JP4088258B2 - Rubber composition and tire using the same - Google Patents
Rubber composition and tire using the same Download PDFInfo
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- JP4088258B2 JP4088258B2 JP2004032136A JP2004032136A JP4088258B2 JP 4088258 B2 JP4088258 B2 JP 4088258B2 JP 2004032136 A JP2004032136 A JP 2004032136A JP 2004032136 A JP2004032136 A JP 2004032136A JP 4088258 B2 JP4088258 B2 JP 4088258B2
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- 229920001971 elastomer Polymers 0.000 title claims description 37
- 239000005060 rubber Substances 0.000 title claims description 37
- 239000000203 mixture Substances 0.000 title claims description 32
- 150000001336 alkenes Chemical class 0.000 claims description 24
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 24
- 229920006164 aromatic vinyl copolymer Polymers 0.000 claims description 19
- 229920003244 diene elastomer Polymers 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 21
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 20
- 239000000178 monomer Substances 0.000 description 20
- 229920003048 styrene butadiene rubber Polymers 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 239000002174 Styrene-butadiene Substances 0.000 description 9
- 150000001993 dienes Chemical class 0.000 description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- 239000005977 Ethylene Substances 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000010734 process oil Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000012763 reinforcing filler Substances 0.000 description 3
- 229920003051 synthetic elastomer Polymers 0.000 description 3
- 239000005061 synthetic rubber Substances 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
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 229920000459 Nitrile rubber Polymers 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000740 bleeding effect Effects 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002223 polystyrene Polymers 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
- 238000003786 synthesis reaction Methods 0.000 description 2
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- GDDROXSGJGOQLV-UHFFFAOYSA-L C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].[Zn+2].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-] Chemical compound C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-].[Zn+2].C(CCCCCCCCCCCCCCCCC)(=[O+][O-])[O-] GDDROXSGJGOQLV-UHFFFAOYSA-L 0.000 description 1
- ZDQGINQVRUXWOY-UHFFFAOYSA-K C1(C=CC=C1)[Ti](OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 Chemical compound C1(C=CC=C1)[Ti](OC1=CC=CC=C1)(OC1=CC=CC=C1)OC1=CC=CC=C1 ZDQGINQVRUXWOY-UHFFFAOYSA-K 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 239000003963 antioxidant agent Substances 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
- 229920005549 butyl rubber Polymers 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- -1 ethylene, propylene, 1-butene Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C PMJHHCWVYXUKFD-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
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010059 sulfur vulcanization Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は、ゴム組成物およびタイヤに関し、とりわけタイヤトレッド用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 and a tire, and more particularly to a rubber composition for a tire tread and a tire using the same.
レース用タイヤをはじめとした競技用タイヤのトレッドゴムには、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。 The tread rubber of racing tires and other racing tires 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ゴム組成物を得るために、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充填したゴム組成物、あるいは該ＳＢＲ、該高軟化点樹脂、該軟化剤または該カーボンブラックを組み合わせて配合したゴム組成物が知られている。しかし、Ｔｇの高いＳＢＲをゴム成分として使用した場合、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、軟化剤またはカーボンブラックを高充填した場合、あるいは粒子径の小さいカーボンブラックを充填した場合、軟化剤またはカーボンブラックの分散性が低下する、あるいは破壊強度または耐摩耗性が低下するという問題がある。 Conventionally, in order to obtain a rubber composition 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, a process oil is highly softened. Equal amount substitution with point resin, rubber composition filled with rubber component, rubber composition filled with softener or carbon black, rubber composition filled with carbon black with small particle diameter, or SBR, high softening A rubber composition in which a point resin, the softener, or the carbon black is combined is known. However, when SBR having a high Tg is used as a rubber component, there is 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. Furthermore, when the softener or carbon black is highly charged, or when carbon black with a small particle size is filled, there is a problem that the dispersibility of the softener or carbon black decreases, or the fracture strength or wear resistance decreases. is there.
