacture a vulcanized rubber product by the method of shape | molding and vulcanizing within a metal mold | die using a well-known vulcanizer. The production of vulcanized rubber products varies greatly depending on the vulcanization method, composition, and application. For example, in the case of press vulcanization, the heating temperature is preferably 140 to 200 ° C., and the heating time is 1 to 60. About minutes.
このようにして得られる加硫ゴムは、静動比が１．０〜１．４であることが好ましく、１．０〜１．３であることが更に好ましい。静動比は、ＪＩＳ Ｋ６３９４に準拠し、ブロック状の試験片を用い、温度２５℃の条件で、７０Ｈｚ，１％の動的歪及び０．１Ｈｚ，１０％の動的歪での動的弾性率を各々測定し、以下の式により算出する値である。
静動比＝（７０Ｈｚ，１％での動的弾性率）／（０．１Ｈｚ，１０％での動的弾性率）
The vulcanized rubber thus obtained preferably has a static / kinetic ratio of 1.0 to 1.4, more preferably 1.0 to 1.3. The static-dynamic ratio is based on JIS K6394, using block-shaped test pieces, and at a temperature of 25 ° C, dynamic elasticity at 70 Hz, 1% dynamic strain and 0.1 Hz, 10% dynamic strain. It is a value calculated by the following equation by measuring the rate.
Static ratio = (dynamic elastic modulus at 70 Hz, 1%) / (dynamic elastic modulus at 0.1 Hz, 10%)
静動比は、１に近いほど防振特性に優れていることを示し、本発明のゴム組成物を加硫することにより上記好ましい範囲の静動比を示す加硫ゴムを容易に得ることができる。 The static-motion ratio is closer to 1, indicating that the vibration-proof property is better. By vulcanizing the rubber composition of the present invention, it is possible to easily obtain a vulcanized rubber exhibiting the above-mentioned preferable static-motion ratio. it can.
以上のゴム組成物及びこのゴム組成物を加硫して得られる加硫ゴムは、一般的なゴム用途は当然のことながら、防振特性に優れるとともに十分な耐久性を有することから、防振材として好適に用いることができ、特にエンジンマウント用防振ゴムのように高温雰囲気となる環境における防振材として好適に使用することができる。 The rubber composition and the vulcanized rubber obtained by vulcanizing this rubber composition are naturally used in general rubber applications, and have excellent vibration proofing properties and sufficient durability. It can be suitably used as a material, and in particular, it can be suitably used as an anti-vibration material in an environment having a high temperature atmosphere such as an anti-vibration rubber for engine mounts.
以下に、実施例に基づき本発明を更に具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。なお、以下の実施例では非共役ポリエンとして５−エチリデン−２−ノルボルネン（ＥＮＢ）を用いた。また、実施例中、部及び％は特に断らない限り質量基準である。 Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. In the following examples, 5-ethylidene-2-norbornene (ENB) was used as the non-conjugated polyene. In the examples, parts and% are based on mass unless otherwise specified.
（Ａ）成分の特性値は以下の様にして求めた。
（極限粘度［η］）
ＪＩＳ Ｋ７３６７−３に準拠して、デカリン（デカヒドロナフタリン）を溶媒として用い、測定温度１３５℃で、ウベローデ形粘度計Ｎｏ．０Ｂにより溶液粘度を測定し、極限粘度を求めた。
（分岐指数（ｇ））
下記式により算出した。
分岐指数（ｇ）＝［η］／［η］blank
（但し、［η］blankは、用いた（Ａ）成分と同一重量平均分子量（標準ポリスチレンを用いたＧＰＣ法により求めた）を有し、且つエチレン含量が７０モル％の直鎖エチレン・プロピレン共重合体の極限粘度である）
（エチレン含量及びＥＮＢ含量）
赤外吸収スペクトル法により質量％として求めた。
（Ｍｎ、Ｍｗ及びＱ値）
以下の条件でＧＰＣ測定を行い。数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）及びＱ値（Ｍｗ／Ｍｎ）を求めた。なお、検量線は東ソー社製の標準ポリスチレンを使用し、常法により作成した。測定データの処理はポリマーラボラトリー社製の「ＣＩＲＲＵＳ」を使用して行った。
ＧＰＣ測定装置：ポリマーラボラトリー社製ＰＬ−ＧＰＣ２２０形
カラム：ポリマーラボラトリー社製ＰＬｇｅｌ １０μｍ ＭｉＸＥＤ−Ｂ ３本を接続
サンプル量：５００μｌ（ポリマー濃度１．０ｍｇ／ｍｌ）
流量：１ｍｌ／ｍｉｎ
温度：１３５℃
溶媒：Ｏ−ジクロルベンゼン
（分子量１×１０5未満の面積割合）
上記のＧＰＣ測定条件にて測定した（Ａ）成分の標準ポリスチレン換算ＧＰＣクロマトグラムから分子量１×１０5未満の低分子量成分の面積割合をポリマーラボラトリー社製の「ＣＩＲＲＵＳ」を使用して算出した。
The characteristic value of the component (A) was determined as follows.
