CN104011128B - Rubber composition for tire and use the pneumatic tyre of this rubber combination - Google Patents
Rubber composition for tire and use the pneumatic tyre of this rubber combination Download PDFInfo
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- CN104011128B CN104011128B CN201280048687.5A CN201280048687A CN104011128B CN 104011128 B CN104011128 B CN 104011128B CN 201280048687 A CN201280048687 A CN 201280048687A CN 104011128 B CN104011128 B CN 104011128B
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- alkyl
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- rubber composition
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 127
- 239000005060 rubber Substances 0.000 title claims abstract description 127
- 239000000203 mixture Substances 0.000 title claims abstract description 126
- 238000000034 method Methods 0.000 claims abstract description 83
- 238000002156 mixing Methods 0.000 claims abstract description 82
- 230000008569 process Effects 0.000 claims abstract description 58
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 50
- 229920001577 copolymer Polymers 0.000 claims abstract description 45
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 29
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 28
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 claims abstract description 27
- 229960001866 silicon dioxide Drugs 0.000 claims abstract description 26
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 171
- 125000000217 alkyl group Chemical group 0.000 claims description 124
- -1 2, 2, 6, 6-tetramethyl piperidine-1-oxide compound Chemical class 0.000 claims description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 25
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 22
- 229940123457 Free radical scavenger Drugs 0.000 claims description 19
- 239000002516 radical scavenger Substances 0.000 claims description 19
- 239000005864 Sulphur Substances 0.000 claims description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 16
- 239000004902 Softening Agent Substances 0.000 claims description 14
- 150000002989 phenols Chemical class 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- 125000001118 alkylidene group Chemical group 0.000 claims description 10
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 244000043261 Hevea brasiliensis Species 0.000 claims description 5
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 5
- 229920003052 natural elastomer Polymers 0.000 claims description 5
- 229920001194 natural rubber Polymers 0.000 claims description 5
- 230000000694 effects Effects 0.000 abstract description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 80
- 239000000126 substance Substances 0.000 description 40
- 150000001875 compounds Chemical class 0.000 description 20
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 20
- 150000003254 radicals Chemical class 0.000 description 18
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 16
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 15
- 239000002174 Styrene-butadiene Substances 0.000 description 14
- 229920003048 styrene butadiene rubber Polymers 0.000 description 14
- 238000004073 vulcanization Methods 0.000 description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 235000019260 propionic acid Nutrition 0.000 description 10
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 10
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 9
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical group C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000011115 styrene butadiene Substances 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000001125 extrusion Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 150000001993 dienes Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 4
- 210000003754 fetus Anatomy 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- BGHCVCJVXZWKCC-UHFFFAOYSA-N Tetradecane Natural products CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 150000005690 diesters Chemical class 0.000 description 3
- 230000002708 enhancing effect Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- 235000014692 zinc oxide Nutrition 0.000 description 3
- FBKDYTLMCDWHAS-UHFFFAOYSA-N 3-(dodecylsulfanylmethyl)-2-methylphenol Chemical compound CCCCCCCCCCCCSCC1=CC=CC(O)=C1C FBKDYTLMCDWHAS-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- 240000005373 Panax quinquefolius Species 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 2
- 229960000541 cetyl alcohol Drugs 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000002596 lactones Chemical group 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- BXWNKGSJHAJOGX-UHFFFAOYSA-N n-hexadecyl alcohol Natural products CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical class CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- MSRJTTSHWYDFIU-UHFFFAOYSA-N octyltriethoxysilane Chemical compound CCCCCCCC[Si](OCC)(OCC)OCC MSRJTTSHWYDFIU-UHFFFAOYSA-N 0.000 description 2
- 229960003493 octyltriethoxysilane Drugs 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- ORHYNUQHIUQGDA-UHFFFAOYSA-N 1-(3-methylbut-1-enyl)-4-propan-2-ylbenzene Chemical compound CC(C)C=CC1=CC=C(C(C)C)C=C1 ORHYNUQHIUQGDA-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-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
- AHHHCDURUBOTCN-UHFFFAOYSA-N 2-(2-ethenylphenyl)-n,n-dimethylethanamine Chemical compound CN(C)CCC1=CC=CC=C1C=C AHHHCDURUBOTCN-UHFFFAOYSA-N 0.000 description 1
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 description 1
- TYENDWOHUUAIJH-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCC1=CC=C(C=C)C=C1 TYENDWOHUUAIJH-UHFFFAOYSA-N 0.000 description 1
- AIDLAEPHWROGFI-UHFFFAOYSA-N 2-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=C(C(O)=O)C=CC=C1C(O)=O AIDLAEPHWROGFI-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-N 3,3'-Thiobispropanoic acid Chemical compound OC(=O)CCSCCC(O)=O ODJQKYXPKWQWNK-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VHOQXEIFYTTXJU-UHFFFAOYSA-N Isobutylene-isoprene copolymer Chemical group CC(C)=C.CC(=C)C=C VHOQXEIFYTTXJU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QYTDEUPAUMOIOP-UHFFFAOYSA-N TEMPO Chemical group CC1(C)CCCC(C)(C)N1[O] QYTDEUPAUMOIOP-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005370 alkoxysilyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 description 1
- ZOQKPJUXNOAXBL-UHFFFAOYSA-N dioxosilane silane Chemical compound [SiH4].O=[Si]=O ZOQKPJUXNOAXBL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010685 fatty oil Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000009499 grossing Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KUQWZSZYIQGTHT-UHFFFAOYSA-N hexa-1,5-diene-3,4-diol Chemical compound C=CC(O)C(O)C=C KUQWZSZYIQGTHT-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DZRKBPWATCKLKY-UHFFFAOYSA-N n-benzyl-n-methylprop-2-en-1-amine Chemical compound C=CCN(C)CC1=CC=CC=C1 DZRKBPWATCKLKY-UHFFFAOYSA-N 0.000 description 1
- GOQYKNQRPGWPLP-UHFFFAOYSA-N n-heptadecyl alcohol Natural products CCCCCCCCCCCCCCCCCO GOQYKNQRPGWPLP-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QADJHAOXTKCYFT-UHFFFAOYSA-N octyl 3-(3-octoxy-3-oxopropyl)sulfanylpropanoate Chemical compound CCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCC QADJHAOXTKCYFT-UHFFFAOYSA-N 0.000 description 1
- CBFCDTFDPHXCNY-UHFFFAOYSA-N octyldodecane Natural products CCCCCCCCCCCCCCCCCCCC CBFCDTFDPHXCNY-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- WMYJOZQKDZZHAC-UHFFFAOYSA-H trizinc;dioxido-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([S-])=S.[O-]P([O-])([S-])=S WMYJOZQKDZZHAC-UHFFFAOYSA-H 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/58—Component parts, details or accessories; Auxiliary operations
- B29B7/72—Measuring, controlling or regulating
- B29B7/726—Measuring properties of mixture, e.g. temperature or density
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/74—Mixing; Kneading using other mixers or combinations of mixers, e.g. of dissimilar mixers ; Plant
- B29B7/7476—Systems, i.e. flow charts or diagrams; Plants
- B29B7/7495—Systems, i.e. flow charts or diagrams; Plants for mixing rubber
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/548—Silicon-containing compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
- B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
- B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
What it is an object of the invention to provide a kind of effect reaching reduction by 60 DEG C of tan �� has the excellent rubber composition for tire of workability, the manufacture method of this rubber combination simultaneously and uses the pneumatic tyre of this rubber composition for tire. the rubber composition for tire of the present invention, it is characterized in that, polydiene contains 1 in conjugated diolefine, 2-key is one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % of 20��40 weight %, 1, the total amount of 2-key is 10��55 weight % of above-mentioned polydiene total amount, by relative to above-mentioned polydiene 100 weight part, the mixed processes mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with specific formula manufactures, and above-mentioned mixed processes does not use vulcanizing agent, mixing temperature in above-mentioned mixed processes is lower than 140 DEG C.
Description
Technical area
The present invention relates to a kind of rubber composition for tire and use the pneumatic tyre of this rubber combination.
Background technology
In the past, found in the triturating of low rolling resistance tyre, compared with conventional silane coupler containing sulfur, by the compounding sulfydryl one type of silane coupling agent of polydiene and silicon-dioxide, it is possible to improve the dispersion of silicon-dioxide, and much slower tan ��. But, owing to the reactivity of sulfydryl one type of silane coupling agent is higher, therefore can increase along with the viscosity of mixture, workability deteriorates (coke burning performance of rubber is poor), this has become a problem. When using sulfydryl one type of silane coupling agent, the temperature of mixing dienes glue, silicon-dioxide, sulfydryl one type of silane coupling agent etc. is generally more than 140 DEG C (such as patent documentation 1).
Prior art literature
Patent documentation
[patent documentation 1] Japanese Patent Laid-Open 2010-270247 publication
The summary of invention
The problem that invention quasi-solution is determined
In the past, when mixing temperature during mixing cpd is lower than 140 DEG C, reaction and a point breaking up for silicon-dioxide between silicon-dioxide-silane coupling agent become insufficient, and 60 DEG C of tan �� can improve.
In addition, when mixing polydiene, silicon-dioxide, sulfydryl one type of silane coupling agent etc. when more than 140 DEG C, the viscosity of general obtained mixture can improve. In view of this, the present application person etc. find, in the mixing process of compound, produce free radical and its concentration to improve gradually be the reason causing mixture viscosity to rise. So, the present application persons etc. expect, if catching the free radical in mixture, then can reduce the viscosity of mixture.
Therefore, it is an object of the invention to provide and a kind of reach there is the rubber composition for tire of excellent workability (the such as viscosity of unvulcanized mixture is low or the surface smoothing of the extrudate of unvulcanized mixture), the manufacture method of this rubber composition for tire simultaneously and using the pneumatic tyre of this rubber composition for tire of the effect that reduces by 60 DEG C of tan ��.
