JP4124758B2 - Rubber composition and tire using the same - Google Patents
Rubber composition and tire using the same Download PDFInfo
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- JP4124758B2 JP4124758B2 JP2004237206A JP2004237206A JP4124758B2 JP 4124758 B2 JP4124758 B2 JP 4124758B2 JP 2004237206 A JP2004237206 A JP 2004237206A JP 2004237206 A JP2004237206 A JP 2004237206A JP 4124758 B2 JP4124758 B2 JP 4124758B2
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- 229920001971 elastomer Polymers 0.000 title claims description 48
- 239000005060 rubber Substances 0.000 title claims description 48
- 239000000203 mixture Substances 0.000 title claims description 35
- 229920001577 copolymer Polymers 0.000 claims description 46
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 28
- 229920002554 vinyl polymer Polymers 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 14
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 11
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 11
- 230000007423 decrease Effects 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000006229 carbon black Substances 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000012763 reinforcing filler Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- -1 4-cyclohexyl Chemical group 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 229920005549 butyl rubber Polymers 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000002156 mixing Methods 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
- 239000002245 particle Substances 0.000 description 2
- 229920001084 poly(chloroprene) Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-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
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Substances OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Description
本発明は、耐摩耗性およびグリップ性能をバランスよく向上させたゴム組成物およびそれを用いたタイヤに関する。 The present invention relates to a rubber composition having improved wear resistance and grip performance in a balanced manner, and a tire using the rubber composition.
高性能タイヤのトレッドとして用いられるゴム組成物には、一般的に高いグリップ性能および耐摩耗性の両立が要求される。 A rubber composition used as a tread for a high-performance tire is generally required to have both high grip performance and wear resistance.
従来、高いグリップ性能を示すタイヤを得るために、たとえば、ガラス転移温度(Tg)の高いスチレン−ブタジエン共重合体ゴム(SBR)をゴム成分として使用したゴム組成物、プロセスオイルを高軟化点樹脂に等量置換し、ゴム成分に充填したゴム組成物、軟化剤またはカーボンブラックを高充填したゴム組成物、粒子径の小さいカーボンブラックを使用したゴム組成物、あるいは該SBR、該高軟化点樹脂、該軟化剤またはカーボンブラックを組み合わせて配合したゴム組成物をタイヤに用いることが知られている。しかし、Tgの高いSBRを使用したゴム組成物は、温度依存性が大きくなり、温度変化に対する性能変化が大きくなるという問題がある。また、プロセスオイルを高軟化点樹脂に等量置換した場合、置換量が多量であると、該高軟化点樹脂の影響により温度依存性が大きくなるという問題がある。さらに、粒子径の小さいカーボンブラックや多量の軟化剤を使用した場合、カーボンブラックの分散性が悪く、耐摩耗性が低下してしまうという問題がある。 Conventionally, in order to obtain a tire exhibiting high grip performance, for example, a rubber composition using a styrene-butadiene copolymer rubber (SBR) having a high glass transition temperature (Tg) as a rubber component, process oil is a high softening point resin. A rubber composition filled with a rubber component, a rubber composition highly filled with a softening agent or carbon black, a rubber composition using carbon black having a small particle diameter, or the SBR and the high softening point resin It is known that a rubber composition containing a combination of the softener or carbon black is used for a tire. However, the rubber composition using SBR having a high Tg has a problem that the temperature dependency is increased and the performance change with respect to the temperature change is increased. Further, when the process oil is replaced with an equal amount of the high softening point resin, if the replacement amount is large, there is a problem that the temperature dependency becomes large due to the influence of the high softening point resin. Further, when carbon black having a small particle diameter or a large amount of softening agent is used, there is a problem that the dispersibility of carbon black is poor and wear resistance is lowered.
これらの問題点を改良するために、低分子量スチレン−ブタジエン共重合体を用いたゴム組成物が提案されている(特許文献1参照)。しかし、低分子量スチレン−ブタジエン共重合体には架橋性を有する二重結合が存在するので、一部の低分子量成分がマトリックスのゴム成分と架橋を形成してマトリックスに取り込まれ、充分にヒステリシスロスを抑制できないという問題がある。また、低分子量成分が架橋によりマトリックスに取り込まれないようにするため、二重結合部を水素添加により飽和結合にした場合、マトリックスとの相容性が著しく低下し、その結果、耐破壊特性が低下したり、低分子量成分がブリードしてくるという問題がある。 In order to improve these problems, a rubber composition using a low molecular weight styrene-butadiene copolymer has been proposed (see Patent Document 1). However, since low molecular weight styrene-butadiene copolymer has crosslinkable double bonds, some low molecular weight components crosslink with the rubber component of the matrix and are incorporated into the matrix, resulting in sufficient hysteresis loss. There is a problem that cannot be suppressed. In addition, in order to prevent low molecular weight components from being incorporated into the matrix by crosslinking, when the double bond portion is saturated by hydrogenation, compatibility with the matrix is significantly reduced, resulting in improved fracture resistance. There is a problem that it is lowered or a low molecular weight component bleeds.
