JP2023157136A - Rubber composition for tires - Google Patents
Rubber composition for tires Download PDFInfo
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- JP2023157136A JP2023157136A JP2022066840A JP2022066840A JP2023157136A JP 2023157136 A JP2023157136 A JP 2023157136A JP 2022066840 A JP2022066840 A JP 2022066840A JP 2022066840 A JP2022066840 A JP 2022066840A JP 2023157136 A JP2023157136 A JP 2023157136A
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- rubber
- conjugated diene
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- aromatic vinyl
- rubber composition
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 96
- 239000005060 rubber Substances 0.000 title claims abstract description 96
- 239000000203 mixture Substances 0.000 title claims abstract description 57
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 67
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229920001577 copolymer Polymers 0.000 claims abstract description 44
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 19
- 150000001993 dienes Chemical group 0.000 claims abstract description 18
- 239000006229 carbon black Substances 0.000 claims abstract description 16
- 229920003244 diene elastomer Polymers 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- 229920003049 isoprene rubber Polymers 0.000 claims abstract description 10
- 230000009477 glass transition Effects 0.000 claims abstract description 9
- 238000001179 sorption measurement Methods 0.000 claims abstract description 7
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 19
- 230000020169 heat generation Effects 0.000 abstract description 4
- 241000872198 Serjania polyphylla Species 0.000 abstract description 3
- 238000003878 thermal aging Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 59
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 52
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 38
- 238000006116 polymerization reaction Methods 0.000 description 28
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 25
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 239000001257 hydrogen Substances 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 230000032683 aging Effects 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 235000019241 carbon black Nutrition 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 11
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 9
- WOAQRZZXGUHRLL-UHFFFAOYSA-N 3-(2,2-dimethoxyazasilolidin-1-yl)propyl-dimethoxysilane Chemical compound C1[Si](N(CC1)CCC[SiH](OC)OC)(OC)OC WOAQRZZXGUHRLL-UHFFFAOYSA-N 0.000 description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 229920003048 styrene butadiene rubber Polymers 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- 239000005062 Polybutadiene Substances 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 230000001186 cumulative effect Effects 0.000 description 8
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 8
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920002857 polybutadiene Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- -1 diene compounds Chemical class 0.000 description 6
- 239000002174 Styrene-butadiene Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-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
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000006232 furnace black Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 229910052759 nickel Inorganic materials 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
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- 239000011787 zinc oxide Substances 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
- XQBHAZDVLGNSOJ-UHFFFAOYSA-N 1-(4-ethenylphenyl)-n,n-dimethylmethanamine Chemical compound CN(C)CC1=CC=C(C=C)C=C1 XQBHAZDVLGNSOJ-UHFFFAOYSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- DXIJHCSGLOHNES-UHFFFAOYSA-N 3,3-dimethylbut-1-enylbenzene Chemical compound CC(C)(C)C=CC1=CC=CC=C1 DXIJHCSGLOHNES-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
- KATNLSJFTSLOCB-UHFFFAOYSA-N 5-phenylpent-4-enenitrile Chemical compound N#CCCC=CC1=CC=CC=C1 KATNLSJFTSLOCB-UHFFFAOYSA-N 0.000 description 1
- KJQMOGOKAYDMOR-UHFFFAOYSA-N CC(=C)C=C.CC(=C)C=C Chemical compound CC(=C)C=C.CC(=C)C=C KJQMOGOKAYDMOR-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005234 alkyl aluminium 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000000412 dendrimer Substances 0.000 description 1
- 229920000736 dendritic polymer Polymers 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- CKFGINPQOCXMAZ-UHFFFAOYSA-N methanediol Chemical class OCO CKFGINPQOCXMAZ-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- PPMXDDJEXJDFMT-UHFFFAOYSA-N n,n-diethyl-3-phenylprop-2-en-1-amine Chemical compound CCN(CC)CC=CC1=CC=CC=C1 PPMXDDJEXJDFMT-UHFFFAOYSA-N 0.000 description 1
- UQADNXUWLBEGLY-UHFFFAOYSA-N n,n-diethyl-4-phenylbut-3-en-1-amine Chemical compound CCN(CC)CCC=CC1=CC=CC=C1 UQADNXUWLBEGLY-UHFFFAOYSA-N 0.000 description 1
- UBHHTPOLMACCDD-UHFFFAOYSA-N n,n-dimethyl-4-phenylbut-3-en-1-amine Chemical compound CN(C)CCC=CC1=CC=CC=C1 UBHHTPOLMACCDD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012766 organic filler Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- MMSLOZQEMPDGPI-UHFFFAOYSA-N p-Mentha-1,3,5,8-tetraene Chemical compound CC(=C)C1=CC=C(C)C=C1 MMSLOZQEMPDGPI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000000611 regression analysis Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
本発明は、ゴム硬度および低発熱性を両立し、耐疲労性、耐オゾン性および耐熱老化性を優れたタイヤ用ゴム組成物に関する。 The present invention relates to a rubber composition for tires that has both rubber hardness and low heat build-up, and has excellent fatigue resistance, ozone resistance, and heat aging resistance.
環境負荷低減のために、タイヤの軽量化、低発熱性化が特に求められている。例えば、ガラス転移温度（Ｔｇ）が低いゴム成分を配合してゴムの損失正接（ｔａｎδ）の挙動を変化させる手法が知られている（例えば特許文献１，２を参照）。Ｔｇが低いゴム成分としてブタジエンゴムが挙げられる。ブタジエンゴムには、Ｔｇが低いことに加え、疲労特性を高くするという特徴があるが、ブタジエンゴムを含有するゴム組成物による改良手法では、ゴム硬度および低発熱性をバランスさせながら、耐オゾン性および耐熱老化性をより優れたものにするのに限界があった。 In order to reduce the environmental burden, there is a particular need for tires to be lighter and generate less heat. For example, a method is known in which a rubber component having a low glass transition temperature (Tg) is blended to change the behavior of the loss tangent (tan δ) of the rubber (see, for example, Patent Documents 1 and 2). Butadiene rubber is an example of a rubber component having a low Tg. In addition to having a low Tg, butadiene rubber has the characteristics of high fatigue properties. However, in an improvement method using a rubber composition containing butadiene rubber, it is possible to balance rubber hardness and low heat build-up while improving ozone resistance. Also, there were limitations in improving heat aging resistance.
しかし、近年、ゴム硬度および低発熱性を両立させてタイヤの軽量化を実現すると共に、耐疲労性、耐オゾン性および耐熱老化性をより優れたものにする要求がより高くなっており、低Ｔｇのブタジエンゴムに頼る配合手法以外で上述した課題を解決するタイヤ用ゴム組成物を開発することが求められていた。 However, in recent years, there has been an increasing demand for tires to be lightweight by achieving both rubber hardness and low heat build-up, as well as better fatigue resistance, ozone resistance, and heat aging resistance. There has been a need to develop a rubber composition for tires that solves the above-mentioned problems using a compounding method other than relying on butadiene rubber of Tg.
本発明の目的は、ゴム硬度および低発熱性を両立しながら、耐疲労性、耐オゾン性および耐熱老化性を従来レベル以上に優れたものにするタイヤ用ゴム組成物を提供することにある。 An object of the present invention is to provide a rubber composition for tires that has both rubber hardness and low heat build-up, and has fatigue resistance, ozone resistance, and heat aging resistance that are superior to conventional levels.
