JP5082543B2 - Method for producing vulcanized rubber - Google Patents
Method for producing vulcanized rubber Download PDFInfo
- Publication number
- JP5082543B2 JP5082543B2 JP2007090062A JP2007090062A JP5082543B2 JP 5082543 B2 JP5082543 B2 JP 5082543B2 JP 2007090062 A JP2007090062 A JP 2007090062A JP 2007090062 A JP2007090062 A JP 2007090062A JP 5082543 B2 JP5082543 B2 JP 5082543B2
- Authority
- JP
- Japan
- Prior art keywords
- oil
- rubber
- parts
- mass
- 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.)
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- 239000004636 vulcanized rubber Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 229920001971 elastomer Polymers 0.000 claims description 128
- 239000005060 rubber Substances 0.000 claims description 127
- 239000000203 mixture Substances 0.000 claims description 66
- 239000003921 oil Substances 0.000 claims description 57
- 229920001577 copolymer Polymers 0.000 claims description 44
- 239000002480 mineral oil Substances 0.000 claims description 32
- 235000010446 mineral oil Nutrition 0.000 claims description 32
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 28
- 239000004711 α-olefin Substances 0.000 claims description 24
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 18
- 239000003431 cross linking reagent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 9
- 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 8
- 238000013329 compounding Methods 0.000 claims description 6
- 238000005259 measurement Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000002156 mixing Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 17
- 238000004898 kneading Methods 0.000 description 16
- 239000010734 process oil Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000004073 vulcanization Methods 0.000 description 12
- 239000000945 filler Substances 0.000 description 9
- -1 diene compound Chemical class 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 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 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 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
- 239000004902 Softening Agent Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 235000014692 zinc oxide Nutrition 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 150000001451 organic peroxides Chemical class 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 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
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 239000000654 additive Substances 0.000 description 2
- 239000010692 aromatic oil Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration 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
- 150000001993 dienes Chemical class 0.000 description 2
- 239000006185 dispersion 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
- 238000001035 drying Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- DZCCLNYLUGNUKQ-UHFFFAOYSA-N n-(4-nitrosophenyl)hydroxylamine Chemical class ONC1=CC=C(N=O)C=C1 DZCCLNYLUGNUKQ-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 229960002447 thiram Drugs 0.000 description 2
- QQIMUPFCBBIKKN-SOFGYWHQSA-N (11E)-tetradeca-1,11-diene Chemical compound CC\C=C\CCCCCCCCC=C QQIMUPFCBBIKKN-SOFGYWHQSA-N 0.000 description 1
- 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
- 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
- HLGNQSCJUXGFRV-UHFFFAOYSA-N 1,1,5-trimethyl-3,3-bis[(2-methylpropan-2-yl)oxy]cyclohexane Chemical compound CC1CC(C)(C)CC(OC(C)(C)C)(OC(C)(C)C)C1 HLGNQSCJUXGFRV-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
- 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
- YKTNISGZEGZHIS-UHFFFAOYSA-N 2-$l^{1}-oxidanyloxy-2-methylpropane Chemical group CC(C)(C)O[O] YKTNISGZEGZHIS-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
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-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
- ZKNNSVGJXBRHRN-UHFFFAOYSA-N 4-ethylidene-6,7-dimethylnona-1,6-diene Chemical compound CCC(C)=C(C)CC(=CC)CC=C ZKNNSVGJXBRHRN-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
- 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
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- XGJONQYTWPCPRL-UHFFFAOYSA-N 7-methylnona-1,7-diene Chemical compound CC=C(C)CCCCC=C XGJONQYTWPCPRL-UHFFFAOYSA-N 0.000 description 1
- ORSOHOYCAKNPQE-UHFFFAOYSA-N 8-methyldeca-1,8-diene Chemical compound CC=C(C)CCCCCC=C ORSOHOYCAKNPQE-UHFFFAOYSA-N 0.000 description 1
- VMEDJHVTTJXKCN-UHFFFAOYSA-N 8-methylnona-1,7-diene Chemical compound CC(C)=CCCCCC=C VMEDJHVTTJXKCN-UHFFFAOYSA-N 0.000 description 1
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
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- KFFQABQEJATQAT-UHFFFAOYSA-N N,N'-dibutylthiourea Chemical compound CCCCNC(=S)NCCCC KFFQABQEJATQAT-UHFFFAOYSA-N 0.000 description 1
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 1
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- PVMNBWXRCLEDCL-UHFFFAOYSA-N acetaldehyde;aniline Chemical compound CC=O.NC1=CC=CC=C1 PVMNBWXRCLEDCL-UHFFFAOYSA-N 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- UVJHQYIOXKWHFD-UHFFFAOYSA-N cyclohexa-1,4-diene Chemical compound C1C=CCC=C1 UVJHQYIOXKWHFD-UHFFFAOYSA-N 0.000 description 1
- NLDGJRWPPOSWLC-UHFFFAOYSA-N deca-1,9-diene Chemical compound C=CCCCCCCC=C NLDGJRWPPOSWLC-UHFFFAOYSA-N 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- PGAXJQVAHDTGBB-UHFFFAOYSA-N dibutylcarbamothioylsulfanyl n,n-dibutylcarbamodithioate Chemical compound CCCCN(CCCC)C(=S)SSC(=S)N(CCCC)CCCC PGAXJQVAHDTGBB-UHFFFAOYSA-N 0.000 description 1
- 229940116901 diethyldithiocarbamate Drugs 0.000 description 1
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 description 1
- IYPLTVKTLDQUGG-UHFFFAOYSA-N dodeca-1,11-diene Chemical compound C=CCCCCCCCCC=C IYPLTVKTLDQUGG-UHFFFAOYSA-N 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
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- 238000005065 mining Methods 0.000 description 1
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- ILSQBBRAYMWZLQ-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-propan-2-ylpropan-2-amine Chemical compound C1=CC=C2SC(SN(C(C)C)C(C)C)=NC2=C1 ILSQBBRAYMWZLQ-UHFFFAOYSA-N 0.000 description 1
- 229940032017 n-oxydiethylene-2-benzothiazole sulfenamide Drugs 0.000 description 1
- LPXPSTWBTULMJE-UHFFFAOYSA-N n-phenylbutan-1-imine Chemical compound CCCC=NC1=CC=CC=C1 LPXPSTWBTULMJE-UHFFFAOYSA-N 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 150000004291 polyenes Chemical class 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
- NEYNBSGIXOOZGZ-UHFFFAOYSA-L zinc;butoxymethanedithioate Chemical compound [Zn+2].CCCCOC([S-])=S.CCCCOC([S-])=S NEYNBSGIXOOZGZ-UHFFFAOYSA-L 0.000 description 1
- PZKZVLYBWITYEF-UHFFFAOYSA-L zinc;n,n-diethylcarbamothioate Chemical compound [Zn+2].CCN(CC)C([O-])=S.CCN(CC)C([O-])=S PZKZVLYBWITYEF-UHFFFAOYSA-L 0.000 description 1
- LAGTXXPOZSLGSF-UHFFFAOYSA-L zinc;n-butyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCCCN(C([S-])=S)C1=CC=CC=C1.CCCCN(C([S-])=S)C1=CC=CC=C1 LAGTXXPOZSLGSF-UHFFFAOYSA-L 0.000 description 1
- KMNUDJAXRXUZQS-UHFFFAOYSA-L zinc;n-ethyl-n-phenylcarbamodithioate Chemical compound [Zn+2].CCN(C([S-])=S)C1=CC=CC=C1.CCN(C([S-])=S)C1=CC=CC=C1 KMNUDJAXRXUZQS-UHFFFAOYSA-L 0.000 description 1
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、エチレン・α−オレフィン・非共役ジエン系油展ゴムを含む油展ゴム組成物を加硫してなる加硫ゴムの製造方法に関する。 The present invention relates to a method for producing a vulcanized rubber obtained by vulcanizing an oil-extended rubber composition containing an ethylene / α-olefin / non-conjugated diene oil-extended rubber.