この点を改良する手法として、低分子量ＳＢＲを用いることが提案されている（特許文献１参照）。しかしながら、低分子量といえどもＳＢＲは架橋性を有する二重結合があるので、一部の低分子量成分はマトリックスのゴムと架橋を形成してマトリックスに取り込まれてしまい、充分なヒステリシスロスや破壊強度が得られないという問題があった。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に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溶性が著しく悪化し、その結果、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った。 As a technique for improving this point, the use of low molecular weight SBR has been proposed (see Patent Document 1). However, even though it has a low molecular weight, SBR has a crosslinkable double bond, so some low molecular weight components are cross-linked with the matrix rubber and incorporated into the matrix, resulting in sufficient hysteresis loss and breaking strength. There was a problem that could not be obtained. In addition, in order to prevent low molecular weight components from being incorporated into the matrix by cross-linking, when the double bond portion is saturated by hydrogenation, the compatibility with the matrix is significantly deteriorated, resulting in a decrease in fracture characteristics. Or low molecular weight components bleed.
本発明は、耐摩耗性とグリップ特性を高次にバランス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。 An object of the present invention is to provide a rubber composition in which wear resistance and grip characteristics are balanced in high order, and a tire using the rubber composition.
本発明は、ジエン系ゴム成分１００重量部に対して、オレフィン−共役ジエン−芳香族ビニル共重合体を５〜２００重量部含むことを特徴とするタイヤトレッド用ゴム組成物に関する。 The present invention relates to a rubber composition for a tire tread, comprising 5 to 200 parts by weight of an olefin-conjugated diene-aromatic vinyl copolymer with respect to 100 parts by weight of a diene rubber component.
前記オレフィン−共役ジエン−芳香族ビニル共重合体の重量平均分子量Ｍｗは、２０００〜５００００であることが好ましい。また、前記オレフィン−共役ジエン−芳香族ビニル共重合体は、エチレン−ブタジエン−スチレン共重合体であることが好ましい。 The weight average molecular weight Mw of the olefin-conjugated diene-aromatic vinyl copolymer is preferably 2000 to 50000. The olefin-conjugated diene-aromatic vinyl copolymer is preferably an ethylene-butadiene-styrene copolymer.
さらに、本発明は、前記タイヤトレッド用ゴム組成物からなるトレッドを有するタイヤに関する。 Furthermore, this invention relates to the tire which has a tread which consists of said rubber composition for tire treads .
本発明によれば、オレフィン−共役ジエン−芳香族ビニル共重合体を配合することにより、耐摩耗性とグリップ特性を高次にバランスさせたゴム組成物、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, by blending an olefin-conjugated diene-aromatic vinyl copolymer, a rubber composition in which wear resistance and grip characteristics are balanced in high order, and a tire using the rubber composition are provided. Can do.
本発明のゴム組成物は、ジエン系ゴム成分およびオレフィン−共役ジエン−芳香族ビニル共重合体からなる。 The rubber composition of the present invention comprises a diene rubber component and an olefin-conjugated diene-aromatic vinyl copolymer.
本発明に使用されるジエン系ゴム成分としては、天然ゴム（ＮＲ）および／またはジエン系合成ゴムが用いられる。ここで、ジエン系合成ゴムとしては、たとえば、ブタジエンゴム（ＢＲ）、スチレンブタジエンゴム（ＳＢＲ）、イソプレン合成ゴム（ＩＲ）、アクリロニトリル−ブタジエンゴム（ＮＢＲ）、イソブチレン−イソプレンゴム（ＩＩＲ）、クロロプレンゴム（ＣＲ）などがあげられる。これらのゴムは、単独で用いてもよく、あるいは２種以上を組み合わせて用いてもよい。 As the diene rubber component used in the present invention, natural rubber (NR) and / or diene synthetic rubber is used. Here, examples of the diene-based synthetic rubber include butadiene rubber (BR), styrene butadiene rubber (SBR), isoprene synthetic rubber (IR), acrylonitrile-butadiene rubber (NBR), isobutylene-isoprene rubber (IIR), and chloroprene rubber. (CR). These rubbers may be used alone or in combination of two or more.
前記ジエン系ゴム成分のなかでも、グリップ性能と耐摩耗性のバランスの点から、ＳＢＲが好ましく用いられる。ＳＢＲを用いる場合、ＳＢＲのガラス転移温度（Ｔｇ）は、―５０℃以上であることが好ましい。Ｔｇが−５０℃未満ではグリップ性能が充分ではない傾向がある。また、Ｔｇは０℃以下が好ましく、−１０℃以下がより好ましい。Ｔｇが０℃をこえると低温時のグリップ性能が低下する傾向がある。 Among the diene rubber components, SBR is preferably used from the viewpoint of a balance between grip performance and wear resistance. When SBR is used, the glass transition temperature (Tg) of SBR is preferably −50 ° C. or higher. If Tg is less than -50 ° C, grip performance tends to be insufficient. Tg is preferably 0 ° C. or lower, more preferably −10 ° C. or lower. When Tg exceeds 0 ° C., grip performance at low temperatures tends to decrease.