Summary of the invention
Present inventor has carried out studying with keen determination discovery for solving above-mentioned problem, following a kind of rubber composition for tire improves workability while can reaching the effect reducing by 60 DEG C of tan ��: polydiene contains 1 in conjugated diolefine, 2-key is one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % of 20��40 weight %, above-mentioned 1, the total amount of 2-key is 10��55 weight % of above-mentioned polydiene total amount, by relative to above-mentioned polydiene 100 weight part, the mixed processes mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with specific formula manufactures, and above-mentioned mixed processes does not use vulcanizing agent, mixing temperature in above-mentioned mixed processes is lower than 140 DEG C.
In addition, the present application persons etc. also find, by the manufacture method of following a kind of rubber composition for tire, while the effect that can reach and reduce by 60 DEG C of tan �� can be produced also can free radical in suppression system thus improve the rubber composition for tire of workability, and complete the present invention: by relative to above-mentioned specific polydiene 100 weight part, the mixed processes mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with specific formula manufactures, and above-mentioned mixed processes does not use vulcanizing agent, in above-mentioned mixed processes, �� A �� mixing temperature is lower than 140 DEG C, and/or �� B �� also uses and is selected from by 2, 2, 6, 6-tetramethyl piperidine, the dialkyl dithiophosphoric acid compounds represented with specific formula, the sulphur represented with specific formula is for dicarboxylic ester, the bi-ester of phosphite represented with specific formula, the acrylate represented with specific formula, at least a kind of free radical scavenger in the group that the phenolic compound represented with specific formula and lactone compound form, relative to above-mentioned polydiene 100 weight part, the amount of above-mentioned free radical scavenger is 0.1��5 weight part.
In conventional mixture, it may also be useful to though be that mixing temperature is higher, also can not cause the material of the composition of mixture thickening, owing to the compound of this kind of composition is used higher mixing temperature, mixing therefore also not too can be occurred bad.
Even and if the invention of this case to be a kind of its also can not cause mixing bad under the mixing temperature lower than 140 DEG C being in the past considered to cause mixing bad, and can shaping processability excellent, it is possible to reduce the novel complexes of 60 DEG C of tan �� further.
That is, the present invention provides following 1��10:
1. a rubber composition for tire, it is characterised in that, polydiene contains in conjugated diolefine 1,2-key is one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % of 20��40 weight %, and the total amount of 1,2-key is 10��55 weight % of above-mentioned polydiene total amount
By relative to above-mentioned polydiene 100 weight part, the mixed processes manufacture mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with following formula (1) manufactures, and not using vulcanizing agent in above-mentioned mixed processes, the mixing temperature in above-mentioned mixed processes is lower than 140 DEG C:
Chemical formula 1
In formula, R11��R12And R13In at least 1 be-O-(R15-O)m-R16(R15To be carbonatoms be 1��30 2 valency alkyl, R16To be carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30, m is the integer of 1��30, R15For when multiple, multiple R15Can be identical, it is also possible to different),
R11��R12And R13In 1 or 2 be above-mentioned-O-(R15-O)m-R16When, it is possible to remaining group is set to alkyl ,-O-R that carbonatoms is 1��1217(R17Alkene base that the alkyl be hydrogen atom, carbonatoms being 1��30, carbonatoms are 2��30, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30), hydrogen atom or carbonatoms be the aryl of 6��30,
R11��R12And R13Can be identical, it is also possible to different,
R14To be carbonatoms be 1��30 2 valency alkyl.
2. rubber composition for tire according to above-mentioned 1, wherein in above-mentioned mixed processes, also using is selected from by 2, 2, 6, 6-tetramethyl piperidine, the dialkyl dithiophosphoric acid compounds represented with following formula (2), the sulphur represented with following formula (3) is for dicarboxylic ester, the bi-ester of phosphite represented with following formula (4), the acrylate represented with following formula (5), at least a kind of free radical scavenger in the group that the phenolic compound represented with following formula (6) and lactone compound form, and relative to above-mentioned polydiene 100 weight part, the amount of above-mentioned free radical scavenger is 0.1��5 weight part:
Chemical formula 2
(in formula (2), R21And R22Separately representing that carbonatoms is the alkyl of 1��18, n is 0 or 1, multiple R21And R22Can distinguish identical also can be different),
Chemical formula 3
(in formula (3), R31Represent that carbonatoms is the alkylidene group of 1��12, R32Represent that carbonatoms is the alkyl of 1��30, multiple R31And R32Can distinguish identical also can be different),
Chemical formula 4
(in formula (4), R41Represent that carbonatoms is the alkoxyl group of 1��4, R42And R43Separately represent that carbonatoms is the alkyl of 1��4, R44Representing that hydrogen atom or carbonatoms are the alkyl of 1��4, q represents the integer of more than 0, and r represents the integer of more than 2, q and r meets the relational expression of q+r=3, multiple R42��R43And R44Can distinguish identical also can be different),
Chemical formula 5
(in formula (5), R51��R55Separately represent that hydrogen atom or carbonatoms are the straight-chain of 1��6 or the alkyl of branch-like),
Chemical formula 6
(in formula (6), R61��R62And R63Separately represent can be the alkyl of 1��30 containing heteroatomic carbonatoms, R61��R62And R63In at least 2 represent be the alkyl of 4��20 and heteroatomic alkyl can be contained containing carbonatoms).
3. rubber composition for tire according to above-mentioned 1 or 2, wherein above-mentioned one kind or two or more aromatic vinyl-conjugated diene copolymer, has hydroxyl at end.
4. rubber composition for tire according to any one of above-mentioned 1��3, it is characterised in that, above-mentioned mixed processes also uses softening agent, and relative to above-mentioned polydiene 100 weight part, the amount of above-mentioned softening agent is below 35 weight parts.
5. rubber composition for tire according to any one of above-mentioned 1��4, it is characterized in that, after above-mentioned mixed processes, the compounding diatomic alcohol compounds as dispersing auxiliary and/or there is the silane compound of alkyl, and relative to above-mentioned polydiene 100 weight part, the amount of above-mentioned dispersing auxiliary is 0.5��5 weight part.
6. rubber composition for tire according to above-mentioned 5, it is characterised in that, in above-mentioned mixed processes, also use softening agent, relative to above-mentioned polydiene 100 weight part, the total amount of above-mentioned dispersing auxiliary and above-mentioned softening agent is below 35 weight parts.
7. rubber composition for tire according to any one of above-mentioned 1��6, it is characterized in that, above-mentioned polydiene is also containing at least a kind be selected from the group being made up of lower than the aromatic vinyl-conjugated diene copolymer of 20 weight %, divinyl rubber and natural rubber 1,2-key.
8. the manufacture method of a rubber composition for tire, it is characterized in that, polydiene contains 1 in conjugated diolefine, 2-key is one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % of 20��40 weight %, and above-mentioned 1, the total amount of 2-key is 10��55 weight % of above-mentioned polydiene total amount
By relative to above-mentioned polydiene 100 weight part, the mixed processes mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with following formula (1) manufactures, and not using vulcanizing agent in above-mentioned mixed processes, the mixing temperature in above-mentioned mixed processes is lower than 140 DEG C:
Chemical formula 7
In formula, R11��R12And R13In at least 1 be-O-(R15-O)m-R16(R15To be carbonatoms be 1��30 2 valency alkyl, R16To be carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30, m is the integer of 1��30, R15For when multiple, multiple R15Can be identical, it is also possible to different),
R11��R12And R13In 1 or 2 be above-mentioned-O-(R15-O)m-R16When, it is possible to remaining group is set to alkyl ,-O-R that carbonatoms is 1��1217(R17Alkene base that the alkyl be hydrogen atom, carbonatoms being 1��30, carbonatoms are 2��30, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30), hydrogen atom or carbonatoms be the aryl of 6��30,
R11��R12And R13Can be identical, it is also possible to different,
R14To be carbonatoms be 1��30 2 valency alkyl.
9. the manufacture method of rubber composition for tire according to above-mentioned 8, wherein in above-mentioned mixed processes, also using is selected from by 2, 2, 6, 6-tetramethyl piperidine, the dialkyl dithiophosphoric acid compounds represented with following formula (2), the sulphur represented with following formula (3) is for dicarboxylic ester, the bi-ester of phosphite represented with following formula (4), the acrylate represented with following formula (5), at least a kind of free radical scavenger in the group that the phenolic compound represented with following formula (6) and lactone compound form, and relative to above-mentioned polydiene 100 weight part, the amount of above-mentioned free radical scavenger is 0.1��5 weight part:
Chemical formula 8
(in formula (2), R21And R22Separately representing that carbonatoms is the alkyl of 1��18, n is 0 or 1, multiple R21And R22Can distinguish identical also can be different),
Chemical formula 9
(in formula (3), R31Represent that carbonatoms is the alkylidene group of 1��12, R32Represent that carbonatoms is the alkyl of 1��30, multiple R31And R32Can distinguish identical also can be different),
Chemical formula 10
(in formula (4), R41Represent that carbonatoms is the alkoxyl group of 1��4, R42And R43Separately represent that carbonatoms is the alkyl of 1��4, R44Representing that hydrogen atom or carbonatoms are the alkyl of 1��4, q represents the integer of more than 0, and r represents the integer of more than 2, q and r meets the relational expression of q+r=3, multiple R42��R43And R44Can distinguish identical also can be different),
Chemical formula 11
(in formula (5), R51��R55Separately represent that hydrogen atom or carbonatoms are the straight-chain of 1��6 or the alkyl of branch-like),
Chemical formula 12
(in formula (6), R61��R62And R63Separately represent can be the alkyl of 1��30 containing heteroatomic carbonatoms, R61��R62And R63In at least 2 represent be the alkyl of 4��20 and heteroatomic alkyl can be contained containing carbonatoms).
10. a pneumatic tyre, the rubber composition for tire using the rubber composition for tire according to any one of above-mentioned 1��7 on its tire tread or being manufactured by the manufacture method of the rubber composition for tire according to above-mentioned 8 or 9.