本発明は、耐摩耗性およびグリップ性能を高次にバランスよく向上させたゴム組成物、およびそれを用いたタイヤを提供することを目的とする。 It is an object of the present invention to provide a rubber composition having improved wear resistance and grip performance in a well-balanced manner, and a tire using the rubber composition.
本発明は、(A)スチレン−ブタジエン共重合体を40重量%以上含むゴム成分100重量部に対して、(B)低分子量芳香族ビニル−共役ジエン共重合体を40〜200重量部含有するゴム組成物であって、スチレン−ブタジエン共重合体(A)の重量平均分子量が5.0×105〜2.5×106、およびスチレン含有量が10〜60重量%であり、低分子量芳香族ビニル−共役ジエン共重合体(B)が、共役ジエン部におけるビニル結合量が20〜70%である低分子量芳香族ビニル−共役ジエン共重合体をエポキシ化したものであって、共重合体(B)の重量平均分子量が1.0×103〜1.0×105、芳香族ビニル含有量が10〜75重量%、およびエポキシ化率が3〜60%であるゴム組成物に関する。 The present invention contains (B) 40 to 200 parts by weight of a low molecular weight aromatic vinyl-conjugated diene copolymer with respect to 100 parts by weight of a rubber component containing 40% by weight or more of (A) a styrene-butadiene copolymer. A rubber composition, wherein the styrene-butadiene copolymer (A) has a weight average molecular weight of 5.0 × 10 5 to 2.5 × 10 6 , a styrene content of 10 to 60% by weight, and a low molecular weight The aromatic vinyl-conjugated diene copolymer (B) is obtained by epoxidizing a low molecular weight aromatic vinyl-conjugated diene copolymer having a vinyl bond content of 20 to 70% in the conjugated diene portion. The rubber composition has a weight average molecular weight of 1.0 × 10 3 to 1.0 × 10 5 , an aromatic vinyl content of 10 to 75% by weight, and an epoxidation rate of 3 to 60%. .
さらに、前記ゴム組成物は、窒素吸着比表面積が100〜300m2/gのシリカ40〜150重量部、およびシランカップリング剤を含有することが好ましい。 Furthermore, the rubber composition preferably contains 40 to 150 parts by weight of silica having a nitrogen adsorption specific surface area of 100 to 300 m 2 / g and a silane coupling agent.
また、本発明は、前記ゴム組成物を用いたタイヤに関する。 The present invention also relates to a tire using the rubber composition.
本発明によれば、特定のミクロ構造を有するスチレン−ブタジエン共重合体をゴム成分として用い、さらに、特定のエポキシ化率を有するエポキシ化低分子量芳香族ビニル−共役ジエン共重合体を配合することで、耐摩耗性およびグリップ性能を高次にバランスよく向上させたゴム組成物およびそれを用いたタイヤを提供することができる。 According to the present invention, using a styrene-butadiene copolymer having a specific microstructure as a rubber component, and further blending an epoxidized low molecular weight aromatic vinyl-conjugated diene copolymer having a specific epoxidation rate. Thus, it is possible to provide a rubber composition having improved wear resistance and grip performance in a well-balanced manner and a tire using the rubber composition.
本発明のゴム組成物は、(A)スチレン−ブタジエン共重合体(共重合体(A))を40重量%以上含有するゴム成分、および(B)低分子量芳香族ビニル−共役ジエン共重合体(共重合体(B))からなる。 The rubber composition of the present invention comprises (A) a rubber component containing 40% by weight or more of a styrene-butadiene copolymer (copolymer (A)), and (B) a low molecular weight aromatic vinyl-conjugated diene copolymer. (Copolymer (B)).
共重合体(A)の含有量は、ゴム成分中に40重量%以上、好ましくは45重量%以上である。含有量が40重量%未満では、タイヤの充分なグリップ性能および耐久性能が得られない。また、共重合体(B)の含有量は200重量%以下であることが好ましく、150重量%以下であることがより好ましい。含有量が200重量%をこえると、加工性が低下する傾向がある。 The content of the copolymer (A) is 40% by weight or more, preferably 45% by weight or more in the rubber component. If the content is less than 40% by weight, sufficient grip performance and durability performance of the tire cannot be obtained. Moreover, it is preferable that content of a copolymer (B) is 200 weight% or less, and it is more preferable that it is 150 weight% or less. If the content exceeds 200% by weight, the processability tends to decrease.
