JP2023075746A - Rubber composition and use thereof - Google Patents
Rubber composition and use thereof Download PDFInfo
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- JP2023075746A JP2023075746A JP2021188839A JP2021188839A JP2023075746A JP 2023075746 A JP2023075746 A JP 2023075746A JP 2021188839 A JP2021188839 A JP 2021188839A JP 2021188839 A JP2021188839 A JP 2021188839A JP 2023075746 A JP2023075746 A JP 2023075746A
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- mass
- rubber composition
- acid
- rubber
- parts
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 88
- 239000005060 rubber Substances 0.000 title claims abstract description 87
- 239000000203 mixture Substances 0.000 title claims abstract description 76
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 65
- -1 polyethylene Polymers 0.000 claims abstract description 54
- 239000004698 Polyethylene Substances 0.000 claims abstract description 46
- 229920000573 polyethylene Polymers 0.000 claims abstract description 46
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 37
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 27
- 239000006229 carbon black Substances 0.000 claims abstract description 26
- 239000000945 filler Substances 0.000 claims abstract description 19
- 239000003795 chemical substances by application Substances 0.000 description 22
- 238000004073 vulcanization Methods 0.000 description 21
- 238000000034 method Methods 0.000 description 20
- 230000003712 anti-aging effect Effects 0.000 description 15
- 238000004132 cross linking Methods 0.000 description 15
- 239000003431 cross linking reagent Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 8
- 150000002978 peroxides Chemical class 0.000 description 8
- 239000010734 process oil Substances 0.000 description 8
- 239000004014 plasticizer Substances 0.000 description 7
- 229920002857 polybutadiene Polymers 0.000 description 7
- 239000005062 Polybutadiene Substances 0.000 description 6
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 6
- 239000011787 zinc oxide Substances 0.000 description 6
- 235000014692 zinc oxide Nutrition 0.000 description 6
- 229920000459 Nitrile rubber Polymers 0.000 description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 description 5
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 244000043261 Hevea brasiliensis Species 0.000 description 4
- 229920000297 Rayon Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 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 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011256 inorganic filler Substances 0.000 description 4
- 229910003475 inorganic filler Inorganic materials 0.000 description 4
- 229920003049 isoprene rubber Polymers 0.000 description 4
- 229920003052 natural elastomer Polymers 0.000 description 4
- 229920001194 natural rubber Polymers 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000012744 reinforcing agent Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 150000003464 sulfur compounds Chemical class 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 4
- 229960002447 thiram Drugs 0.000 description 4
- 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 3
- 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 3
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 235000021314 Palmitic acid Nutrition 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- WBHHMMIMDMUBKC-XLNAKTSKSA-N ricinelaidic acid Chemical compound CCCCCC[C@@H](O)C\C=C\CCCCCCCC(O)=O WBHHMMIMDMUBKC-XLNAKTSKSA-N 0.000 description 3
- 229960003656 ricinoleic acid Drugs 0.000 description 3
- FEUQNCSVHBHROZ-UHFFFAOYSA-N ricinoleic acid Natural products CCCCCCC(O[Si](C)(C)C)CC=CCCCCCCCC(=O)OC FEUQNCSVHBHROZ-UHFFFAOYSA-N 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-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
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004641 Diallyl-phthalate Substances 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 description 2
- RSHFXVVRRRVVNQ-YOJQQDEFSA-N Phleixanthophyll Natural products CC(=C/C=C/C=C(C)/C=C/C=C(C)/C=C/C1=C(C)CCCC1(C)C)C=CC=C(/C)C=CC=C(/C)C=CC(O)C(C)(C)OC2OC(CO)C(O)C(O)C2O RSHFXVVRRRVVNQ-YOJQQDEFSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 2
- IAXXETNIOYFMLW-GYSYKLTISA-N [(1r,3r,4r)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@@]2(C)[C@H](OC(=O)C(=C)C)C[C@@H]1C2(C)C IAXXETNIOYFMLW-GYSYKLTISA-N 0.000 description 2
- 125000004018 acid anhydride group Chemical group 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000008116 calcium stearate Substances 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001875 compounds Chemical class 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
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IUJLOAKJZQBENM-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-2-methylpropan-2-amine Chemical compound C1=CC=C2SC(SNC(C)(C)C)=NC2=C1 IUJLOAKJZQBENM-UHFFFAOYSA-N 0.000 description 2
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 2
- NHLUYCJZUXOUBX-UHFFFAOYSA-N nonadec-1-ene Chemical compound CCCCCCCCCCCCCCCCCC=C NHLUYCJZUXOUBX-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920003192 poly(bis maleimide) Polymers 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- BOOBDAVNHSOIDB-UHFFFAOYSA-N (2,3-dichlorobenzoyl) 2,3-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC=CC(C(=O)OOC(=O)C=2C(=C(Cl)C=CC=2)Cl)=C1Cl BOOBDAVNHSOIDB-UHFFFAOYSA-N 0.000 description 1
- FVQMJJQUGGVLEP-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2-ethylhexaneperoxoate Chemical compound CCCCC(CC)C(=O)OOOC(C)(C)C FVQMJJQUGGVLEP-UHFFFAOYSA-N 0.000 description 1
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- LTQBNYCMVZQRSD-UHFFFAOYSA-N (4-ethenylphenyl)-trimethoxysilane Chemical compound CO[Si](OC)(OC)C1=CC=C(C=C)C=C1 LTQBNYCMVZQRSD-UHFFFAOYSA-N 0.000 description 1
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-UHFFFAOYSA-N 0.000 description 1
- OTMBZPVYOQYPBE-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclododecane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCCCCCCCC1 OTMBZPVYOQYPBE-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-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
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 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
- VYNQWGXTLZDYFX-UHFFFAOYSA-N 1-benzoylperoxyhexyl benzenecarboperoxoate Chemical compound C=1C=CC=CC=1C(=O)OOC(CCCCC)OOC(=O)C1=CC=CC=C1 VYNQWGXTLZDYFX-UHFFFAOYSA-N 0.000 description 1
- 229940106006 1-eicosene Drugs 0.000 description 1
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 1
- JPOUDZAPLMMUES-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)octane Chemical compound CCCCCCC(C)(OOC(C)(C)C)OOC(C)(C)C JPOUDZAPLMMUES-UHFFFAOYSA-N 0.000 description 1
- SPSPIUSUWPLVKD-UHFFFAOYSA-N 2,3-dibutyl-6-methylphenol Chemical compound CCCCC1=CC=C(C)C(O)=C1CCCC SPSPIUSUWPLVKD-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- ODBCKCWTWALFKM-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhex-3-yne Chemical compound CC(C)(C)OOC(C)(C)C#CC(C)(C)OOC(C)(C)C ODBCKCWTWALFKM-UHFFFAOYSA-N 0.000 description 1
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- 239000003566 sealing material Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical compound ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000010689 synthetic lubricating oil Substances 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000003784 tall oil Substances 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
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 description 1
- FRGPKMWIYVTFIQ-UHFFFAOYSA-N triethoxy(3-isocyanatopropyl)silane Chemical compound CCO[Si](OCC)(OCC)CCCN=C=O FRGPKMWIYVTFIQ-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 1
- 239000005050 vinyl trichlorosilane Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 239000012991 xanthate Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- 229940098697 zinc laurate Drugs 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は、低発熱性能に優れ、且つ、耐摩耗性が良好なゴム組成物に関する。 TECHNICAL FIELD The present invention relates to a rubber composition having excellent low heat build-up performance and good wear resistance.
ゴム(加硫ゴム)は優れたゴム弾性と耐熱性を有することから、自動車用のタイヤや防振ゴム及び各種シール材として幅広く利用されている。その原料ゴムには、天然ゴムをはじめとして、スチレン・ブタジエンゴムやブタジエンゴム、およびエチレン・プロピレン
ゴムなどの合成ゴムが用いられている。
BACKGROUND ART Rubber (vulcanized rubber) has excellent rubber elasticity and heat resistance, and is therefore widely used as automobile tires, anti-vibration rubber, and various sealing materials. Raw material rubbers include synthetic rubbers such as natural rubbers, styrene-butadiene rubbers, butadiene rubbers, and ethylene-propylene rubbers.
そして、環境負荷低減の観点から、空気入りタイヤには、高い強度、燃費を向上させる性能等が望まれている。
例えば、特許文献1には、ジエン系ゴムと、充填剤と、酸変性ポリエチレンとを含有し、酸変性ポリエチレンの密度が0.94~0.98であり、前記酸変性ポリエチレンの含有量が、前記ジエン系ゴム100質量部に対して、2~30質量部配合してなるゴム組成物が記載されている。
From the viewpoint of reducing the environmental burden, pneumatic tires are desired to have high strength, performance to improve fuel efficiency, and the like.
For example, Patent Document 1 contains a diene rubber, a filler, and an acid-modified polyethylene, the density of the acid-modified polyethylene is 0.94 to 0.98, and the content of the acid-modified polyethylene is A rubber composition containing 2 to 30 parts by mass per 100 parts by mass of the diene rubber is described.
また、特許文献2には、ジエン系ゴムと、特定構造のビスマレイミド(BMI)と、酸変性ポリエチレンとを配合するゴム組成物が記載されている。
しかしながら、上記特許文献1や特許文献2に記載のゴム組成物中の特定の高密度酸変性ポリエチレンを含有するゴム組成物は、低発熱性能を維持しつつ、耐摩耗性を十分に改良することができない虞がある。
Further, Patent Document 2 describes a rubber composition in which diene rubber, bismaleimide (BMI) having a specific structure, and acid-modified polyethylene are blended.