(Intrinsic viscosity [η])
In accordance with JIS K7367-3, decalin (decahydronaphthalene) was used as a solvent, the measurement temperature was 135 ° C., and the Ubbelohde viscometer No. The solution viscosity was measured by 0B to determine the intrinsic viscosity.
(Branching index (g))
It was calculated by the following formula.
Branch index (g) = [η] / [η] blank
(However, [η] blank has the same weight average molecular weight as the component (A) used (determined by the GPC method using standard polystyrene) and has an ethylene content of 70 mol%. (It is the intrinsic viscosity of the polymer)
(Ethylene content and ENB content)
It calculated | required as the mass% by the infrared absorption spectrum method.
(Mn, Mw and Q value)
Perform GPC measurement under the following conditions. The number average molecular weight (Mn), weight average molecular weight (Mw) and Q value (Mw / Mn) were determined. The calibration curve was prepared by a conventional method using standard polystyrene manufactured by Tosoh Corporation. The measurement data was processed using “CIRRUS” manufactured by Polymer Laboratories.
GPC measuring device: PL-GPC220 type column manufactured by Polymer Laboratories Column: PLgel 10 μm MixED-B manufactured by Polymer Laboratories Connected sample amount: 500 μl (polymer concentration 1.0 mg / ml)
Flow rate: 1 ml / min
Temperature: 135 ° C
Solvent: O-dichlorobenzene (area ratio of molecular weight less than 1 × 10 5 )
From the standard polystyrene conversion GPC chromatogram of the component (A) measured under the above GPC measurement conditions, the area ratio of the low molecular weight component having a molecular weight of less than 1 × 10 5 was calculated using “CIRRUS” manufactured by Polymer Laboratory.
（使用原料）
（Ｂ）成分
オイルＰＷ９０：出光興産社製、商品名「ダイアナプロセスＰＷ９０」
（Ｃ）成分
シリカ：日本シリカ社製、商品名「ＥＲ」
ＳＲＦカーボン：東海カーボン社製、商品名「シーストＳ」
（Ｄ）成分
ジクミルペルオキシド：日本油脂社製、商品名「パークミルＤ−４０」、純度４０％
イオウ：鶴見化学工業社製、商品名「イオウ」
（その他の添加剤）
酸化亜鉛：白水化学工業社製、商品名「酸化亜鉛２種」
カップリング剤：東芝シリコーン社製、商品名「ＴＳＬ８３７０」
ステアリン酸：花王社製 商品名「ルナックＳ３０」
(Raw material)
(B) Component oil PW90: manufactured by Idemitsu Kosan Co., Ltd., trade name “Diana Process PW90”
(C) Component silica: Nippon Silica Co., Ltd., trade name “ER”
SRF Carbon: Tokai Carbon Co., Ltd., trade name “Seast S”
(D) Component dicumyl peroxide: manufactured by Nippon Oil & Fats Co., Ltd., trade name “Park Mill D-40”, purity 40%
Sulfur: Tsurumi Chemical Industry Co., Ltd., trade name “Sulfur”
(Other additives)
Zinc oxide: manufactured by Hakusui Chemical Co., Ltd., trade name "Zinc oxide 2 types"
Coupling agent: Toshiba Silicone, trade name “TSL8370”
Stearic acid: product name “Lunac S30” manufactured by Kao Corporation
（実施例１）
（Ａ）成分として、極限粘度［η］が５．７ｄｌ／ｇ、エチレン含量が６８％、ＥＮＢ含量が４．６％、Ｑ値が２．１、Ｍｎが６３８０００、Ｍｗが１３３００００、分岐指数（ｇ）が０．８４であるエチレン・α−オレフィン・ＥＮＢ共重合体を用い、この共重合体のヘキサン溶液中に（Ｂ）成分（可塑化材料）としてオイルＰＷ９０を共重合体１００部に対し４０部添加して、撹拌し、スチームストリッピングにより組成物を得た。その後、乾燥してゴム組成物（Ｉ）を得た。
Example 1
As component (A), intrinsic viscosity [η] is 5.7 dl / g, ethylene content is 68%, ENB content is 4.6%, Q value is 2.1, Mn is 638000, Mw is 1330000, branching index ( g) is an ethylene / α-olefin / ENB copolymer having a 0.84 content, and oil PW90 as a component (B) (plasticizing material) is added to 100 parts of the copolymer in a hexane solution of the copolymer. 40 parts were added, stirred, and a composition was obtained by steam stripping. Then, it dried and obtained rubber composition (I).