共重合体(A)の重量平均分子量は5.0×105以上、好ましくは7.5×105以上である。重量平均分子量が5.0×105未満では、耐摩耗性が低下する。また、重量平均分子量は2.5×106以下、好ましくは2.0×106以下である。重量平均分子量が2.5×106をこえると、加工性が低下する。 The weight average molecular weight of the copolymer (A) is 5.0 × 10 5 or more, preferably 7.5 × 10 5 or more. When the weight average molecular weight is less than 5.0 × 10 5 , the wear resistance is lowered. The weight average molecular weight is 2.5 × 10 6 or less, preferably 2.0 × 10 6 or less. When the weight average molecular weight exceeds 2.5 × 10 6 , workability is deteriorated.
共重合体(A)のスチレン含有量は、共重合体(A)中に10重量%以上、好ましくは20重量%以上である。スチレン含有量が10重量%未満では、グリップ性能が低下する。また、スチレン含有量は60重量%以下、好ましくは50重量%以下である。スチレン含有量が60重量%をこえると、耐摩耗性が低下し、また低温時のグリップ性能も低下する。 The styrene content of the copolymer (A) is 10% by weight or more, preferably 20% by weight or more in the copolymer (A). When the styrene content is less than 10% by weight, grip performance is lowered. The styrene content is 60% by weight or less, preferably 50% by weight or less. When the styrene content exceeds 60% by weight, the wear resistance is lowered and the grip performance at a low temperature is also lowered.
共重合体(A)のブタジエン部におけるビニル結合量は20%以上であることが好ましく、30%以上であることがより好ましい。ビニル結合量が20%未満では、グリップ性能が低下する傾向がある。また、ビニル結合量は70%以下であることが好ましく、60%以下であることがより好ましい。70%をこえると、耐摩耗性が低下し、また低温時のグリップ性能も低下する傾向がある。 The vinyl bond content in the butadiene portion of the copolymer (A) is preferably 20% or more, and more preferably 30% or more. If the vinyl bond amount is less than 20%, the grip performance tends to decrease. Further, the vinyl bond amount is preferably 70% or less, and more preferably 60% or less. If it exceeds 70%, the wear resistance tends to decrease, and the grip performance at low temperatures tends to decrease.
ゴム成分としては、ポリイソプレンゴム(IR)、ポリブタジエンゴム(BR)、エチレン−プロピレン−ジエンゴム、クロロプレンゴム(CR)、ブチルゴム(IIR)、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、天然ゴムなどを共重合体(A)と併用することができる。また、共重合体(A)の重量平均分子量またはスチレン含有量を満たさないスチレン−ブタジエンゴム(SBR)やイソブチレンとp−メチルスチレンとの共重合体も、共重合体(A)と併用することができる。とくに耐摩耗性およびグリップ性能を高次にバランスよく向上させることから、前記SBR、またはイソブチレンとp−メチルスチレンとの共重合体を共重合体(A)と併用してゴム成分とすることが好ましく、イソブチレンとp−メチルスチレンとの共重合体を共重合体(A)と併用してゴム成分とすることがとくに好ましい。 As rubber components, polyisoprene rubber (IR), polybutadiene rubber (BR), ethylene-propylene-diene rubber, chloroprene rubber (CR), butyl rubber (IIR), halogenated butyl rubber, acrylonitrile-butadiene rubber, natural rubber, etc. It can be used in combination with the coalescence (A). In addition, a copolymer of styrene-butadiene rubber (SBR) or isobutylene and p-methylstyrene that does not satisfy the weight average molecular weight or styrene content of the copolymer (A) should be used in combination with the copolymer (A). Can do. In particular, in order to improve wear resistance and grip performance in a well-balanced manner, the SBR or the copolymer of isobutylene and p-methylstyrene may be used in combination with the copolymer (A) as a rubber component. It is particularly preferable to use a copolymer of isobutylene and p-methylstyrene as a rubber component in combination with the copolymer (A).
低分子量芳香族ビニル−共役ジエン共重合体(B)における芳香族ビニル成分としては、たとえばスチレン、α−メチルスチレン、1−ビニルナフタレン、3−ビニルトルエン、エチルビニルベンゼン、ジビニルベンゼン、4−シクロヘキシルスチレン、2,4−トリメチルスチレンなどのビニル芳香族炭化水素単量体があげられる。これらは一種単独で用いても、二種以上を混合してもよいが、なかでもスチレンであることが好ましい。 Examples of the aromatic vinyl component in the low molecular weight aromatic vinyl-conjugated diene copolymer (B) include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, and 4-cyclohexyl. Examples thereof include vinyl aromatic hydrocarbon monomers such as styrene and 2,4-trimethylstyrene. These may be used singly or in combination of two or more, and among them, styrene is preferable.