However, the rubber composition containing the specific high-density acid-modified polyethylene among the rubber compositions described in Patent Document 1 and Patent Document 2 has sufficient improvement in wear resistance while maintaining low heat build-up performance. There is a risk that it will not be possible.
本発明の目的は、より低発熱性能に優れ、且つ、耐摩耗性が良好なゴム組成物を得ることにある。 An object of the present invention is to obtain a rubber composition having excellent low heat build-up performance and good abrasion resistance.
本発明は、ジエン系ゴム(A)、充填剤(B)、および、密度が0.950-0.980g/cm3の範囲にある酸変性ポリエチレン(C)を含み、前記充填剤(B)が、カーボンブラック(B1)およびシリカ(B2)を含み、前記酸変性ポリエチレン(C)の含有量が、前記ジエン系ゴム(A)100質量部に対して、1~9質量部の範囲であり、前記カーボンブラック(B1)の質量をWA、前記シリカ(B2)の質量をWB、前記酸変性ポリエチレン(C)の質量をWXとした場合に、WX/(WA+WB)が0.01~0.16の範囲であることを特徴とするゴム組成物に係る。 The present invention comprises a diene rubber (A), a filler (B), and an acid-modified polyethylene (C) having a density in the range of 0.950-0.980 g/cm 3 , the filler (B) contains carbon black (B1) and silica (B2), and the content of the acid-modified polyethylene (C) is in the range of 1 to 9 parts by mass with respect to 100 parts by mass of the diene rubber (A). , where WA is the mass of the carbon black (B1), WB is the mass of the silica (B2), and WX is the mass of the acid-modified polyethylene (C), WX/(WA+WB) is 0.01 to 0.01. 16 range.
本発明のゴム組成物は、高い低発熱性を維持しつつ、耐摩耗性に優れるゴム組成物を提供することができる。
また、本発明のゴム組成物から形成される空気入りタイヤは、低発熱性能、および耐摩耗性に優れる。
ADVANTAGE OF THE INVENTION The rubber composition of this invention can provide the rubber composition which is excellent in abrasion resistance, maintaining high low heat build-up.
Moreover, the pneumatic tire formed from the rubber composition of the present invention is excellent in low heat build-up performance and wear resistance.
<ジエン系ゴム(A)>
本発明のゴム組成物に含まれる成分の一つであるジエン系ゴム(A)は、主鎖に二重結合を有するものであれば特に限定されない。ジエン系ゴムとしては、例えば、天然ゴム(NR)、イソプレンゴム(IR)、ブタジエンゴム(BR)、芳香族ビニル-共役ジエン共重合ゴム、クロロプレンゴム(CR)、アクリロニトリルブタジエンゴム(NBR)、エチレン-プロピレン-ジエン共重合体ゴム(EPDM)、スチレン-イソプレンゴム、イソプレン-ブタジエンゴム、ニトリルゴム、水添ニトリルゴム等が挙げられる。
<Diene rubber (A)>
The diene rubber (A), which is one of the components contained in the rubber composition of the present invention, is not particularly limited as long as it has a double bond in its main chain. Diene rubbers include, for example, natural rubber (NR), isoprene rubber (IR), butadiene rubber (BR), aromatic vinyl-conjugated diene copolymer rubber, chloroprene rubber (CR), acrylonitrile butadiene rubber (NBR), ethylene - propylene-diene copolymer rubber (EPDM), styrene-isoprene rubber, isoprene-butadiene rubber, nitrile rubber, hydrogenated nitrile rubber, and the like.
本発明に係るジエン系ゴム(A)はそれぞれ単独でまたは2種以上を組み合わせて使用することができる。これらジエン系ゴムのなかでも、芳香族ビニル-共役ジエン共重合ゴム、NR、BRが好ましい。
芳香族ビニル-共役ジエン共重合ゴムとしては、例えば、スチレン-ブタジエンゴム(SBR)、スチレン-イソプレンゴムが挙げられる。なかでもSBRが好ましい。
The diene rubber (A) according to the present invention can be used either alone or in combination of two or more. Among these diene rubbers, aromatic vinyl-conjugated diene copolymer rubbers, NR and BR are preferred.
Examples of aromatic vinyl-conjugated diene copolymer rubber include styrene-butadiene rubber (SBR) and styrene-isoprene rubber. Among them, SBR is preferable.
本発明に係るジエン系ゴム(A)の重量平均分子量は特に限定されないが、加工性の観点から、50,000~3,000,000であることが好ましく、100,000~2,000,000がより好ましい。なお、ジエン系ゴムの重量平均分子量(Mw)は、テトラヒドロフランを溶媒とするゲルパーミエーションクロマトグラフィー(GPC)による測定値をもとにした標準ポリスチレン換算値である。 Although the weight average molecular weight of the diene rubber (A) according to the present invention is not particularly limited, it is preferably 50,000 to 3,000,000, more preferably 100,000 to 2,000,000 from the viewpoint of workability. is more preferred. The weight average molecular weight (Mw) of the diene rubber is a standard polystyrene conversion value based on a measurement by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.
本発明に係るジエン系ゴム(A)は、空気入りタイヤを形成できる限り、特に限定はされないが、ムーニー粘度〔ML(1+4)100℃,JIS K6300〕が20~120のものが好ましく、40~80がより好ましい。 The diene rubber (A) according to the present invention is not particularly limited as long as it can form a pneumatic tire. 80 is more preferred.
<充填剤(B)>
本発明のゴム組成物に含まれる成分の一つである充填剤(B)は、ゴムや樹脂に添加される補強剤や無機充填剤であり、種々、公知の充填剤(B)を用い得る。
<Filler (B)>
The filler (B), which is one of the components contained in the rubber composition of the present invention, is a reinforcing agent or inorganic filler added to rubber or resin, and various known fillers (B) can be used. .
〈補強剤〉
補強剤は、架橋ゴムの引張強度、引き裂き強度、耐摩耗性などの機械的性質を高める効果がある。このような補強剤としては、特に限定されないが、たとえば、カーボンブラック、グラファイト、シランカップリング剤などにより表面処理が施されているこれらのカーボンブラック、微粉ケイ酸、シリカ、アルミナ、酸化マグネシウム、酸化バリウム、酸化カルシウムなどの酸化物系フィラー、水酸化アルミニウム、水酸化マグネシウムなどの水酸化物系フィラー、珪藻土、石灰岩などの堆積岩系フィラー、カオリナイト、モンモリオナイトなどの粘土鉱物系フィラー、フェライト、鉄、コバルトなどの磁性系フィラー、銀、金、銅、合金などの導電性フィラーなどが挙げられる。中でも、カーボンブラックとシリカを含有することが好ましい。
<Reinforcing agent>
Reinforcing agents have the effect of enhancing mechanical properties such as tensile strength, tear strength, and wear resistance of crosslinked rubber. Examples of such reinforcing agents include, but are not limited to, carbon black, graphite, carbon black surface-treated with a silane coupling agent or the like, finely divided silicic acid, silica, alumina, magnesium oxide, oxide Oxide fillers such as barium and calcium oxide, hydroxide fillers such as aluminum hydroxide and magnesium hydroxide, sedimentary rock fillers such as diatomaceous earth and limestone, clay mineral fillers such as kaolinite and montmorillonite, ferrite, Examples include magnetic fillers such as iron and cobalt, and conductive fillers such as silver, gold, copper and alloys. Among them, it is preferable to contain carbon black and silica.
〈カーボンブラック(B1)〉
本発明に係るカーボンブラック(B1)としては、SAF、ISAF、HAF、EPC、XCF、FEF、GPF、HMF、SRF、FT、MTなどが挙げられる。これらは、単独で用いてもよく、2種以上を併用してもよい。
<Carbon black (B1)>
Examples of carbon black (B1) according to the present invention include SAF, ISAF, HAF, EPC, XCF, FEF, GPF, HMF, SRF, FT and MT. These may be used alone or in combination of two or more.
本発明に係るカーボンブラック(B-1)は、通常、窒素吸着比表面積(N2SA)が70~200m2/gであり、好ましくは100~170m2/gである。カーボンブラック(B1)の窒素吸着比表面積は、JIS K6217-2:2001によって求められる。 Carbon black (B-1) according to the present invention usually has a nitrogen adsorption specific surface area (N 2 SA) of 70 to 200 m 2 /g, preferably 100 to 170 m 2 /g. The nitrogen adsorption specific surface area of carbon black (B1) is determined according to JIS K6217-2:2001.
本発明に係るカーボンブラック(B1)は、通常、ジブチルフタレート吸油量(DBP)が50~200mL/100gであり、好ましくは100~150mL/100gである。カーボンブラックのDBPは、JIS-K6217-4:2001に準拠して測定できる。 Carbon black (B1) according to the present invention usually has a dibutyl phthalate oil absorption (DBP) of 50 to 200 mL/100 g, preferably 100 to 150 mL/100 g. The DBP of carbon black can be measured according to JIS-K6217-4:2001.
本発明に係るカーボンブラック(B1)は、通常、平均粒子径が8~25nmであり、好ましくは10~20nmである。なお、カーボンブラック(B1)の平均粒子径は、数平均粒子径であり、透過型電子顕微鏡により測定される。 Carbon black (B1) according to the present invention usually has an average particle size of 8 to 25 nm, preferably 10 to 20 nm. The average particle size of carbon black (B1) is the number average particle size and is measured with a transmission electron microscope.