エチレン・α−オレフィン・非共役ジエン共重合ゴムは、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各種ゴム製品のベースポリマーとして幅広く使用されている。これらは一般に、ＪＩＳ Ａ硬度で１０〜９０程度の硬度を有するものであり、目的とする硬度及び他の特性に応じて、補強剤、充填剤、軟化剤、加硫剤、加硫促進剤等の各種添加剤が配合される。
ここで、例えば、電子写真装置や各種金融端末機などに使用される給紙または搬送用のゴムロール等のような低硬度のゴム組成物については、硬度を低くして紙類との密着性を高めて、正確に紙類を搬送するために、軟化剤を多量に配合することが行われている。しかし、軟化剤の配合量を増やすとべたつきが生じ、使用に耐えないものとなったり、また、共重合ゴムと軟化剤を均一に混合することが困難となり、混練時間が長くなったり、充填剤等の他の添加剤が分散不良となったり、さらには、分散不良に起因して物理的特性が低下するという問題がある。
Ethylene / α-olefin / non-conjugated diene copolymer rubber is a rubber material for automobiles, rubber materials for building materials, rubber belts / rubber rollers, rubber materials for vibration isolation, thermoplastic elastomer modifiers, tubes, hoses, and general rubber products. It is widely used as a base polymer for various rubber products. These generally have a JIS A hardness of about 10 to 90, and depending on the desired hardness and other characteristics, reinforcing agents, fillers, softeners, vulcanizing agents, vulcanization accelerators, etc. These various additives are blended.
Here, for example, for a rubber composition having a low hardness such as a rubber roll for paper feeding or conveyance used in an electrophotographic apparatus or various financial terminals, the hardness is lowered to improve the adhesion to papers. In order to enhance and accurately convey papers, a large amount of a softener is blended. However, when the blending amount of the softening agent is increased, stickiness occurs and it becomes unusable, and it becomes difficult to uniformly mix the copolymer rubber and the softening agent. Other additives such as these cause poor dispersion, and further, there is a problem that physical properties deteriorate due to poor dispersion.
低硬度のゴム組成物としては、例えば、（Ａ）エチレン／α−オレフィンのモル比７５／２５〜８３／１７、ヨウ素価５〜５０、１３５℃のデカリン中で測定した極限粘度〔η〕３．２〜５．５ｄｌ／ｇのエチレン・α−オレフィン・ジエン共重合体１００重量部に対して、（Ｂ）鉱物油系オイル１０５重量部以上を添加して伸展させたことを特徴とするエチレン・α−オレフィン・ジエン共重合体組成物が開示されている（特許文献１）。
また、α−オレフィンの炭素数が４以上２０以下、α−オレフィンの含量が２０モル％以上５０モル％未満、１００℃におけるムーニー粘度（ＭＬ1+4）が４０以上２００未満、ヨウ素価が３以上５０以下、かつ、ゲルパーミエーションクロマトグラフィーで求めた分子量分布（重量平均分子量／数平均分子量）が３以下であるエチレン／α−オレフィン／非共役ジエン共重合体ゴム１００重量部と、軟化剤５０重量部以上１５０重量部以下からなる低硬度ゴム組成物が開示されている（特許文献２）。
さらに、（Ａ）極限粘度（デカリン溶媒中、１３５℃で測定）が５．５ｄｌ／ｇ以上である超高分子量エチレン・α−オレフィン・非共役ジエン共重合ゴム１００重量部に対し、（Ｂ）鉱物油系伸展油Ｘ重量部を含有する油展ゴムであって、油展ゴムのムーニー粘度Ｙ（ＭＬ1+4,１９０℃）と油展量Ｘ重量部が、式 Ｙ≧−０．５Ｘ＋８０を満たすことを特徴とする油展ゴムが開示されている（特許文献３）。
The α-olefin has 4 to 20 carbon atoms, the α-olefin content is 20 to 50 mol%, the Mooney viscosity (ML 1 + 4 ) at 100 ° C. is 40 to 200, and the iodine value is 3 100 parts by weight of an ethylene / α-olefin / non-conjugated diene copolymer rubber having a molecular weight distribution (weight average molecular weight / number average molecular weight) determined by gel permeation chromatography of 3 or less and 50 or less, and a softening agent A low-hardness rubber composition comprising 50 parts by weight or more and 150 parts by weight or less is disclosed (Patent Document 2).
Furthermore, (A) with respect to 100 parts by weight of ultrahigh molecular weight ethylene / α-olefin / non-conjugated diene copolymer rubber having an intrinsic viscosity (measured in decalin solvent at 135 ° C.) of 5.5 dl / g or more, (B) An oil-extended rubber containing X parts by weight of a mineral oil-based extending oil, wherein the Mooney viscosity Y (ML 1 + 4, 190 ° C.) and the oil extension amount X parts by weight of the oil-extended rubber are expressed by the formula Y ≧ −0.5X + 80 An oil-extended rubber characterized by satisfying the above has been disclosed (Patent Document 3).
特許文献１〜３の技術によると、加工性が良好で、ブリード等を生じることのない低硬度の加硫ゴムを得ることができる。しかし、鉱物油系オイルの量を増やすなどして、さらに低硬度（例えば、デュロＡ硬度１５以下）の加硫ゴムを得ようとすると、混練に必要なトルクが得られ難くなる現象（混練性の悪化）や、オイルがブリードし易くなる現象（耐オイルブリード性の悪化）が生じるという問題がある。
そこで、本発明は、加硫時の混練に必要なトルクを短時間で確実に得ることができ、かつ、軟化剤であるオイルのブリードが生じることのない油展ゴム組成物を用いて製造される低硬度の加硫ゴムの製造方法を提供することを目的とする。
According to the techniques of Patent Documents 1 to 3, it is possible to obtain a vulcanized rubber having a low hardness that has good processability and does not cause bleeding. However, if a vulcanized rubber having a lower hardness (for example, duro A hardness of 15 or less) is obtained by increasing the amount of mineral oil-based oil or the like, it becomes difficult to obtain the torque necessary for kneading (kneading property). Deterioration) and a phenomenon that oil tends to bleed (deterioration of oil bleed resistance) occurs.
Therefore, the present invention is manufactured using an oil-extended rubber composition that can reliably obtain the torque necessary for kneading during vulcanization in a short time and does not cause oil bleeding as a softening agent. Another object of the present invention is to provide a method for producing a low hardness vulcanized rubber.
本発明によれば、特定のエチレン含有率等を有するエチレン・α−オレフィン・非共役ジエン共重合ゴム１００質量部に対して、特定の量の鉱物油系オイルを添加して、伸展し、油展ゴム組成物を得る工程と、上記油展ゴム組成物に対して、架橋剤、及び、特定の量の鉱物油系オイルを添加して架橋し、硬度（ＪＩＳ Ａ）が１８以下である加硫ゴムを得る工程とを含む加硫ゴムの製造方法が提供されて、本発明の上記目的が達成される。 According to the present invention, the ethylene-alpha-olefin-non-conjugated diene copolymer rubber to 100 parts by mass having a specific ethylene content, etc., by adding a specific amount of a mineral oil-based oils, and extended oil A step of obtaining a spread rubber composition , and a cross-linking agent and a specific amount of mineral oil-based oil are added to the oil-extended rubber composition for crosslinking, and the hardness (JIS A) is 18 or less. A method for producing a vulcanized rubber including a step of obtaining a vulcanized rubber is provided to achieve the above object of the present invention.