得られたゴム組成物（Ｉ）１４０部（（Ａ）成分１００部）、シリカ３０部、ＳＲＦカーボン５部、酸化亜鉛５部、カップリング剤３部、及びステアリン酸０．５部を、容量２５０ＣＣのプラストミルを用いて１５０℃で５分間混練してゴム組成物（ＩＩ）を得た。得られたゴム組成物（ＩＩ）１８３．５部（（Ａ）成分１００部）、ジクミルペルオキシド５部及びイオウ０．２部を、６インチのオープンロールで混練りし、ゴム組成物（ＩＩＩ）を得た。 140 parts of rubber composition (I) obtained (100 parts of component (A)), 30 parts of silica, 5 parts of SRF carbon, 5 parts of zinc oxide, 3 parts of coupling agent, and 0.5 part of stearic acid, A rubber composition (II) was obtained by kneading at 150 ° C. for 5 minutes using a 250 CC plast mill. The obtained rubber composition (II) 183.5 parts (100 parts of component (A)), 5 parts of dicumyl peroxide and 0.2 parts of sulfur were kneaded with a 6-inch open roll, and the rubber composition (III )
（実施例２〜４及び比較例１、２）
（Ａ）成分として、表１に示す特性のエチレン・α−オレフィン共重合体又はエチレン・α−オレフィン・ＥＮＢ共重合体を用い、オイルＰＷ９０を表１に示す量添加した以外は実施例１と同様にしてゴム組成物（Ｉ）を得、表１に示す量の各成分を加えた以外は実施例１と同様にしてゴム組成物（ＩＩ）を得、実施例１と同様にしてゴム組成物（ＩＩＩ）を得た。
(Examples 2 to 4 and Comparative Examples 1 and 2)
As component (A), an ethylene / α-olefin copolymer or an ethylene / α-olefin / ENB copolymer having the characteristics shown in Table 1 was used, and Example 1 was used except that oil PW90 was added in the amount shown in Table 1. A rubber composition (I) was obtained in the same manner, and a rubber composition (II) was obtained in the same manner as in Example 1 except that the components shown in Table 1 were added. The product (III) was obtained.
（性能評価）
表１に示す各ゴム組成物（ＩＩＩ）を１７０℃のプレス成型機により、プレス圧１５０ｋｇｆ／ｃｍ2の圧力下で２０分間加熱して、厚さ２ｍｍの試験片（加硫ゴムのシート）を作製した。また、以下の粘弾性試験に用いた試験片（加硫ゴムのサンプル）は、各ゴム組成物（ＩＩＩ）を２０分間加熱することにより作製した。得られた試験片を用いて以下に記載の方法により性能評価を行った。その結果を表１の加硫ゴムの特性の項に示す。
(Performance evaluation)
Each rubber composition (III) shown in Table 1 was heated with a press molding machine at 170 ° C. under a pressure of 150 kgf / cm 2 for 20 minutes to obtain a test piece (vulcanized rubber sheet) having a thickness of 2 mm. Produced. Moreover, the test piece (sample of vulcanized rubber) used for the following viscoelasticity tests was produced by heating each rubber composition (III) for 20 minutes. Performance evaluation was performed by the method as described below using the obtained test piece. The results are shown in the section of characteristics of vulcanized rubber in Table 1.
引張り試験：
ＪＩＳ Ｋ６２５１に準拠し、加硫ゴムのシートから得た３号型試験片を用い、測定温度２３℃、引張り速度５００ｍｍ／ｍｉｎの条件で、引張り強さＴB及び破断伸びＥBを測定した（常態物性）。また、生ゴム強度は生ゴムのプレスシートから同様に試験片を採り、同条件にて測定した。
硬さ試験：
ＪＩＳ Ｋ６２５３に準拠し、加硫ゴムのシートから得た試験片のスプリング硬さ（デュローメーターＡ硬度）を測定した。
粘弾性（ＡＲＥＳＳ）試験：
ＪＩＳ Ｋ６３９４に準拠し、加硫ゴムのサンプルから得たブロック状の試験片を用い、レオメトリック社製「ＡＲＥＳＳ」により、温度２５℃の条件で、７０Ｈｚ，１％の動的歪及び０．１Ｈｚ，１０％の動的歪での動的弾性率を各々測定した。そして、以下の式により、静動比を算出した。
静動比＝（７０Ｈｚ，１％での動的弾性率）／（０．１Ｈｚ，１０％での動的弾性率）
圧縮永久歪：
ＪＩＳ Ｋ６２６２に準拠し、１２０℃×７０時間の条件で測定した。
Tensile test:
Conforming to JIS K6251, using a No. 3 type test piece was obtained from a sheet of vulcanized rubber, measurement temperature 23 ° C., under the conditions of a tensile speed of 500 mm / min, to measure the strength T B and elongation at break E B Tensile ( Normal physical properties). Further, the strength of raw rubber was measured under the same conditions by taking a test piece from a raw rubber press sheet.