本発明に使用されるオレフィン−共役ジエン−芳香族ビニル共重合体におけるオレフィンのモノマー成分としては、たとえば、エチレン、プロプレン、１−ブテン、２−ブテン、イソブテン、１−ヘキセン、１−オクテン、１−ヘプテン、１−デセンなどのオレフィンがあげられる。これらは１種単独で用いても、２種以上を混合してもよい。なかでも汎用性、経済性、反応性等の点で、エチレンが好ましい。 Examples of the olefin monomer component in the olefin-conjugated diene-aromatic vinyl copolymer used in the present invention include ethylene, propylene, 1-butene, 2-butene, isobutene, 1-hexene, 1-octene, 1 -Olefin such as heptene and 1-decene. These may be used individually by 1 type, or may mix 2 or more types. Of these, ethylene is preferred from the viewpoints of versatility, economy and reactivity.
前記オレフィンモノマーユニット比は、５重量％以上が好ましく、１０重量％以上がより好ましい。オレフィンモノマーユニット比が５重量％未満では加硫中に架橋阻害が生じるため、耐摩耗性が低下する傾向がある。また、オレフィンモノマーユニット比は、８０重量％以下が好ましく、７０重量％以下がより好ましい。オレフィンモノマーユニット比が８０重量％をこえるとマトリックスのゴム成分とオレフィン−共役ジエン−芳香族ビニル共重合体の相溶性が悪化し、ブリードアウトしやすくなる傾向がある。 The olefin monomer unit ratio is preferably 5% by weight or more, and more preferably 10% by weight or more. If the olefin monomer unit ratio is less than 5% by weight, cross-linking inhibition occurs during vulcanization, so that the wear resistance tends to decrease. The olefin monomer unit ratio is preferably 80% by weight or less, and more preferably 70% by weight or less. When the olefin monomer unit ratio exceeds 80% by weight, the compatibility between the rubber component of the matrix and the olefin-conjugated diene-aromatic vinyl copolymer tends to deteriorate, and bleeding tends to occur.
共役ジエンのモノマー成分としては、たとえば、１，３−ブタジエン、イソプレン、１，３−ペンタンジエン、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１種単独で用いても、２種以上を混合してもよい。なかでも汎用性、経済性、反応性等の点で、１，３−ブタジエンが好ましい。 Examples of the monomer component of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentanediene, 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. Of these, 1,3-butadiene is preferred in view of versatility, economy, reactivity, and the like.
前記共役ジエンモノマーユニット比は、５重量％以上が好ましく、１０重量％以上がより好ましい。共役ジエンモノマーユニット比が５重量％未満ではマトリックスのゴム成分とオレフィン−共役ジエン−芳香族ビニル共重合体の相溶性が悪化し、ブリードアウトしやすくなる傾向がある。また、共役ジエンモノマーユニット比は、８０重量％以下が好ましく、７０重量％以下がより好ましい。共役ジエンモノマーユニット比が８０重量％をこえると加硫中に架橋阻害が生じるため、耐摩耗性が低下する傾向がある。 The conjugated diene monomer unit ratio is preferably 5% by weight or more, and more preferably 10% by weight or more. When the conjugated diene monomer unit ratio is less than 5% by weight, the compatibility between the rubber component of the matrix and the olefin-conjugated diene-aromatic vinyl copolymer tends to deteriorate, and bleeding tends to occur. The conjugated diene monomer unit ratio is preferably 80% by weight or less, and more preferably 70% by weight or less. When the conjugated diene monomer unit ratio exceeds 80% by weight, cross-linking inhibition occurs during vulcanization, so that wear resistance tends to be lowered.
芳香族ビニルのモノマー成分としては、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、２，４，６−トリメチルスチレンなどのビニル芳香族炭化水素モノマーがあげられる。これらは１種単独で用いても、２種以上を混合してもよい。なかでも汎用性、経済性、反応性などの点で、スチレンが好ましい。 Examples of aromatic vinyl monomer components include vinyl aroma such as styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, 4-cyclohexylstyrene, and 2,4,6-trimethylstyrene. Group hydrocarbon monomers. These may be used individually by 1 type, or may mix 2 or more types. Of these, styrene is preferable in terms of versatility, economy, and reactivity.