すなわち、本発明は、以下の［１］〜［２］を提供するものである。
［１］ （ａ）エチレン単位と炭素数３以上のα−オレフィン単位との合計量中のエチレン単位の含有率が５０〜６５質量％であり、かつ、極限粘度〔η〕（デカリン溶媒中、１３５℃で測定）が４．０〜７．５ｄｌ／ｇであるエチレン・α−オレフィン・非共役ジエン共重合ゴム１００質量部に対して、（ｂ）鉱物油系オイルを１３５〜１６０質量部添加して、伸展し、油展ゴム組成物を得る工程と、
上記油展ゴム組成物に対して、架橋剤、及び、該油展ゴム組成物中の（ａ）共重合ゴム１００質量部当たり５０〜２３０質量部の配合量の鉱物油系オイルを添加して架橋し、硬度（ＪＩＳ Ａ）が１８以下である加硫ゴムを得る工程と
を含む加硫ゴムの製造方法。
［２］ 上記加硫ゴムの硬度（ＪＩＳ Ａ）が１５以下である上記［２］に記載の加硫ゴムの製造方法。
That is, the present invention provides the following [1] to [ 2 ].
[ 1 ] (a) The content of ethylene units in the total amount of ethylene units and α-olefin units having 3 or more carbon atoms is 50 to 65% by mass, and intrinsic viscosity [η] (in decalin solvent, (B) 135 to 160 parts by mass of mineral oil-based oil is added to 100 parts by mass of ethylene / α-olefin / non-conjugated diene copolymer rubber having a measurement of 4.0 to 7.5 dl / g (measured at 135 ° C.). And extending to obtain an oil-extended rubber composition;
To the oil-extended rubber composition, a cross-linking agent and (a) a mineral oil-based oil having a compounding amount of 50 to 230 parts by mass per 100 parts by mass of the copolymer rubber in the oil-extended rubber composition are added. And a step of obtaining a vulcanized rubber having a hardness (JIS A) of 18 or less.
[ 2 ] The method for producing a vulcanized rubber according to the above [ 2 ], wherein the hardness (JIS A) of the vulcanized rubber is 15 or less.
本発明の加硫ゴムの製造方法で用いる原料の一つである油展ゴム組成物（以下、本発明の油展ゴム組成物ともいう。）は、架橋剤及び特定の量の鉱物油系オイルを添加した場合の優れた混練り性、及び架橋した場合の耐オイルブリード性に優れ、低硬度の加硫ゴムを与えることができる。
本発明の製造方法で得られる加硫ゴム（以下、本発明の加硫ゴムともいう。）は、低い硬度と良好な機械的特性を有するため、ゴムロール等の用途に好適に用いることができる。
An oil-extended rubber composition (hereinafter also referred to as the oil-extended rubber composition of the present invention), which is one of the raw materials used in the method for producing a vulcanized rubber of the present invention, comprises a crosslinking agent and a specific amount of mineral oil-based oil. Excellent kneadability when added, and oil bleed resistance when crosslinked, giving a low hardness vulcanized rubber.
The vulcanized rubber obtained by the production method of the present invention (hereinafter also referred to as the vulcanized rubber of the present invention) has low hardness and good mechanical properties, and therefore can be suitably used for applications such as rubber rolls.
［油展ゴム組成物］
本発明の油展ゴム組成物は、（ａ）エチレン単位と炭素数３以上のα−オレフィン単位との合計量中のエチレン単位の含有率が５０〜６５質量％であり、かつ、極限粘度〔η〕（デカリン溶媒中、１３５℃で測定）が４．０〜７．５ｄｌ／ｇであるエチレン・α−オレフィン・非共役ジエン共重合ゴム１００質量部に対して、（ｂ）鉱物油系オイルを１３０〜２００質量部添加してなるものである。
本発明で用いられる（ａ）エチレン・α−オレフィン・非共役ジエン共重合ゴムは、エチレン単位の含有率が５０〜６５質量％のものである。該含有率が５０質量％未満では、共重合ゴムの分子量を上げることが困難であり、極限粘度〔η〕（デカリン溶媒中、１３５℃で測定）が４．０以上の共重合ゴムを得ることができない。すなわち、油展ゴム組成物を用いて製造されるゴムロール等の用途に適する加硫ゴムを得ようとする本発明の目的に合わないことがある。該含有率が６５質量％を超えると、油展ゴム組成物に架橋剤及び鉱物油系オイルを添加して混練りし、架橋を行なうときに、混練性や耐オイルブリード性が悪化する傾向がある。
（ａ）エチレン・α−オレフィン・非共役ジエン共重合ゴム（本明細書中において、（ａ）共重合ゴムともいう。）は、エチレン、α−オレフィン、及び非共役ジエン化合物を共重合してなるゴムである。
α−オレフィンとしては、炭素数３〜２０のものが好ましく、例えば、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る。中でも、入手の容易性等の観点から、プロピレン、１−ブテン、１−ヘキセン、１−オクテンがより好ましく、プロピレンがさらに好ましい。これらのα−オレフィンは、単独でまたは２種以上を併用することができる。
[Oil-extended rubber composition]
In the oil-extended rubber composition of the present invention, (a) the content of ethylene units in the total amount of ethylene units and α-olefin units having 3 or more carbon atoms is 50 to 65% by mass , and the intrinsic viscosity [ η] (measured in decalin solvent at 135 ° C.) with respect to 100 parts by mass of an ethylene / α-olefin / nonconjugated diene copolymer rubber having a viscosity of 4.0 to 7.5 dl / g , (b) mineral oil-based oil 130-200 mass parts is added.
The (a) ethylene / α-olefin / non-conjugated diene copolymer rubber used in the present invention has an ethylene unit content of 50 to 65 mass%. When the content is less than 50% by mass, it is difficult to increase the molecular weight of the copolymer rubber, and a copolymer rubber having an intrinsic viscosity [η] (measured in decalin solvent at 135 ° C.) of 4.0 or more is obtained. I can't. That is, it may not meet the purpose of the present invention to obtain a vulcanized rubber suitable for uses such as a rubber roll produced using an oil-extended rubber composition. When the content exceeds 65% by mass, the kneadability and oil bleed resistance tend to deteriorate when the oil-extended rubber composition is kneaded by adding a cross-linking agent and mineral oil-based oil and performing cross-linking. is there.
(A) An ethylene / α-olefin / non-conjugated diene copolymer rubber (also referred to as (a) a copolymer rubber in this specification) is obtained by copolymerizing ethylene, an α-olefin, and a non-conjugated diene compound. It is a rubber.
As an alpha olefin, a C3-C20 thing is preferable, For example, a propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene etc. are mentioned. Of these, propylene, 1-butene, 1-hexene and 1-octene are more preferable, and propylene is more preferable from the viewpoint of availability. These α-olefins can be used alone or in combination of two or more.
非共役ジエン化合物としては、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。
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−ヘキサジエン等が好ましく、５−エチリデン−２−ノルボルネンがさらに好ましい。
これらの非共役ジエン化合物は、単独でまたは２種以上を併用することができる。
Examples of the non-conjugated diene compound include 5-ethylidene-2-norbornene, dicyclopentadiene, 5-propylidene-2-norbornene, 5-vinyl-2-norbornene, 2,5-norbornadiene, 1,4-cyclohexadiene, Cyclic polyenes such as 1,4-cyclooctadiene and 1,5-cyclooctadiene, 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- Tylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-octadiene, 7-methyl-4-ethylidene-1,6-nonadiene, 7-ethyl-4-ethylidene-1,6-nonadiene, A chain polyene having an internal unsaturated bond having 6 to 15 carbon atoms, such as 6,7-dimethyl-4-ethylidene-1,6-octadiene, 6,7-dimethyl-4-ethylidene-1,6-nonadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11-dodecadiene, 1,12-tridecadiene, 1, Examples include α, ω-dienes such as 13-tetradecadiene.