上記目的を達成する本発明のタイヤ用ゴム組成物は、イソプレン系ゴムを２０～７０質量％および水添芳香族ビニル－共役ジエン共重合体を含むジエン系ゴム１００質量部に、窒素吸着比表面積が３０～１００ｍ２／ｇであるカーボンブラックを２０～８０質量部配合したタイヤ用ゴム組成物であって、前記水添芳香族ビニル－共役ジエン共重合体の重量平均分子量が２０万以上、ガラス転移温度が－４０℃以下、水添率が６０％以上、下記式（１）で表される疲労指数が１００超であることを特徴とする。
疲労指数＝－４．６６×Ｓｔ＋２．０１×Ｖｎ－３．１５×Ｈ＋３０５ （１）
（式（１）中、Ｓｔは水添芳香族ビニル－共役ジエン共重合体のスチレン量（％）、Ｖｎは水素添加前の共役ジエン部分におけるビニル量（質量％）、Ｈは共役ジエン部分への水添率（％）を表す。）
The tire rubber composition of the present invention, which achieves the above object, has a nitrogen adsorption specific surface area of A rubber composition for tires containing 20 to 80 parts by mass of carbon black having a molecular weight of 30 to 100 m 2 /g, wherein the hydrogenated aromatic vinyl-conjugated diene copolymer has a weight average molecular weight of 200,000 or more, and glass It is characterized by having a transition temperature of −40° C. or less, a hydrogenation rate of 60% or more, and a fatigue index expressed by the following formula (1) of more than 100.
Fatigue index = -4.66 x St + 2.01 x Vn - 3.15 x H + 305 (1)
(In formula (1), St is the amount of styrene in the hydrogenated aromatic vinyl-conjugated diene copolymer (%), Vn is the amount of vinyl in the conjugated diene part before hydrogenation (mass%), and H is the amount of styrene in the conjugated diene part before hydrogenation. represents the hydrogenation rate (%).)
本発明のタイヤ用ゴム組成物は、特定の水添芳香族ビニル－共役ジエン共重合体を含有するようにしたので、ゴム硬度および低発熱性を両立しながら、耐疲労性、耐オゾン性および耐熱老化性を従来レベル以上に優れたものにすることができる。 Since the tire rubber composition of the present invention contains a specific hydrogenated aromatic vinyl-conjugated diene copolymer, it has good fatigue resistance, ozone resistance and The heat aging resistance can be made superior to the conventional level.
タイヤ用ゴム組成物は、前記ジエン系ゴム１００質量％中、前記水添芳香族ビニル－共役ジエン共重合体を３０質量％以上含むとよい。 The tire rubber composition preferably contains 30% by mass or more of the hydrogenated aromatic vinyl-conjugated diene copolymer based on 100% by mass of the diene rubber.
上述したタイヤ用ゴム組成物からなるサイドウォールおよび／またはリムクッションを有するタイヤは、軽量化および低燃費性能を両立しながら、耐疲労性、耐オゾン性および耐熱老化性に優れる。 A tire having a sidewall and/or rim cushion made of the tire rubber composition described above has excellent fatigue resistance, ozone resistance, and heat aging resistance while achieving both weight reduction and fuel efficiency.
本発明のタイヤ用ゴム組成物は、ジエン系ゴムとして、イソプレン系ゴムおよび水添芳香族ビニル－共役ジエン共重合体を含む。イソプレン系ゴムを含むことにより、未加硫ゴムの加工性および物性のバランスに優れたゴム組成物にすることができる。イソプレン系ゴムとして、天然ゴム、イソプレンゴムが挙げられる。イソプレン系ゴムの含有量は、ジエン系ゴム１００質量％中、２０～７０質量％、好ましくは２５～６５質量％、より好ましくは３０～６０質量％である。イソプレン系ゴムが２０質量％未満であると、加工性の改善効果が十分に得られない。また、７０質量％を超えると、水添芳香族ビニル－共役ジエン共重合体の効果が十分に得られない。 The tire rubber composition of the present invention contains an isoprene rubber and a hydrogenated aromatic vinyl-conjugated diene copolymer as the diene rubber. By including the isoprene rubber, it is possible to obtain a rubber composition with excellent balance between unvulcanized rubber processability and physical properties. Examples of isoprene rubber include natural rubber and isoprene rubber. The content of isoprene rubber is 20 to 70% by weight, preferably 25 to 65% by weight, and more preferably 30 to 60% by weight based on 100% by weight of diene rubber. If the isoprene rubber content is less than 20% by mass, the effect of improving processability cannot be sufficiently obtained. Moreover, if it exceeds 70% by mass, the effect of the hydrogenated aromatic vinyl-conjugated diene copolymer cannot be sufficiently obtained.
タイヤ用ゴム組成物は、特定の水添芳香族ビニル－共役ジエン共重合体を含むことにより、ブタジエンゴムと同等の耐疲労性を確保しながら、ゴム硬度および低発熱性を両立し、かつ耐オゾン性および耐熱老化性を従来レベル以上に優れたものにすることができる。水添芳香族ビニル－共役ジエン共重合体は、重量平均分子量が２０万以上、ガラス転移温度が－４０℃以下、水添率が６０％以上、下記式（１）で表される疲労指数が１００超であることを特徴とする。
疲労指数＝－４．６６×Ｓｔ＋２．０１×Ｖｎ－３．１５×Ｈ＋３０５ （１）
（式（１）中、Ｓｔは水添芳香族ビニル－共役ジエン共重合体のスチレン量（％）、Ｖｎは水素添加前の共役ジエン部分におけるビニル量（質量％）、Ｈは共役ジエン部分への水添率（％）を表す。）
By containing a specific hydrogenated aromatic vinyl-conjugated diene copolymer, the tire rubber composition achieves both rubber hardness and low heat build-up while ensuring fatigue resistance equivalent to that of butadiene rubber. Ozone resistance and heat aging resistance can be made superior to conventional levels. The hydrogenated aromatic vinyl-conjugated diene copolymer has a weight average molecular weight of 200,000 or more, a glass transition temperature of -40°C or less, a hydrogenation rate of 60% or more, and a fatigue index expressed by the following formula (1). It is characterized by being over 100.
Fatigue index = -4.66 x St + 2.01 x Vn - 3.15 x H + 305 (1)
(In formula (1), St is the amount of styrene in the hydrogenated aromatic vinyl-conjugated diene copolymer (%), Vn is the amount of vinyl in the conjugated diene part before hydrogenation (mass%), and H is the amount of styrene in the conjugated diene part before hydrogenation. represents the hydrogenation rate (%).)