本発明に係るカーボンブラック(B1)は市販されており、例えば、旭カーボン(株)、キャボットジャパン(株)、東海カーボン(株)、三菱化学(株)、ライオン(株)、新日化カーボン(株)、コロンビアカーボン社等の製品を使用できる。 Carbon black (B1) according to the present invention is commercially available, for example, Asahi Carbon Co., Ltd., Cabot Japan Co., Ltd., Tokai Carbon Co., Ltd., Mitsubishi Chemical Co., Ltd., Lion Corporation, Shin Nikka Carbon Products of Co., Ltd., Columbia Carbon Co., etc. can be used.
〈シリカ(B2)〉
本発明に係るシリカ(B2)としては特に限定されず、例えば、乾式法シリカ(無水ケイ酸)、湿式法シリカ(含水ケイ酸)などが挙げられる。これらは、単独で用いてもよく、2種以上を併用してもよい。なかでも、シラノール基が多いという理由から、湿式法シリカが好ましい。これらのシリカは、ヘキサメチルジシラザン、クロロシラン、アルコキシシラン等の反応性シランあるいは低分子量のシロキサン等で表面処理されていてもよい。
<Silica (B2)>
The silica (B2) according to the present invention is not particularly limited, and examples thereof include dry silica (anhydrous silicic acid) and wet silica (hydrous silicic acid). These may be used alone or in combination of two or more. Among them, wet-process silica is preferable because it has many silanol groups. These silicas may be surface-treated with reactive silanes such as hexamethyldisilazane, chlorosilane and alkoxysilane, or with low-molecular-weight siloxanes.
本発明に係るシリカ(B2)は、通常、窒素吸着比表面積(N2SA)が50~300m2/gであり、好ましくは150~250m2/gである。シリカ(B2)のN2SAは、ASTM D3037-81に準拠して測定できる。 Silica (B2) according to the present invention usually has a nitrogen adsorption specific surface area (N 2 SA) of 50 to 300 m 2 /g, preferably 150 to 250 m 2 /g. The N 2 SA of silica (B2) can be measured according to ASTM D3037-81.
本発明に係るシリカ(B2)は市販されており、例えば、デグッサ社、ローディア社、東ソー・シリカ(株)、ソルベイジャパン(株)、(株)トクヤマ等の製品を使用できる。 Silica (B2) according to the present invention is commercially available, and for example, products of Degussa, Rhodia, Tosoh Silica, Solvay Japan, Tokuyama, etc. can be used.
〈無機充填剤〉
本発明に係る無機充填剤としては、特に限定されないが、例えば、軽質炭酸カルシウム、重質炭酸カルシウム、タルク、クレーなどが挙げられる。これらの無機充填材は、目的に応じて、単独で、あるいは2種以上組み合わせて用いることができる。
<Inorganic filler>
The inorganic filler according to the present invention is not particularly limited, but examples thereof include light calcium carbonate, heavy calcium carbonate, talc, clay and the like. These inorganic fillers can be used alone or in combination of two or more depending on the purpose.
<酸変性ポリエチレン(C)>
本発明のゴム組成物に含まれる成分の一つである酸変性ポリエチレン(C)は、変性基としてカルボキシ基又は酸無水物基を有し、主鎖がポリエチレンであるグラフト変性重合体で、密度が0.950~0.980g/cm3の好ましくは0.955~0.975g/cm3、さらに好ましくは、0.960~0.970g/cm3の範囲にある。
酸変性ポリエチレン(C)として、上記範囲の密度を有する酸変性ポリエチレンを用いるとゴム組成物から得られる成形体は、より耐摩耗性に優れる。
<Acid-modified polyethylene (C)>
The acid-modified polyethylene (C), which is one of the components contained in the rubber composition of the present invention, is a graft-modified polymer having a carboxy group or an acid anhydride group as a modifying group and a polyethylene main chain. is in the range of 0.950 to 0.980 g/cm 3 , preferably 0.955 to 0.975 g/cm 3 , more preferably 0.960 to 0.970 g/cm 3 .
When an acid-modified polyethylene having a density within the above range is used as the acid-modified polyethylene (C), the molded article obtained from the rubber composition is more excellent in abrasion resistance.
〈ポリエチレン〉
酸変性ポリエチレン(C)の主鎖であるポリエチレンは、エチレンの単独重合体、若しくは、エチレンと炭素数3以上のα-オレフィン、具体的には、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、1-ウンデセン、1-ドデセン、1-トリデセン、1-テトラデセン、1-ペンタデセン、1-ヘキサデセン、1-ヘプタデセン、1-オクタデセン、1-ノナデセン、1-エイコセン等のα-オレフィンとの共重合体であり、通常、高密度ポリエチレン、中密度ポリエチレンなどの名称で、製造販売されている。
<polyethylene>
The polyethylene that is the main chain of the acid-modified polyethylene (C) is an ethylene homopolymer, or ethylene and an α-olefin having 3 or more carbon atoms, specifically propylene, 1-butene, 1-pentene, 1- hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, It is a copolymer with α-olefin such as 1-eicosene, and is usually manufactured and sold under the names of high-density polyethylene, medium-density polyethylene, and the like.
本発明に係るポリエチレンは、通常、密度が0.950-0.980g/cm3、好ましくは0.955~0.975g/cm3、より好ましくは0.960~0.970g/cm3の範囲にある。 The polyethylene according to the present invention usually has a density in the range of 0.950-0.980 g/cm 3 , preferably 0.955-0.975 g/cm 3 , more preferably 0.960-0.970 g/cm 3 It is in.
また、本発明に係るポリエチレンは、通常、JIS K 7210に準拠し、190℃、2.16kg荷重(kgf)の条件下で測定されるメルトフローレート(MFR)が、0.1~20g/10分、好ましくは0.1~15.0g/10分の範囲にある。 Further, the polyethylene according to the present invention usually has a melt flow rate (MFR) of 0.1 to 20 g/10 measured under conditions of 190° C. and a load of 2.16 kg (kgf) in accordance with JIS K 7210. minutes, preferably in the range 0.1 to 15.0 g/10 minutes.
〈変性基〉
本発明に係る酸変性ポリエチレン(C)の変性基は、カルボキシ基又は酸無水物基を有する基である。
かかる変性基は、不飽和カルボン酸又は不飽和カルボン酸無水物を上記ポリエチレンに、グラフト変性することのより変性される基である。
<Modifying group>
The modifying group of the acid-modified polyethylene (C) according to the present invention is a group having a carboxy group or an acid anhydride group.
Such modified groups are groups modified by graft-modifying unsaturated carboxylic acids or unsaturated carboxylic acid anhydrides to the polyethylene.
不飽和カルボン酸、および不飽和カルボン酸無水物としては、例えば、マレイン酸、フマル酸、(メタ)アクリル酸、クロトン酸、イタコン酸、これらの各酸の酸無水物などが挙げられる。
これらのうち、無水マレイン酸がとくに好ましい。
Examples of unsaturated carboxylic acids and unsaturated carboxylic anhydrides include maleic acid, fumaric acid, (meth)acrylic acid, crotonic acid, itaconic acid, and acid anhydrides of these acids.
Of these, maleic anhydride is particularly preferred.
〈酸変性ポリエチレン(C)の製造方法〉
本発明に係る酸変性ポリエチレン(C)は、上記ポリエチレンを上記不飽和カルボン酸又不飽和カルボン酸無水物でグラフト変性する方法は、公知の種々の方法を採用することができる。具体的には、例えば、押出機を使用して、ポリエチレンを溶融し、そこに不飽和カルボン酸および/または不飽和カルボン酸無水物を添加してグラフト反応させる方法、あるいはポリエチレンを溶媒に溶解して溶液とし、そこに不飽和カルボン酸または不飽和カルボン酸無水物を添加してグラフト反応させる方法などが挙げられる。いずれの場合にも前記不飽和カルボン酸および/または不飽和カルボン酸無水物を効率よくグラフト共重合させるためには、ラジカル開始剤の存在下にグラフト反応を実施することが好ましい。グラフト反応は、通常60~350℃の条件で行われる。ラジカル開始剤の使用割合は変性前のポリエチレン100質量部に対して、通常0.001~1質量部の範囲である。
<Method for producing acid-modified polyethylene (C)>
For the acid-modified polyethylene (C) according to the present invention, various known methods can be employed for graft-modifying the above-mentioned polyethylene with the above-mentioned unsaturated carboxylic acid or unsaturated carboxylic acid anhydride. Specifically, for example, an extruder is used to melt polyethylene, and an unsaturated carboxylic acid and/or an unsaturated carboxylic acid anhydride is added thereto for graft reaction, or a method in which polyethylene is dissolved in a solvent. a solution, and an unsaturated carboxylic acid or an unsaturated carboxylic acid anhydride is added thereto for graft reaction. In any case, the graft reaction is preferably carried out in the presence of a radical initiator in order to efficiently graft-copolymerize the unsaturated carboxylic acid and/or unsaturated carboxylic acid anhydride. The graft reaction is usually carried out at 60-350°C. The ratio of the radical initiator to be used is usually in the range of 0.001 to 1 part by mass per 100 parts by mass of polyethylene before modification.