The effect of invention
The rubber composition for tire of the present invention can reach reduce by 60 DEG C of tan �� effect while excellent workability. The manufacture method of the rubber composition for tire according to the present invention, can obtain can reach reduce by 60 DEG C of tan �� effect while and the rubber composition for tire of excellent workability. Use the rubber composition for tire of the present invention or the effect height reducing by 60 DEG C of tan �� of the pneumatic tyre by the rubber composition for tire of the manufacture method acquisition of the rubber composition for tire of the present invention, and productivity is excellent.
Accompanying drawing explanation
Fig. 1 is the part sectioned view that display uses the tire meridian direction of an example of the enforcement mode of the pneumatic tyre of rubber composition for tire of the present invention, it.
Embodiment
Below, the present invention is described in detail.
The rubber composition for tire of the present invention, it is characterised in that,
Polydiene contains one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % that 1,2-key in conjugated diolefine is 20��40 weight %, and the total amount of 1,2-key is 10��55 weight % of above-mentioned polydiene total amount,
By relative to above-mentioned polydiene 100 weight part, the mixed processes manufacture mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with following formula (1) manufactures, and not using vulcanizing agent in above-mentioned mixed processes, the mixing temperature in above-mentioned mixed processes is lower than 140 DEG C:
Chemical formula 13
In formula, R11��R12And R13In at least 1 be-O-(R15-O)m-R16(R15To be carbonatoms be 1��30 2 valency alkyl, R16To be carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30, m is the integer of 1��30, R15For when multiple, multiple R15Can be identical, it is also possible to different),
R11��R12And R13In 1 or 2 be above-mentioned-O-(R15-O)m-R16When, it is possible to remaining group is set to alkyl ,-O-R that carbonatoms is 1��1217(R17Alkene base that the alkyl be hydrogen atom, carbonatoms being 1��30, carbonatoms are 2��30, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30), hydrogen atom or carbonatoms be the aryl of 6��30,
R11��R12And R13Can be identical, it is also possible to different,
R14To be carbonatoms be 1��30 2 valency alkyl.
<polydiene>
Below, polydiene is described.
In the present invention, polydiene contains 1 in conjugated diolefine, 2-key is one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % of 20��40 weight %, and the total amount of 1,2-key is 10��55 weight % of above-mentioned polydiene total amount, even if therefore the mixing temperature in mixed processes is low, also mixing can not be caused bad, it is possible to suppress the generation of free radical, suppress the rising of mixture viscosity, excellent workability, reduces by 60 DEG C of tan ��.
The polydiene used in the present application is the one kind or two or more aromatic vinyl-conjugated diene copolymer of 20��40 weight % containing the 1,2-key in conjugated diolefine.
To the aromatic vinyl-conjugated diene copolymer being contained in polydiene, there is no particular restriction, as long as the amount forming the 1,2-key in the conjugated diene unit of this multipolymer is 20��40 weight % of this multipolymer.
The skeleton of aromatic vinyl-conjugated diene copolymer, can be made up of the multipolymer making conjugated diene monomer and aromatic vinyl monomer copolymerization and obtain. As conjugated diene monomer, include, for example 1,3-divinyl, isoprene (2-methyl isophthalic acid, 3 divinyl), 2,3-dimethyl-1,3-divinyl, the chloro-1,3-divinyl of 2-, 1,3-pentadiene etc. In addition, as aromatic vinyl monomer, include, for example vinylbenzene, 2-methyl styrene, 3-vinyl toluene, 4-vinyl toluene, alpha-methyl styrene, 2,4-dimethyl styrene, 2,4-di-isopropyl vinylbenzene, 4-t-butyl styrene, Vinylstyrene, t-butoxystyrene, vinylbenzyl dimethyl amine, (4-vinyl benzyl) dimethylaminoethyl ether, N, N-dimethylaminoethyl vinylbenzene and vinyl pyridine etc.
The skeleton of aromatic vinyl-conjugated diene copolymer is preferably styrene butadiene ribber.
From reducing by 60 DEG C of tan �� and the angle of excellent workability, the present invention forms 1 in the conjugated diene unit of aromatic vinyl-conjugated diene copolymer, the amount of 2-structure is 20��40 weight % of this multipolymer, it is preferable to 22��40 weight %, it is more preferable to be 25��40 weight %.
Aromatic vinyl-conjugated diene copolymer also can have functional group, such as hydroxyl, alkoxysilyl, amino etc. The bonding end in aromatic vinyl-conjugated diene copolymer of functional group and/or be bonded as side chain. Functional group can directly or across group bonding on the skeleton of aromatic vinyl-conjugated diene copolymer. As the group of the skeleton separating functional group and aromatic vinyl-conjugated diene copolymer, include, for example organic radical, the polysiloxane etc. such as alkyl.
From reducing by 60 DEG C of tan ��, improve the angle of workability, the weight-average molecular weight of aromatic vinyl-conjugated diene copolymer is preferably 6.0 �� 105��15 �� 105, it is more preferable to it is 8.0 �� 105��14 �� 105. The weight-average molecular weight (Mw) of aromatic vinyl-conjugated diene copolymer is taking tetrahydrofuran (THF) (THF) as solvent, utilizes gel permeation chromatography (GPC) to measure and obtains through polystyrene standard conversion.
Aromatic vinyl-conjugated diene copolymer can individually use, it is possible to is used in combination of two or more. As aromatic vinyl-conjugated diene copolymer, end can be used to have the one kind or two or more of hydroxyl. For the manufacture of aromatic vinyl-conjugated diene copolymer, there is no particular restriction.
From reducing by 60 DEG C of tan �� and the angle of excellent workability, 30��90 weight % that in the present invention, the amount of aromatic vinyl-conjugated diene copolymer is polydiene total amount, it is preferable that 35��85 weight %, it is more preferable to 40��85 weight %.
In the present invention, polydiene can be that other polydienes beyond the aromatic vinyl-conjugated diene copolymer of 20��40 weight % are as rubber constituent containing the 1,2-key in conjugated diolefine. As other polydienes, the 1,2-key that include, for example in natural rubber, synthetic polyisoprene, divinyl rubber, conjugated diolefine is aromatic vinyl-conjugated diene copolymer (the such as styrene butadiene ribber beyond 20��40 weight %. 1,2-key is lower than 20 weight % or more than the aromatic vinyl-conjugated diene copolymer of 40 weight %), isoprene-isobutylene rubber, halogenated butyl rubber etc. From reducing by 60 DEG C of tan �� further and the angle of excellent workability, it is preferable to the 1,2-key in natural rubber, divinyl rubber, conjugated diolefine is the styrene butadiene ribber beyond 20��40 weight %.
Other polydiene is 1 in conjugated diolefine, when 2-key is the aromatic vinyl-conjugated diene copolymer beyond 20��40 weight %, from reducing by 60 DEG C of tan �� further and the angle of excellent workability, 1,2-key in preferred conjugated diolefine is lower than the aromatic vinyl-conjugated diene copolymer of 20 weight %.
Other polydiene can individually use, it is also possible to is used in combination of two or more.
Other polydiene is 1 in conjugated diolefine, when 2-key is the aromatic vinyl-conjugated diene copolymer beyond 20��40 weight %, from reducing by 60 DEG C of tan �� further and the angle of excellent workability, the content of other polydiene is preferably 15��55 weight % of polydiene total amount, it is more preferable to be 20��53 weight %.
The weight-average molecular weight that 1,2-key is the aromatic vinyl-conjugated diene copolymer beyond 20��40 weight % is preferably 6.0 �� 105��15 �� 105, it is more preferable to it is 8.0 �� 105��14 �� 105��
When other polydiene is beyond aromatic vinyl-conjugated diene copolymer (such as divinyl rubber, natural rubber), from further reducing by 60 DEG C of tan �� and the more excellent angle of workability, the content of other polydienes is preferably 10��70 weight % of polydiene total amount, it is more preferable to be 10��65 weight %.
From reducing by 60 DEG C of tan �� and the angle of excellent workability, in the present invention, the total amount of 1,2-key is 10��55 weight % of polydiene total amount, it is preferable to 15��55 weight %, it is more preferable to be 20��55 weight %. in addition, polydiene is also containing 1 in conjugated diolefine, when 2-key is the aromatic vinyl-conjugated diene copolymer beyond 20��40 weight %, and/or containing having 1 beyond aromatic vinyl-conjugated diene copolymer, when polydiene (such as the divinyl rubber) of 2-structure, 1, 2-key amount, it is 1 in conjugated diolefine, 2-key be the aromatic vinyl-conjugated diene copolymer of 20��40 weight % have 1, 2-key, in conjugated diolefine 1, 2-key be the aromatic vinyl-conjugated diene copolymer beyond 20��40 weight % have 1, 2-key, and have 1 beyond aromatic vinyl-conjugated diene copolymer, the polydiene of 2-key have 1, the sum total of the amount of 2-key.
<silane coupling agent>
Hereinafter, silane coupling agent is described. The silane coupling agent used in the present invention is the compound (silane coupling agent containing sulfydryl) represented with following formula (1):
Chemical formula 14
In formula, R11��R12And R13In at least 1 be-O-(R15-O)m-R16(R15To be carbonatoms be 1��30 2 valency alkyl, R16To be carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30, m is the integer of 1��30, R15For when multiple, multiple R15Can be identical, it is also possible to different),
R11��R12And R13In 1 or 2 be above-mentioned-O-(R15-O)m-R16When, it is possible to remaining group is set to alkyl ,-O-R that carbonatoms is 1��1217(R17Alkene base that the alkyl be hydrogen atom, carbonatoms being 1��30, carbonatoms are 2��30, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30), hydrogen atom or carbonatoms be the aryl of 6��30,
R11��R12And R13Can be identical, it is also possible to different,
R14To be carbonatoms be 1��30 2 valency alkyl.
As with R14��R15Represent carbonatoms be 1��30 2 valency alkyl, include, for example alkylidene group (such as methylene radical, dimethylene, trimethylene) etc. aliphatic alkyl; Aromatic hydrocarbyl; And their combination.