Of these, 5-ethylidene-2-norbornene, dicyclopentadiene, 5-vinyl-2-norbornene, 7-methyl-1,6-octadiene, 5-methyl-1,4-hexadiene and the like are preferable, and 5-ethylidene-2 -Norbornene is more preferred.
These non-conjugated diene compounds can be used alone or in combination of two or more.
（ａ）共重合ゴムの極限粘度〔η〕（デカリン溶媒中、１３５℃で測定）は、４．０〜７．５ｄｌ／ｇ、好ましくは５．０〜７．５ｄｌ／ｇである。該値をこの範囲内にすれば、共重合ゴム１００質量部に対して鉱物油系オイルを１３０質量部以上添加して伸展した油展ゴム組成物の乾燥供給が容易になるとともに、ゴム組成物としての混練加工が可能になる。
（ａ）共重合体ゴム中の非共役ジエン化合物単位の含量は、ヨウ素価として表わすことができる。ヨウ素価は、好ましくは０〜５０、より好ましくは５〜４０である。該値をこの範囲内とすれば、加硫ゴムとしての性能を発揮する架橋密度を得ることができる点で好ましい。
(A) intrinsic viscosity of the copolymer rubber [η] (in decalin solvent, measured at 135 ° C.) it is, 4.0~7.5dl / g, preferably from 5.0~7.5dl / g. When the value is within this range, the oil-extended rubber composition extended by adding 130 parts by mass or more of mineral oil based on 100 parts by mass of the copolymer rubber can be easily dried and supplied. As a result, kneading can be performed.
(A) The content of the non-conjugated diene compound unit in the copolymer rubber can be expressed as an iodine value. The iodine value is preferably 0 to 50, more preferably 5 to 40. When the value is within this range, it is preferable in that a crosslinking density that exhibits the performance as a vulcanized rubber can be obtained.
（ａ）共重合ゴムに油展される（ｂ）鉱物油系オイルとしては、パラフィン系、ナフテン系、アロマティック系等のオイルが挙げられる。中でも、パラフィン系、ナフテン系のオイルが好ましい。
パラフィン系伸展油としては、出光興産（株）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（株）製の、フッコールプロセスＰ−１００，Ｐ−２００，Ｐ−３００，Ｐ４００，Ｐ−５００、日鉱共石（株）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（株）製の、ルブレックス２６，同１００，同４６０、エクソンモービル（有）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（有）製のナプレックス３２、日石三菱（株）〔旧三菱石油（株）〕製の三菱１０ライトプロセス油などが挙げられる。
(A) Oils extended to copolymer rubber (b) Examples of mineral oil-based oils include paraffinic, naphthenic, and aromatic oils. Of these, paraffinic and naphthenic oils are preferred.
As the paraffinic extension oil, Diana Process Oil PW-90, PW-380, PS-32, PS-90, PS-430 manufactured by Idemitsu Kosan Co., Ltd., and Fukkor Process P manufactured by Fuji Kosan Co., Ltd. are used. -100, P-200, P-300, P400, P-500, manufactured by Nikko Kokeishi Co., Ltd., Kyoishi Process P-200, P-300, P-500, Kokeishi EPT750, 1000, Kokeshi Process S90, manufactured by Shell Chemical Co., Ltd., Lubrex 26, 100, 460, manufactured by ExxonMobil Corporation, manufactured by Esso Process Oil 815, 845, the same B-1, manufactured by ExxonMobil Corporation. Plex 32, Mitsubishi 10 Light Process Oil manufactured by Mitsubishi Oil Corporation (former Mitsubishi Oil Co., Ltd.), and the like.
ナフテン系オイルとしては、出光興産（株）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（有）製のナプレックス３８、富士興産（株）製の、フッコールＦＬＥＸ＃１０６０Ｎ，＃１１５０Ｎ，＃１４００Ｎ，＃２０４０Ｎ，＃２０５０Ｎ、日鉱共石（株）製の、共石プロセスＲ２５，Ｒ５０，Ｒ２００，Ｒ１０００、シェル化学（株）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、日石三菱（株）〔旧日本石油（株）〕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（有）製の、エッソプロセスオイルＬ−２，同７６５、日石三菱（株）〔旧三菱石油（株）〕製の三菱２０ライトプロセス油などが挙げられる。 As naphthenic 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., Fuji Kosan Fukukor FLEX # 1060N, # 1150N, # 1400N, # 2040N, # 2050N, manufactured by Nikko Kyoishi Co., Ltd., Kyoishi Process R25, R50, R200, R1000, manufactured by Shell Chemical Co., Ltd. , Shelf Rex 371JY, 371N, 451, 451, N-40, 22, 22, 22R, 32R, 100R, 100S, 100SA, 220RS, 220S, 260, 320R, 680, Sun KOMO REX No. 2 process oil manufactured by Ishi Mitsubishi Corporation [former Nippon Oil Co., Ltd.], manufactured by ExxonMobil Corporation Process Oil L-2, the same 765, and the like Nisseki Mitsubishi Corporation [old Mitsubishi Oil Co.] manufactured by Mitsubishi 20 Light Process Oil.
アロマティック系オイルとしては、出光興産（株）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（有）製の、モービルゾールＫ，同２２，同１３０、日鉱共石（株）製の、共石プロセスＸ５０，Ｘ１００，Ｘ１４０、シェル化学（株）製の、レゾックスNo．３、デュートレックス７２９ＵＫ、日石三菱（株）〔旧日本石油（株）〕製の、コウモレックス２００，３００，５００，７００、エクソンモービル（有）製の、エッソプロセスオイル１１０，同１２０、日石三菱（株）〔旧三菱石油（株）〕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 oils include Diana Process Oil AC-12, AC460, AH-16, AH-58, manufactured by Idemitsu Kosan Co., Ltd., Mobilsol K, 22, 130, manufactured by ExxonMobil Corporation. Kyoishi Process X50, X100, and X140 manufactured by Nippon Mining & Co., Ltd., and Resox No. manufactured by Shell Chemical Co., Ltd. 3. Deutrex 729UK, manufactured by Mitsubishi Oil Corporation (former Nippon Oil Co., Ltd.), Komorex 200, 300, 500, 700, manufactured by ExxonMobil Corporation, Esso Process Oil 110, 120, Japan Mitsubishi 34 Heavy Process Oil, Mitsubishi 44 Heavy Process Oil, Mitsubishi 38 Heavy Process Oil, Mitsubishi 39 Heavy Process Oil, etc. manufactured by Ishi Mitsubishi Corporation [former Mitsubishi Oil Co., Ltd.].
（ｂ）鉱物油系オイルの添加量は、（ａ）エチレン・α−オレフィン・非共役ジエン共重合ゴム１００質量部に対して、１３５〜１６０質量部である。該配合量が１３０質量部未満では、加硫して低硬度ゴムを得ようとした場合、後添加の鉱物油系オイルの配合量を大きくする必要が生じ、混練り性が悪化する。一方、該配合量を２００質量部以下にすれば、充填剤等の他の成分の分散性が良好になるなどの利点がある。 (B) the addition amount of the mineral oil-based oil, with respect to (a) ethylene-alpha-olefin-non-conjugated diene copolymer rubber to 100 parts by mass, it is 135 to 160 parts by weight. If the blending amount is less than 130 parts by mass, it is necessary to increase the blending amount of the post-added mineral oil-based oil when the low-hardness rubber is vulcanized to deteriorate the kneadability. On the other hand, when the blending amount is 200 parts by mass or less, there is an advantage that dispersibility of other components such as a filler is improved.