ラジカル開始剤としては、有機ペルオキシドが好ましく、例えばベンゾイルペルオキシド、ジクロルベンゾイルペルオキシド、ジクミルペルオキシド、ジ-tert-ブチルペルオキシド、2,5-ジメチル-2,5-ジ(ペルオキシドベンゾエート)ヘキシン-3、1,4-ビス(tert-ブチルペルオキシイソプロピル)ベンゼン、ラウロイルペルオキシド、tert-ブチルペルアセテート、2,5-ジメチル-2,5-ジ(tert-ブチルペルオキシ)ヘキシン-3、2,5-ジメチル-2.5-ジ(tert-ブチルペルオキシ)ヘキサン、tert-ブチルペルベンゾエート、tert-ブチルペルフェニルアセテート、tert-ブチルペルイソブチレート、tert-ブチルペル-sec-オクトエート、tert-ブチルペルピバレート、クミルペルピバレートおよびtert-ブチルペルジエチルアセテートなどが挙げられる。その他アゾ化合物、例えばアゾビスイソブチロニトリル、ジメチルアゾイソブチレートなどを用いることもできる。 As radical initiators, organic peroxides are preferred, such as benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(peroxidobenzoate)hexyne-3, 1,4-bis(tert-butylperoxyisopropyl)benzene, lauroyl peroxide, tert-butylperacetate, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexyne-3,2,5-dimethyl- 2.5-di(tert-butylperoxy)hexane, tert-butyl perbenzoate, tert-butyl perphenylacetate, tert-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, chloro Examples include mil perpivalate and tert-butyl perdiethyl acetate. Other azo compounds such as azobisisobutyronitrile and dimethylazoisobutyrate can also be used.
≪ゴム組成物≫
本発明のゴム組成物は、上記ジエン系ゴム(A)、充填剤(B)、および、上記酸変性ポリエチレン(C)を含み、充填剤(B)がカーボンブラック(B1)およびシリカ(B2)を含み、酸変性ポリエチレン(C)の含有量が、ジエン系ゴム(A)100質量部に対して、1~9質量部、好ましくは1~6質量部、さらに好ましくは3~6質量部の範囲で含み、カーボンブラック(B1)の質量をWA、シリカ(B2)の質量をWB、酸変性ポリエチレン(C)の質量をWXとした場合に、WX/(WA+WB)が0.01~0.16、好ましくは0.03-0.16、より好ましくは0.04~0.11、さらに好ましくは0.04~0.08の範囲にある。
<<Rubber composition>>
The rubber composition of the present invention contains the diene rubber (A), the filler (B), and the acid-modified polyethylene (C), and the filler (B) is carbon black (B1) and silica (B2). and the content of the acid-modified polyethylene (C) is 1 to 9 parts by mass, preferably 1 to 6 parts by mass, more preferably 3 to 6 parts by mass with respect to 100 parts by mass of the diene rubber (A) When the mass of carbon black (B1) is WA, the mass of silica (B2) is WB, and the mass of acid-modified polyethylene (C) is WX, WX/(WA+WB) is from 0.01 to 0.01. 16, preferably 0.03-0.16, more preferably 0.04-0.11, still more preferably 0.04-0.08.
本発明のゴム組成物は、酸変性ポリエチレン(C)を上記範囲で含むことにより、耐摩耗がより改良された成形体が得られる。
また、本発明のゴム組成物は、ゴム組成物に含まれる酸変性ポリエチレン(C)の質量(WX)とカーボンブラック(B1)の質量(WA)とシリカ(B2)の質量(WB)の合計量(WA+WB)との比〔WX/(WA+WB)〕が上記範囲にあると、耐摩耗がより改良された成形体が得られる。
By containing the acid-modified polyethylene (C) in the above range, the rubber composition of the present invention can provide a molded article with improved abrasion resistance.
Further, the rubber composition of the present invention is the sum of the weight (WX) of acid-modified polyethylene (C), the weight (WA) of carbon black (B1), and the weight (WB) of silica (B2) contained in the rubber composition. When the ratio [WX/(WA+WB)] to the amount (WA+WB) is within the above range, a molded article having improved wear resistance can be obtained.
本発明のゴム組成物は、ジエン系ゴム(A)100質量部に対するカーボンブラック(B1)充填剤(B)の含有量は、通常、1~100質量部であり、好ましくは1~50質量部である。
また、ジエン系ゴム(A)100質量部に対するシリカ(B2)の含有量は、通常、10~100質量部であり、好ましくは20~80質量部である。
In the rubber composition of the present invention, the content of carbon black (B1) filler (B) with respect to 100 parts by mass of diene rubber (A) is usually 1 to 100 parts by mass, preferably 1 to 50 parts by mass. is.
The content of silica (B2) is usually 10 to 100 parts by mass, preferably 20 to 80 parts by mass, based on 100 parts by mass of diene rubber (A).
本発明のゴム組成物は、上記ジエン系ゴム(A)、カーボンブラック(B1)およびシリカ(B2)を含む上記充填剤(B)、並びに上記酸変性ポリエチレン(C)に加え、必要に応じて、その他の成分、例えば、シランカップリング剤、架橋剤、可塑剤、加硫促進剤、共架橋剤、加硫助剤、加工助剤、老化防止剤、活性剤等の種々の添加剤が挙げられる。また、必要に応じて、公知の発泡剤、発泡助剤、着色剤、分散剤、難燃剤、耐熱安定剤、耐候安定剤、帯電防止剤、着色剤、滑剤および増粘剤等もその他の成分として用いうる。 The rubber composition of the present invention contains the diene rubber (A), the filler (B) containing carbon black (B1) and silica (B2), and the acid-modified polyethylene (C), and optionally , Other components such as silane coupling agents, cross-linking agents, plasticizers, vulcanization accelerators, co-crosslinking agents, vulcanization aids, processing aids, anti-aging agents, various additives such as activators. be done. In addition, known foaming agents, foaming assistants, colorants, dispersants, flame retardants, heat stabilizers, weather stabilizers, antistatic agents, colorants, lubricants, thickeners, etc. may also be used as other components, if necessary. can be used as
《その他の成分》
〈シランカップリング剤〉
本発明のゴム組成物に配合されるシランカップリング剤しては、例えば、ビニルトリメトキシシラン、ビニルトリエトキシシラン、ビニルトリス(2-メトキシエトキシ)シラン、ビニルトリクロルシラン、N-(2-アミノエチル)-3-アミノプロピルメチルジメトキシシラン、N-(2-アミノエチル)-3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、N-2-(アミノエチル)-3-アミノプロピルトリエトキシシラン、3-アミノプロピルトリメトキシシラン、3-アミノプロピルトリエトキシシラン、N-フェニル-3-アミノプロピルトリメトキシシラン、3-グリシドキシプロピルトリメトキシシラン、3-グリシドキシプロピルトリエトキシシラン、3-グリシドキシプロピルメチルジメトキシシラン、3-グリシドキシプロピルメチルジエトキシシラン、2-(3,4-エポキシシクロヘキシル)エチルトリメトキシシラン、3-イソシアネートプロピルトリエトキシシラン、3-メタクリロキシプロピルトリメトキシシラン、3-メタクリロキシプロピルメチルジメトキシシラン、3-メタクリロキシプロピルメチルジエトキシシラン、3-メタクリロキシプロピルトリエトキシシラン、3-メルカプトプロピルトリメトキシシラン、3-ウレイドプロピルトリエトキシシラン、N-(1,3-ジメチルブチリデン)-3-(トリエトキシシリル)-1-プロパンアミン、N,N'-ビス(3-(トリメトキシシリル)プロピル)エチレンジアミン、ポリオキシエチレンプロピルトリアルコキシシラン、ポリエトキシジメチルシロキサン、p-スチリルトリメトキシシラン、3-アクリロキシプロピルトリメトキシシランが挙げられる。
《Other Ingredients》
<Silane coupling agent>
Examples of the silane coupling agent blended in the rubber composition of the present invention include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, vinyltrichlorosilane, N-(2-aminoethyl )-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltri methoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-( 1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propanamine, N,N'-bis(3-(trimethoxysilyl)propyl)ethylenediamine, polyoxyethylenepropyltrialkoxysilane, polyethoxy dimethylsiloxane, p-styryltrimethoxysilane, 3-acryloxypropyltrimethoxysilane.
本発明のゴム組成物が、シランカップリング剤を含む場合は、その配合量は、ジエン系ゴム(A)100質量部に対して、0.2~10質量部、好ましくは0.5~9質量部、さらに好ましくは1~8質量部の範囲である。 When the rubber composition of the present invention contains a silane coupling agent, the amount thereof is 0.2 to 10 parts by mass, preferably 0.5 to 9 parts by mass, per 100 parts by mass of the diene rubber (A). parts by weight, more preferably in the range of 1 to 8 parts by weight.
〈加硫剤〉
本発明のゴム組成物に配合される加硫剤は、上記ジエン系ゴム(A)が加硫可能である限り特に限定されず、硫黄系化合物、過酸化物系架橋剤などゴムの分野において通常用いられる種々のものであってもよい。
<Vulcanizing agent>
The vulcanizing agent to be blended in the rubber composition of the present invention is not particularly limited as long as the diene rubber (A) can be vulcanized. Various materials may be used.
本発明においては、好適な加硫剤として、イオウ系化合物が挙げられる。イオウ系化合物によりゴム組成物を架橋することで、ジクミルパーオキサイド等の過酸化物系架橋剤を用いた場合と比べて、成形体に同等の低温特性を与えつつ、格段に優れた柔軟性や機械的特性を付与することができる。 Suitable vulcanizing agents in the present invention include sulfur compounds. By cross-linking the rubber composition with a sulfur-based compound, compared to the case where a peroxide-based cross-linking agent such as dicumyl peroxide is used, the same low-temperature properties are imparted to the molded product, while significantly superior flexibility is achieved. and mechanical properties can be imparted.