前記芳香族ビニルモノマーユニット比は、５重量％以上が好ましく、１０重量％以上がより好ましい。芳香族ビニルモノマーユニット比が５重量％未満ではグリップ性能の向上効果が小さい傾向がある。また、芳香族ビニルモノマーユニット比は、７０重量％以下が好ましく、６０重量％以下がより好ましい。芳香族ビニルモノマーユニット比が７０重量％をこえると低温時のグリップ性能の向上効果が小さい傾向がある。 The aromatic vinyl monomer unit ratio is preferably 5% by weight or more, and more preferably 10% by weight or more. If the aromatic vinyl monomer unit ratio is less than 5% by weight, the effect of improving the grip performance tends to be small. The aromatic vinyl monomer unit ratio is preferably 70% by weight or less, and more preferably 60% by weight or less. If the aromatic vinyl monomer unit ratio exceeds 70% by weight, the effect of improving the grip performance at low temperatures tends to be small.
前記各モノマーの組み合わせとしては、具体的には、エチレン−ブタジエン−スチレン、プロピレン−ブタジエン−スチレン、プロピレン−イソプレン−スチレン、エチレン−イソプレン−スチレンなどがあげられる。とくに汎用性、経済性、耐熱性等の点で、エチレン−ブタジエン−スチレン共重合体が好ましく用いられる。 Specific examples of the combination of the monomers include ethylene-butadiene-styrene, propylene-butadiene-styrene, propylene-isoprene-styrene, and ethylene-isoprene-styrene. In particular, an ethylene-butadiene-styrene copolymer is preferably used in terms of versatility, economy, heat resistance, and the like.
前記各モノマーの配列としては、ブロック、ランダムのどちらでもよいが、グリップ性能と耐摩耗性のバランスの観点からは、ランダムであることが好ましい。 The arrangement of each monomer may be either block or random, but is preferably random from the viewpoint of a balance between grip performance and wear resistance.
前記オレフィン−共役ジエン−芳香族ビニル共重合体の重量平均分子量Ｍｗは、ＧＰＣ測定によるポリスチレン換算分子量で２０００以上が好ましく、３０００以上がより好ましく、４０００以上がとくに好ましい。重量平均分子量が２０００未満であると耐摩耗性が充分に得られない傾向がある。また、該共重合体の重量平均分子量は、５００００以下が好ましく、４００００以下がより好ましく、３００００以下がとくに好ましい。５００００をこえるとグリップ性能が低下する。 The weight average molecular weight Mw of the olefin-conjugated diene-aromatic vinyl copolymer is preferably 2,000 or more, more preferably 3,000 or more, and particularly preferably 4,000 or more in terms of polystyrene equivalent molecular weight by GPC measurement. When the weight average molecular weight is less than 2000, there is a tendency that sufficient wear resistance cannot be obtained. Further, the weight average molecular weight of the copolymer is preferably 50000 or less, more preferably 40000 or less, and particularly preferably 30000 or less. If it exceeds 50000, the grip performance will deteriorate.
前記オレフィン−共役ジエン−芳香族ビニル共重合体の分子量分布（Ｍｗ／Ｍｎ）は、２以下であることが好ましい。分子量分布が２をこえると、耐摩耗性、耐熱性等の耐久性が低下する傾向がある。 The molecular weight distribution (Mw / Mn) of the olefin-conjugated diene-aromatic vinyl copolymer is preferably 2 or less. When the molecular weight distribution exceeds 2, durability such as wear resistance and heat resistance tends to decrease.
前記オレフィン−共役ジエン−芳香族ビニル共重合体の含有量は、前記ジエン系ゴム成分１００重量部に対して、５重量部以上であり、好ましくは１０重量部以上、より好ましくは１５重量部以上である。５重量部未満ではグリップ性能の改善効果が小さい。また、該共重合体の含有量は、２００重量部以下であり、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。２００重量部をこえると耐摩耗性が低下する。 The content of the olefin-conjugated diene-aromatic vinyl copolymer is 5 parts by weight or more, preferably 10 parts by weight or more, more preferably 15 parts by weight or more with respect to 100 parts by weight of the diene rubber component. It is. If it is less than 5 parts by weight, the effect of improving the grip performance is small. The content of the copolymer is 200 parts by weight or less, preferably 180 parts by weight or less, more preferably 150 parts by weight or less. When the amount exceeds 200 parts by weight, the wear resistance is lowered.