油展ゴム組成物は、例えば、（ａ）エチレン・α−オレフィン・非共役ジエン共重合ゴムの重合溶液に（ｂ）鉱物油系オイルを添加し、溶液状態で混合することによって製造される。この方法は、操作上、（ａ）共重合ゴムと（ｂ）鉱物油系オイル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。具体的には、重合体溶液、好ましくは重合反応後の重合体溶液（すなわち、重合停止剤の添加後の溶液）に、鉱物油系オイルを必要量添加して、溶液状態で良く混合することによって、油展を行う。その後、重合体溶液中にスチームを吹き込むスチームストリッピング法によってクラムを得るか、あるいは重合体溶液をエクストルーダー、デボラチライザーなどの手段により、脱溶剤処理を行なって、油展ゴム組成物と溶剤とを分離する。さらに、必要に応じて、真空乾燥機、熱風乾燥機やロールなどにより乾燥し、目的とする油展ゴム組成物を単離することができる。
また、油展ゴム組成物は、（ａ）共重合ゴムと（ｂ）鉱物油系オイルとを溶融状態でブレンドして調製することもできる。この場合、ブレンド手段としては、単軸押し出し機、二軸押し出し機、バンバリー、ロール、ニーダー、プラストミルなどが採用される。溶融混練温度は６０〜１８０℃が好適である。
なお、（ａ）エチレン・α−オレフィン・非共役ジエン共重合ゴムは、気相重合法、溶液重合法、スラリー重合法などの公知の重合方法で、例えば、バナジウム系、チタン系、メタロセン系等の触媒を用いて重合することができる。
The oil-extended rubber composition is produced, for example, by adding (b) a mineral oil-based oil to a polymerization solution of (a) an ethylene / α-olefin / non-conjugated diene copolymer rubber and mixing in a solution state. This method is preferable in terms of operation, since the process of mixing (a) the copolymer rubber and (b) the mineral oil-based oil can be omitted, and the mixing uniformity of both is excellent. Specifically, the required amount of mineral oil oil is added to the polymer solution, preferably the polymer solution after the polymerization reaction (that is, the solution after the addition of the polymerization terminator) and mixed well in the solution state. By doing oil exhibition. Thereafter, a crumb is obtained by a steam stripping method in which steam is blown into the polymer solution, or the polymer solution is subjected to a solvent removal treatment by means of an extruder, a devolatizer, etc., and the oil-extended rubber composition and the solvent And are separated. Furthermore, if necessary, the desired oil-extended rubber composition can be isolated by drying with a vacuum dryer, a hot air dryer or a roll.
The oil-extended rubber composition can also be prepared by blending (a) a copolymer rubber and (b) a mineral oil-based oil in a molten state. In this case, as the blending means, a single screw extruder, a twin screw extruder, a banbury, a roll, a kneader, a plast mill or the like is employed. The melt kneading temperature is preferably 60 to 180 ° C.
The (a) ethylene / α-olefin / non-conjugated diene copolymer rubber is a known polymerization method such as a gas phase polymerization method, a solution polymerization method, or a slurry polymerization method. For example, vanadium, titanium, metallocene, etc. It can polymerize using the catalyst of this.
油展ゴム組成物のムーニー粘度（ＭＬ1+4,125℃）は、好ましくは１５〜６５、より好ましくは２０〜６０、特に好ましくは２５〜５０である。該値をこの範囲内とすれば、油展ゴム組成物に架橋剤及び鉱物油系オイルを添加して加硫を行なうときの混練性等を、より良好にすることができる。
なお、油展ゴム組成物は、通常、エチレン・α−オレフィン・非共役ジエン共重合ゴム及び鉱物油系オイルのみからなる。すなわち、油展ゴム組成物の調製時には、通常、エチレン・α−オレフィン・非共役ジエン共重合ゴムと鉱物油系オイル以外の成分は配合しない。ただし、必要に応じて、油展ゴム組成物の調製時に他の成分を配合することは可能である。この場合、他の成分（例えば、老化防止剤等）の配合割合は、油展ゴム組成物中、好ましくは５質量％以下である。
The Mooney viscosity (ML 1 + 4 , 125 ° C.) of the oil-extended rubber composition is preferably 15 to 65, more preferably 20 to 60, and particularly preferably 25 to 50. When the value is within this range, the kneading property and the like when vulcanizing by adding a crosslinking agent and a mineral oil-based oil to the oil-extended rubber composition can be improved.
The oil-extended rubber composition usually comprises only ethylene / α-olefin / non-conjugated diene copolymer rubber and mineral oil-based oil. That is, when preparing the oil-extended rubber composition, components other than ethylene / α-olefin / non-conjugated diene copolymer rubber and mineral oil-based oil are usually not blended. However, if necessary, it is possible to mix other components when preparing the oil-extended rubber composition. In this case, the blending ratio of other components (for example, anti-aging agent) is preferably 5% by mass or less in the oil-extended rubber composition.
［加硫ゴム］
本発明の加硫ゴムは、上述の油展ゴム組成物に対して、架橋剤と、該油展ゴム組成物中の（ａ）共重合ゴム１００質量部当たり５０〜２３０質量部の配合量の鉱物油系オイルと、必要に応じて配合される充填剤等を添加してなるものを、架橋することによって得られる。
油展ゴム組成物に添加される鉱物油系オイルの例としては、上述の油展ゴム組成物の調製時に用いる鉱物油系オイルの例示物と同じものが挙げられる。なお、油展ゴム組成物に添加される鉱物油系オイルは、油展ゴム組成物の調製時に用いる鉱物油系オイルと同じでもよいし異なってもよい。
鉱物油系オイルの配合量は、油展ゴム組成物中の（ａ）共重合ゴム１００質量部に対して、５０〜２３０質量部、好ましくは６０〜２１０質量部、より好ましくは７０〜２００質量部である。該配合量を上記の範囲内とすることにより、良好な混練性及び耐オイルブリード性、さらには、加硫ゴムの低硬度及び良好な機械的特性を得ることができる。
[Vulcanized rubber]
The vulcanized rubber of the present invention comprises a crosslinking agent and a blending amount of 50 to 230 parts by mass per 100 parts by mass of the copolymer rubber (a) in the oil-extended rubber composition. It can be obtained by crosslinking a mineral oil-based oil and a filler added as necessary.
As an example of the mineral oil type oil added to an oil extended rubber composition, the same thing as the example of the mineral oil type oil used at the time of preparation of the above-mentioned oil extended rubber composition is mentioned. The mineral oil-based oil added to the oil-extended rubber composition may be the same as or different from the mineral oil-based oil used when preparing the oil-extended rubber composition.
The blending amount of the mineral oil-based oil is 50 to 230 parts by weight, preferably 60 to 210 parts by weight, more preferably 70 to 200 parts by weight with respect to 100 parts by weight of the copolymer rubber (a) in the oil-extended rubber composition. Part. By setting the blending amount within the above range, good kneadability and oil bleed resistance, as well as low hardness and good mechanical properties of the vulcanized rubber can be obtained.
油展ゴム組成物に添加される架橋剤としては、イオウ；塩化イオウ、二塩化イオウ、モルホリンジスルフイド、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のイオウ系化合物；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の有機過酸化物などを挙げることができる。中でも、イオウ、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。 The crosslinking agent added to the oil-extended rubber composition includes sulfur; sulfur compounds such as sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dimethyldithiocarbamate; dicumyl peroxide; 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, 2,5-dimethyl-2,5-dimethyl-2, Organic peroxides such as 5-di (tert-butylperoxy) hexyne-3, di-tert-butyl peroxide, di-tert-butyloxy-3,3,5-trimethylcyclohexane, and tert-butyl hydroperoxide . Of these, sulfur, dicumyl peroxide, di-tert-butyl peroxide, and di-tert-butyl peroxy-3,3,5-trimethylcyclohexane are preferable.