As with R16��R17Represent carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl, carbonatoms be the aralkyl of 7��30, include, for example the alkyl such as methyl, ethyl; The alkene base such as vinyl, propenyl; The aryl such as phenyl, tolyl; And the aralkyl such as phenmethyl, styroyl.
M is preferably the integer of 1��30.
R11��R12And R13In 1 or 2 be above-mentioned-O-(R15-O)m-R16When, as residue group and carbonatoms be 1��12 alkyl, carbonatoms be the aryl of 6��30, include, for example the alkyl such as methyl, ethyl; The aryl such as phenyl, tolyl.
From reducing by 60 DEG C of tan �� further and the angle of excellent workability, the compound represented with formula (1) is preferably the product being " VPSi363 " of solid Sa (DEGUSSA) company of moral. VPSi363 represents with following formula (1a).
Chemical formula 15
In formula (1a), R11��R12And R13In 2 be-O-(C2H4-O)n-C13H27, remaining is-O-C2H5, the mean number of n is 5, R14For trimethylene. R11��R13In ,-O-C2H5-the C having2H5Average content be less than 33%.
Silane coupling agent can individually use, it is also possible to is used in combination of two or more.
From reducing by 60 DEG C of tan �� and the angle of excellent workability, relative to polydiene 100 weight part, in the present invention, the amount of silane coupling agent is 0.5��20 weight part, it is preferable to 1.0��18 weight parts, it is more preferable to be 2.0��15 weight parts.
<silicon-dioxide>
Below, silicon-dioxide is described. There is no particular restriction for the silicon-dioxide used in the present application. Include, for example wet silicon dioxide (moisture silicic acid), dry type silicon-dioxide (anhydrous silicic acid), Calucium Silicate powder, pure aluminium silicate etc. Wherein, from further reducing by 60 DEG C of tan �� and the more excellent angle of workability, it is preferable to precipitated silica. Silicon-dioxide can individually use, it is also possible to is used in combination of two or more.
From reducing by 60 DEG C of tan �� and the angle of excellent workability, relative to polydiene 100 weight part, the amount of the silicon-dioxide used in mixed processes in the present invention is 20��120 weight parts, it is preferable to 30��110 weight parts.
<free radical scavenger>
In mixed processes, also can use is selected from by 2,2, at least a kind of free radical scavenger in the group that 6,6-tetramethyl piperidine, the dialkyl dithiophosphoric acid compounds represented with following formula (2), the sulphur represented with following formula (3) form for dicarboxylic ester, the bi-ester of phosphite represented with following formula (4), the acrylate represented with following formula (5), the phenolic compound represented with following formula (6) and lactone compound. When mixed processes also uses free radical scavenger, 60 DEG C of tan �� can be reduced further and workability is more excellent.
(dialkyl dithiophosphoric acid compounds)
Chemical formula 16
(in formula (2), R21And R22Separately representing that carbonatoms is the alkyl of 1��18, n is 0 or 1. Multiple R21And R22Can distinguish identical also can be different)
Carbonatoms be 1��18 alkyl include, for example methyl, ethyl, propyl group, own base, octyl group and the last of the ten Heavenly stems base etc. When n is 0,2 sulphur atoms can Direct Bonding.
(2,2,6,6-tetramethyl piperidine)
2,2,6,6-tetramethyl piperidine is the compound represented with following formula. 2,2,6,6-tetramethyl piperidine has nitroxyl free radical.
Chemical formula 17
(sulphur is for dicarboxylic ester)
The sulphur used in the rubber composition for tire of the present invention is the compound represented with following formula (3) for dicarboxylic ester:
Chemical formula 18
In above-mentioned formula (3), R31Separately represent that carbonatoms is the alkylidene group of 1��12, wherein for the reason that the workability of the rubber composition for tire of the present invention is more excellent, it is preferable that carbonatoms is the alkylidene group of 1��2. It is the concrete example of the alkylidene group of 1��2 as carbonatoms, vinyl etc. can be enumerated. Multiple R31Can distinguish identical also can be different.
In above-mentioned formula (3), R32Represent that carbonatoms is the alkyl of 1��30, wherein, for the reason that the workability of the rubber composition for tire of the present invention is more excellent, preferred carbonatoms is the alkyl of 1��24, more preferably carbonatoms is the alkyl of 6��24, and especially preferably carbonatoms is the alkyl of 6��18, and more specifically preferably carbonatoms is the alkyl of 8��18, particularly preferably carbonatoms is the alkyl of 12��18, it is most preferred that carbonatoms is the alkyl of 12��14. It is the concrete example of the alkyl of 12��18 as carbonatoms, dodecyl, hexadecyl, tetradecyl and octadecyl etc. can be enumerated. Multiple R32Can distinguish identical also can be different.
As the optimal way of above-mentioned sulphur for dicarboxylic ester, include, for example 3, 3'-thiobis propionic acid dioctyl ester, 3, 3'-thiobis propionic acid didecyl, 3, two ten diester of 3'-thiobis propionic acid, 3, the two tetradecane alcohol ester of the two propionic acid of 3'-thiobis, 3, the two cetyl alcohol ester of 3'-thiobis propionic acid, and 3, the two Stearyl alcohol esters of 3'-thiobis propionic acid etc., wherein, workability for the rubber composition for tire of the present invention is more excellent, and the reason of 60 DEG C of tan �� can be reduced further, preferably 3, two ten diester of 3'-thiobis propionic acid, 3, the two tetradecane alcohol ester of 3'-thiobis propionic acid, 3, the two cetyl alcohol ester of 3'-thiobis propionic acid, and 3, the two Stearyl alcohol ester of 3'-thiobis propionic acid, more preferably 3, two ten diester of 3'-thiobis propionic acid, 3, the two tetradecane alcohol ester of 3'-thiobis propionic acid.
(bi-ester of phosphite)
The bi-ester of phosphite used in the rubber composition for tire of the present invention is the compound represented with following formula (4):
Chemical formula 19
In above-mentioned formula (4), R41Represent that carbonatoms is the alkoxyl group of 1��4, wherein, for the reason that the workability of the rubber composition for tire of the present invention is more excellent, it is preferable to oxyethyl group or propoxy-, it is more preferable to be oxyethyl group.
In above-mentioned formula (4), R42And R43Separately represent that carbonatoms is the alkyl of 1��4, wherein, for the reason that the workability of the rubber composition for tire of the present invention is more excellent, it is preferable that propyl group or butyl, it is more preferable to the tertiary butyl. Multiple R42And R43Can distinguish identical also can be different.
In above-mentioned formula (4), R44Represent that hydrogen atom or carbonatoms are the alkyl of 1��4, wherein for the reason that the workability of the rubber composition for tire of the present invention is more excellent, it is preferable that hydrogen atom or methyl. Multiple R44Can be identical, it is also possible to different.
In above-mentioned formula (4), q represents the integer of more than 0, and r represents the integer of more than 2, and wherein, the workability for the rubber composition for tire of the present invention is more excellent, and reduces the reason of 60 DEG C of tan �� further, it is preferable that q is 0, r is 3. Q and r meets the relational expression of q+r=3.
As the optimal way of above-mentioned bi-ester of phosphite, include, for example multiple R in above-mentioned formula (4)42And R43In at least 1 be the tertiary butyl, multiple R44In at least one be the compound of hydrogen atom or methyl, as its concrete example, three (2,4-di-tert-butyl-phenyl) phosphorous acid ester, two (2,4-di-t-butyl-6-aminomethyl phenyl) ethide phosphite ester etc. can be enumerated.
(acrylate)
The acrylate used in the rubber composition for tire of the present invention is the acrylate represented with following formula (5):
Chemical formula 20
In above-mentioned formula (5), R51Represent hydrogen atom or carbonatoms be 1��6 straight-chain or branch-like alkyl (such as methyl, ethyl, the tertiary butyl, 1,1-dimethyl propyl etc.), wherein workability for the rubber composition for tire of the present invention is more excellent, and the reason of 60 DEG C of tan �� can be reduced further, being preferably carbonatoms is the straight-chain of 1��6 or the alkyl of branch-like, it is more preferable to be methyl.
In above-mentioned formula (5), R52And R55Separately represent hydrogen atom or carbonatoms be 1��6 straight-chain or branch-like alkyl (such as methyl, ethyl, the tertiary butyl, 1,1-dimethyl propyl etc.), wherein, workability for the rubber composition for tire of the present invention is more excellent, and reduce the reason of 60 DEG C of tan �� further, preferred carbonatoms is the straight-chain of 1��6 or the alkyl of branch-like, more preferably carbonatoms is the alkyl of the branch-like of 1��6, especially preferred tertiary butyl or 1,1-dimethyl propyl, particularly preferably 1,1-dimethyl propyl.
In above-mentioned formula (5), R53And R54Separately represent hydrogen atom or carbonatoms be 1��6 straight-chain or branch-like alkyl (such as methyl, ethyl, the tertiary butyl, 1,1-dimethyl propyl etc.), wherein, workability for the rubber composition for tire of the present invention is more excellent, and reduce the reason of 60 DEG C of tan �� further, it is preferable that carbonatoms is the straight-chain of 1��6 or the alkyl of branch-like, it is more preferable to carbonatoms is the alkyl of the branch-like of 1��6, especially preferably 1,1-dimethyl propyl.
As the optimal way of aforesaid propylene acid esters, include, for example R in above-mentioned formula (5)51For hydrogen atom, R52And R55For the tertiary butyl, R53And R54For the compound of methyl, and R in above-mentioned formula (5)51For methyl, R52��R53��R54And R55For the compound etc. of 1,1-dimethyl propyl, wherein, the workability for the rubber composition for tire of the present invention is more excellent, and reduces the reason of 60 DEG C of tan �� further, it is preferable that R in above-mentioned formula (5)51For methyl, R52��R53��R54And R55For the compound of 1,1-dimethyl propyl.