イオウ系化合物の種類としては、イオウ、塩化イオウ、二塩化イオウ、モルフォリンジスルフィド、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、ジチオカルバミン酸セレン等が挙げられる。この中でも、イオウやテトラメチルチウラムジスルフィドが好ましい。 Types of sulfur compounds include sulfur, sulfur chloride, sulfur dichloride, morpholine disulfide, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate, and the like. Among these, sulfur and tetramethylthiuram disulfide are preferred.
一方、ジエン系ゴム(A)の種類によっては、加硫剤として過酸化物系架橋剤を用いることもできる。 On the other hand, depending on the type of diene rubber (A), a peroxide cross-linking agent may be used as a vulcanizing agent.
過酸化物系架橋剤としては、
1,1-ビス(t-ブチルパーオキシ)-3,3,5-トリメチルシクロヘキサン、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン、2,2-ビス(t-ブチルパーオキシ)オクタン、1,1-ビス(t-ブチルパーオキシ)シクロドデカンなどのパーオキシケタール、並びに、
ジ-t-ブチルパーオキサイド、t-ブチルクミルパーオキサイド、ジクミルパーオキサイド、α、α'-ビス(t-ブチルパーオキシ-m-イソプロピル)ベンゼン、2,5-ジメチル-2,5-ジ(t-ブチルパーオキシ)ヘキシン-3、t-ブチルパーオキシ-2-エチルヘキサノエート、t-ブチルパーオキシ-3,5,5-トリメチルヘキサノエート、2,5-ジメチル-2,5-ジ(ベンゾイルパーオキシ)ヘキサンなどのジアルキルパーオキサイド等が挙げられる。
As a peroxide-based cross-linking agent,
1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)octane, peroxyketals such as 1,1-bis(t-butylperoxy)cyclododecane, and
Di-t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di (t-butylperoxy)hexyne-3, t-butylperoxy-2-ethylhexanoate, t-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5 -Dialkyl peroxides such as di(benzoylperoxy)hexane.
本発明のゴム組成物が、加硫剤を含む場合は、その配合量は、ジエン系ゴム(A)100質量部に対して、0.2~15質量部、好ましくは0.3~10質量部、さらに好ましくは1~7質量部である。 When the rubber composition of the present invention contains a vulcanizing agent, the amount thereof is 0.2 to 15 parts by mass, preferably 0.3 to 10 parts by mass, per 100 parts by mass of the diene rubber (A). parts, more preferably 1 to 7 parts by mass.
〈可塑剤〉
本発明のゴム組成物は、その用途に応じて、可塑剤、具体的には、ゴムの分野において軟化剤として一般的に用いられる公知の可塑剤をさらに含んでいてもよい。
<Plasticizer>
The rubber composition of the present invention may further contain a plasticizer, specifically a known plasticizer generally used as a softener in the field of rubber, depending on its use.
このような可塑剤の具体例としては、プロセスオイル、潤滑油、パラフィン油、流動パラフィン、石油アスファルト、およびワセリン等の石油系軟化剤;コールタール、およびコールタールピッチ等のコールタール系軟化剤;ひまし油、アマニ油、ナタネ油、大豆油、およびヤシ油等の脂肪油系軟化剤;蜜ロウ、カルナウバロウ、およびラノリン等のロウ類;リシノール酸、パルミチン酸、ステアリン酸、ステアリン酸バリウム、ステアリン酸カルシウム、およびラウリン酸亜鉛等の脂肪酸またはその塩;ナフテン酸、パイン油、およびロジンまたはその誘導体;テルペン樹脂、石油樹脂、アタクチックポリプロピレン、およびクマロンインデン樹脂等の合成高分子物質;ジオクチルフタレート、ジオクチルアジペート、およびジオクチルセバケート等のエステル系軟化剤;その他、マイクロクリスタリンワックス、液状ポリブタジエン、変性液状ポリブタジエン、液状チオコール、炭化水素系合成潤滑油、トール油、およびサブ(ファクチス)などが挙げられる。なかでも、石油系軟化剤が好ましい。石油系軟化剤の中では、石油系プロセスオイルが好ましく、この中でもパラフィン系プロセスオイル、ナフテン系プロセスオイル、アロマ系プロセスオイル(芳香族系プロセスオイル)等がさらに好ましい。 Specific examples of such plasticizers include petroleum softeners such as process oils, lubricating oils, paraffin oil, liquid paraffin, petroleum asphalt, and petrolatum; coal tar softeners such as coal tar and coal tar pitch; Fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, and coconut oil; waxes such as beeswax, carnauba wax, and lanolin; ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, fatty acids such as and zinc laurate or salts thereof; naphthenic acid, pine oil, and rosin or derivatives thereof; synthetic polymeric substances such as terpene resins, petroleum resins, atactic polypropylene, and coumarone-indene resins; dioctyl phthalate, dioctyl adipate , and ester softeners such as dioctyl sebacate; others include microcrystalline wax, liquid polybutadiene, modified liquid polybutadiene, liquid thiocol, hydrocarbon-based synthetic lubricating oils, tall oil, and sub (factice). Among them, petroleum-based softeners are preferred. Among petroleum-based softeners, petroleum-based process oils are preferred, and paraffinic process oils, naphthenic process oils, aromatic process oils (aromatic process oils), and the like are more preferred.
ここで、上記可塑剤の含有量は、その用途により適宜選択でき、通常、ジエン系ゴム(A)100質量部に対して、最大200質量部、好ましくは最大150質量部、より好ましくは最大130質量部が望ましい。 Here, the content of the plasticizer can be appropriately selected depending on the application. Parts by mass are preferred.
〈加硫促進剤〉
本発明に係るゴム組成物は、上記成分に加え加硫促進剤をさらに含んでいてもよい。
加硫促進剤の具体例としては、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(例えば、「サンセラーCM」(商品名;三新化学工業株式会社製)など)、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、N-(tert-2-ベンゾチアゾールスルフェンアミド(略号:TBBS)(例えば、「サンセラーNS-G」(商品名;三新化学工業株式会社製)など)、2-メルカプトベンゾチアゾール(例えば、「サンセラーM」(商品名;三新化学工業株式会社製)など)、2-(4-モルホリノジチオ)ペンゾチアゾール(例えば、「ノクセラーMDB-P」(商品名;三新化学工業株式会社製)など)、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-モルフォリノチオ)ベンゾチアゾール、ジベンゾチアジルジスルフィド等のチアゾール系;ジフェニルグアニジン(略号:DPG)(例えば、「サンセラーD、サンセラーD-G」(商品名;三新化学工業株式会社製)など)、トリフェニルグアニジン、ジオルソトリルグアニジン等のグアニジン系;アセトアルデヒド-アニリン縮合物、ブチルアルデヒド-アニリン縮合物、アルデヒドアミン系;2-メルカプトイミダゾリン等のイミダゾリン系;ジエチルチオウレア、ジブチルチオウレア等のチオウレア系;テトラメチルチウラムモノスルフィド、ジベンゾチアジルジスルフィド(略号:MBTS)(例えば、「サンセラーDM、サンセラーDM-G」(商品名:(商品名;三新化学工業株式会社製)など)、テトラメチルチウラムジスルフィド(例えば、「サンセラーTT」(商品名;三新化学工業株式会社製)など)等のチウラム系;ジメチルジチオカルバミン酸亜鉛、ジエチルジチオカルバミン酸亜鉛、ジブチルジチオカルバミン酸亜鉛(例えば、「サンセラーBZ」(商品名;三新化学工業株式会社製)など)、ジエチルジチオカルバミン酸テルル等のジチオ酸塩系;エチレンチオ尿素(例えば、「サンセラー22-C」(商品名;三新化学工業株式会社製)など)、N,N'-ジエチルチオ尿素等のチオウレア系;ジブチルキサトゲン酸亜鉛等のザンテート系;その他亜鉛華(例えば、「META-Z102」(商品名;井上石灰工業株式会社製)などの酸化亜鉛)等が挙げられる。
<Vulcanization accelerator>
The rubber composition according to the present invention may further contain a vulcanization accelerator in addition to the above components.
Specific examples of vulcanization accelerators include N-cyclohexyl-2-benzothiazolesulfenamide (e.g., "Suncellar CM" (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), N-oxydiethylene-2- Benzothiazolesulfenamide, N,N'-diisopropyl-2-benzothiazolesulfenamide, N-(tert-2-benzothiazolesulfenamide (abbreviation: TBBS) (for example, "Suncellar NS-G" (trade name ; manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), 2-mercaptobenzothiazole (e.g., "Sancellar M" (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), 2-(4-morpholinodithio) benzothiazole (For example, "Nocceler MDB-P" (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), etc.), 2-(2,4-dinitrophenyl)mercaptobenzothiazole, 2-(2,6-diethyl-4-morpho thiazoles such as benzothiazole and dibenzothiazyl disulfide; Guanidine series such as phenylguanidine and diorthotolylguanidine; acetaldehyde-aniline condensate, butyraldehyde-aniline condensate, aldehyde amine series; imidazoline series such as 2-mercaptoimidazoline; thiourea series such as diethylthiourea and dibutylthiourea; Thiuram monosulfide, dibenzothiazyl disulfide (abbreviation: MBTS) (e.g., "Sancera DM, Sansera DM-G" (trade name: (trade name; manufactured by Sanshin Chemical Co., Ltd.), etc.), tetramethylthiuram disulfide (e.g., , "Suncellar TT" (trade name; manufactured by Sanshin Chemical Industry Co., Ltd.), etc.); Shin Kagaku Kogyo Co., Ltd.), etc.), dithioate salts such as tellurium diethyldithiocarbamate; '-Thiourea-based such as diethylthiourea; xanthate-based such as zinc dibutylxatate; and other zinc white (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)) and the like. .