共重合体(B)における共役ジエン成分としては、たとえば、1,3−ブタジエン、イソプレン、1,3−ペンタジエン、2,3−ジメチルブタジエン、2−フェニル−1,3−ブタジエンなどがあげられる。これらは一種単独で用いても、二種以上を混合してもよいが、なかでも1,3−ブタジエンであることが好ましい。 Examples of the conjugated diene component in the copolymer (B) include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene and the like. These may be used individually by 1 type, or may mix 2 or more types, Especially, it is preferable that it is 1, 3- butadiene.
共重合体(B)は、共役ジエン部におけるビニル結合量が20〜70%である共重合体をエポキシ化したものである。ビニル結合量の下限値としては30%であることが好ましい。ビニル結合量が20%未満では、充分なグリップ性能が得られず、70%をこえると、耐摩耗性が低下する。 The copolymer (B) is obtained by epoxidizing a copolymer having a vinyl bond content in the conjugated diene portion of 20 to 70%. The lower limit of the vinyl bond amount is preferably 30%. If the vinyl bond amount is less than 20%, sufficient grip performance cannot be obtained, and if it exceeds 70%, the wear resistance is lowered.
共重合体(B)における重量平均分子量は1.0×103以上、好ましくは2.0×103以上である。重量平均分子量が1.0×103未満では、耐摩耗性が充分でない。また、重量平均分子量は1.0×105以下、好ましくは8.0×104以下である。重量平均分子量が1.0×105をこえると、充分なグリップ性能が得られない。 The weight average molecular weight in the copolymer (B) is 1.0 × 10 3 or more, preferably 2.0 × 10 3 or more. When the weight average molecular weight is less than 1.0 × 10 3 , the wear resistance is not sufficient. The weight average molecular weight is 1.0 × 10 5 or less, preferably 8.0 × 10 4 or less. When the weight average molecular weight exceeds 1.0 × 10 5 , sufficient grip performance cannot be obtained.
共重合体(B)における芳香族ビニル含有量は10重量%以上、好ましくは20重量%以上である。芳香族ビニル含有量が10%未満では、充分なグリップ性能が得られない。また、芳香族ビニル含有量は75重量%以下、好ましくは50重量%以下である。芳香族ビニル含有量が75重量%をこえると、耐摩耗性が低下する。 The aromatic vinyl content in the copolymer (B) is 10% by weight or more, preferably 20% by weight or more. If the aromatic vinyl content is less than 10%, sufficient grip performance cannot be obtained. The aromatic vinyl content is 75% by weight or less, preferably 50% by weight or less. When the aromatic vinyl content exceeds 75% by weight, the wear resistance decreases.
共重合体(B)のエポキシ化率は3%以上、好ましくは5%以上である。エポキシ化率が3%未満では、ゴム組成物中において補強用充填剤として使用されるシリカの分散性を向上させることができず、充分なグリップ性能および耐摩耗性が得られない。また、エポキシ化率は60%以下、好ましくは50%以下である。エポキシ化率が60%をこえると、ゴム成分との相容性が悪化し、グリップ性能および耐久性が低下する傾向がある。 The epoxidation rate of the copolymer (B) is 3% or more, preferably 5% or more. When the epoxidation rate is less than 3%, the dispersibility of silica used as a reinforcing filler in the rubber composition cannot be improved, and sufficient grip performance and wear resistance cannot be obtained. The epoxidation rate is 60% or less, preferably 50% or less. When the epoxidation rate exceeds 60%, compatibility with the rubber component is deteriorated, and grip performance and durability tend to be lowered.
共重合体(B)の含有量は、ゴム成分100重量部に対して10重量部以上、好ましくは15重量部以上、さらに好ましくは20重量部以上である。含有量が10重量部未満では、充分なグリップ性能が得られない。また、共重合体(B)の含有量は200重量部以下、好ましくは180重量部以下、より好ましくは150重量部以下である。含有量が200重量部をこえると、加工性が低下するだけでなく、耐摩耗性も低下する。 The content of the copolymer (B) is 10 parts by weight or more, preferably 15 parts by weight or more, and more preferably 20 parts by weight or more with respect to 100 parts by weight of the rubber component. If the content is less than 10 parts by weight, sufficient grip performance cannot be obtained. The content of the copolymer (B) is 200 parts by weight or less, preferably 180 parts by weight or less, more preferably 150 parts by weight or less. When the content exceeds 200 parts by weight, not only the workability is lowered but also the wear resistance is lowered.