(phenolic compound)
The phenolic compound used in the rubber composition for tire of the present invention is the compound represented with following formula (6):
Chemical formula 21
In above-mentioned formula (6), R61��R62And R63Separately represent can be the alkyl of 1��30 containing heteroatomic carbonatoms. As the concrete example of alkyl that can be containing heteroatomic carbonatoms 1��30, methyl can be enumerated, ethyl, propyl group, following carbonatoms be 4��20 alkyl, octyl group thiomethyl and dodecylthiomethyl etc.
In addition, R61��R62And R63In at least 2 represent that containing carbonatoms be the alkyl of 4��20, and heteroatomic alkyl can be contained.
Herein, above-mentioned alkyl containing alkyl can also to be above-mentioned carbonatoms be 4��20 alkyl self.
It is the concrete example of the alkyl of 4��20 as carbonatoms, butyl (normal-butyl, sec-butyl, isobutyl-, the tertiary butyl), amyl group, heptyl, octyl group, dodecyl and octadecyl etc. can be enumerated.
Workability for the rubber composition for tire of the present invention is more excellent, and reduces the reason of 60 DEG C of tan ��, above-mentioned R further61��R62And R63In at least 1 be preferably containing the alkyl of heteroatoms (nitrogen-atoms, Sauerstoffatom, phosphorus atom, sulphur atom etc.), more preferably the group being selected from the group that the group represented by following formula (7)��(9) forms, the group especially preferably represented with following formula (7).
We speculate, above-mentioned R61��R62And R63In at least 1 when being containing the alkyl of heteroatoms (nitrogen-atoms, Sauerstoffatom, phosphorus atom, sulphur atom etc.), above-mentioned heteroatomic unpaired electron can with the polyether chain (above-mentioned-O-(R of above-mentioned silane coupling agent15-O)m-R16) interact, its result is, it is possible to suppresses the interaction of phenolic compound and silicon-dioxide, and improves the dispersion of silicon-dioxide, reduces by 60 DEG C of tan �� further.
In addition, also speculate: owing to above-mentioned heteroatoms can act on the phenolic hydroxyl group of phenolic compound, so the stability of the free radical of phenolic compound can improve, and workability can improve further.
Chemical formula 22
In above-mentioned formula (7), R71The carbonatoms of expression straight-chain is the alkylidene group of 1��3, is wherein preferably vinyl.
In above-mentioned formula (7), R72The carbonatoms of expression straight-chain or branch-like is the alkyl of 4��18, and wherein preferably carbonatoms is the alkyl of more than 12.
In above-mentioned formula (7), * represents bonding position.
Chemical formula 23
In above-mentioned formula (8), R81The carbonatoms of expression straight-chain or branch-like is the alkyl of 4��8, and wherein preferably carbonatoms is the alkyl of more than 6. Multiple R81Can distinguish identical also can be different.
In above-mentioned formula (8), * represents bonding position.
Chemical formula 24
In above-mentioned formula (9), R91The carbonatoms of expression straight-chain is the alkylidene group of 1��4, is wherein preferably methylene radical.
In above-mentioned formula (9), R92The carbonatoms of expression straight-chain or branch-like is the alkyl of 4��12, wherein workability for the rubber composition for tire of the present invention is more excellent, and reduce the reason of 60 DEG C of tan �� further, it is preferable that carbonatoms is the alkyl of 8��12, it is more preferable to carbonatoms is the alkyl of 8��10.
In above-mentioned formula (9), * represents bonding position.
As the concrete example of the compound represented with above-mentioned formula (6), 2 can be enumerated, 6-ditertbutylparacresol, iso-octyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2, two (pungent sulphur the base)-6-(4-hydroxyl-3 of 4-, 5-di-tert-butyl amido)-1, 3, 5-triazine, 4, two (dodecylthiomethyl) ortho-cresol of 6-, and 4, two (pungent sulphur ylmethyl) ortho-cresols of 6-etc., wherein preferred octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester, 2, two (pungent sulphur the base)-6-(4-hydroxyl-3 of 4-, 5-di-tert-butyl amido)-1, 3, 5-triazine, 4, two (dodecylthiomethyl) ortho-cresol of 6-, and 4, two (the pungent sulphur ylmethyl) ortho-cresol of 6-, more preferably octadecyl-3-(3, 5-di-tert-butyl-hydroxy phenyl) propionic ester.
(lactone compound)
The lactone compound used in the rubber composition for tire of the present invention is not particularly limited, as long as have the compound of lactone structure. Lactone structure herein has carboxylicesters bonding-C(=O in finger ring) ring texture of-O-.
As the 1st optimal way of above-mentioned lactone compound, can enumerate with compound that following formula (10) represents:
Chemical formula 25
In above-mentioned formula (10), R101And R102Separately the carbonatoms of expression hydrogen atom or straight-chain or branch-like is the alkyl of 1��10, and the workability for the rubber composition for tire of the present invention is more excellent, and reduces the reason of 60 DEG C of tan �� further, it is preferable to hydrogen atom. Multiple R101And R102Can distinguish identical also can be different.
In above-mentioned formula (10), m represents the integer of 1��3, and the workability for the rubber composition for tire of the present invention is more excellent, and reduces the reason of 60 DEG C of tan �� further, it is preferable to 2.
As the 2nd optimal way of above-mentioned lactone compound, can enumerate with compound that following formula (11) represents:
Chemical formula 26
In above-mentioned formula (11), R111The carbonatoms of expression hydrogen atom or straight-chain or branch-like is the alkyl of 1��10, workability for the rubber composition for tire of the present invention is more excellent, and reduce the reason of 60 DEG C of tan �� further, it is preferable that the carbonatoms of hydrogen atom or straight-chain or branch-like is the alkyl of 1��7. Multiple R121Can distinguish identical also can be different.
In above-mentioned formula (11), n represents the integer of 1��3.
From further reducing by 60 DEG C of tan �� and the more excellent angle of workability, relative to polydiene 100 weight part, the amount of free radical scavenger is preferably 0.1��5 weight part, it is more preferable to be 0.2��4 weight part.
Mixed processes also can use softening agent. When also using softening agent in mixed processes, workability is more excellent. Softening agent is not particularly limited. Such as, petroleum-type mineral oil, coal tar class mineral oil, fatty oils vegetables oil, resol, dioctyl phthalate (DOP), polyester, dioctyl sebacate and terpine resin etc. can be enumerated. Softening agent can be added in polydiene (such as aromatic vinyl-conjugated diene copolymer) in advance.
From further reducing by 60 DEG C of tan �� and the more excellent angle of workability, relative to polydiene 100 weight part, the amount of softening agent is preferably below 35 weight parts, it is more preferable to be 5��30 weight parts.
Described in following, when using dispersing auxiliary after mixed processes, from further reducing by 60 DEG C of tan �� and the more excellent angle of workability, relative to polydiene 100 weight part, the total amount of dispersing auxiliary and softening agent is preferably below 35 weight parts, it is more preferable to be 10��35 weight parts.
The silane coupling agent in the present invention, at least mix polydiene in mixed processes, representing with formula (1) and silicon-dioxide.
From the generation suppressing free radical, reducing by 60 DEG C of tan ��, and the angle of excellent workability is set out, the mixing temperature of mixed processes is lower than 140 DEG C, it is preferable to 120��138 DEG C, it is more preferable to be 125��135 DEG C.
In mixed processes, do not use vulcanizing agent and/or vulcanization accelerator or vulcanization aid. Mixed processes uses vulcanizing agent, vulcanization accelerator, vulcanization aid, from further reducing by 60 DEG C of tan �� and the more excellent angle of workability, relative to polydiene 100 weight part, the total amount of vulcanizing agent, vulcanization accelerator, vulcanization aid is preferably below 2 weight parts.
There is no particular restriction for blending means in mixed processes. Such as, the mixing rolls such as closed mixing machine, cylinder, Banbury mixer can be used to carry out mixing, manufacture mixture.
The rubber composition for tire of the present invention manufactures by mixed processes. In addition, in the present application, can using the mixture manufactured by mixed processes (mixing the 1st step), then as required, setting is added mixing the 2nd step of dispersing auxiliary, is added vulcanizing agent and/or vulcanization aid, or the mixing of vulcanization aid the 3rd step.
In the present application, in mixed processes (mixing the 1st step) when mixing the 2nd step of setting use dispersing auxiliary afterwards, to dispersing auxiliary, there is no particular restriction, normally used material on rubber combination. Such as, diatomic alcohol compounds, the silane compound with alkyl and polysiloxane compound etc. can be enumerated.
From further reducing by 60 DEG C of tan �� and the more excellent angle of workability, dispersing auxiliary is preferably diatomic alcohol compounds and/or has the silane compound of alkyl.
As diatomic alcohol compounds, include, for example ethylene glycol, glycol ether, propylene glycol and polypropylene glycol etc.
As the silane compound with alkyl, include, for example the compound in 1 Siliciumatom with more than 1 alkyl. The carbonatoms of alkyl can be 1��18. Silane compound, except alkyl, can have 1��3 alkoxyl group. Specifically, include, for example the alkyltrialkoxysilaneand such as octyltri-ethoxysilane, octyl group Trimethoxy silane; Dialkyl dialkoxy silicane; And trialkyl alkoxy silane.
From further reducing by 60 DEG C of tan �� and the more excellent angle of workability, relative to polydiene 100 weight part, the amount of dispersing auxiliary is preferably 0.5��5 weight part, it is more preferable to be 1��5 weight part.
The mixing temperature mixing the 2nd step is preferably lower than 140 DEG C.
There is no particular restriction to mix the blending means of the 2nd step. The mixing machinery of known rubber can be used, such as Ban Buli mixing machine, kneader and cylinder etc.
In the present application, at mixed processes (mixing the 1st step) afterwards or after mixing the 2nd step when setting mixing the 3rd step, to the vulcanizing agent, the vulcanization accelerator that use in mixing the 3rd step, there is no particular restriction for vulcanization aid, normally used material in rubber combination. Include, for example current known lubricating oil.
Relative to polydiene 100 weight part, the amount of vulcanizing agent (such as sulphur) is preferably 0.5��5.0 weight part.
The mixing temperature mixing the 3rd step is preferably lower than 140 DEG C.