水添芳香族ビニル－共役ジエン共重合体は、芳香族ビニル－共役ジエン共重合体を水素添加したゴム成分である。芳香族ビニル－共役ジエン共重合体は、芳香族ビニルおよび共役ジエンの共重合体であり、好ましくはランダム共重合体である。芳香族ビニル－共役ジエン共重合体を構成する芳香族ビニル化合物として、スチレン、メチルスチレン、エチルスチレン、ｔ－ブチルスチレン、α－メチルスチレン、α－メチル－ｐ－メチルスチレン、クロルスチレン、ブロモスチレン、メトキシスチレン、ジメチルアミノメチルスチレン、ジメチルアミノエチルスチレン、ジエチルアミノメチルスチレン、ジエチルアミノエチルスチレン、シアノエチルスチレン、ビニルナフタレンなどが挙げられる。これらのなかでも、スチレンが好ましい。また、芳香族ビニル－共役ジエン共重合体を構成する共役ジエン化合物として、１，３－ブタジエン、イソプレン（２－メチル－１，３－ブタジエン）、２，３－ジメチル－１，３－ブタジエン、２－クロロ－１，３－ブタジエン、１，３－ペンタジエンなどが挙げられる。芳香族ビニル－共役ジエン共重合体として、スチレン－ブタジエン共重合体ゴム（ＳＢＲ）、スチレン－イソプレン共重合体ゴムなどが挙げられる。芳香族ビニル－共役ジエン共重合体は、芳香族ビニル化合物および共役ジエン化合物以外に、任意に他の共重合性モノマーを用いてもよい。芳香族ビニル－共役ジエン共重合体の重合法は、溶液重合法、気相重合法、バルク重合法のいずれを用いてもよいが、溶液重合法が好ましい。また、重合形式としては、回分式及び連続式のいずれを用いてもよい。 The hydrogenated aromatic vinyl-conjugated diene copolymer is a rubber component obtained by hydrogenating an aromatic vinyl-conjugated diene copolymer. The aromatic vinyl-conjugated diene copolymer is a copolymer of aromatic vinyl and a conjugated diene, and is preferably a random copolymer. Aromatic vinyl compounds constituting the aromatic vinyl-conjugated diene copolymer include styrene, methylstyrene, ethylstyrene, t-butylstyrene, α-methylstyrene, α-methyl-p-methylstyrene, chlorstyrene, and bromostyrene. , methoxystyrene, dimethylaminomethylstyrene, dimethylaminoethylstyrene, diethylaminomethylstyrene, diethylaminoethylstyrene, cyanoethylstyrene, vinylnaphthalene, and the like. Among these, styrene is preferred. In addition, the conjugated diene compounds constituting the aromatic vinyl-conjugated diene copolymer include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3-butadiene, Examples include 2-chloro-1,3-butadiene and 1,3-pentadiene. Examples of the aromatic vinyl-conjugated diene copolymer include styrene-butadiene copolymer rubber (SBR) and styrene-isoprene copolymer rubber. The aromatic vinyl-conjugated diene copolymer may optionally contain other copolymerizable monomers in addition to the aromatic vinyl compound and the conjugated diene compound. The aromatic vinyl-conjugated diene copolymer may be polymerized by any of solution polymerization, gas phase polymerization, and bulk polymerization, but solution polymerization is preferred. Further, as the polymerization method, either a batch method or a continuous method may be used.
芳香族ビニル－共役ジエン重合体を水素添加（水添）する反応の方法及び条件は、所望の水添率が得られるのであれば、特に制限されるものではない。芳香族ビニル－共役ジエン重合体の水添方法の例としては、チタンの有機金属化合物を主成分とする触媒を水添触媒として使用する方法、鉄、ニッケル、コバルトの有機化合物とアルキルアルミニウム等の有機金属化合物からなる触媒を使用する方法、ルテニウム、ロジウム等の有機金属化合物の有機錯体を使用する方法、パラジウム、白金、ルテニウム、コバルト、ニッケル等の金属を、カーボン、シリカ、アルミナ等の担体に担持した触媒を使用する方法などがある。 The reaction method and conditions for hydrogenating the aromatic vinyl-conjugated diene polymer are not particularly limited as long as a desired hydrogenation rate can be obtained. Examples of hydrogenation methods for aromatic vinyl-conjugated diene polymers include a method using a catalyst containing an organometallic compound of titanium as the main component, a method using an organic compound of iron, nickel, or cobalt and a method using alkyl aluminum, etc. A method using a catalyst made of an organometallic compound, a method using an organic complex of an organometallic compound such as ruthenium or rhodium, or a method using a metal such as palladium, platinum, ruthenium, cobalt, or nickel on a carrier such as carbon, silica, or alumina. There are methods that use supported catalysts.
水添芳香族ビニル－共役ジエン共重合体は、重量平均分子量が２０万以上、好ましくは２０万～７０万、より好ましくは３０万～６０万である。水添芳香族ビニル－共役ジエン共重合体の重量平均分子量が２０万以上であると、ゴム組成物のゴム硬度や引張破断強度を高くすることができる。また、重量平均分子量を７０万以下にすると、タイヤ用ゴム組成物の粘度上昇が抑えられ加工性と強度を両立できるので好ましい。本明細書において、水添芳香族ビニル－共役ジエン共重合体の重量平均分子量は、ゲルパーミエーションクロマトグラフィ（ＧＰＣ）によって測定されるポリスチレン換算の値とすることができる。 The hydrogenated aromatic vinyl-conjugated diene copolymer has a weight average molecular weight of 200,000 or more, preferably 200,000 to 700,000, more preferably 300,000 to 600,000. When the weight average molecular weight of the hydrogenated aromatic vinyl-conjugated diene copolymer is 200,000 or more, the rubber hardness and tensile strength at break of the rubber composition can be increased. Furthermore, it is preferable that the weight average molecular weight is 700,000 or less, since this suppresses the increase in viscosity of the rubber composition for tires and achieves both processability and strength. In this specification, the weight average molecular weight of the hydrogenated aromatic vinyl-conjugated diene copolymer can be a polystyrene equivalent value measured by gel permeation chromatography (GPC).
水添芳香族ビニル－共役ジエン共重合体は、ガラス転移温度が－４０℃以下、好ましくは－８０℃～－４０℃、より好ましくは－７５℃～－５０℃である。水添芳香族ビニル－共役ジエン共重合体のガラス転移温度が－４０℃以下であると、寒冷地での使用においても柔軟性を十分に確保することができる。また、ガラス転移温度を－８０℃以上にすると、硬度と柔軟性のバランスに優れたゴム組成物にすることができる。本明細書において、ガラス転移温度は、示差走査熱量測定（ＤＳＣ）により２０℃／分の昇温速度条件によりサーモグラムを測定し、転移域の中点の温度とすることができる。 The hydrogenated aromatic vinyl-conjugated diene copolymer has a glass transition temperature of -40°C or lower, preferably -80°C to -40°C, more preferably -75°C to -50°C. When the glass transition temperature of the hydrogenated aromatic vinyl-conjugated diene copolymer is −40° C. or lower, sufficient flexibility can be ensured even when used in cold regions. Furthermore, when the glass transition temperature is set to -80°C or higher, a rubber composition with an excellent balance between hardness and flexibility can be obtained. In this specification, the glass transition temperature can be determined by measuring a thermogram using differential scanning calorimetry (DSC) at a heating rate of 20° C./min, and can be defined as the temperature at the midpoint of the transition region.
水添芳香族ビニル－共役ジエン共重合体は、水素添加率（水添率）が６０％以上、好ましくは６０～９０％、より好ましくは６０～８０％である。水添率が６０％未満であると、耐オゾン性が悪化する。また、ゴム硬度および低発熱性を両立しながら、耐疲労性および耐熱老化を改良することができない。さらに、引張破断強度も十分には得られない。水添率を１００％未満にすることにより、水添芳香族ビニル－共役ジエン共重合体に架橋性を付与することができる。本明細書において、水添率は、芳香族ビニル－共役ジエン共重合体が有する共役ジエン部分において、水素添加する前の炭素－炭素二重結合部の合計１００％に対する、水素添加された炭素－炭素結合部の百分率（％）をいう。水添率が１００％であるとき、共役ジエン部分の炭素－炭素二重結合が完全に水素添加されたことを意味する。なお、水添率は、１Ｈ－ＮＭＲを測定して得られたスペクトルの共役ジエン部分における不飽和結合部のスペクトル減少率から計算することができる。 The hydrogenated aromatic vinyl-conjugated diene copolymer has a hydrogenation rate (hydrogenation rate) of 60% or more, preferably 60 to 90%, more preferably 60 to 80%. If the hydrogenation rate is less than 60%, ozone resistance will deteriorate. Further, it is not possible to improve fatigue resistance and heat aging resistance while achieving both rubber hardness and low heat build-up. Furthermore, sufficient tensile strength at break cannot be obtained. By setting the hydrogenation rate to less than 100%, crosslinking properties can be imparted to the hydrogenated aromatic vinyl-conjugated diene copolymer. In the present specification, the hydrogenation rate refers to the hydrogenated carbon- It refers to the percentage (%) of carbon bonding parts. When the hydrogenation rate is 100%, it means that the carbon-carbon double bonds of the conjugated diene moiety are completely hydrogenated. Note that the hydrogenation rate can be calculated from the spectral reduction rate of the unsaturated bond in the conjugated diene portion of the spectrum obtained by measuring 1 H-NMR.