本発明のゴム組成物は、さらに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、主としてカーボンブラックが好ましい。 The rubber composition of the present invention preferably further contains a reinforcing filler. The reinforcing filler can be arbitrarily selected from those conventionally used in rubber compositions for tires, but carbon black is mainly preferred.
前記カーボンブラックのチッ素吸着比表面積は、８０ｍ2／ｇ以上であることが好ましく、とくには１００ｍ2／ｇ以上であることが好ましい。チッ素吸着比表面積が８０ｍ2／ｇ未満では、グリップ性能、耐摩耗性がともに低下する傾向がある。また、チッ素吸着比表面積は、２８０ｍ2／ｇ以下であることが好ましく、とくには２００ｍ2／ｇ以下であることが好ましい。２８０ｍ2／ｇをこえると、良好な分散が得られにくく耐摩耗性が低下する傾向がある。 The carbon black has a nitrogen adsorption specific surface area of preferably 80 m 2 / g or more, particularly preferably 100 m 2 / g or more. When the nitrogen adsorption specific surface area is less than 80 m 2 / g, both grip performance and wear resistance tend to decrease. Further, the nitrogen adsorption specific surface area is preferably 280 m 2 / g or less, and particularly preferably 200 m 2 / g or less. If it exceeds 280 m 2 / g, good dispersion is difficult to obtain, and the wear resistance tends to decrease.
前記カーボンブラックの含有量は、前記ジエン系ゴム成分１００重量部に対して１０重量部以上、とくには２０重量部以上であることが好ましい。カーボンブラックの含有量が１０重量部未満では耐摩耗性が低下する傾向がある。また、カーボンブラックの含有量は、２００重量部以下、とくには１５０重量部以下であることが好ましい。２００重量部をこえると加工性が低下する傾向がある。前記補強用充填剤は単独で用いてもよく、２種以上を組み合わせて用いてもよい。 The content of the carbon black is preferably 10 parts by weight or more, particularly 20 parts by weight or more with respect to 100 parts by weight of the diene rubber component. If the content of carbon black is less than 10 parts by weight, the wear resistance tends to decrease. The carbon black content is preferably 200 parts by weight or less, particularly 150 parts by weight or less. If it exceeds 200 parts by weight, the workability tends to be lowered. 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、前記成分の他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, the rubber composition of the present invention includes various chemicals usually used in the rubber industry in addition to the above components, such as vulcanizing agents such as sulfur, various vulcanization accelerators, various softening agents, and various anti-aging agents. Additives such as stearic acid, antioxidants, and ozone degradation inhibitors can be blended.
軟化剤を配合する場合、軟化剤の含有量は、前記ジエン系ゴム成分１００重量部に対して１００重量部以下であることが好ましい。軟化剤の含有量が１００重量部をこえるとグリップ性能、操縦安定性等が低下する傾向がある。 When a softener is blended, the content of the softener is preferably 100 parts by weight or less with respect to 100 parts by weight of the diene rubber component. When the content of the softening agent exceeds 100 parts by weight, grip performance, steering stability and the like tend to decrease.
本発明のタイヤは、本発明のゴム組成物を、とくにトレッド部に用いて、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の各部材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。このようにして得られた本発明のタイヤは、グリップ性能、耐摩耗性のバランスに優れるものである。 The tire of the present invention is produced by a usual method using the rubber composition of the present invention, particularly in the tread portion. That is, if necessary, the rubber composition of the present invention blended with the above various chemicals is extruded in accordance with the shape of each member of the tire at an unvulcanized stage and is processed on a tire molding machine by a normal method. Mold to form an unvulcanized tire. This unvulcanized tire is heated and pressurized in a vulcanizer to obtain a tire. The tire of the present invention thus obtained has an excellent balance between grip performance and wear resistance.
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.