There is no particular restriction to mix the blending means of the 3rd step. The mixing machinery of known rubber can be used, such as Ban Buli mixing machine, kneader and cylinder etc.
The rubber composition for tire of the present invention, also can compounding other weighting agents except silicon-dioxide. As other weighting agents beyond silicon-dioxide, include, for example carbon black, clay, mica, talcum, calcium carbonate, aluminium hydroxide, aluminum oxide and titanium oxide etc.
The rubber composition for tire of the present invention, it is possible to as required, in the scope not damaging its effect and object and then containing additive. As additive, include, for example the normally used various Synergist S-421 95 on rubber composition for tire such as the silane coupling agent beyond formula (1), antiaging agent, processing aid, liquid polymers, terpenoid resin and thermosetting resin. Additive can method routinely carry out mixing, makes rubber combination, it may also be useful in sulfuration or crosslinked. As long as the compounding amount of additive not object with the present invention run counter to, traditional general compounding amount can be adopted.
There is no particular restriction for condition during the rubber composition for tire of sulfuration the present invention.
The rubber composition for tire of the present invention or the rubber composition for tire manufactured by the manufacture method of the rubber composition for tire of following the present invention are applicable in pneumatic tyre (such as tire tread).
Hereinafter, just the manufacture method of the rubber composition for tire of the present invention is described.
The manufacture method of the rubber composition for tire of the present invention is as follows:
Polydiene contains one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % that 1,2-key in conjugated diolefine is 20��40 weight %, and the total amount of above-mentioned 1,2-key is 10��55 weight % of above-mentioned polydiene total amount,
By relative to above-mentioned polydiene 100 weight part, the mixed processes mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with following formula (1) manufactures, and not using vulcanizing agent in above-mentioned mixed processes, the mixing temperature in above-mentioned mixed processes is lower than 140 DEG C:
Chemical formula 27
In formula, R11��R12And R13In at least 1 be-O-(R15-O)m-R16(R15To be carbonatoms be 1��30 2 valency alkyl, R16To be carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30, m is the integer of 1��30, R15For when multiple, multiple R15Can be identical, it is also possible to different),
R11��R12And R13In 1 or 2 be above-mentioned-O-(R15-O)m-R16When, it is possible to remaining group is set to alkyl ,-O-R that carbonatoms is 1��1217(R17Alkene base that the alkyl be hydrogen atom, carbonatoms being 1��30, carbonatoms are 2��30, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30), hydrogen atom or carbonatoms be the aryl of 6��30,
R11��R12And R13Can be identical, it is also possible to different,
R14To be carbonatoms be 1��30 2 valency alkyl.
By the manufacture method of the rubber composition for tire of the present invention, the rubber composition for tire of the present invention can be produced.
The composition used in the manufacture method of the rubber composition for tire of the present invention is identical with the composition used in the rubber composition for tire of the present invention.
In mixed processes, preferably also using is selected from by 2,2, at least a kind of free radical scavenger in the group that 6,6-tetramethyl piperidine, the dialkyl dithiophosphoric acid compounds represented with following formula (2), the sulphur represented with above-mentioned formula (3) form for dicarboxylic ester, the bi-ester of phosphite represented with above-mentioned formula (4), the acrylate represented with above-mentioned formula (5), the phenolic compound represented with above-mentioned formula (6) and above-mentioned lactone compound. When mixed processes also uses free radical scavenger, 60 DEG C of tan �� can be reduced further and workability is more excellent.
Chemical formula 28
(in formula (2), R21And R22Separately representing that carbonatoms is the alkyl of 1��18, n is 0 or 1. Multiple R21And R22Can distinguish identical also can be different)
The amount of free radical scavenger is same as described above.
In the manufacture method of the rubber composition for tire of the present invention, the mixing temperature of mixed processes is lower than 140 DEG C, and this is same as described above. From further reducing by 60 DEG C of tan �� and the more excellent angle of workability, it is preferable to lower than 120��140 DEG C.
When free radical scavenger is 2,2,6,6-tetramethyl piperidine, mixing temperature is preferably lower than 120��140 DEG C.
Free radical scavenger for represent with formula (2) dialkyl dithiophosphoric acid compounds when, mixing temperature is preferably lower than 120��140 DEG C.
Below, the pneumatic tyre of the present invention is described. The pneumatic tyre of the present invention is the rubber composition for tire employing the present invention at tire tread or the pneumatic tyre of the rubber composition for tire manufactured by the manufacture method of the rubber composition for tire of the present invention.
Below, with reference to accompanying drawing, the pneumatic tyre of the present invention is described.
Fig. 1 illustrates an example of the enforcement mode of the pneumatic tyre using rubber composition for tire. In Fig. 1,1 is fetus face, and 2 is that side of sidewall portion, 3 is for bead part.
In Fig. 1, extend between the bead part 3 of left and right and it is provided with 2 layers of cord body 4, its both ends are around the bead core 5 being embedded in bead part 3, turn back from tire axial Inside To Outside, being clipped in the middle by bead-core 6, described cord body 4 is by arranging the enhancing curtain line extended to tire radial direction with appointed interval towards tire circumference and is embedded in rubber layer. It is configured with air retaining wall 7 in the inner side of cord body 4. Outer circumferential side at the cord body 4 of fetus face 1 is configured with 2 layers of belt 8, described belt 8 by by tire peripheral, oblique the enhancing curtain line that extends arrange with appointed interval towards tire axial and be embedded in rubber layer. The enhancing curtain line of these 2 layers of belts 8 is and intersection reciprocal relative to the vergence direction of tire circumference between layer. Outer circumferential side at belt 8 is configured with band cap layer 9. At the outer circumferential side of this band cap layer 9, it is formed with the fetus face 1 being made up of tread rubber layer 12. Tread rubber layer 12 is made up of the rubber composition for tire of the present invention. Being configured with side rubber layer 13 in the outside of the cord body 4 of each side of sidewall portion 2, the return portion arranged outside at the cord body 4 of each bead part 3 has wheel rim cushion rubber layer 14.
The pneumatic tyre of the present invention, except the tyre surface that the rubber composition for tire by the rubber composition for tire of the present invention or by the manufacture method manufacture of the rubber composition for tire of the present invention is used for pneumatic tyre, there is no particular restriction, such as, can manufacture according to known method. In addition, as the gas filled in tire, except the air of routine or except the air of oxygen partial pressure adjustment, it is also possible to use the rare gas elementes such as nitrogen, argon, helium.
Embodiment
Below, show example and the present invention is specifically described. But the present invention is not limited to this.<manufacture of rubber composition for tire>
Composition with the table below is used with the amount (weight part) shown in mixing the 1st step of each table, closed mixing machine is used it to be discharged after mixing 6 minutes with the mixing temperature shown in each table, the mixture obtained adds the composition shown in mixing the 2nd step with table, mixing the 3rd step with amount (weight part) with the table below, use mill to carry out mixing to it, thus it is modulated into rubber composition for tire (unvulcanized).
Mix the mixed processes that the 1st step is equivalent to the present application.
The mixing temperature of mixing the 2nd step of table 1, table 2 is 130 DEG C, and the mixing temperature of mixing the 3rd step of table 1, table 2 is 130 DEG C. The mixing temperature of mixing the 2nd step of table 3, table 4 is 130 DEG C, and the mixing temperature of mixing the 3rd step of table 3, table 4 is 130 DEG C. The mixing temperature of mixing the 2nd step of table 5, table 6 is 130 DEG C, and the mixing temperature of mixing the 3rd step of table 5, table 6 is 110 DEG C.
<manufacture of vulcanized rubber sample>
In the mould of regulation shape, rubber composition for tire press vulcanization 20 minutes at 160 DEG C that will be obtained by above method, make vulcanized rubber sample.
<assessment>
Use the unvulcanized rubber composition for tire obtained by above method, processibility, Free radicals and mooney viscosity can be extruded according to method shown below assessment. In addition, it may also be useful to the vulcanized rubber sample obtained as mentioned above, measures the tan �� of 60 DEG C according to method shown below. Result is as shown in each table.
In addition, about the result of Free radicals, the tan �� of 60 DEG C, table 1, table 2 assess taking standard example 1 as standard, and table 3, table 4 assess taking standard example 2 as standard, and table 5, table 6, table 7 assess taking standard example 3 as standard.
Processibility can be extruded
According to ASTMD2230, the condition of surface of visual assessment extrudate. Evaluation criteria divides following 5 evaluation grades, and more than 4 is allowed band.
5=extrudes good; 4=can extrude; 3=can not extrude; 2=can not extrude and the surperficial skin state difference of extrudate; 1=can not extrude and the surperficial skin state of extrudate is very poor
Free radicals
Use the free radical monitor JES-FR30EX of NEC Inc., measure the number of free radical in unvulcanized rubber. Unvulcanized rubber test portion (width 5mm �� length 30mm �� thickness 1mm) is installed in sample hose, measures when 20 DEG C. The measurement result herein obtained comprises carbon, these two kinds of free radicals of sulphur. Mark as spectrum (ESR), it may also be useful to make Mn2+The MgO become in thermodiffusion to MgO. Utilizing Mn(manganese) relative area (index) when being set to 100 of the peak value area that marks represents the number of free radical in each test portion. Index is more big, represents that the number of free radical of rubber is more high.
Mooney viscosity
According to JISK6300, measure at 100 DEG C. Index is more low, then represent that workability is more excellent.
The tan �� of 60 DEG C
Use (Co., Ltd.) Japan essence mechanism to make made viscoelasticity spectrometer, measured when initial strain 10%, amplitude �� 2%, frequency 20Hz. Index is more low, then represent that the effect reducing rolling resistance is more obvious.
Table 1
Table 2
The detailed content of each composition shown in table 1, table 2 as follows described in.