架橋剤としてイオウまたはイオウ化合物を用いる場合、その配合量は、油展ゴム中の（ａ）共重合ゴム１００質量部に対して、通常、０．１〜１０質量部、好ましくは０．５〜５質量部である。
架橋剤として有機過酸化物を用いる場合、その配合量は、油展ゴム中の（ａ）共重合ゴム１００質量部に対して、通常、０．１〜１５質量部、好ましくは０．５〜１０質量部である。
加硫剤としてイオウまたはイオウ系化合物を用いる場合、必要に応じて、加硫促進剤、加硫助剤等を併用することができる。
When sulfur or a sulfur compound is used as the cross-linking agent, the blending amount is usually 0.1 to 10 parts by mass, preferably 0.5 to 100 parts by mass with respect to 100 parts by mass of the (a) copolymer rubber in the oil-extended rubber. 5 parts by mass.
When using an organic peroxide as a cross-linking agent, the blending amount is usually 0.1 to 15 parts by mass, preferably 0.5 to 100 parts by mass of (a) copolymer rubber in the oil-extended rubber. 10 parts by mass.
When sulfur or a sulfur-based compound is used as a vulcanizing agent, a vulcanization accelerator, a vulcanization aid, or the like can be 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−スルフエンアミド、Ｎ−オキシジエチレン−２−ベンゾチアゾール−スルフエンアミド、Ｎ，Ｎ−ジイソプロピル−２−ベンゾチアゾールスルフエンアミド、２−メルカプトベンゾチアゾール、２−（２，４−ジニトロフエニル）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−ジスルフイド；ジフエニルグアニジン、トリフエニルグアニジン、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、ジフエ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イオ、テトラメチルチウラムジスフイド、テトラエチルチウラムジスルフイド、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イド、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、エチルフエニルジチオカルバミン酸亜鉛、ブチルフエ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。
加硫促進剤の配合量は、油展ゴム組成物中の（ａ）共重合ゴム１００質量部に対して、通常、０．１〜２０質量部、好ましくは０．２〜１０質量部である。
加硫助剤としては、酸化マグネシウム、亜鉛華などの金属酸化物を挙げることができるが、亜鉛華の使用が好ましい。
加硫助剤の配合量は、油展ゴム組成物中の（ａ）共重合ゴム１００質量部に対して、通常、１〜２０質量部、好ましくは３〜１０質量部である。
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, diorthotolylguanidine, ortho Trilbiguanide, diphenylguanidine phthalate; acetaldehyde-aniline reactant, butyraldehyde-aniline condensate, hexamethylenetetramine, acetaldehyde ammonia; 2-mercaptoimidazo Thiocarbanilide, diethylthiourea, dibutylthiourea, trimethylthiourea, diorthotolylthiourea; tetramethylthiuram monosulfio, tetramethylthiuramdisulfide, tetraethylthiuramdisulfide, tetrabutylthiuramdisulfide, pentamethylene Thiuram tetrasulfide, zinc dimethyldithiocarbamate, zinc diethylthiocarbamate, zinc di-n-butyldithiocarbamate, zinc ethylphenyldithiocarbamate, zinc butylphenyldithiocarbamate, sodium dimethyldithiocarbamate, selenium dimethyldithiocarbamate, Examples thereof include tellurium diethyldithiocarbamate; zinc dibutylxanthate.
The compounding amount of the vulcanization accelerator is usually 0.1 to 20 parts by mass, preferably 0.2 to 10 parts by mass with respect to 100 parts by mass of the copolymer rubber (a) in the oil-extended rubber composition. .
Examples of the vulcanization aid include metal oxides such as magnesium oxide and zinc white, but the use of zinc white is preferable.
The compounding quantity of a vulcanization | cure adjuvant is 1-20 mass parts normally with respect to 100 mass parts of (a) copolymer rubber in an oil-extended rubber composition, Preferably it is 3-10 mass parts.
架橋剤として有機過酸化物を用いる場合、ｐ−キノンジオキシムなどのキノンジオキシム系化合物や、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、イオウ、及びイオウ化合物などの架橋助剤を使用してもよい。
架橋助剤の配合量は、油展ゴム組成物中の（ａ）共重合ゴム１００質量部に対して、通常、０．１〜２０質量部、好ましくは０．１〜１０質量部である。
When organic peroxide is used as a crosslinking agent, crosslinking aids such as quinonedioxime compounds such as p-quinonedioxime, polyethylene glycol dimethacrylate, diallyl phthalate, triallyl cyanurate, divinylbenzene, sulfur and sulfur compounds are used. An agent may be used.
The compounding amount of the crosslinking aid is usually 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the copolymer rubber (a) in the oil-extended rubber composition.
本発明において、油展ゴム組成物及び架橋剤と共に、充填剤等の任意成分を配合することができる。
充填剤としては、カーボンブラック、微粉ケイ酸、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、フッ素樹脂などを挙げることができる。
中でも、カーボンブラックは、加硫ゴムの機械的強度の向上、及び加硫ゴムの製造コストの点から好ましく用いられる。カーボンブラックには、ＳＲＦ、ＧＰＦ、ＦＥＦ、ＨＡＦ、ＩＳＡＦ、ＳＡＦ、ＦＴ、ＭＴなどの種類があり、いずれも使用することができるが、中でもＳＲＦ、ＦＥＦ、ＧＰＦの使用が好ましい。
充填剤の配合量は、（Ａ）油展ゴム中の（ａ）共重合ゴム１００質量部に対して、通常、５〜３００質量部、好ましくは２０〜２００質量部、より好ましくは５５〜１５０質量部である。該配合量が５質量部未満であると、充填剤の添加の目的（機械的強度の向上等）を十分に達成することができない。該配合量が３００質量部を超えると、低硬度ゴムを得るために多量の鉱物油系オイルを配合する必要が生じ、混練り性が悪化する。
In this invention, arbitrary components, such as a filler, can be mix | blended with an oil extended rubber composition and a crosslinking agent.
Examples of the filler include carbon black, finely divided silicic acid, glass powder, glass beads, mica, calcium carbonate, potassium titanate whisker, talc, clay, barium sulfate, glass flake, and fluororesin.
Among these, carbon black is preferably used from the viewpoint of improving the mechanical strength of the vulcanized rubber and the production cost of the vulcanized rubber. There are various types of carbon black such as SRF, GPF, FEF, HAF, ISAF, SAF, FT, and MT, and any of them can be used. Among them, use of SRF, FEF, and GPF is preferable.
The blending amount of the filler is usually 5 to 300 parts by mass, preferably 20 to 200 parts by mass, more preferably 55 to 150 parts per 100 parts by mass of (a) copolymer rubber in (A) oil-extended rubber. Part by mass. When the blending amount is less than 5 parts by mass, the purpose of adding the filler (improving mechanical strength, etc.) cannot be sufficiently achieved. When the blending amount exceeds 300 parts by mass, it is necessary to blend a large amount of mineral oil-based oil in order to obtain a low hardness rubber, and the kneadability deteriorates.
充填剤以外の他の任意成分として、酸化防止剤、帯電防止剤、耐候安定剤、紫外線吸収剤、滑剤、ブロッキング防止剤、シール性改良剤、結晶核剤、難燃化剤、防菌剤、防かび剤、粘着付与剤、可塑剤、着色剤(酸化チタン、カーボンブラック等)、ステアリン酸等の分散剤等を適宜配合することができる。また、ゴム質重合体(ブチルゴムやＮＢＲ等)、熱可塑性樹脂、熱可塑性エラストマー(低結晶性プロピレン系重合体、水添ジエン系重合体等)等の重合体を適宜配合することができる。 As optional components other than fillers, antioxidants, antistatic agents, weathering stabilizers, UV absorbers, lubricants, antiblocking agents, sealability improvers, crystal nucleating agents, flame retardants, antibacterial agents, An antifungal agent, a tackifier, a plasticizer, a colorant (titanium oxide, carbon black, etc.), a dispersant such as stearic acid, and the like can be appropriately blended. In addition, polymers such as rubbery polymers (such as butyl rubber and NBR), thermoplastic resins, and thermoplastic elastomers (such as low crystalline propylene polymers and hydrogenated diene polymers) can be appropriately blended.