本発明のゴム組成物は、さらにシリカ、カーボンブラックなどの補強用充填剤を含有することが好ましい。補強用充填剤としては、従来タイヤ用ゴム組成物において慣用されるもののなかから任意に選択して用いることができるが、主としてシリカが好ましい。 The rubber composition of the present invention preferably further contains a reinforcing filler such as silica or carbon black. The reinforcing filler can be arbitrarily selected from those conventionally used in rubber compositions for tires, and silica is mainly preferred.
シリカのチッ素吸着比表面積(N2SA)は100m2/g以上であることが好ましく、110m2/g以上であることがより好ましい。N2SAが100m2/g未満では、耐摩耗性が低下する傾向がある。また、N2SAは300m2/g以下であることが好ましく、250m2/g以下であることがより好ましい。N2SAが300m2/gをこえると、加工性が低下する傾向がある。 The nitrogen adsorption specific surface area (N 2 SA) of silica is preferably 100 m 2 / g or more, and more preferably 110 m 2 / g or more. When N 2 SA is less than 100 m 2 / g, the wear resistance tends to decrease. Further, N 2 SA is preferably 300 m 2 / g or less, and more preferably 250 m 2 / g or less. When N 2 SA exceeds 300 m 2 / g, the workability tends to decrease.
シリカの含有量は、ゴム成分100重量部に対して40重量部以上であることが好ましく、50重量部以上であることがより好ましい。含有量が40重量部未満では、耐摩耗性が低下する傾向がある。また、シリカの含有量は150重量部以下であることが好ましく、130重量部以下であることがより好ましい。150重量部をこえると、加工性が低下する傾向がある。 The content of silica is preferably 40 parts by weight or more and more preferably 50 parts by weight or more with respect to 100 parts by weight of the rubber component. When the content is less than 40 parts by weight, the wear resistance tends to decrease. Further, the content of silica is preferably 150 parts by weight or less, and more preferably 130 parts by weight or less. When it exceeds 150 parts by weight, the workability tends to be lowered.
補強用充填剤としてシリカを使用する場合、シランカップリング剤をシリカと併用することができる。 When silica is used as the reinforcing filler, a silane coupling agent can be used in combination with silica.
シランカップリング剤としては、たとえば、ビス(3−トリエトキシシリルプロピル)ジスルフィド、ビス(3−トリエトキシシリルプロピル)テトラスルフィド、ビス(3−トリメトキシシリルプロピル)テトラスルフィド、ビス(2−トリエトキシシリルプロピル)テトラスルフィド、3−メルカプトプロピルトリエトキシシラン、2−メルカプトエチルトリメトキシシランなどがあげられ、これらをそれぞれ単独で、または任意に組み合わせて用いることができるが、加工性が良好であることから、ビス(3−トリエトキシシリルプロピル)テトラスルフィド(Si69)を用いることが好ましい。 Examples of the silane coupling agent include bis (3-triethoxysilylpropyl) disulfide, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-trimethoxysilylpropyl) tetrasulfide, and bis (2-triethoxy). Silylpropyl) tetrasulfide, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, and the like. These can be used alone or in any combination, but have good workability. Therefore, it is preferable to use bis (3-triethoxysilylpropyl) tetrasulfide (Si69).
シランカップリング剤の含有量は、シリカ100重量部に対して2〜20重量部であることが好ましい。含有量が2重量部未満では、カップリング効果が充分ではなく、耐摩耗性が低下する傾向がある。また、20重量部をこえて添加しても、充分な添加効果が得られないだけでなく、加工性が低下する傾向がある。 The content of the silane coupling agent is preferably 2 to 20 parts by weight with respect to 100 parts by weight of silica. When the content is less than 2 parts by weight, the coupling effect is not sufficient, and the wear resistance tends to decrease. Moreover, even if it adds exceeding 20 weight part, not only a sufficient addition effect is not acquired, but there exists a tendency for workability to fall.
前記補強用充填剤は単独で用いてもよく、2種以上組み合わせて用いてもよい。 The reinforcing fillers may be used alone or in combination of two or more.