SBR1: 20 weight parts oil-filled relative to SBR100 weight part and the SBR that becomes, Vn(1,2-key amount) be 60 weight %, have OH modification, weight-average molecular weight to be 9.3 �� 105, Japanese auspicious father-in-law (ZEON) Inc. NipolNS530
SBR2: 37.5 weight parts oil-filled relative to SBR100 weight part and become styrene butadiene ribber, Vn(1,2-key amount in SBR) be 43 weight %, have OH modification, weight-average molecular weight to be 12.6 �� 105, Inc. of Asahi Chemical Industry E581
SBR3: 25 weight parts oil-filled relative to SBR100 weight part and become styrene butadiene ribber, Vn(1,2-key amount in SBR) be 33 weight %, have OH modification, weight-average molecular weight to be 13.3 �� 105, Japan Rui Weng Inc. NipolNS570
SBR4: 37.5 weight parts oil-filled relative to SBR100 weight part and become styrene butadiene ribber, Vn(1,2-key amount in SBR) be 10 weight %, be 6.3 �� 10 without OH modification, weight-average molecular weight5, Inc. of Asahi Chemical Industry Tufdene1534
SBR6: 37.5 weight parts oil-filled relative to SBR100 weight part and become styrene butadiene ribber, Vn(1,2-key amount in SBR) be 71.5 weight %, weight-average molecular weight be 7.8 �� 105, bright Sheng (LANXESS) Inc., trade(brand)name BUNAVSL5025-HM1
BR: the Vn(1,2-key amount in divinyl rubber, BR) it is 1 weight %, it is 5.0 �� 10 without OH modification, weight-average molecular weight5, Japan Rui Weng Inc. Nipol1220
Silica 1: Luo Diya (RHODIA) Inc., " Zeosil1165MP "
Silane coupling agent 1: sulfide-based silane coupling agent, De Gusa DEGUSSA Inc. Si69VP
Silane coupling agent 2: solid Sa (DEGUSSA) the Inc. VPSi363 of moral
Zinc white: zinc oxide, just same chemical industry (Co., Ltd.) system, " 3 kinds, zinc oxide "
Stearic acid: Japan grease Inc., " pearl stearic acid "
Antiaging agent: Fu Laikesi (FLEXSYS) Inc., " 6PPD "
Oil: Showa Shell Oil Co. system, " Extract4 S "
Dispersing auxiliary 1: Wan Shan petroleum chemistry Inc., " divinyl ethylene glycol "
Dispersing auxiliary 2: chemical industry Inc. of SHIN-ETSU HANTOTAI, " octyltri-ethoxysilane "
Sulphur: He Jian chemical industry Inc., " Jinhua stamp-pad ink powder sulphur in a subtle way "
Vulcanization accelerator 1: the emerging chemical industry Inc. of imperial palace, " NoccelerCZ-G "
The new chemical industry vulcanization accelerator SANCELERD-G table 3 of vulcanization accelerator 2: three
Table 4
Composition shown in table 3, table 4 is specific as follows.
SBR1: Rui Weng Inc. NipolNS530(is identical with the SBR1 of table 1 in Japan)
SBR3: Rui Weng Inc. NipolNS570(is identical with the SBR3 of table 1 in Japan)
SBR5: 37.5 weight parts oil-filled relative to SBR100 weight part and become styrene butadiene ribber, Vn(1,2-key amount in SBR) be 72 weight %, weight-average molecular weight be 11.7 �� 105, DOW Chemical (DOWCHEMICAL) Inc. SLR6430
TEMPO: Tokyo chemical conversion industrial reagent 2,2,6,6-Tetramethylpiperidine1-OxylOFreeRadical
Composition other than the above and table 1 are identical.
Table 5
Table 6
Composition shown in table 5, table 6 is specific as follows.
SBR1: identical with the SBR1 of table 1
SBR3: identical with the SBR3 of table 1
SBR5: identical with the SBR5 of table 3
DTP: the zinc dithiophosphate salt represented with following formula, bright Sheng (LANXESS) Inc. RhenocureZBOP/S
Chemical formula 29
(in formula, R1��R2For with CpH2p+1The alkyl that (p=1��18) represent, n is 1)
Composition other than the above and table 1 are identical.
Table 7
Composition shown in table 7 is specific as follows.
GM:SumilizerGM(sumitomo chemical company system) (the compound represented with above-mentioned formula (5). Herein, R51For hydrogen atom. R52And R55For the tertiary butyl. R53And R54For methyl)
GS:SumilizerGS(sumitomo chemical company system) (the compound represented with above-mentioned formula (5). Herein, R51For methyl, R52��R53��R54And R55For 1,1-dimethyl propyl)
Composition other than the above and table 1 are identical.
As can be seen from the result shown in table, when mixing not containing 1 in conjugated diolefine at 135 DEG C, 2-key is the aromatic vinyl-conjugated diene copolymer of 20��40 weight %, and during the higher comparative example �� I ��-1 of the average ethylene amount in polydiene, occur mixing bad, the rubber surface that unvulcanized mixture obtains after extrusion is coarse, and workability is poor. Mixing temperature is the Free radicals height of the comparative example �� I ��-2,3 of more than 140 DEG C, and the rubber surface that unvulcanized mixture obtains after extrusion is coarse, and workability is poor. Measure in the comparative example �� I ��-4 lower than 0.5 weight part, conjugated diolefine the 1 of the silane coupling agent represented with formula (1), 2-key is that the content of the one kind or two or more aromatic vinyl-conjugated diene copolymer of 20��40 weight % is lower than 30 weight %, and 1, the total amount of 2-key is lower than in the comparative example �� I ��-7 of 10 weight % of polydiene total amount, 60 DEG C of tan �� height, rolling resistance height. The amount of the silane coupling agent represented with formula (1) is more than the comparative example �� I ��-5,1 of 20 weight parts, the total amount of 2-key exceedes 1 in the comparative example �� I ��-6 of 55 weight % in polydiene total amount, conjugated diolefine, 2-key is that the content of the one kind or two or more aromatic vinyl-conjugated diene copolymer of 20��40 weight % is more than in the comparative example �� I ��-8 of 90 weight %, the rubber surface that unvulcanized mixture obtains after extrusion is coarse, and workability is poor.
The total amount of 1,2-key exceedes in the comparative example �� II ��-1 of 55 weight % of polydiene total amount, comparative example �� III ��-1, and the rubber surface that unvulcanized mixture obtains after extrusion is coarse, and workability is poor. Mixing temperature be more than 140 DEG C comparative example �� II ��-2,3, in comparative example �� III ��-2,3, Free radicals height, the rubber surface that unvulcanized mixture obtains after extrusion is coarse, and workability is poor, and mooney viscosity height.
Relative to this, embodiment �� I ��-1��11, embodiment �� II ��-1��5, embodiment �� III ��-1��5, embodiment �� IV ��-1��4, can suppress to mix generation that is bad and/or free radical, (viscosity of mixture is low for workability, can implement to extrude processing, rubber surface after extrusion is smooth) excellent, and 60 DEG C of tan �� can be reduced.
Nomenclature
1 fetus face
12 tread rubber layers
Claims (10)
1. a rubber composition for tire, it is characterized in that, polydiene contains in conjugated diolefine 1,2-key is one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % of 20��40 weight %, and 1, the total amount of 2-key is 10��55 weight % of described polydiene total amount
By relative to described polydiene 100 weight part, the mixed processes mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with following formula (1) manufactures, and in described mixed processes, do not use vulcanizing agent, mixing temperature in described mixed processes is lower than 140 DEG C
In formula, R11��R12And R13In at least 1 be-O-(R15-O)m-R16, R15To be carbonatoms be 1��30 2 valency alkyl, R16To be carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30, m is the integer of 1��30, R15For when multiple, multiple R15Can be identical, it is also possible to different,
R11��R12And R13In 1 or 2 be described-O-(R15-O)m-R16When, it is possible to remaining group is set to alkyl ,-O-R that carbonatoms is 1��1217, hydrogen atom or carbonatoms be the aryl of 6��30, R17Alkene base that the alkyl be hydrogen atom, carbonatoms being 1��30, carbonatoms are 2��30, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30,
R11��R12And R13Can be identical, it is also possible to different,
R14To be carbonatoms be 1��30 2 valency alkyl.
2. rubber composition for tire according to claim 1, wherein in above-mentioned mixed processes, also using is selected from by 2, 2, 6, 6-tetramethyl piperidine-1-oxide compound, the dialkyl dithiophosphoric acid compounds represented with following formula (2), the sulphur represented with following formula (3) is for dicarboxylic ester, the bi-ester of phosphite represented with following formula (4), the acrylate represented with following formula (5), at least a kind of free radical scavenger in the group that the phenolic compound represented with following formula (6) and lactone compound form, and relative to described polydiene 100 weight part, the amount of described free radical scavenger is 0.1��5 weight part,
In formula (2), R21And R22Separately representing that carbonatoms is the alkyl of 1��18, n is 0 or 1, multiple R21And R22Can distinguish identical also can be different,
In formula (3), R31Represent that carbonatoms is the alkylidene group of 1��12, R32Represent that carbonatoms is the alkyl of 1��30, multiple R31And R32Can distinguish identical also can be different,
In formula (4), R41Represent that carbonatoms is the alkoxyl group of 1��4, R42And R43Separately represent that carbonatoms is the alkyl of 1��4, R44Representing that hydrogen atom or carbonatoms are the alkyl of 1��4, q represents the integer of more than 0, and r represents the integer of more than 2, q and r meets the relational expression of q+r=3, multiple R42��R43And R44Can distinguish identical also can be different,
In formula (5), R51��R55Separately represent that hydrogen atom or carbonatoms are the straight-chain of 1��6 or the alkyl of branch-like,
In formula (6), R61��R62And R63Separately represent can be the alkyl of 1��30 containing heteroatomic carbonatoms, R61��R62And R63In at least 2 represent and be the alkyl of 4��20 and heteroatomic alkyl can be contained containing carbonatoms.
3., according to rubber composition for tire according to claim 1 or claim 2, wherein said one kind or two or more aromatic vinyl-conjugated diene copolymer, has hydroxyl at end.