水添芳香族ビニル－共役ジエン共重合体は、下記式（１）で表される疲労指数が１００超であるものとする。
疲労指数＝－４．６６×Ｓｔ＋２．０１×Ｖｎ－３．１５×Ｈ＋３０５ （１）
（式（１）中、Ｓｔは水添芳香族ビニル－共役ジエン共重合体のスチレン量（％）、Ｖｎは水素添加前の共役ジエン部分におけるビニル量（質量％）、Ｈは共役ジエン部分における水添率（％）を表す。）
The hydrogenated aromatic vinyl-conjugated diene copolymer shall have a fatigue index expressed by the following formula (1) of more than 100.
Fatigue index = -4.66 x St + 2.01 x Vn - 3.15 x H + 305 (1)
(In formula (1), St is the amount of styrene in the hydrogenated aromatic vinyl-conjugated diene copolymer (%), Vn is the amount of vinyl in the conjugated diene portion before hydrogenation (% by mass), and H is the amount of vinyl in the conjugated diene portion Represents hydrogenation rate (%).)
前記式（１）中、Ｓｔは水添芳香族ビニル－共役ジエン共重合体のスチレン量（％）を表す。なお、芳香族ビニル化合物がスチレン以外のときは、その芳香族ビニル化合物の含有率（％）を表す。スチレン量（％）は、１Ｈ－ＮＭＲにより測定することができる。 In the formula (1), St represents the amount of styrene (%) in the hydrogenated aromatic vinyl-conjugated diene copolymer. In addition, when the aromatic vinyl compound is other than styrene, the content (%) of the aromatic vinyl compound is expressed. The amount of styrene (%) can be measured by 1 H-NMR.
前記式（１）中、Ｖｎは水素添加前の芳香族ビニル－共役ジエン共重合体において、共役ジエン部分中のビニル量（質量％）を表す。すなわち、水素添加前の共役ジエン部分は、シス－１，４結合、トランス－１，４結合および１，２－結合等の繰り返し単位からなり、ビニル量（質量％）は、これらの合計１００質量％中の１，２－結合の百分率（質量％）をいう。共役ジエン部分のビニル量（質量％）は１Ｈ－ＮＭＲにより測定することができる。 In the formula (1), Vn represents the amount of vinyl in the conjugated diene moiety (% by mass) in the aromatic vinyl-conjugated diene copolymer before hydrogenation. That is, the conjugated diene moiety before hydrogenation consists of repeating units such as cis-1,4 bonds, trans-1,4 bonds, and 1,2-bonds, and the vinyl content (mass%) is 100% by mass in total. It refers to the percentage (mass%) of 1,2-bonds in %. The amount of vinyl in the conjugated diene moiety (% by mass) can be measured by 1 H-NMR.
前記式（１）中、Ｈは共役ジエン部分における水添率（％）を表す。水添率（％）については、上述したとおりである。 In the formula (1), H represents the hydrogenation rate (%) in the conjugated diene moiety. The hydrogenation rate (%) is as described above.
前記式（１）は、水添芳香族ビニル－共役ジエン共重合体の疲労特性試験の結果と、水添芳香族ビニル－共役ジエン共重合体のスチレン量Ｓｔ、ビニル量Ｖｎ、および水添率Ｈの関係について、重回帰分析を行って得られた関係式である。本発明において、前記式（１）で表される疲労指数は１００超、好ましくは１５０超、より好ましくは２００超である。疲労指数が１００以下であると、疲労特性が十分に得られない。 The above formula (1) is based on the results of the fatigue property test of the hydrogenated aromatic vinyl-conjugated diene copolymer, the amount of styrene St, the amount of vinyl Vn, and the hydrogenation rate of the hydrogenated aromatic vinyl-conjugated diene copolymer. This is a relational expression obtained by performing multiple regression analysis regarding the relationship of H. In the present invention, the fatigue index represented by the above formula (1) is over 100, preferably over 150, and more preferably over 200. If the fatigue index is less than 100, sufficient fatigue properties cannot be obtained.
水添芳香族ビニル－共役ジエン共重合体は、ジエン系ゴム１００質量％中、好ましくは３０質量％以上、より好ましくは３０～８０質量％、さらに好ましくは３５～７５質量％含有するとよい。水添芳香族ビニル－共役ジエン共重合体を３０質量％以上含有することにより、ゴム硬度および低発熱性を両立し、かつ耐疲労性、耐オゾン性および耐熱老化性を優れたものにする確からしさが高くなる。また、引張破断強度が大きくなり、タイヤにしたとき耐摩耗性を改良することができ好ましい。 The hydrogenated aromatic vinyl-conjugated diene copolymer is preferably contained in an amount of 30% by mass or more, more preferably 30 to 80% by mass, and still more preferably 35 to 75% by mass based on 100% by mass of the diene rubber. By containing 30% by mass or more of a hydrogenated aromatic vinyl-conjugated diene copolymer, it is sure to achieve both rubber hardness and low heat build-up, as well as excellent fatigue resistance, ozone resistance, and heat aging resistance. It becomes more unique. It is also preferable because the tensile strength at break becomes large, and when it is made into a tire, the wear resistance can be improved.
タイヤ用ゴム組成物は、イソプレン系ゴムおよび水添芳香族ビニル－共役ジエン共重合体以外の他のジエン系ゴムを含むことができる。他のジエン系ゴムとして、例えば水素添加していない芳香族ビニル－共役ジエン共重合体（スチレンブタジエンゴム）、ブタジエンゴム、ブチルゴム、ハロゲン化ブチルゴム、アクリロニトリル－ブタジエンゴム、等を例示することができる。これら他のジエン系ゴムは、官能基を有する変性ジエン系ゴムであってもよく、単独又は任意のブレンドとして使用することができる。他のジエン系ゴムの含有量は、ジエン系ゴム１００質量％中、好ましくは０～４０質量％、より好ましくは０～３０質量％であるとよい。 The rubber composition for tires can contain diene rubber other than isoprene rubber and hydrogenated aromatic vinyl-conjugated diene copolymer. Examples of other diene rubbers include non-hydrogenated aromatic vinyl-conjugated diene copolymers (styrene-butadiene rubber), butadiene rubber, butyl rubber, halogenated butyl rubber, acrylonitrile-butadiene rubber, and the like. These other diene rubbers may be modified diene rubbers having functional groups, and can be used alone or as an arbitrary blend. The content of the other diene rubber is preferably 0 to 40% by mass, more preferably 0 to 30% by mass based on 100% by mass of the diene rubber.
タイヤ用ゴム組成物は、ジエン系ゴムに、カーボンブラックを配合することにより、ゴム組成物のゴム強度やゴム硬度を高くすることができる。カーボンブラックは、ジエン系ゴム１００質量部に、２０～８０質量部、好ましくは２５～７５質量部、より好ましくは
３０～７０質量部配合する。カーボンブラックが２０質量部未満であると、ゴム組成物のゴム強度やゴム硬度が不足し、タイヤにしたときの操縦安定性や耐摩耗性が十分に得られない。また、カーボンブラックが８０質量部を超えると、発熱性を十分に抑制することができない。
A rubber composition for a tire can have high rubber strength and hardness by blending carbon black with a diene rubber. Carbon black is blended in an amount of 20 to 80 parts by weight, preferably 25 to 75 parts by weight, more preferably 30 to 70 parts by weight, to 100 parts by weight of the diene rubber. If the amount of carbon black is less than 20 parts by mass, the rubber composition will have insufficient rubber strength and rubber hardness, and when made into a tire, sufficient steering stability and wear resistance will not be obtained. Moreover, if carbon black exceeds 80 parts by mass, heat generation cannot be sufficiently suppressed.