製造例１〜３（オレフィン−共役ジエン−芳香族ビニル共重合体の合成）
充分にチッ素置換した５０ｍＬ容器に、トルエン１５ｍＬ、シクロペンタジエニルトリフェノキシチタンおよびメチルアルミノキサン（ＭＡＯ）のトルエン溶液（［Ａｌ］／［Ｔｉ］＝５００、［Ａｌ］＝３．４ｍｏｌ／Ｌ）４ｍＬ、スチレン４ｍＬ、ブタジエン４ｍＬを入れた。７０℃で攪拌しながらエチレンを分圧が１．２ｋｇ／ｃｍ2になるように入れ、１時間重合したのち、メタノール−塩酸（２％）溶液を入れて反応を停止させて、オレフィン−共役ジエン−芳香族ビニル共重合体１を得た。
Production Examples 1 to 3 (Synthesis of olefin-conjugated diene-aromatic vinyl copolymer)
In a 50 mL container fully substituted with nitrogen, 15 mL of toluene, a toluene solution of cyclopentadienyltriphenoxytitanium and methylaluminoxane (MAO) ([Al] / [Ti] = 500, [Al] = 3.4 mol / L) 4 mL, 4 mL of styrene, and 4 mL of butadiene were added. While stirring at 70 ° C., ethylene is introduced so that the partial pressure becomes 1.2 kg / cm 2, and after polymerization for 1 hour, the reaction is stopped by adding methanol-hydrochloric acid (2%) solution, and olefin-conjugated diene is obtained. -Aromatic vinyl copolymer 1 was obtained.
共重合体２、３については、仕込み量、反応温度、反応時間等を変え、同様の処方により合成した。
（共重合体２〜３の構造式）
Copolymers 2 and 3 were synthesized according to the same prescription by changing the charged amount, reaction temperature, reaction time and the like.
(Structural formula of copolymers 2 to 3)
製造例４（スチレン−ブタジエン共重合体の合成）
充分にチッ素置換された５０ｍＬの容器に、シクロヘキサン１５ｍＬ、１，３−ブタジエン２ｍＬ、スチレン１ｍＬ、テトラヒドロフラン０．５ｍＬを入れた。これにｎ−ブチルリチウム０．３ｍｍｏｌを加えたのち、４０℃で５分間重合を行ない、メタノールを入れて反応を停止した。
Production Example 4 (Synthesis of styrene-butadiene copolymer)
In a 50 mL container sufficiently substituted with nitrogen, 15 mL of cyclohexane, 2 mL of 1,3-butadiene, 1 mL of styrene, and 0.5 mL of tetrahydrofuran were placed. After adding 0.3 mmol of n-butyllithium thereto, polymerization was carried out at 40 ° C. for 5 minutes, and methanol was added to stop the reaction.
（重量平均分子量Ｍｗ）
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換算した。
(Weight average molecular weight Mw)
For the weight average molecular weight Mw, a GPC-8000 series apparatus manufactured by Tosoh Corporation was used, a differential refractometer was used as a detector, and the molecular weight was converted to standard polystyrene.
（モノマーユニット比）
２５℃にてＪＥＯＬ ＪＮＭ−Ａ ４００ＮＭＲ装置を用いて１Ｈ ＮＭＲを測定した。
シグナルＡ：δ６．５−７．５ｐｐｍのスチレン部のベンゼン環のプロトン（−Ｃ6Ｈ5）、
シグナルＢ：δ５．２−５．８ｐｐｍのブタジエン部のメチンプロトン（−ＣＨ＝）、
シグナルＣ：δ４．７−５．２ｐｐｍのブタジエン部の１，２結合によるメチレンプロトン（＝ＣＨ2）、
シグナルＤ：δ０．５−３．０ｐｐｍの単結合のメチレンプロトン（−ＣＨ2−）メチンプロトン（−ＣＨ−）、
から、以下の式によりモノマーユニット比を求めた。
［エチレン］：［ブタジエン］：［スチレン］＝
｛−３［Ａ］／５−２［Ｂ］−２［Ｃ］＋［Ｄ］｝／４：
［Ｂ］／２＋［Ｃ］／２：
［Ａ］／５
(Monomer unit ratio)
1H NMR was measured using a JEOL JNM-A 400 NMR apparatus at 25 ° C.
Signal A: δ6.5-7.5ppm styrene portion of the benzene ring proton (-C 6 H 5),
Signal B: methine proton (-CH =) of butadiene part of δ 5.2-5.8 ppm,
Signal C: methylene proton (= CH 2 ) due to 1,2 bond of butadiene portion of δ 4.7-5.2 ppm,
Signal D: δ 0.5-3.0 ppm single-bonded methylene proton (—CH 2 —) methine proton (—CH—),
From this, the monomer unit ratio was determined by the following equation.