本発明の加硫ゴムは、油展ゴム組成物、及び必要に応じて配合される充填剤、オイル等の成分を、混練機を用いて混練し、ゴム組成物を得た後、更に架橋剤等を混練りして、このゴム組成物を加熱成形することによって目的の加硫ゴムを得ることができる。
具体的には、まず、油展ゴム組成物に他の成分を添加し、例えば、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て混練することによって、ゴム組成物を調製する。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って加硫すれば、加硫ゴムからなる製品を得ることができる。
得られる加硫ゴムは、非常に低い硬度を有するものである、加硫ゴムの硬度（ＪＩＳ Ａ；デュロＡともいう。）は、１８以下、好ましくは１５以下、特に好ましくは１２以下である。
The vulcanized rubber of the present invention is obtained by kneading an oil-extended rubber composition and components such as a filler and oil blended as necessary using a kneading machine to obtain a rubber composition, and then a crosslinking agent. The desired vulcanized rubber can be obtained by kneading and the like and thermoforming the rubber composition.
Specifically, first, other components are added to the oil-extended rubber composition, and the rubber composition is prepared by, for example, kneading using an open roll mill, a Banbury mixer, a kneader, or the like. Then, after the rubber composition is molded into a desired shape by an extruder or a mold, vulcanized by a heating device such as a high-frequency heating device, an air oven, PCM, or LCM, a product made of vulcanized rubber can be obtained. .
The obtained vulcanized rubber has a very low hardness. The hardness (JIS A; also referred to as Duro A) of the vulcanized rubber is 18 or less , preferably 15 or less, particularly preferably 12 or less.
以下、本発明を実施例により具体的に説明するが、本発明はこれらの実施例に何ら限定されるものではない。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。
［油展ゴム組成物の調製］
反応媒体としてｎ−ヘキサンを収容した攪拌重合槽内において、単量体としてエチレン、プロピレン、及び５−エチリデン−２−ノルボルネン（ＥＮＢ）、触媒として三塩化オキシバナジウム及びエチルアルミニウムセスキクロリドを用い、かつ、分子量調節剤として水素ガスを用いて、一般的な溶液重合法により、共重合ゴムを含むポリマー溶液を得た後、この共重合ゴム（エチレン・プロピレン・非共役ジエン共重合ゴム）を含むｎ−ヘキサン溶液中に、鉱物油系オイルとしてパラフィン系オイル（ダイアナプロセスオイルＰＷ９０（商品名：出光興産社製））を、共重合ゴム１００質量部当たり表１に示す量（質量部）だけ添加して、攪拌し、スチームストリッピングにより油展ゴム組成物を得た。
油展ゴム組成物の特性値は、以下のようにして求めた。
（エチレン含量）
鉱物油系オイルを添加する前のポリマー溶液を乾燥させるか、または、油展ゴムをエタノール／トルエンの質量比が３／１である混合液にて沸点抽出した後、オイル抽出されたゴム分を乾燥させて、共重合ゴムを得た後、この共重合ゴムを対象にして、赤外線吸収スペクトル法によりエチレン含量を測定した。
（ヨウ素価）
前記の「エチレン含量」の測定対象を得る方法と同様にして共重合ゴムを得た後、この共重合ゴムを対象にして、ヨウ素価を測定した。
（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。
（ムーニー粘度ML1+4,125℃）
測定温度１２５℃、予熱時間１分、ロータ回転時間４分で測定した。
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In the examples, parts and% are based on mass unless otherwise specified.
[Preparation of oil-extended rubber composition]
In a stirred polymerization tank containing n-hexane as a reaction medium, ethylene, propylene, and 5-ethylidene-2-norbornene (ENB) are used as monomers, oxyvanadium trichloride and ethylaluminum sesquichloride are used as catalysts, and After obtaining a polymer solution containing a copolymer rubber by a general solution polymerization method using hydrogen gas as a molecular weight regulator, n containing this copolymer rubber (ethylene / propylene / non-conjugated diene copolymer rubber) -A paraffinic oil (Diana Process Oil PW90 (trade name: manufactured by Idemitsu Kosan Co., Ltd.)) as a mineral oil-based oil is added to the hexane solution in an amount (part by mass) shown in Table 1 per 100 parts by mass of the copolymer rubber. The resulting oil-extended rubber composition was obtained by stirring and steam stripping.
The characteristic value of the oil-extended rubber composition was determined as follows.
(Ethylene content)
The polymer solution before adding the mineral oil-based oil is dried, or the oil-extended rubber is subjected to boiling point extraction with a mixed solution having a mass ratio of ethanol / toluene of 3/1, and then the oil-extracted rubber component is removed. After drying to obtain a copolymer rubber, the ethylene content of the copolymer rubber was measured by an infrared absorption spectrum method.
(Iodine number)
A copolymer rubber was obtained in the same manner as in the method for obtaining the “ethylene content” measurement object, and then the iodine value was measured for the copolymer rubber.
(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.
(Mooney viscosity ML1 + 4,125 ℃)
Measurement was performed at a measurement temperature of 125 ° C., a preheating time of 1 minute, and a rotor rotation time of 4 minutes.
［実施例１］
表１に記載のＥＰＤＭ（１）を用い、ＥＰＤＭ（１）２５１部、亜鉛華５部、ステアリン酸１部、ＳＲＦカーボン６０部、軟化剤１６９部、及び重質炭酸カルシウム３０部を、容量１．７リットルのバンバリーミキサーを使用し、７０℃に温度を調整して混練し、混合物を得た。得られた混合物に対して、硫黄１．５部、促進剤ＣＺ１．５部、促進剤ＢＺ１．５部、促進剤ＴＲＡ０．７部、促進剤ＴＥＴ０．７部を添加し、オープンロールで５０〜７０℃、約６分間混練することにより、ゴム組成物を得た。なお、各種配合成分としては、以下の（１）〜（１１）に示すものを使用した。
（１）亜鉛華：商品名「酸化亜鉛２種」（白水化学工業社製）
（２）ステアリン酸：商品名「ルナックＳ３０」（花王社製）
（３）ＳＲＦカーボン：商品名「シーストＳ」（東海カーボン社製）
（４）重質炭酸カルシウム：商品名「スーパーＳ」（丸尾カルシウム社製）
（６）後添加のオイル：商品名「ダイアナプロセスＰＷ３８０」（出光興産社製）
（７）加硫促進剤：商品名「ノクセラーＣＺ」（大内新興社製）
（８）加硫促進剤：商品名「ノクセラーＢＺ」（大内新興社製）
（９）加硫促進剤：商品名「ノクセラーＴＲＡ」（大内新興社製）
（１０）加硫促進剤：商品名「ノクセラーＴＥＴ」（大内新興社製）
（１１）加硫剤：商品名「イオウ」（鶴見化学工業社製）
[Example 1]
Using EPDM (1) described in Table 1, 251 parts of EPDM (1), 5 parts of zinc white, 1 part of stearic acid, 60 parts of SRF carbon, 169 parts of softener, and 30 parts of heavy calcium carbonate were added at a capacity of 1 Using a 7 liter Banbury mixer, the temperature was adjusted to 70 ° C. and kneaded to obtain a mixture. 1.5 parts of sulfur, 1.5 parts of accelerator CZ, 1.5 parts of accelerator BZ, 0.7 parts of accelerator TRA, 0.7 parts of accelerator TET are added to the resulting mixture, and 50 to 50 in an open roll. A rubber composition was obtained by kneading at 70 ° C. for about 6 minutes. In addition, as various compounding components, those shown in the following (1) to (11) were used.