Hardness test:
In accordance with JIS K6253, the spring hardness (durometer A hardness) of a test piece obtained from a vulcanized rubber sheet was measured.
Viscoelasticity (ARESS) test:
Based on JIS K6394, a block-shaped test piece obtained from a sample of vulcanized rubber was used, and a rheometric "ARESS" was used, at a temperature of 25 ° C, 70 Hz, 1% dynamic strain and 0.1 Hz. The dynamic modulus at 10% dynamic strain was measured. And the static-dynamic ratio was computed with the following formula | equation.
Static ratio = (dynamic elastic modulus at 70 Hz, 1%) / (dynamic elastic modulus at 0.1 Hz, 10%)
Compression set:
Based on JIS K6262, it measured on the conditions of 120 degreeC x 70 hours.
表１より実施例１〜４で得られた本発明の加硫ゴムは、比較例１〜２で得られた加硫ゴムと比べていずれも、常温の引張り強度及び伸びに優れていることがわかる。更に、実施例１〜４で得られた加硫ゴムは比較例１〜２で得られた加硫ゴムに比べ静動比特性、圧縮永久歪の特性においても好適な範囲にあり、強度、防振特性のバランスに極めて優れたゴム組成物であることがわかる。 From Table 1, the vulcanized rubbers of the present invention obtained in Examples 1 to 4 are all excellent in tensile strength and elongation at room temperature as compared with the vulcanized rubbers obtained in Comparative Examples 1 and 2. Recognize. Furthermore, the vulcanized rubbers obtained in Examples 1 to 4 are in a suitable range in terms of static ratio characteristics and compression set characteristics as compared with the vulcanized rubbers obtained in Comparative Examples 1 and 2, and the strength, resistance It can be seen that the rubber composition has an extremely excellent balance of vibration characteristics.
本発明のゴム組成物から形成される加硫ゴムは、強度、圧縮永久歪に優れることから一般的なゴム用途に好適に用いることができ、更に、防振特性に優れる特性を有することから、エンジンマウント用防振ゴムのような防振材として、好適に使用することができる。 The vulcanized rubber formed from the rubber composition of the present invention can be suitably used for general rubber applications because it is excellent in strength and compression set, and further has characteristics excellent in anti-vibration properties. It can be suitably used as a vibration-proof material such as a vibration-proof rubber for engine mounts.
Claims (6)
（Ｂ）可塑化材料
を含有するゴム組成物。
（但し、［η］は、デカリンを用いて測定温度１３５℃でＪＩＳ Ｋ７３６７−３に準拠して測定して求めた極限粘度であり、［η］ｂｌａｎｋは、その極限粘度［η］のエチレン・α−オレフィン共重合体又はエチレン・α−オレフィン・非共役ポリエン共重合体と同一重量平均分子量（標準ポリスチレンを用いたＧＰＣ法により求めた）を有し、且つエチレン含量が７０モル％の直鎖エチレン・プロピレン共重合体の極限粘度である。） (A) The intrinsic viscosity [η] is 4.5 to 10 dl / g , the branching index (g) represented by [η] / [η] blank is 0.75 or more , and in the GPC chromatogram thereof, An ethylene / α-olefin copolymer and / or an ethylene / α-olefin / non-conjugated polyene copolymer, which is a copolymer in which the area ratio of the low molecular weight region having a molecular weight of less than 1 × 10 5 is 4% or less ; and (B) A rubber composition containing a plasticizing material.
(However, [η] is the intrinsic viscosity determined by measuring in accordance with JIS K7367-3 at a measurement temperature of 135 ° C. using decalin, and [η] blank is the ethylene viscosity of the intrinsic viscosity [η]. A straight chain having the same weight average molecular weight (determined by GPC method using standard polystyrene) as the α-olefin copolymer or ethylene / α-olefin / non-conjugated polyene copolymer, and having an ethylene content of 70 mol% (This is the intrinsic viscosity of ethylene / propylene copolymer.)
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