カーボンブラックの窒素吸着比表面積は、３０～１００ｍ２／ｇ、好ましくは３０～８０ｍ２／ｇ、より好ましくは３０～７５ｍ２／ｇである。窒素吸着比表面積が３０ｍ２／ｇ未満であると、ゴム組成物のゴム強度やゴム硬度が不足する。１００ｍ２／ｇを超えると、発熱性を十分に抑制することができない。本明細書において、カーボンブラックの窒素吸着比表面積は、ＪＩＳ Ｋ６２１７－２に準拠して、測定することができる。 The nitrogen adsorption specific surface area of carbon black is 30 to 100 m 2 /g, preferably 30 to 80 m 2 /g, more preferably 30 to 75 m 2 /g. If the nitrogen adsorption specific surface area is less than 30 m 2 /g, the rubber strength and hardness of the rubber composition will be insufficient. If it exceeds 100 m 2 /g, heat generation cannot be sufficiently suppressed. In this specification, the nitrogen adsorption specific surface area of carbon black can be measured in accordance with JIS K6217-2.
カーボンブラックとしては、ファーネスブラック、アセチレンブラック、サーマルブラック、チャンネルブラック、グラファイトなどのカーボンブラックを配合してもよい。これらの中でも、ファーネスブラックが好ましい。カーボンブラックは、単独あるいは２種以上を組み合わせて用いることができる。また、カーボンブラックを種々の酸化合物等で化学修飾を施した表面処理カーボンブラックも用いることができる。 As the carbon black, carbon blacks such as furnace black, acetylene black, thermal black, channel black, and graphite may be blended. Among these, furnace black is preferred. Carbon black can be used alone or in combination of two or more types. Furthermore, surface-treated carbon black obtained by chemically modifying carbon black with various acid compounds can also be used.
タイヤ用ゴム組成物は、カーボンブラック以外の他の補強性充填剤を配合することができる。他の補強性充填剤として、例えばシリカ、クレイ、水酸化アルミニウム、炭酸カルシウム、マイカ、タルク、水酸化アルミニウム、酸化アルミニウム、酸化チタン、硫酸バリウム等の無機フィラーや、セルロース、レシチン、リグニン、デンドリマー等の有機フィラーを例示することができる。 The rubber composition for tires may contain reinforcing fillers other than carbon black. Other reinforcing fillers include inorganic fillers such as silica, clay, aluminum hydroxide, calcium carbonate, mica, talc, aluminum hydroxide, aluminum oxide, titanium oxide, barium sulfate, cellulose, lecithin, lignin, dendrimers, etc. The following organic fillers can be exemplified.
タイヤ用ゴム組成物には、上記成分以外に、常法に従って、加硫又は架橋剤、加硫促進剤、老化防止剤、加工助剤、可塑剤、液状ポリマー、熱硬化性樹脂、熱可塑性樹脂などのタイヤ用ゴム組成物に一般的に使用される各種配合剤を配合することができる。このような配合剤は一般的な方法で混練してゴム組成物とし、加硫又は架橋するのに使用することができる。これらの配合剤の配合量は本発明の目的に反しない限り、従来の一般的な配合量とすることができる。タイヤ用ゴム組成物は、公知のゴム用混練機械、例えば、バンバリーミキサー、ニーダー、ロール等を使用して、上記各成分を混合することによって調製することができる。 In addition to the above ingredients, the tire rubber composition may contain a vulcanizing or crosslinking agent, a vulcanization accelerator, an anti-aging agent, a processing aid, a plasticizer, a liquid polymer, a thermosetting resin, a thermoplastic resin, in accordance with a conventional method. Various compounding agents commonly used in rubber compositions for tires such as the following can be blended. Such compounding agents can be kneaded in a conventional manner to form a rubber composition, which can be used for vulcanization or crosslinking. The amounts of these compounding agents can be any conventional and common amounts as long as they do not contradict the purpose of the present invention. The rubber composition for tires can be prepared by mixing the above-mentioned components using a known rubber kneading machine such as a Banbury mixer, kneader, roll, etc.
タイヤ用ゴム組成物は、タイヤのサイドウォールおよび／またはリムクッションを形成するのに好適であり、とりわけサイドウォールを形成するのに好適である。サイドウォールおよび／またはリムクッションを、上述したゴム組成物で形成したタイヤは、軽量化および低燃費性能を両立しながら、耐疲労性、耐オゾン性および耐熱老化性を従来レベル以上に優れたものにすることができる。 The rubber composition for tires is suitable for forming the sidewall and/or rim cushion of a tire, and is particularly suitable for forming the sidewall. Tires whose sidewalls and/or rim cushions are made of the above-mentioned rubber composition are lightweight and have low fuel consumption, while also having fatigue resistance, ozone resistance, and heat aging resistance that are better than conventional levels. It can be done.
以下、実施例によって本発明をさらに説明するが、本発明の範囲はこれらの実施例に限定されるものではない。 The present invention will be further explained below with reference to Examples, but the scope of the present invention is not limited to these Examples.
以下の実施例において、表１に記載したスチレンブタジエンゴム（ＳＢＲ）および水添芳香族ビニル－共役ジエン共重合体（水添ＳＢＲ１～水添ＳＢＲ８）を使用した。また、ＳＢＲおよび水添ＳＢＲ１～水添ＳＢＲ８は、以下の重合方法により調整した。 In the following examples, styrene butadiene rubber (SBR) and hydrogenated aromatic vinyl-conjugated diene copolymers (hydrogenated SBR1 to hydrogenated SBR8) listed in Table 1 were used. Further, SBR and hydrogenated SBR1 to hydrogenated SBR8 were prepared by the following polymerization method.
表１に記載のＳＢＲの重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（９０ｇ，０．８６ｍｏｌ）、ブタジエン（５１０ｇ，９．４６ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．０５７ｇ，０．３１ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．９５ｍｌ、ｎ－ブチルリチウムが４．５８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、未水添ＳＢＲを得た。そのスチレン量は１５質量％、ビニル量はブタジエン中で３０質量％、重量平均分子量は４１０，０００であった。
Polymerization method for SBR listed in Table 1 Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (90 g, 0.86 mol), butadiene (510 g, 9.46 mol) and tetrahydrofuran (0.433 g, 6 .0 mmol) and 2,2-di(2-tetrahydrofuryl)propane (0.057 g, 0.31 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.95 ml at a concentration of 1.55 mol/L, 4.58 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain unhydrogenated SBR. The amount of styrene was 15% by weight, the amount of vinyl was 30% by weight in butadiene, and the weight average molecular weight was 410,000.
水添ＳＢＲ１の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（１８０ｇ，１．７３ｍｏｌ）、ブタジエン（４２０ｇ，７．７９ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．３７８ｇ，２．０５ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．９５ｍｌ、ｎ－ブチルリチウムが４．５８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（８０．１ｍｇ，２．５ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は３０質量％、ビニル量はブタジエン中で５０質量％、重量平均分子量は３９０，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ１を得た。その水添率は６０％であった。
Polymerization method for hydrogenated SBR1: Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (180 g, 1.73 mol), butadiene (420 g, 7.79 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) were placed. and 2,2-di(2-tetrahydrofuryl)propane (0.378 g, 2.05 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.95 ml at a concentration of 1.55 mol/L, 4.58 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (80.1 mg, 2.5 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 30% by weight, the amount of vinyl was 50% by weight in butadiene, and the weight average molecular weight was 390,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR1. The hydrogenation rate was 60%.