(1) Zinc flower: Trade name "Zinc oxide 2 types" (manufactured by Hakusui Chemical Co., Ltd.)
(2) Stearic acid: Trade name “Lunac S30” (manufactured by Kao Corporation)
(3) SRF carbon: Trade name “Seast S” (manufactured by Tokai Carbon Co., Ltd.)
(4) Heavy calcium carbonate: Trade name “Super S” (manufactured by Maruo Calcium)
(6) Post-added oil: Trade name “Diana Process PW380” (manufactured by Idemitsu Kosan Co., Ltd.)
(7) Vulcanization accelerator: Trade name “Noxeller CZ” (Ouchi Shinsei Co., Ltd.)
(8) Vulcanization accelerator: Trade name “Noxeller BZ” (made by Ouchi Shinsei)
(9) Vulcanization accelerator: Trade name “Noxeller TRA” (manufactured by Ouchi Shinsei)
(10) Vulcanization accelerator: Trade name “Noxeller TET” (manufactured by Ouchi Shinsei)
(11) Vulcanizing agent: Trade name “Sulfur” (manufactured by Tsurumi Chemical Co., Ltd.)
得られたゴム組成物を、プレス成型機を使用して１７０℃、１５０ｋｇｆ／ｃｍ２のプレス圧力下で１５分間加熱し、厚さ２ｍｍの試験片（加硫ゴムシート）を作製した。また、得られたゴム組成物を２０分間加熱することにより、オイルブリード試験用のブロック状試験片を作製した。
得られたゴム組成物及び加硫ゴムの物性を次のようにして評価した。評価結果を表２に示す。
（１）混練性
１．７Ｌのバンバリーミキサーを使用し、７０℃で６〜３０分間混練し、練り時間を判定基準とした。トルクが急上昇して、練り時間が１０分以内のものを「○」（良好）、トルクの上昇が遅く、練り時間が１０分を超え、１５分以内のものを「△」（やや不良）、トルクの上昇が非常に遅く、練り時間が１５分を超えるものを「×」（不良）、混練できないものを「混練不可」として評価した。
（２）硬度
ＪＩＳ Ｋ６２５３に準拠し、試験片のスプリング硬さ（ＪＩＳ Ａ硬度；デュロＡ硬度）を測定した。
（３）耐オイルブリード性
ＪＩＳＫ６２６２に規定の大型試験片を用い、７０℃、２５％圧縮した状態で１０日間放置後、開放し、試験片表面の液状物の有無にて評価した。
液状物が無い場合を「○」、液状物が微量の場合を「△」、液状物が多量の場合を「×」として評価した。
The obtained rubber composition was heated using a press molding machine at 170 ° C. under a pressing pressure of 150 kgf / cm 2 for 15 minutes to prepare a test piece (vulcanized rubber sheet) having a thickness of 2 mm. Moreover, the obtained rubber composition was heated for 20 minutes to produce a block-shaped test piece for an oil bleed test.
The physical properties of the obtained rubber composition and vulcanized rubber were evaluated as follows. The evaluation results are shown in Table 2.
(1) Kneadability A 1.7 L Banbury mixer was used and kneaded at 70 ° C. for 6 to 30 minutes, and the kneading time was used as a criterion. Torque suddenly rises when the kneading time is less than 10 minutes “Good” (good), torque rise is slow, the kneading time exceeds 10 minutes and less than 15 minutes “△” (somewhat bad), The case where the increase in torque was very slow and the kneading time exceeded 15 minutes was evaluated as “x” (poor), and the case where kneading was impossible was evaluated as “unmixable”.
(2) Hardness Based on JIS K6253, the spring hardness (JIS A hardness; Duro A hardness) of the test piece was measured.
(3) Oil bleed resistance A large test piece specified in JISK6262 was used for 10 days in a state compressed at 70 ° C. and 25%, then opened, and evaluated by the presence or absence of a liquid on the surface of the test piece.
The case where there was no liquid substance was evaluated as “◯”, the case where the liquid substance was very small, “Δ”, and the case where there was a large amount of liquid substance was evaluated as “X”.
実施例１のゴム組成物の混練性は、「○」であった。このゴム組成物を用いて作製した試験片の硬度（デュロＡ）は、１０であった。このゴム組成物を用いて作製したブロック状試験片の耐オイルブリード性は、「○」であった。 The kneadability of the rubber composition of Example 1 was “◯”. The hardness (duro A) of the test piece produced using this rubber composition was 10. The oil bleed resistance of the block-shaped test piece prepared using this rubber composition was “◯”.
［実施例２〜３、比較例１〜４］
表２に示す配合処方とすること以外は、前述の実施例１と同様にして、ゴム組成物、及び試験片（加硫ゴムシート）、及びブロック状試験片を作製した。ゴム組成物の混練性、及び、作製した試験片（加硫ゴムシート）及びブロック状試験片の硬度、耐オイルブリード性の評価結果を、表２に示す。
[Examples 2-3, Comparative Examples 1-4]
A rubber composition, a test piece (vulcanized rubber sheet), and a block-shaped test piece were prepared in the same manner as in Example 1 except that the formulation shown in Table 2 was used. Table 2 shows the kneadability of the rubber composition, and the evaluation results of the hardness and oil bleed resistance of the prepared test pieces (vulcanized rubber sheet) and block-like test pieces.
表１から、本発明に属する実施例１〜３のゴム組成物は、混練性に優れることがわかる。また、実施例１〜３の加硫ゴムは、低硬度であり、耐オイルブリード性に優れることがわかる。一方、本発明に属さない比較例１〜４の加硫ゴムは、混練性、耐オイルブリード性のいずれか１つ以上が劣ることがわかる。 From Table 1, it can be seen that the rubber compositions of Examples 1 to 3 belonging to the present invention are excellent in kneadability. Further, it can be seen that the vulcanized rubbers of Examples 1 to 3 have low hardness and excellent oil bleed resistance. On the other hand, it can be seen that the vulcanized rubbers of Comparative Examples 1 to 4 which do not belong to the present invention are inferior in any one or more of kneadability and oil bleed resistance.
本発明の加硫ゴムは、素材の特性が重要な役割を果たすゴム製品分野で幅広く使用することができ、具体的には、工業製品、絶縁製品、土木・建築材料、タイヤ・チューブ、自動車部品、パッキン、ＯＡロール、防振材、ホース等の材料として使用される。 The vulcanized rubber of the present invention can be widely used in the field of rubber products where the characteristics of the material play an important role. Specifically, industrial products, insulating products, civil engineering / building materials, tires / tubes, automobile parts , Packing, OA roll, anti-vibration material, hose and other materials.
Claims (2)
上記油展ゴム組成物に対して、架橋剤、及び、該油展ゴム組成物中の（ａ）共重合ゴム１００質量部当たり５０〜２３０質量部の配合量の鉱物油系オイルを添加して架橋し、硬度（ＪＩＳ Ａ）が１８以下である加硫ゴムを得る工程と
を含む加硫ゴムの製造方法。 (A) The content of ethylene units in the total amount of ethylene units and α-olefin units having 3 or more carbon atoms is 50 to 65% by mass, and the intrinsic viscosity [η] (in decalin solvent at 135 ° C. (B) 135 to 160 parts by mass of mineral oil-based oil is added to 100 parts by mass of ethylene / α-olefin / non-conjugated diene copolymer rubber having a measurement of 4.0 to 7.5 dl / g, Extending and obtaining an oil-extended rubber composition;
To the oil-extended rubber composition, a cross-linking agent and (a) a mineral oil-based oil having a compounding amount of 50 to 230 parts by mass per 100 parts by mass of the copolymer rubber in the oil-extended rubber composition are added. And a step of obtaining a vulcanized rubber having a hardness (JIS A) of 18 or less.
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