さらに、本発明のゴム組成物には、前記成分のほかにゴム工業で通常使用されている各種薬品、たとえば、硫黄などの加硫剤、各種加硫促進剤、各種軟化剤、各種老化防止剤、ステアリン酸、酸化亜鉛、酸化防止剤、オゾン劣化防止剤などの添加剤を配合することができる。 Further, in addition to the above components, the rubber composition of the present invention includes various chemicals usually used in the rubber industry, such as vulcanizing agents such as sulfur, various vulcanization accelerators, various softening agents, and various anti-aging agents. , Additives such as stearic acid, zinc oxide, antioxidants, ozone deterioration inhibitors can be blended.
本発明のタイヤは、本発明のゴム組成物を用いて通常の方法によって製造される。すなわち、必要に応じて前記各種薬品を配合した本発明のゴム組成物を未加硫の段階でタイヤトレッドの形状に合わせて押し出し加工し、タイヤ成型機上にて通常の方法にて成形し、未加硫タイヤを形成する。この未加硫タイヤを加硫機中で加熱加圧してタイヤを得る。得られたタイヤは、レースなどの過酷な条件においても優れた耐摩耗性およびウェットグリップ性能を奏することができる。 The tire of the present invention is produced by an ordinary method using the rubber composition of the present invention. That is, the rubber composition of the present invention blended with the various chemicals as necessary is extruded according to the shape of the tire tread at an unvulcanized stage, and molded by a normal method on a tire molding machine, Form an unvulcanized tire. This unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire. The obtained tire can exhibit excellent wear resistance and wet grip performance even under severe conditions such as racing.
以下、実施例および比較例によって、本発明をさらに詳しく説明するが、本発明の技術的範囲をこれらの実施例に限定するものではないことは言うまでもない。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further in detail, it cannot be overemphasized that the technical scope of this invention is not limited to these Examples.
実施例1、3〜4および比較例1〜5
(共重合体A−1の合成)
充分にチッ素置換した拌翼つきの2Lオートクレーブに、シクロヘキサン1000g、テトラヒドロフラン(THF)20g、1,3−ブタジエン80gおよびスチレン40gを導入し、オートクレーブ内の温度を25℃に調整した。つぎに、n−ブチルリチウム0.05gを加えて昇温条件下で60分間重合し、モノマーの転化率が99%であることを確認した。その後、老化防止剤として2,6−ジ−t−ブチル−p−クレゾールを1.5g加えた。
Examples 1 , 3-4 and Comparative Examples 1-5
(Synthesis of copolymer A-1)
1000 g of cyclohexane, 20 g of tetrahydrofuran (THF), 80 g of 1,3-butadiene, and 40 g of styrene were introduced into a 2 L autoclave with a nitrogen blade sufficiently substituted with nitrogen, and the temperature in the autoclave was adjusted to 25 ° C. Next, 0.05 g of n-butyllithium was added, and polymerization was performed for 60 minutes under a temperature rising condition, and it was confirmed that the monomer conversion rate was 99%. Thereafter, 1.5 g of 2,6-di-t-butyl-p-cresol was added as an antioxidant.
(共重合体A−2およびA−3の合成)
モノマーの仕込み比、触媒量などを変えた他は前記と同様にして合成した。
(Synthesis of copolymers A-2 and A-3)
The synthesis was carried out in the same manner as described above except that the monomer charge ratio and the amount of catalyst were changed.
前記合成方法により得られた共重合体A−1〜A−3の特性値を表1に示す。なお、
重量平均分子量(Mw)は、東ソー(株)製GPC−8000シリーズの装置を用い、検知器として示差屈折計を用い、分子量は標準ポリスチレンより校正した。また、スチレン含有量およびビニル結合量は、25℃にてJEOL JNM−A 400NMR装置を用いて1H NMRを測定し、そのスペクトルより求めた6.7〜7.2ppmのスチレン単位に基づくフェニルプロトンと4.7〜5.2ppmのブタジエン単位に基づくビニル結合のメチレンプロトンの比から決定した。
Table 1 shows the characteristic values of the copolymers A-1 to A-3 obtained by the synthesis method. In addition,
The weight average molecular weight (Mw) was calibrated from standard polystyrene using a differential refractometer as a detector using a GPC-8000 series apparatus manufactured by Tosoh Corporation. The styrene content and vinyl bond content were measured by measuring 1 H NMR using a JEOL JNM-A 400 NMR apparatus at 25 ° C., and phenyl protons based on 6.7 to 7.2 ppm styrene units determined from the spectrum. And the ratio of methylene protons with vinyl bonds based on 4.7 to 5.2 ppm butadiene units.