水添ＳＢＲ２の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（１２０ｇ，１．１５ｍｏｌ）、ブタジエン（４８０ｇ，８．９１ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．３７８ｇ，２．０５ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．５７ｍｌ、ｎ－ブチルリチウムが３．９８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（６７．３ｍｇ，２．１ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は２０質量％、ビニル量はブタジエン中で５０質量％、重量平均分子量は４７０，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ２を得た。その水添率は８０％であった。
Polymerization method for hydrogenated SBR2 Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (120 g, 1.15 mol), butadiene (480 g, 8.91 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) were placed. and 2,2-di(2-tetrahydrofuryl)propane (0.378 g, 2.05 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.57 ml at a concentration of 1.55 mol/L, 3.98 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (67.3 mg, 2.1 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 20% by weight, the amount of vinyl was 50% by weight in butadiene, and the weight average molecular weight was 470,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR2. The hydrogenation rate was 80%.
水添ＳＢＲ３の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（９０ｇ，０．８６ｍｏｌ）、ブタジエン（５１０ｇ，９．４６ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．０５７ｇ，０．３１ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．９５ｍｌ、ｎ－ブチルリチウムが４．５８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（８０．１ｍｇ，２．５ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は１５質量％、ビニル量はブタジエン中で３０質量％、重量平均分子量は４００，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ３を得た。その水添率は６０％であった。
Polymerization method for hydrogenated SBR3 Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (90 g, 0.86 mol), butadiene (510 g, 9.46 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) were placed. and 2,2-di(2-tetrahydrofuryl)propane (0.057 g, 0.31 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.95 ml at a concentration of 1.55 mol/L, 4.58 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (80.1 mg, 2.5 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 15% by weight, the amount of vinyl was 30% by weight in butadiene, and the weight average molecular weight was 400,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR3. The hydrogenation rate was 60%.
水添ＳＢＲ４の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（９０ｇ，０．８６ｍｏｌ）、ブタジエン（５１０ｇ，９．４６ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．６０４ｇ，３．２８ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．９５ｍｌ、ｎ－ブチルリチウムが４．５８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（８０．１ｍｇ，２．５ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は１５質量％、ビニル量はブタジエン中で５５質量％、重量平均分子量は３９０，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ４を得た。その水添率は６０％であった。
Polymerization method for hydrogenated SBR4 Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (90 g, 0.86 mol), butadiene (510 g, 9.46 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) were placed. and 2,2-di(2-tetrahydrofuryl)propane (0.604 g, 3.28 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.95 ml at a concentration of 1.55 mol/L, 4.58 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (80.1 mg, 2.5 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 15% by weight, the amount of vinyl was 55% by weight in butadiene, and the weight average molecular weight was 390,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR4. The hydrogenation rate was 60%.
水添ＳＢＲ５の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（１５０ｇ，１．４４ｍｏｌ）、ブタジエン（４５０ｇ，８．３５ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．６０４ｇ，３．２８ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．９５ｍｌ、ｎ－ブチルリチウムが４．５８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（８０．１ｍｇ，２．５ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は２５質量％、ビニル量はブタジエン中で５５質量％、重量平均分子量は４００，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ５を得た。その水添率は６０％であった。
Polymerization method for hydrogenated SBR5 Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (150 g, 1.44 mol), butadiene (450 g, 8.35 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) were added. and 2,2-di(2-tetrahydrofuryl)propane (0.604 g, 3.28 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.95 ml at a concentration of 1.55 mol/L, 4.58 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (80.1 mg, 2.5 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 25% by weight, the amount of vinyl was 55% by weight in butadiene, and the weight average molecular weight was 400,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR5. The hydrogenation rate was 60%.
水添ＳＢＲ６の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（９０ｇ，０．８６ｍｏｌ）、ブタジエン（５１０ｇ，９．４６ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．９６６ｇ，５．２４ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．９５ｍｌ、ｎ－ブチルリチウムが４．５８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（８０．１ｍｇ，２．５ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は１５質量％、ビニル量はブタジエン中で６０質量％、重量平均分子量は４２０，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ６を得た。その水添率は８０％であった。
Polymerization method for hydrogenated SBR6 Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (90 g, 0.86 mol), butadiene (510 g, 9.46 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) were placed. and 2,2-di(2-tetrahydrofuryl)propane (0.966 g, 5.24 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.95 ml at a concentration of 1.55 mol/L, 4.58 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (80.1 mg, 2.5 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 15% by weight, the amount of vinyl was 60% by weight in butadiene, and the weight average molecular weight was 420,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR6. The hydrogenation rate was 80%.
水添ＳＢＲ７の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（３０ｇ，０．２９ｍｏｌ）、ブタジエン（５７０ｇ，１０．５８ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．６０４ｇ，３．２８ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．９５ｍｌ、ｎ－ブチルリチウムが４．５８ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（８０．１ｍｇ，２．５ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は５質量％、ビニル量はブタジエン中で５５質量％、重量平均分子量は４００，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ７を得た。その水添率は９０％であった。
Polymerization method for hydrogenated SBR7 Into a 10 L autoclave reactor purged with nitrogen, 4200 g of cyclohexane, styrene (30 g, 0.29 mol), butadiene (570 g, 10.58 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) were added. and 2,2-di(2-tetrahydrofuryl)propane (0.604 g, 3.28 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.95 ml at a concentration of 1.55 mol/L, 4.58 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (80.1 mg, 2.5 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 5% by weight, the amount of vinyl was 55% by weight in butadiene, and the weight average molecular weight was 400,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR7. The hydrogenation rate was 90%.
水添ＳＢＲ８の重合方法
窒素置換された内容量１０Ｌのオートクレーブ反応器に、シクロヘキサン４２００ｇ、スチレン（３０ｇ，０．２９ｍｏｌ）、ブタジエン（５７０ｇ，１０．５８ｍｏｌ）およびテトラヒドロフラン（０．４３３ｇ，６．０ｍｍｏｌ）と２，２－ジ（２－テトラヒドロフリル）プロパン（０．６０４ｇ，３．２８ｍｍｏｌ）を仕込み、攪拌を開始した。反応容器内の内容物の温度を５０℃にした後、ｎ－ブチルリチウムのヘキサン溶液（１．５５ｍｏｌ／Ｌ濃度で２．７５ｍｌ、ｎ－ブチルリチウムが４．２６ｍｍｏｌ）を添加した。重合転化率がほぼ１００％に到達した後、２，２－ジメトキシ－１－（３－卜リメトキシシリルプロピル）－１－アザ－２－シラシクロペンタン（０．２５４ｇ，０．８２ｍｍｏｌ）を添加し、３０分間反応させた。反応後メタノール（９２．９ｍｇ，２．９ｍｍｏｌ）を添加し反応を停止させ、一部を抜き出し乾燥させた後分析を行った。そのスチレン量は５質量％、ビニル量はブタジエン中で６０質量％、重量平均分子量は３４０，０００であった。反応液を８０℃以上にして系内に水素を導入した。次いで、チタノセンジクロライドを主体とする触媒０．７０ｇ、ジエチルアルミニウムクロライド１．２ｇおよびｎ－ブチルリチウム０．３０ｇを加え、水素圧１．０ＭＰａを保つように反応させた。所定の水素積算流量に到達後、反応液を常温、常圧に戻して反応容器より抜き出し、重合溶液を得た。中和後、スチームストリッピング法により固体状のゴムを回収した。得られた固体ゴムをロールにより脱水し、乾燥機中で乾燥を行い、水添ＳＢＲ８を得た。その水添率は９５％であった。
Polymerization method of hydrogenated SBR8 In a nitrogen-purged autoclave reactor with an internal capacity of 10 L, 4200 g of cyclohexane, styrene (30 g, 0.29 mol), butadiene (570 g, 10.58 mol), and tetrahydrofuran (0.433 g, 6.0 mmol) and 2,2-di(2-tetrahydrofuryl)propane (0.604 g, 3.28 mmol) were charged, and stirring was started. After the temperature of the contents in the reaction vessel was brought to 50° C., a hexane solution of n-butyllithium (2.75 ml at a concentration of 1.55 mol/L, 4.26 mmol of n-butyl lithium) was added. After the polymerization conversion rate reached approximately 100%, 2,2-dimethoxy-1-(3-dimethoxysilylpropyl)-1-aza-2-silacyclopentane (0.254 g, 0.82 mmol) was added. and allowed to react for 30 minutes. After the reaction, methanol (92.9 mg, 2.9 mmol) was added to stop the reaction, and a portion was extracted and dried for analysis. The amount of styrene was 5% by weight, the amount of vinyl was 60% by weight in butadiene, and the weight average molecular weight was 340,000. The reaction solution was heated to 80°C or higher and hydrogen was introduced into the system. Next, 0.70 g of a catalyst mainly composed of titanocene dichloride, 1.2 g of diethylaluminum chloride, and 0.30 g of n-butyllithium were added, and the mixture was reacted while maintaining a hydrogen pressure of 1.0 MPa. After reaching a predetermined cumulative hydrogen flow rate, the reaction solution was returned to normal temperature and pressure and extracted from the reaction vessel to obtain a polymerization solution. After neutralization, solid rubber was recovered by steam stripping. The obtained solid rubber was dehydrated using a roll and dried in a drier to obtain hydrogenated SBR8. The hydrogenation rate was 95%.