本発明のゴム組成物が加硫促進剤を含む場合は、その含有量は、ジエン系ゴム(A)100質量部に対して、好ましくは0.1~15質量部、より好ましくは0.5~10質量部である。このような含有量でゴム組成物に加硫促進剤が含まれることにより、ゴム組成物が優れた架橋特性を有し、得られる成形体からのブルームの発生がより低減する。 When the rubber composition of the present invention contains a vulcanization accelerator, its content is preferably 0.1 to 15 parts by mass, more preferably 0.5 parts by mass, based on 100 parts by mass of the diene rubber (A). ~10 parts by mass. By including the vulcanization accelerator in such a content in the rubber composition, the rubber composition has excellent cross-linking properties, and the occurrence of bloom in the resulting molded article is further reduced.
〈共架橋剤〉
上記架橋剤として過酸化物系架橋剤を用いる場合には、ゴム組成物の加硫速度改善や、得られる成形体の物性などを目的として、必要に応じて、適宜な共架橋剤をさらに含むことができる。
<Co-crosslinking agent>
When a peroxide-based cross-linking agent is used as the cross-linking agent, an appropriate co-cross-linking agent is further included as necessary for the purpose of improving the vulcanization speed of the rubber composition and the physical properties of the resulting molded product. be able to.
共架橋剤の例として、ブレンマーPDE-100(日本油脂株式会社製商品名)の如きポリエチレングリコールジメタクリレート(PEGDM)、ジアリルフタレート(DAP)、タイク(日本化成株式会社製商品名)の如きトリアリルイソシアヌレート(TAIC)、タック(株式会社武蔵野化学研究所製商品名)の如きトリアリルシアヌレート(TAC)、アクリエステルTHF(三菱レーヨン株式会社製商品名)の如きメタクリル酸テトラヒドロフルフリル(THFMA)、サンエステルEG(三新化学工業株式会社製商品名)やアクリエステルED(三菱レーヨン株式会社製商品名)の如きジメタクリル酸エチレン(EDMA)、アクリエステルBD(三菱レーヨン株式会社製商品名)の如きジメタクリル酸1,3-ブチレン(BDMA)、サンエステルTMPMA(三新化学工業株式会社製商品名)やアクリエステルTMP(三菱レーヨン株式会社製商品名)やハイクロスM(精工化学株式会社製商品名)の如きトリメタクリル酸トリメチロールプロパン(TMPMA)などが挙げられる。 Examples of co-crosslinking agents include polyethylene glycol dimethacrylate (PEGDM) such as Blemmer PDE-100 (trade name manufactured by NOF Co., Ltd.), diallyl phthalate (DAP), triallyl such as Tyke (trade name manufactured by Nippon Kasei Co., Ltd.) isocyanurate (TAIC), triallyl cyanurate (TAC) such as TAC (trade name manufactured by Musashino Chemical Laboratory Co., Ltd.), tetrahydrofurfuryl methacrylate (THFMA) such as acrylic THF (trade name manufactured by Mitsubishi Rayon Co., Ltd.) , Ethylene dimethacrylate (EDMA) such as Sunester EG (manufactured by Sanshin Chemical Industry Co., Ltd.) and Acryester ED (manufactured by Mitsubishi Rayon Co., Ltd.), Acryester BD (manufactured by Mitsubishi Rayon Co., Ltd.) 1,3-butylene dimethacrylate (BDMA) such as Sunester TMPMA (manufactured by Sanshin Chemical Industry Co., Ltd.), Acryester TMP (manufactured by Mitsubishi Rayon Co., Ltd.) and Hicross M (Seiko Chemical Co., Ltd.) product name), and trimethylolpropane trimethacrylate (TMPMA).
本発明のゴム組成物が共架橋剤を含む場合は、その量は、ジエン系ゴム(A)100質量部に対して、1~10質量部程度が適当である。
またこの態様のゴム組成物においては、過酸化物系架橋剤を用いた架橋の際にメタクリル酸エステルやタイク(日本化成株式会社)の如きトリアリルイソシアヌレート(TAIC)、などを加硫助剤としてさらに添加してもよい。
When the rubber composition of the present invention contains a co-crosslinking agent, the appropriate amount thereof is about 1 to 10 parts by mass with respect to 100 parts by mass of the diene rubber (A).
In addition, in the rubber composition of this embodiment, a methacrylic acid ester or a triallyl isocyanurate (TAIC) such as TAIC (Nippon Kasei Co., Ltd.) is used as a vulcanization aid during crosslinking using a peroxide-based crosslinking agent. may be further added as
〈加硫助剤〉
加硫助剤の具体的例としては、酸化マグネシウム、亜鉛華(例えば、「META-Z102」(商品名;井上石灰工業株式会社製)などの酸化亜鉛)などが挙げられる。
本発明のゴム組成物が加硫助剤を含む場合は、その量は、ジエン系ゴム(A)100質量部に対して、通常、1~20質量部である。
<Vulcanization aid>
Specific examples of vulcanization aids include magnesium oxide and zinc white (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Inoue Lime Industry Co., Ltd.)).
When the rubber composition of the present invention contains a vulcanization aid, the amount thereof is usually 1 to 20 parts by mass with respect to 100 parts by mass of the diene rubber (A).
〈加工助剤〉
本発明のゴム組成物は、加工助剤をさらに含んでいてもよい。
加工助剤としては、通常のゴムの加工に使用される化合物を使用することができる。具体的には、リシノール酸、ステアリン酸、パルチミン酸、ラウリン酸等の高級脂肪酸;ステアリン酸バリウム、ステアリン酸亜鉛、ステアリン酸カルシウム等の高級脂肪酸の塩;リシノール酸、ステアリン酸、パルチミン酸、ラウリン酸等の高級脂肪酸のエステル類などが挙げられる。
<Processing aid>
The rubber composition of the present invention may further contain processing aids.
As processing aids, compounds which are used in customary rubber processing can be used. Specifically, higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, lauric acid; salts of higher fatty acids such as barium stearate, zinc stearate, calcium stearate; ricinoleic acid, stearic acid, palmitic acid, lauric acid, etc. and higher fatty acid esters.
本発明のゴム組成物が加工助剤を含む場合は、その量はジエン系ゴム(A)100質量部に対して、10質量部以下、好ましくは5質量部以下の量で用いられるが、要求される物性値に応じて適宜最適量を決定することが望ましい。 When the rubber composition of the present invention contains a processing aid, it is used in an amount of 10 parts by mass or less, preferably 5 parts by mass or less per 100 parts by mass of the diene rubber (A). It is desirable to appropriately determine the optimum amount according to the physical properties to be used.
〈老化防止剤〉
本発明のゴム組成物は、架橋して得られる成形体の製品寿命を長くするために、老化防止剤を含有してもよい。また、老化防止剤としては、従来公知の老化防止剤、例えばアミン系老化防止剤、フェノール系老化防止剤、イオウ系老化防止剤等が挙げられる。
<Anti-aging agent>
The rubber composition of the present invention may contain an antiaging agent in order to prolong the product life of the molded article obtained by crosslinking. Anti-aging agents include conventionally known anti-aging agents such as amine-based anti-aging agents, phenol-based anti-aging agents, and sulfur-based anti-aging agents.
老化防止剤としては、具体的には、フェニルブチルアミン、N,N-ジ-2-ナフチル-p-フェニレンジアミン、N-フェニル-N'-(1,3-ジメチルブチル)-p-フェニレンジアミン(例えば、「ノクラック6C」商品名 大内新興化学工業株式会社製)等の芳香族第2級アミン系老化防止剤、ジブチルヒドロキシトルエン、テトラキス-[メチレン-3-(3',5'-ジ-t-ブチル-4'-ヒドロキシフェニル)プロピオネート]メタン等のフェノール系老化防止剤;ビス[2-メチル-4-(3-n-アルキルチオプロピオニルオキシ)-5-t-ブチルフェニル]スルフィド等のチオエーテル系老化防止剤;ジブチルジチオカルバミン酸ニッケル等のジチオカルバミン酸塩系老化防止剤;2-メルカプトベンゾイルイミダゾール、2-メルカプトベンゾイミダゾールの亜鉛塩、ジラウリルチオジプロピオネート、ジステアリルチオジプロピオネート等のイオウ系老化防止剤等が挙げられる。これらの老化防止剤は、1種単独であるいは2種以上の組み合わせで用いることがでる。 Specific examples of anti-aging agents include phenylbutylamine, N,N-di-2-naphthyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine ( For example, "Nocrac 6C" (trade name, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.) and other aromatic secondary amine antioxidants, dibutylhydroxytoluene, tetrakis-[methylene-3-(3',5'-di- Phenolic antioxidants such as t-butyl-4′-hydroxyphenyl)propionate]methane; thioethers such as bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]sulfide anti-aging agents; dithiocarbamate-based anti-aging agents such as nickel dibutyldithiocarbamate; system anti-aging agents and the like. These antioxidants can be used singly or in combination of two or more.
本発明のゴム組成物が老化防止剤を含む場合は、その量は、ジエン系ゴム(A)100質量部に対して、通常、0.3~10質量部、好ましくは0.5~7.0質量部、さらに好ましくは0.7~5.0質量部である。老化防止剤の量が上記範囲内であると、ゴム組成物を架橋(加硫)する際の加硫阻害を低減することができ、得られる成形体からブルームの発生を低減することができる。 When the rubber composition of the present invention contains an anti-aging agent, the amount thereof is usually 0.3 to 10 parts by mass, preferably 0.5 to 7.0 parts by mass, per 100 parts by mass of the diene rubber (A). 0 parts by mass, more preferably 0.7 to 5.0 parts by mass. When the amount of the anti-aging agent is within the above range, vulcanization inhibition during cross-linking (vulcanization) of the rubber composition can be reduced, and blooming from the obtained molded article can be reduced.