(共重合体B−0の合成)
充分に窒素置換した拌翼つきの2Lオートクレーブに、シクロヘキサン1000g、テトラヒドロフラン(THF)20g、1,3−ブタジエン150gおよびスチレン50gを導入し、オートクレーブ内の温度を25℃に調整した。つぎに、n−ブチルリチウム2.0gを加えて昇温条件下で15分間重合し、モノマーの転化率が99%であることを確認した。その後、老化防止剤として2,6−ジ−t−ブチル−p−クレゾールを1.5g加えた。
(Synthesis of copolymer B-0)
1000 g of cyclohexane, 20 g of tetrahydrofuran (THF), 150 g of 1,3-butadiene, and 50 g of styrene were introduced into a 2 L autoclave with a stirring blade sufficiently purged with nitrogen, and the temperature in the autoclave was adjusted to 25 ° C. Next, 2.0 g of n-butyllithium was added and polymerized for 15 minutes under elevated temperature conditions, and it was confirmed that the monomer conversion rate was 99%. Thereafter, 1.5 g of 2,6-di-t-butyl-p-cresol was added as an antioxidant.
(共重合体B−1の合成)
耐圧容器において共重合体B−0200gをトルエン300gに溶解させ、蟻酸6.43g、2,6−ジ−t−ブチル−p−クレゾール2gを加え、45℃に調整した過酸化水素を18.5g添加し、3時間攪拌、反応させた。反応終了後放冷し、水酸化ナトリウムで中和、水洗後、トルエンを減圧除去して共重合体を回収した。
(Synthesis of copolymer B-1)
In a pressure vessel, copolymer B-0200 g was dissolved in 300 g of toluene, 6.43 g of formic acid and 2 g of 2,6-di-t-butyl-p-cresol were added, and 18.5 g of hydrogen peroxide adjusted to 45 ° C. The mixture was added and stirred for 3 hours to react. After completion of the reaction, the mixture was allowed to cool, neutralized with sodium hydroxide, washed with water, and toluene was removed under reduced pressure to recover the copolymer.
(共重合体B−3〜B−5の合成)
蟻酸、過酸化水素の添加量を変更した以外は、前記B−1と同様にして合成した。
(Synthesis of copolymers B- 3 to B-5)
The synthesis was performed in the same manner as in B-1 except that the addition amounts of formic acid and hydrogen peroxide were changed.
前記合成方法により得られた共重合体B−0、B−1、B−3〜B−5の特性値を表2に示す。なお、重量平均分子量(Mw)、スチレン含有量およびビニル結合量は、前記した方法により測定した。また、エポキシ化率については、共重合体を臭化テトラエチルアンモニウム/酢酸混合溶媒に一定量加えて溶液とし、1/10N−過塩素酸/酢酸溶液で滴定することで算出した。 Table 2 shows the characteristic values of the copolymers B-0 , B-1, and B-3 to B-5 obtained by the synthesis method. The weight average molecular weight (Mw), styrene content and vinyl bond amount were measured by the methods described above. The epoxidation rate was calculated by adding a certain amount of the copolymer to a tetraethylammonium bromide / acetic acid mixed solvent to form a solution, and titrating with a 1/10 N-perchloric acid / acetic acid solution.
以下に、実施例および比較例において、前記共重合体以外に使用した各種薬品について説明する。 Hereinafter, various chemicals used in addition to the copolymer in Examples and Comparative Examples will be described.
イソブチレンとp−メチルスチレンとの共重合体(共重合体C):エクソン化学(株)製のExxpro 90−10
カーボンブラック:昭和キャボット(株)製のショウブラックN110
シリカ:デグッサ社製のウルトラシルVN3(N2SA:210m2/g)
シランカップリング剤:デグッサ社製のSi69
軟化剤:出光興産(株)製のダイアナプロセスAH−16
ステアリン酸:日本油脂(株)製のステアリン酸
酸化亜鉛:三井金属鉱業(株)製の酸化亜鉛2号
硫黄:鶴見化学工業(株)製の粉末硫黄
加硫促進剤1:大内新興化学工業(株)製のノクセラーNS
加硫促進剤2:大内新興化学工業(株)製のノクセラーD
Copolymer of isobutylene and p-methylstyrene (copolymer C): Exxpro 90-10 manufactured by Exxon Chemical Co., Ltd.
Carbon black: Show Black N110 manufactured by Showa Cabot Corporation
Silica: Ultrasil VN3 manufactured by Degussa (N 2 SA: 210 m 2 / g)
Silane coupling agent: Si69 manufactured by Degussa
Softener: Diana Process AH-16 manufactured by Idemitsu Kosan Co., Ltd.
Stearic acid: Zinc stearate manufactured by Nippon Oil & Fats Co., Ltd .: Zinc oxide No. 2 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Sulfur powder vulcanization accelerator manufactured by Tsurumi Chemical Co., Ltd. Noxeller NS made by
Vulcanization accelerator 2: Noxeller D manufactured by Ouchi Shinsei Chemical Industry Co., Ltd.