表４に示す共通の配合剤処方を有し、表２，３に示す配合からなる１４種類のタイヤ用ゴム組成物（実施例１～１０、比較例１～４）を調製するに当たり、それぞれ硫黄および加硫促進剤を除く成分を秤量し、１．７リットルの密閉式バンバリーミキサーで５分間混練した後、そのマスターバッチをミキサー外に放出し室温冷却した。このマスターバッチを同バンバリーミキサーに供し、硫黄および加硫促進剤を加えて混合し、タイヤ用ゴム組成物を得た。なお、表４の配合剤処方は、表２，３に記載したジエン系ゴム１００質量部に対する質量部で記載している。 In preparing 14 types of tire rubber compositions (Examples 1 to 10, Comparative Examples 1 to 4) having the common compounding agent formulation shown in Table 4 and having the formulations shown in Tables 2 and 3, each sulfur The components except the vulcanization accelerator were weighed and kneaded for 5 minutes in a 1.7 liter internal Banbury mixer, and then the masterbatch was discharged from the mixer and cooled at room temperature. This masterbatch was subjected to the same Banbury mixer, and sulfur and a vulcanization accelerator were added and mixed to obtain a tire rubber composition. The compounding agent formulations in Table 4 are expressed in parts by mass based on 100 parts by mass of the diene rubber described in Tables 2 and 3.
上記で得られたタイヤ用ゴム組成物を、それぞれ所定形状の金型中で、１６０℃、２０分間加硫して評価用試料を作製した。得られた評価用試料を使用し、２３℃のゴム硬度、動的粘弾性（損失正接ｔａｎδ）、耐疲労性、耐オゾン性、老化硬度を以下の方法で測定した。 The tire rubber compositions obtained above were each vulcanized in a mold of a predetermined shape at 160° C. for 20 minutes to prepare evaluation samples. Using the obtained evaluation sample, rubber hardness at 23°C, dynamic viscoelasticity (loss tangent tan δ), fatigue resistance, ozone resistance, and aging hardness were measured by the following methods.
２３℃のゴム硬度（タイヤ軽量化）
得られたタイヤ用ゴム組成物の評価用試料を用いて、ＪＩＳ Ｋ６２５３に準拠して、デュロメータのタイプＡにより温度２３℃のゴム硬度を測定した。得られた結果は比較例１の値を１００にする指数として「ゴム硬度」の欄に記載した。この指数が大きいほど耐外傷性に優れるため、サイドゲージを薄くすることができタイヤを軽量化することが可能であることを意味する。
Rubber hardness at 23℃ (tire weight reduction)
Using the obtained evaluation sample of the tire rubber composition, the rubber hardness at a temperature of 23° C. was measured using a durometer type A in accordance with JIS K6253. The obtained results are listed in the column of "Rubber Hardness" as an index that takes the value of Comparative Example 1 to 100. The larger the index, the better the resistance to external damage, which means that the side gauge can be made thinner and the tire can be made lighter.
動的粘弾性（損失正接ｔａｎδ）
得られたタイヤ用ゴム組成物の評価用試料の動的粘弾性を、岩本製作所（株）製の粘弾性スペクトロメーターを用い、伸張変形歪率１０±２％、振動数２０Ｈｚ、温度６０℃、の条件にて測定し、ｔａｎδ（６０℃）を求めた。得られたｔａｎδ（６０℃）の値は、比較例１の値を１００にする指数として「ｔａｎδ（６０℃）」の欄に記載した。この指数が小さいほど発熱性が小さく、低転がり抵抗であることを意味する。
Dynamic viscoelasticity (loss tangent tanδ)
The dynamic viscoelasticity of the obtained evaluation sample of the rubber composition for tires was measured using a viscoelastic spectrometer manufactured by Iwamoto Seisakusho Co., Ltd. at an extensional deformation strain rate of 10 ± 2%, a frequency of 20 Hz, a temperature of 60 ° C. The tan δ (60° C.) was determined under the following conditions. The obtained value of tan δ (60° C.) was written in the “tan δ (60° C.)” column as an index that makes the value of Comparative Example 1 100. The smaller the index, the lower the heat generation and the lower the rolling resistance.
耐疲労性
得られたタイヤ用ゴム組成物の評価用試料を用いて、３号ダンベル型試験片を切り出した。ＪＩＳ Ｋ６２７０に準拠して、３号ダンベル型試験片に１００％に歪みを繰り返し与え、破断するまでの繰り返し回数を測定した。得られた破断するまでの回数は、比較例１の値を１００にする指数として「耐疲労性」の欄に記載した。この指数が大きいほど耐疲労性が優れることを意味する。
Fatigue Resistance Using the obtained evaluation sample of the tire rubber composition, a No. 3 dumbbell-shaped test piece was cut out. In accordance with JIS K6270, a No. 3 dumbbell-shaped test piece was repeatedly strained to 100%, and the number of repetitions until it broke was measured. The obtained number of times until breakage was described in the column of "fatigue resistance" as an index with the value of Comparative Example 1 set to 100. It means that the larger this index is, the better the fatigue resistance is.
耐オゾン性
得られたタイヤ用ゴム組成物の評価用試料を用いて、ＪＩＳ Ｋ６２５１に準拠した３号ダンベル型試験片を切り出した。この試験片を４０％伸長、オゾン濃度５０ｐｐｈｍ、４０℃、４８時間という条 件で、ＪＩＳ Ｋ６２５９に準拠してオゾン劣化させた。その後、試験片表面の亀裂（オゾンクラック）の有無を目視（肉眼および１０倍の拡大鏡）で観察し、亀裂の状態を以下の判定基準に基づき５段階で評価した。得られた結果を「耐オゾン性」の欄に示した。この評点が大きいほど耐オゾン性が優れることを意味する。
５：肉眼および１０倍の拡大鏡で亀裂が確認されない。
４：肉眼では見えないが１０倍の拡大鏡で亀裂があると認められる。
３：亀裂が肉眼で観察され、深くて比較的大きい（長さ１ｍｍ未満）。
２：深くて大きい亀裂（長さ１ｍｍ以上３ｍｍ未満）が確認された。
１：長さ３ｍｍ以上の亀裂が確認されるか、または試験片が切断された。
Ozone Resistance A No. 3 dumbbell-shaped test piece conforming to JIS K6251 was cut out using the obtained evaluation sample of the tire rubber composition. This test piece was subjected to ozone deterioration in accordance with JIS K6259 under the conditions of 40% elongation, 50 pphm ozone concentration, 40°C, and 48 hours. Thereafter, the presence or absence of cracks (ozone cracks) on the surface of the test piece was visually observed (with the naked eye and with a 10x magnifying glass), and the state of the cracks was evaluated on a 5-grade scale based on the following criteria. The obtained results are shown in the "Ozone resistance" column. The higher the score, the better the ozone resistance.