<ゴム組成物の調製方法>
本発明のゴム組成物の調製方法としては、例えば、ゴム組成物に含まれる各成分を、例えば、ミキサー、ニーダー、ロール等の従来知られる混練機、さらに二軸押出機のような連続混練機等を用いて混合する方法、ゴム組成物に含まれる各成分が溶解または分散した溶液を調製し、溶媒を除去する方法等が挙げられる。
<Method for preparing rubber composition>
As a method for preparing the rubber composition of the present invention, for example, each component contained in the rubber composition is mixed with a conventionally known kneader such as a mixer, a kneader, and a roll, and further a continuous kneader such as a twin-screw extruder. and the like, a method of preparing a solution in which each component contained in the rubber composition is dissolved or dispersed, and a method of removing the solvent.
ゴム組成物の調製方法は、特に限定されるものではなく、一般的なゴム配合物の調製方法を特に制限なく採用することができる。たとえば、本発明のゴム組成物が任意成分を含有する場合、任意成分の少なくとも一部を、ジエン系ゴム(A)とあらかじめ混合した後に残りの任意成分を配合してもよく、また、ジエン系ゴム(A)を配合した後に任意成分を添加して配合してもよい。 The method of preparing the rubber composition is not particularly limited, and general methods of preparing rubber compounds can be employed without particular limitations. For example, when the rubber composition of the present invention contains optional components, at least part of the optional components may be premixed with the diene rubber (A) and then the remaining optional components may be blended. Optional components may be added and blended after the rubber (A) is blended.
たとえばバンバリーミキサー、ニーダー、インターミックス等のインターナルミキサー類を用いて、ジエン系ゴム(A)、充填剤(B)、および、酸変性ポリエチレン(C)、および必要に応じて配合する他の成分を、80~170℃の温度で3~10分間混練した後、必要に応じて架橋剤およびさらに必要に応じて架橋促進剤、架橋助剤、発泡剤などを加えて、オープンロールなどのロール類あるいはニーダーを用いて、ロール温度40~80℃で5~30分間混練した後、分出しすることにより調製することができる。このようにして通常リボン状またはシート状のゴム組成物が得られる。上記のインターナルミキサー類での混練温度が低い場合には、架橋剤、架橋促進剤、発泡剤などを同時に混練することもできる。 For example, using an internal mixer such as a Banbury mixer, a kneader, or an intermix, a diene rubber (A), a filler (B), an acid-modified polyethylene (C), and other ingredients to be blended as necessary After kneading for 3 to 10 minutes at a temperature of 80 to 170 ° C., a cross-linking agent and optionally a cross-linking accelerator, a cross-linking aid, a foaming agent, etc. are added, and rolls such as open rolls are added. Alternatively, it can be prepared by kneading with a kneader at a roll temperature of 40 to 80° C. for 5 to 30 minutes and then separating. In this way, a ribbon-like or sheet-like rubber composition is usually obtained. When the kneading temperature in the above internal mixers is low, the cross-linking agent, cross-linking accelerator, foaming agent and the like can be kneaded at the same time.
<成形体>
本発明の成形体は、前述の本発明のゴム組成物を加硫(架橋とも表示する)することにより得られる。なお、加硫の際には、金型を用いても、用いなくてもよい。金型を用いない場合には、ゴム組成物は、通常、連続的に成形、架橋される。
<Molded body>
The molded article of the present invention is obtained by vulcanizing (also referred to as cross-linking) the rubber composition of the present invention. A mold may or may not be used during vulcanization. When no mold is used, the rubber composition is usually continuously molded and crosslinked.
ゴム組成物を加硫する方法としては、(a)加硫剤を含有するゴム組成物を、通常、押出し成形、プレス成形、インジェクション成形等の成形法や、ロール加工により所望形状に予備成形し、成形と同時にまたは成形物を架橋槽内に導入して加熱する方法や、(b)加硫剤を含有するゴム組成物を、(a)の方法と同様の方法で予備成形し、次いで電子線を照射する方法を例示することができる。 As a method for vulcanizing a rubber composition, (a) a rubber composition containing a vulcanizing agent is usually preformed into a desired shape by a molding method such as extrusion molding, press molding, injection molding, or roll processing. , a method of heating simultaneously with molding or introducing the molded product into a cross-linking tank and heating it; A method of irradiating rays can be exemplified.
上記ゴム組成物を加熱により架橋する場合には、通常、硫黄、硫黄系化合物、過酸化物などの加硫剤を含むゴム組成物を用いて、熱空気、ガラスビーズ流動床、UHF(極超短波電磁波)、スチームまたはLCM(熱溶融塩槽)などの加熱形態の架橋槽を用いて、150~270℃の温度で1~30分間加熱することが好ましい。硫黄架橋または過酸化物架橋は、架橋工程に特殊な装置を必要としない利点があるため、従来からゴム組成物の架橋工程に広く用いられている。 When the rubber composition is crosslinked by heating, a rubber composition containing a vulcanizing agent such as sulfur, a sulfur-based compound, or a peroxide is generally used, and heated air, glass bead fluidized bed, UHF (ultrahigh frequency) It is preferable to heat at a temperature of 150 to 270° C. for 1 to 30 minutes using a heating form of cross-linking bath such as electromagnetic wave), steam or LCM (hot molten salt bath). Sulfur cross-linking or peroxide cross-linking has the advantage of not requiring a special device for the cross-linking process, and thus has been widely used in the cross-linking process of rubber compositions.
<空気入りタイヤ>
本発明の空気入りタイヤは、本発明のゴム組成物で形成される空気入りタイヤであり、ゴム組成物で形成される部位は、とくに限定されず、例えば、タイヤトレッド部、サイドウォール部、ビード部、カーカス層、ベルト層が挙げられる。
<Pneumatic tire>
The pneumatic tire of the present invention is a pneumatic tire formed from the rubber composition of the present invention, and the parts formed from the rubber composition are not particularly limited, and examples include the tire tread portion, the sidewall portion, and the bead. part, carcass layer and belt layer.
なかでも、タイヤトレッド部を本発明のゴム組成物で形成することが好ましく、キャップトレッド及びアンダートレッドからなる群から選ばれる少なくとも1種を本発明のゴム組成物で形成することがより好ましく、キャップトレッドがさらに好ましい。 Among them, it is preferable to form the tire tread portion from the rubber composition of the present invention, and it is more preferable to form at least one selected from the group consisting of a cap tread and an undertread from the rubber composition of the present invention. A tread is more preferred.
本発明の空気入りタイヤは、例えば、従来公知の方法に従って製造することができる。また、タイヤに充填する気体としては、例えば、通常のまたは酸素分圧を調整した空気の他、窒素、アルゴン、ヘリウムなどの不活性ガスを用いることができる。 The pneumatic tire of the present invention can be manufactured, for example, according to a conventionally known method. As the gas to be filled in the tire, for example, in addition to normal air or air with adjusted oxygen partial pressure, an inert gas such as nitrogen, argon, or helium can be used.
以下、実施例に基づいて本発明をより具体的に説明するが、本発明はこれら実施例に何ら限定されるものではない。 EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.
[物性の測定条件]
<メルトフローレート(MFR)>
JIS K7210に従い、190℃、2.16kg荷重の下、MFRを測定した。
<密度>
JIS K7112(密度勾配管法)に準拠して密度を測定した。
<ムーニー粘度(ML(1+4)100℃)>
アクリルゴムベールのムーニー粘度(ML(1+4)100℃)は、JISK6300の未架橋ゴム物理試験法に従って測定した。
[Measurement conditions of physical properties]
<Melt flow rate (MFR)>
MFR was measured at 190° C. under a load of 2.16 kg according to JIS K7210.
<Density>
Density was measured according to JIS K7112 (density gradient tube method).
<Mooney viscosity (ML (1+4) 100°C)>
The Mooney viscosity (ML(1+4) 100° C.) of the acrylic rubber veil was measured according to JIS K6300 Uncrosslinked Rubber Physical Test Method.
実施例及び比較例で用いた原料成分は以下の通りである。
〔ジエン系ゴム(A)〕
下記実施例および比較例ではジエン系ゴム(A)として、以下市販品を用いた。
(A-1);スチレン-ブタジエンゴム(SBR) ZSエラストマー社製 商品名 Nipol NS116R(結合スチレン量=21%、ML(1+4)100℃=45)。
Raw material components used in Examples and Comparative Examples are as follows.
[Diene rubber (A)]
In the following examples and comparative examples, the following commercially available products were used as the diene rubber (A).
(A-1); Styrene-butadiene rubber (SBR) trade name Nipol NS116R manufactured by ZS Elastomer Co. (bound styrene content = 21%, ML (1 + 4) 100°C = 45).
〔カーボンブラック(B1)〕
下記実施例および比較例ではカーボンブラック(B1)として、以下の市販品を用いた。
(B1-1):HAF 旭カーボン社製 商品名 旭#70。
[Carbon black (B1)]
In the following examples and comparative examples, the following commercially available products were used as carbon black (B1).
(B1-1): HAF Asahi Carbon Co., Ltd. trade name Asahi #70.
〔シリカ(B2)〕
下記実施例および比較例ではシリカ(B2)として、以下の市販品を用いた。
(B2-1):湿式シリカ 東ソー・シリカ社製 商品名 Nipsil VN3。
[Silica (B2)]
In the following examples and comparative examples, the following commercial products were used as silica (B2).