4. according to rubber composition for tire according to claim 1 or claim 2, it is characterised in that, described mixed processes also uses softening agent, and relative to described polydiene 100 weight part, the amount of described softening agent is below 35 weight parts.
5. according to rubber composition for tire according to claim 1 or claim 2, it is characterized in that, after described mixed processes, the compounding diatomic alcohol compounds as dispersing auxiliary and/or there is the silane compound of alkyl, and relative to described polydiene 100 weight part, the amount of described dispersing auxiliary is 0.5��5 weight part.
6. rubber composition for tire according to claim 5, it is characterised in that, in described mixed processes, also use softening agent, relative to described polydiene 100 weight part, the total amount of described dispersing auxiliary and described softening agent is below 35 weight parts.
7. according to rubber composition for tire according to claim 1 or claim 2, it is characterized in that, described polydiene is also containing at least a kind be selected from the group being made up of lower than the aromatic vinyl-conjugated diene copolymer of 20 weight %, divinyl rubber and natural rubber 1,2-key.
8. the manufacture method of a rubber composition for tire, it is characterized in that, polydiene contains 1 in conjugated diolefine, 2-key is one kind or two or more aromatic vinyl-conjugated diene copolymer 30��90 weight % of 20��40 weight %, and described 1, the total amount of 2-key is 10��55 weight % of described polydiene total amount
By relative to described polydiene 100 weight part, the mixed processes mixing silane coupling agent 0.5��20 weight part and silicon-dioxide 20��120 weight part represented with following formula (1) manufactures, and described mixed processes does not use vulcanizing agent, mixing temperature in described mixed processes is lower than 140 DEG C
In formula, R11��R12And R13In at least 1 be-O-(R15-O)m-R16, R15To be carbonatoms be 1��30 2 valency alkyl, R16To be carbonatoms be 1��30 alkyl, carbonatoms be 2��30 alkene base, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30, m is the integer of 1��30, R15For when multiple, multiple R15Can be identical, it is also possible to different,
R11��R12And R13In 1 or 2 be described-O-(R15-O)m-R16When, it is possible to remaining group is set to alkyl ,-O-R that carbonatoms is 1��1217, hydrogen atom or carbonatoms be the aryl of 6��30, R17Alkene base that the alkyl be hydrogen atom, carbonatoms being 1��30, carbonatoms are 2��30, carbonatoms be 6��30 aryl or carbonatoms be the aralkyl of 7��30,
R11��R12And R13Can be identical, it is also possible to different,
R14To be carbonatoms be 1��30 2 valency alkyl.
9. the manufacture method of rubber composition for tire according to claim 8, in wherein said mixed processes, also using is selected from by 2, 2, 6, 6-tetramethyl piperidine-1-oxide compound, the dialkyl dithiophosphoric acid compounds represented with following formula (2), the sulphur represented with following formula (3) is for dicarboxylic ester, the bi-ester of phosphite represented with following formula (4), the acrylate represented with following formula (5), at least a kind of free radical scavenger in the group that the phenolic compound represented with following formula (6) and lactone compound form, and relative to described polydiene 100 weight part, the amount of described free radical scavenger is 0.1��5 weight part,
In formula (2), R21And R22Separately representing that carbonatoms is the alkyl of 1��18, n is 0 or 1, multiple R21And R22Can distinguish identical also can be different,
In formula (3), R31Represent that carbonatoms is the alkylidene group of 1��12, R32Represent that carbonatoms is the alkyl of 1��30, multiple R31And R32Can distinguish identical also can be different,
In formula (4), R41Represent that carbonatoms is the alkoxyl group of 1��4, R42And R43Separately represent that carbonatoms is the alkyl of 1��4, R44Representing that hydrogen atom or carbonatoms are the alkyl of 1��4, q represents the integer of more than 0, and r represents the integer of more than 2, q and r meets the relational expression of q+r=3, multiple R42��R43And R44Can distinguish identical also can be different,
In formula (5), R51��R55Separately represent that hydrogen atom or carbonatoms are the straight-chain of 1��6 or the alkyl of branch-like,
In formula (6), R61��R62And R63Separately represent can be the alkyl of 1��30 containing heteroatomic carbonatoms, R61��R62And R63In at least 2 represent and be the alkyl of 4��20 and heteroatomic alkyl can be contained containing carbonatoms.
10. a pneumatic tyre, the rubber composition for tire employing the rubber composition for tire according to any one of claim 1 to claim 7 on tire tread or being manufactured by the manufacture method according to claim 8 or rubber composition for tire according to claim 9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-216300 | 2011-09-30 | ||
| JP2011216300A JP5668660B2 (en) | 2011-09-30 | 2011-09-30 | Rubber composition for tire and pneumatic tire using the same |
| PCT/JP2012/074191 WO2013047356A1 (en) | 2011-09-30 | 2012-09-21 | Rubber composition for tyre and pneumatic tyre using the same |
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| Publication Number | Publication Date |
|---|---|
| CN104011128A CN104011128A (en) | 2014-08-27 |
| CN104011128B true CN104011128B (en) | 2016-06-01 |
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| CN201280048687.5A Active CN104011128B (en) | 2011-09-30 | 2012-09-21 | Rubber composition for tire and use the pneumatic tyre of this rubber combination |
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| Country | Link |
|---|---|
| JP (1) | JP5668660B2 (en) |
| KR (1) | KR101604585B1 (en) |
| CN (1) | CN104011128B (en) |
| DE (1) | DE112012004088B9 (en) |
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| JP6135041B2 (en) * | 2012-04-02 | 2017-05-31 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire |
| JP6155683B2 (en) * | 2012-05-23 | 2017-07-05 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire |
| JP5994418B2 (en) * | 2012-06-20 | 2016-09-21 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire |
| JP6119132B2 (en) * | 2012-07-13 | 2017-04-26 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire |
| JP6197424B2 (en) * | 2013-07-12 | 2017-09-20 | 横浜ゴム株式会社 | Rubber composition for tire and pneumatic tire |
| JP6459307B2 (en) * | 2014-08-27 | 2019-01-30 | 横浜ゴム株式会社 | Rubber composition for tire tread and pneumatic tire |
| US11077711B2 (en) * | 2015-05-01 | 2021-08-03 | The Yokohama Rubber Co., Ltd. | Rubber composition and pneumatic tire |
| JP6729089B2 (en) * | 2016-07-01 | 2020-07-22 | 横浜ゴム株式会社 | Pneumatic tire |
| JP7009812B2 (en) * | 2016-09-30 | 2022-01-26 | 住友ゴム工業株式会社 | Manufacturing method of rubber composition for tires and manufacturing method of tires |
| JP6958056B2 (en) * | 2017-07-20 | 2021-11-02 | 住友ゴム工業株式会社 | Manufacturing method of rubber composition for tires and manufacturing method of tires |
| JP7020939B2 (en) * | 2018-01-31 | 2022-02-16 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tires and pneumatic tires |
| JP6997643B2 (en) * | 2018-01-31 | 2022-01-17 | Ｔｏｙｏ Ｔｉｒｅ株式会社 | Rubber composition for tires and pneumatic tires |
| CN109777154A (en) * | 2019-02-01 | 2019-05-21 | 彤程化学（中国）有限公司 | A kind of response type white carbon black functional additive and its preparation method and application based on vegetable fatty acids |
| WO2021100465A1 (en) * | 2019-11-21 | 2021-05-27 | 住友ゴム工業株式会社 | Tread rubber composition and tire |
| JP7403297B2 (en) * | 2019-12-10 | 2023-12-22 | 株式会社ブリヂストン | Compositions and polymer moldings |
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| JP5614308B2 (en) * | 2011-01-28 | 2014-10-29 | 横浜ゴム株式会社 | Method for producing rubber composition for tire |
| JP5628744B2 (en) * | 2011-05-26 | 2014-11-19 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP5623946B2 (en) * | 2011-03-23 | 2014-11-12 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP5628735B2 (en) * | 2011-04-22 | 2014-11-19 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| JP5623947B2 (en) * | 2011-03-23 | 2014-11-12 | 住友ゴム工業株式会社 | Rubber composition and pneumatic tire |
| EP2679629B1 (en) * | 2011-03-25 | 2015-08-05 | Sumitomo Rubber Industries, Ltd. | Rubber composition and pneumatic tire |
| DE112012003530B4 (en) * | 2011-08-26 | 2017-03-02 | The Yokohama Rubber Co., Ltd. | Tire tread rubber composition and use thereof |
-
2011
- 2011-09-30 JP JP2011216300A patent/JP5668660B2/en active Active
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2012
- 2012-09-21 DE DE112012004088.0T patent/DE112012004088B9/en active Active
- 2012-09-21 KR KR1020147008877A patent/KR101604585B1/en active IP Right Grant
- 2012-09-21 CN CN201280048687.5A patent/CN104011128B/en active Active
- 2012-09-21 WO PCT/JP2012/074191 patent/WO2013047356A1/en active Application Filing
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| CN1769331A (en) * | 2004-11-01 | 2006-05-10 | 住友橡胶工业株式会社 | Rubber composition and tire comprising the same |
| WO2010046139A1 (en) * | 2008-10-22 | 2010-04-29 | Bridgestone Corporation | Winter tyre tread mix |
| WO2010084114A1 (en) * | 2009-01-22 | 2010-07-29 | Lanxess Deutschland Gmbh | Rubber mixtures containing silane and having possibly functionalized diene rubbers and microgels, a method for the production thereof, and use thereof |
| WO2011058441A2 (en) * | 2009-11-10 | 2011-05-19 | Bridgestone Corporation | Tread mix |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104011128A (en) | 2014-08-27 |
| WO2013047356A1 (en) | 2013-04-04 |
| DE112012004088B4 (en) | 2020-07-09 |
| JP5668660B2 (en) | 2015-02-12 |
| JP2013075977A (en) | 2013-04-25 |
| DE112012004088B9 (en) | 2020-09-24 |
| DE112012004088T5 (en) | 2014-09-04 |
| KR101604585B1 (en) | 2016-03-18 |
| KR20140057651A (en) | 2014-05-13 |
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