5: No cracks are observed with the naked eye or with a 10x magnifying glass.
4: Cracks are not visible to the naked eye, but can be seen with a 10x magnification.
3: Cracks are visible to the naked eye and are deep and relatively large (less than 1 mm in length).
2: Deep and large cracks (length of 1 mm or more and less than 3 mm) were confirmed.
1: A crack with a length of 3 mm or more was confirmed, or the test piece was cut.
老化硬度
前記２３℃のゴム硬度の値を、各実施例のゴム硬度の初期値とする。
タイヤ用ゴム組成物の評価用試料を７０℃で１６８時間熱老化処理を行い、処理した評価用試料の２３℃のゴム硬度を上記と同様に測定し、熱老化後のゴム硬度とした。
各実施例において、（熱老化後のゴム硬度）／（ゴム硬度の初期値）×１００の値を算出し、「老化硬度（％）」の欄に記載した。この値が小さいほど、熱老化によるゴムの硬化が抑制され優れていることを意味する。
Aging Hardness The value of the rubber hardness at 23° C. is the initial value of the rubber hardness of each example.
An evaluation sample of a tire rubber composition was subjected to heat aging treatment at 70° C. for 168 hours, and the rubber hardness of the treated evaluation sample at 23° C. was measured in the same manner as above, and was taken as the rubber hardness after heat aging.
In each example, the value of (rubber hardness after heat aging)/(initial value of rubber hardness) x 100 was calculated and recorded in the column of "aging hardness (%)". The smaller this value is, the better the rubber hardening caused by heat aging is suppressed.
表２，３において使用した原材料の種類を下記に示す。
・ＮＲ：天然ゴム、ＴＳＲ２０
・ＢＲ：ブタジエンゴム、日本ゼオン社製 Ｎｉｐｏｌ ＢＲ１２２０
・ＳＢＲ、水添ＳＢＲ１～水添ＳＢＲ８：表１に記載したスチレンブタジエンゴムおよび水添芳香族ビニル－共役ジエン共重合体
・ＣＢ：カーボンブラック、東海カーボン社製シーストＦ、窒素吸着比表面積が４１ｍ２／ｇ
The types of raw materials used in Tables 2 and 3 are shown below.
・NR: Natural rubber, TSR20
・BR: Butadiene rubber, Nipol BR1220 manufactured by Nippon Zeon Co., Ltd.
・SBR, hydrogenated SBR1 to hydrogenated SBR8: styrene butadiene rubber and hydrogenated aromatic vinyl-conjugated diene copolymer listed in Table 1
・CB: Carbon black, Seast F manufactured by Tokai Carbon Co., Ltd., nitrogen adsorption specific surface area 41 m 2 /g
表４において使用した原材料の種類を下記に示す。
・酸化亜鉛：正同化学工業社製酸化亜鉛３種
・ステアリン酸：ＮＯＦ ＣＯＲＰＯＲＡＴＩＯＮ社製ビーズステアリン酸
・老化防止剤：ＬＡＮＸＥＳＳ社製ＶＵＬＫＡＮＯＸ４０２０
・ワックス：日本精鑞社製オゾエース００１５
・アロマオイル：昭和シェル石油社製エキストラクト４号Ｓ
・硫黄：鶴見化学工業社製金華印油入微粉硫黄
・加硫促進剤：大内新興化学社製ノクセラーＮＳ－Ｐ
The types of raw materials used in Table 4 are shown below.
・Zinc oxide: 3 types of zinc oxide manufactured by Seido Kagaku Kogyo Co., Ltd. ・Stearic acid: Bead stearic acid manufactured by NOF CORPORATION ・Antioxidant: VULKANOX4020 manufactured by LANXESS
・Wax: Ozoace 0015 manufactured by Nippon Seirinsha
・Aroma oil: Showa Shell Sekiyu Extract No. 4 S
・Sulfur: Fine powder sulfur with Kinkain oil manufactured by Tsurumi Chemical Industry Co., Ltd. ・Vulcanization accelerator: Noxela NS-P manufactured by Ouchi Shinko Chemical Co., Ltd.
表２，３から明らかなように実施例１～１０のタイヤ用ゴム組成物は、２３℃のゴム硬度、動的粘弾性（損失正接ｔａｎδ）、耐疲労性、耐オゾン性、老化硬度に優れることが確認された。
比較例２のタイヤ用ゴム組成物は、ガラス転移温度が－４０℃より高く、疲労指数が１００以下なので、ｔａｎδ（６０℃）が大きく、耐疲労性が劣る。
比較例３のタイヤ用ゴム組成物は、疲労指数が１００以下なので、ｔａｎδ（６０℃）が大きく、耐疲労性が劣る。
比較例４のタイヤ用ゴム組成物は、イソプレン系ゴムを含まないので、ｔａｎδ（６０℃）が大きく、耐疲労性が劣る。
As is clear from Tables 2 and 3, the tire rubber compositions of Examples 1 to 10 are excellent in rubber hardness at 23°C, dynamic viscoelasticity (loss tangent tan δ), fatigue resistance, ozone resistance, and aging hardness. This was confirmed.
The tire rubber composition of Comparative Example 2 has a glass transition temperature higher than -40°C and a fatigue index of 100 or less, so tan δ (60°C) is large and fatigue resistance is poor.
Since the tire rubber composition of Comparative Example 3 has a fatigue index of 100 or less, tan δ (60° C.) is large and fatigue resistance is poor.
Since the tire rubber composition of Comparative Example 4 does not contain isoprene rubber, it has a large tan δ (60° C.) and poor fatigue resistance.
Claims (3)
疲労指数＝－４．６６×Ｓｔ＋２．０１×Ｖｎ－３．１５×Ｈ＋３０５ （１）
（式（１）中、Ｓｔは水添芳香族ビニル－共役ジエン共重合体のスチレン量（％）、Ｖｎは水素添加前の共役ジエン部分におけるビニル量（質量％）、Ｈは共役ジエン部分への水添率（％）を表す。） 20 to 80 parts of carbon black having a nitrogen adsorption specific surface area of 30 to 100 m 2 /g is added to 100 parts by mass of diene rubber containing 20 to 70 mass % of isoprene rubber and a hydrogenated aromatic vinyl-conjugated diene copolymer. A rubber composition for tires containing parts by mass, wherein the hydrogenated aromatic vinyl-conjugated diene copolymer has a weight average molecular weight of 200,000 or more, a glass transition temperature of -40°C or less, and a hydrogenation rate of 60% or more. A rubber composition for a tire, characterized in that the fatigue index represented by the following formula (1) is more than 100.
Fatigue index = -4.66 x St + 2.01 x Vn - 3.15 x H + 305 (1)
(In formula (1), St is the amount of styrene in the hydrogenated aromatic vinyl-conjugated diene copolymer (%), Vn is the amount of vinyl in the conjugated diene part before hydrogenation (mass%), and H is the amount of styrene in the conjugated diene part before hydrogenation. represents the hydrogenation rate (%).)
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