(B2-1): Wet Silica Trade name Nipsil VN3 manufactured by Tosoh Silica Corporation.
〔酸変性ポリエチレン(C)〕
(C-1):無水マレイン酸グラフト変性ポリエチレン(三井化学社製 商品名 アドマーHE810)、密度=0.96g/cm3、MFR=1.7g/10分。
(C-2):無水マレイン酸グラフト変性ポリエチレン(三井化学社製 商品名 アドマーHB030)、密度=0.94g/cm3、MFR=0.4g/10分。
[Acid-modified polyethylene (C)]
(C-1): Maleic anhydride-grafted modified polyethylene (manufactured by Mitsui Chemicals, Inc., trade name Admer HE810), density = 0.96 g/cm 3 , MFR = 1.7 g/10 min.
(C-2): Maleic anhydride-grafted modified polyethylene (manufactured by Mitsui Chemicals, Inc., trade name Admer HB030), density = 0.94 g/cm 3 , MFR = 0.4 g/10 min.
〔高密度ポリエチレン(F)〕
(F-1):高密度ポリエチレン、密度=0.96g/cm3、MFR=13g/10分(プライムポリマー社製 商品名 ハイゼックスTM 1300J)。
[High density polyethylene (F)]
(F-1): high-density polyethylene, density = 0.96 g/cm 3 , MFR = 13 g/10 min (trade name HI-ZEX ™ 1300J manufactured by Prime Polymer Co., Ltd.).
〔添加剤〕
シランカップリング剤:ビス[3-(トリエトキシシリル)プロピル]テトラスルフィド(EVONIK社製 商品名 Si-69)。
酸化亜鉛:酸化亜鉛2種(ハクスイテック社製)
ステアリン酸:ステアリン酸(日油社製)
老化防止剤:ノクラック6C、大内新興化学工業社製)
可塑剤:芳香族系プロセスオイル:商品名 ダイアナ プロセスオイルAH-16(出光興産社製)
硫黄:硫黄(純正化学社製)
加硫促進剤(MBTS):サンセラー DM-G(三新化学工業社製)
加硫促進剤(DPG):サンセラー D-G(三新化学工業社製)
加硫促進剤(TBBS):サンセラー NS-G(三新化学工業社製)
〔Additive〕
Silane coupling agent: bis[3-(triethoxysilyl)propyl]tetrasulfide (manufactured by EVONIK, trade name Si-69).
Zinc oxide: 2 types of zinc oxide (manufactured by Hakusui Tech)
Stearic acid: stearic acid (manufactured by NOF Corporation)
Antiaging agent: Nocrac 6C, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd.)
Plasticizer: Aromatic process oil: Product name Diana Process Oil AH-16 (manufactured by Idemitsu Kosan Co., Ltd.)
Sulfur: Sulfur (manufactured by Junsei Chemical Co., Ltd.)
Vulcanization accelerator (MBTS): Suncellar DM-G (manufactured by Sanshin Chemical Industry Co., Ltd.)
Vulcanization accelerator (DPG): Sancellar DG (manufactured by Sanshin Chemical Industry Co., Ltd.)
Vulcanization accelerator (TBBS): Sancellar NS-G (manufactured by Sanshin Chemical Industry Co., Ltd.)
〔実施例1〕
原料成分として、ジエン系ゴム(A-1)、カーボンブラック(B1-1)、シリカ(B2-1)、酸変性ポリエチレン(C-1)、および、加硫系成分(硫黄および含硫黄加硫促進剤)を除く添加剤を表1に示す量で、バンバリーミキサーを用いて約3分間140~160℃の温度範囲で混練りし混合物を得た。次に、得られた混合物に加硫系成分を加え、6インチオープンロールで混練し、ゴム組成物を得た。
[Example 1]
Raw material components include diene rubber (A-1), carbon black (B1-1), silica (B2-1), acid-modified polyethylene (C-1), and vulcanization components (sulfur and sulfur-containing vulcanization Accelerator) were added in the amounts shown in Table 1 and kneaded for about 3 minutes in a temperature range of 140 to 160°C using a Banbury mixer to obtain a mixture. Next, vulcanization system components were added to the obtained mixture, and the mixture was kneaded with a 6-inch open roll to obtain a rubber composition.
得られたゴム組成物を所定の金型中、170℃で20分間プレス加硫して縦15cm×横15cm×厚さ2mmの平板の加硫ゴムシートを作製し、さらに170℃で10分間プレス加硫して縦10cm×横10cm×厚さ1mmの平板の加硫ゴムシートを作製した。
得られた加硫ゴムシートを用いて、以下の測定方法で物性を測定した。
The obtained rubber composition is pressed and vulcanized in a predetermined mold at 170°C for 20 minutes to prepare a vulcanized rubber sheet having a length of 15 cm x width of 15 cm x thickness of 2 mm, and is further pressed at 170°C for 10 minutes. It was vulcanized to prepare a flat vulcanized rubber sheet of 10 cm long×10 cm wide×1 mm thick.
Using the obtained vulcanized rubber sheet, physical properties were measured by the following measuring methods.
〔発熱性〕
厚さ1mmの加硫ゴムシートを使用し、動的粘弾性計測装置(RSA-G2 TA Instruments社製)を用いて、伸張変形歪率1%、周波数10Hz、温度60℃、窒素雰囲気下の条件で、損失正接tanδ(60℃)を測定した。本発明ではtanδ(60℃)の指数が小さいほど、低発熱性に優れることを意味する。
[Pyrogenicity]
Using a vulcanized rubber sheet with a thickness of 1 mm, using a dynamic viscoelasticity measuring device (RSA-G2 TA Instruments), the strain rate of extensional deformation is 1%, the frequency is 10 Hz, the temperature is 60 ° C., and the conditions are under a nitrogen atmosphere. , the loss tangent tan δ (60°C) was measured. In the present invention, the smaller the tan δ (60° C.) index, the better the low heat build-up.
〔耐摩耗性〕
厚さ2mmの加硫ゴムシートをテーバー摩耗試験機(ロータリーアブレージョンテスタ TS-2型、東洋精機製作所製)に設置して、摩耗輪H-18に荷重9.8N(1000g)をかけて、1000回回転させて試験片の摩耗損失量を測定した。摩耗損失量の指数が小さい程、耐摩耗性に優れることを意味する。
結果を表1に示す。
[Abrasion resistance]
A vulcanized rubber sheet with a thickness of 2 mm was installed in a Taber abrasion tester (rotary abrasion tester TS-2, manufactured by Toyo Seiki Seisakusho), and a load of 9.8 N (1000 g) was applied to the abrasion wheel H-18, The amount of wear loss of the test piece was measured by rotating it 10 times. It means that the smaller the wear loss index, the better the wear resistance.
Table 1 shows the results.
〔実施例2、比較例1~4〕
実施例1で用いた原料成分、および添加剤を表1に記載の成分および量に替える以外は、実施例1と同様に行いゴム組成物を得た。得られたゴム組成物を上記方法で評価した。
結果を表1に示す。
[Example 2, Comparative Examples 1 to 4]
A rubber composition was obtained in the same manner as in Example 1 except that the raw material components and additives used in Example 1 were changed to the components and amounts shown in Table 1. The obtained rubber composition was evaluated by the above method.
Table 1 shows the results.
〔標準例1〕
実施例1で用いた原料成分、および添加剤を表1に記載の成分および量に替える以外は、実施例1と同様に行いゴム組成物を得た。得られたゴム組成物を上記方法で評価した。
結果を表1に示す。
[Standard example 1]
A rubber composition was obtained in the same manner as in Example 1 except that the raw material components and additives used in Example 1 were changed to the components and amounts shown in Table 1. The obtained rubber composition was evaluated by the above method.
Table 1 shows the results.
tanδ(60℃)の指数として、標準例1を100とし、INDEX表記で、105以下であれば同等もしくは、同等以上の性能と判断した。
摩耗損失量は、標準例1を100とし、INDEX表記で、80以下であれば耐摩耗性が改善傾向ありと判断した。
As an index of tan δ (60° C.), standard example 1 was set to 100, and in INDEX notation, if it was 105 or less, it was judged to be equivalent or equivalent or superior in performance.
The amount of wear loss was defined as 100 for Standard Example 1, and it was judged that the wear resistance tended to improve if it was 80 or less in INDEX notation.
〔実施例3~5、比較例5~9、標準例2〕
実施例1で用いた原料成分、および添加剤を表1に記載の成分および量に替える以外は、実施例1と同様に行いゴム組成物を得た。得られたゴム組成物を上記方法で評価した。
結果を表2に示す。
[Examples 3-5, Comparative Examples 5-9, Standard Example 2]
A rubber composition was obtained in the same manner as in Example 1 except that the raw material components and additives used in Example 1 were changed to the components and amounts shown in Table 1. The obtained rubber composition was evaluated by the above method.
Table 2 shows the results.
tanδ(60℃)の指数として、標準例2を100とし、INDEX表記で、105以下であれば同等もしくは、同等以上の性能と判断した。
摩耗損失量は、標準例2を100とし、INDEX表記で、80以下であれば耐摩耗性が改善傾向ありと判断した。
As an index of tan δ (60° C.), standard example 2 was set to 100, and in INDEX notation, if it was 105 or less, it was judged to be equivalent or equivalent or superior in performance.
The amount of wear loss was 100 for Standard Example 2, and it was judged that the wear resistance tended to improve if it was 80 or less in INDEX notation.
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