表3に示す配合内容に従って、前記各種薬品を混練り配合し、各種供試ゴム組成物を得た。これらの配合物をトレッド形状として他のタイヤ部材と貼りあわせ、170℃で20分間プレス加硫することで試験タイヤを作製した。これらについて以下に示す各特性の試験を行なった。 According to the blending contents shown in Table 3, the various chemicals were kneaded and blended to obtain various test rubber compositions. Test tires were produced by laminating these blends in the form of a tread with other tire members and press vulcanizing at 170 ° C. for 20 minutes. These were tested for the following characteristics.
(ウェットグリップ性能)
試験タイヤを用いて、水を散布し、ウェット状態のアスファルト路面のテストコースにて実車走行を行なった。その際における操舵時のコントロールの安定性をテストドライバーが評価し、比較例1を100として指数表示した。数値が大きいほどウェットグリップ性能が大きく、優れていることを示している。
(Wet grip performance)
Using the test tires, water was sprayed and the vehicle was run on a wet asphalt road test course. The test driver evaluated the stability of the control at the time of steering at that time, and the comparative example 1 was set to 100 and indicated as an index. The larger the value, the greater the wet grip performance and the better.
(摩耗試験)
前記試験タイヤを用いてテストコースを20周走行し、走行前後における溝の深さを測定し、比較例1を100として指数表示をした。数値が大きいほど耐摩耗性が大きく、優れていることを示している。
(Abrasion test)
Using the test tire, the test course was run 20 laps, the groove depth before and after the run was measured, and indexed with Comparative Example 1 as 100. The larger the value, the greater the wear resistance and the better.
以上の試験より得られた評価結果を表3に示す。 Table 3 shows the evaluation results obtained from the above tests.
Claims (3)
スチレン−ブタジエン共重合体(A)の重量平均分子量が5.0×105〜2.5×106、およびスチレン含有量が10〜60重量%であり、
低分子量芳香族ビニル−共役ジエン共重合体(B)が、共役ジエン部におけるビニル結合量が20〜70%である低分子量芳香族ビニル−共役ジエン共重合体をエポキシ化したものであって、共重合体(B)の重量平均分子量が1.0×103〜1.0×105、芳香族ビニル含有量が10〜75重量%、およびエポキシ化率が3〜60%であるゴム組成物。 (A) A rubber composition containing 40 to 200 parts by weight of a low molecular weight aromatic vinyl-conjugated diene copolymer with respect to 100 parts by weight of a rubber component containing 40% by weight or more of a styrene-butadiene copolymer. There,
The weight average molecular weight of the styrene-butadiene copolymer (A) is 5.0 × 10 5 to 2.5 × 10 6 , and the styrene content is 10 to 60% by weight,
The low molecular weight aromatic vinyl-conjugated diene copolymer (B) is obtained by epoxidizing a low molecular weight aromatic vinyl-conjugated diene copolymer having a vinyl bond amount in the conjugated diene portion of 20 to 70%, The rubber composition in which the copolymer (B) has a weight average molecular weight of 1.0 × 10 3 to 1.0 × 10 5 , an aromatic vinyl content of 10 to 75% by weight, and an epoxidation rate of 3 to 60%. object.
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JP2004237206A JP4124758B2 (en) | 2004-08-17 | 2004-08-17 | Rubber composition and tire using the same |
EP10009146A EP2261282A3 (en) | 2003-11-28 | 2004-10-06 | Rubber composition for a tire and tire using the same |
EP10009147A EP2261283A3 (en) | 2003-11-28 | 2004-10-06 | Rubber composition for a tire and tire using the same |
EP04023793A EP1535959B1 (en) | 2003-11-28 | 2004-10-06 | Rubber composition for a tire and tire using the same |
US10/960,273 US7253235B2 (en) | 2003-11-28 | 2004-10-08 | Rubber composition for a tire and tire using the same |
CNB2004100957423A CN100406509C (en) | 2003-11-28 | 2004-11-17 | Rubber composition for a tire and tire using the same |
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JP5189253B2 (en) * | 2006-06-07 | 2013-04-24 | 株式会社ブリヂストン | Pneumatic tire |
JP6258177B2 (en) | 2014-09-25 | 2018-01-10 | 住友ゴム工業株式会社 | Rubber composition for tire and tire |
JP2017052329A (en) * | 2015-09-07 | 2017-03-16 | 株式会社ブリヂストン | Pneumatic tire for passenger car |
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