[Ethylene]: [Butadiene]: [Styrene] =
{-3 [A] / 5-2 [B] -2 [C] + [D]} / 4:
[B] / 2 + [C] / 2:
[A] / 5
以下に、実施例および比較例で用いた各種薬品について説明する。
ＳＢＲ；旭化成工業（株）のＴＵＦＤＥＮＥ３３３０（Ｔｇ：−４３℃）
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（チッ素吸着比表面積：１４３ｍ2／ｇ）
オレフィン−共役ジエン−芳香族ビニル共重合体１；重量平均分子量Ｍｗ＝２５００、分子量分布（Ｍｗ／Ｍｎ）＝１．３４、［エチレン］：［ブタジエン］：［スチレン］＝２１：６５：１４
オレフィン−共役ジエン−芳香族ビニル共重合体２；重量平均分子量Ｍｗ＝５０００、分子量分布（Ｍｗ／Ｍｎ）＝１．４２、［エチレン］：［ブタジエン］：［スチレン］＝２０：６７：１３
オレフィン−共役ジエン−芳香族ビニル共重合体３：重量平均分子量Ｍｗ＝５００、分子量分布（Ｍｗ／Ｍｎ）＝１．２５、［エチレン］：［ブタジエン］：［スチレン］＝１８：６８：１４
スチレン−ブタジエン共重合体：重量平均分子量Ｍｗ＝２５００、［ブタジエン］：［スチレン］＝８５：１５
軟化剤：出光興産（株）製のダイアナプロセスオイル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）製の亜鉛華１号
硫黄：鶴見化学工業（株）製の粉末硫黄
加硫促進剤：大内新興化学工業（株）製のノクセラーＣＺ
Below, various chemical | medical agents used by the Example and the comparative example are demonstrated.
SBR: TUFDENE 3330 (Tg: -43 ° C) from Asahi Kasei Corporation
Carbon black; Show Black N110 (Nitrogen adsorption specific surface area: 143 m 2 / g) manufactured by Showa Cabot Co., Ltd.
Olefin-conjugated diene-aromatic vinyl copolymer 1; weight average molecular weight Mw = 2500, molecular weight distribution (Mw / Mn) = 1.34, [ethylene]: [butadiene]: [styrene] = 21: 65: 14
Olefin-conjugated diene-aromatic vinyl copolymer 2; weight average molecular weight Mw = 5000, molecular weight distribution (Mw / Mn) = 1.42, [ethylene]: [butadiene]: [styrene] = 20: 67: 13
Olefin-conjugated diene-aromatic vinyl copolymer 3: weight average molecular weight Mw = 500, molecular weight distribution (Mw / Mn) = 1.25, [ethylene]: [butadiene]: [styrene] = 18: 68: 14
Styrene-butadiene copolymer: weight average molecular weight Mw = 2500, [butadiene]: [styrene] = 85: 15
Softener: Diana Process Oil AH-16 manufactured by Idemitsu Kosan Co., Ltd.
Stearic acid: Zinc stearate oxide manufactured by Nippon Oil & Fats Co., Ltd .: Zinc Hua No. 1 manufactured by Mitsui Mining & Smelting Co., Ltd. Sulfur: Powder sulfur vulcanization accelerator manufactured by Tsurumi Chemical Industry Co., Ltd. Noxeller CZ made by
実施例１〜３および比較例１〜２
表１に示す配合処方にしたがって混練り配合し、各種供試ゴム組成物を得た。これらの配合物を１７０℃で２０分間プレス加硫して加硫物を得て、これらについて以下に示す各特性の試験を行なった。
Examples 1-3 and Comparative Examples 1-2
According to the formulation shown in Table 1, kneading and compounding were performed to obtain various test rubber compositions. These blends were press vulcanized at 170 ° C. for 20 minutes to obtain vulcanizates, which were tested for the following characteristics.
（グリップ性能）
前記のゴム組成物からなるトレッドを有するタイヤを作製した。このタイヤを用いて、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として指数表示をした。数値が大きいほどグリップ性能が高いことを示す。
(Grip performance)
A tire having a tread made of the rubber composition was produced. Using this tire, a real vehicle was run on an asphalt road test course. The test driver evaluated the stability of control during steering at that time, and the comparative example 1 was set to 100 and displayed as an index. The larger the value, the higher the grip performance.
（耐摩耗性）
前記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計測し、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よいことを示す。
(Abrasion resistance)
Using the tire, the test course was run 20 laps, the depth of the groove before and after the run was measured, and indexed with Comparative Example 1 being 100. The larger the value, the better the wear resistance.
それぞれの試験結果を表１に示す。 Each test result is shown in Table 1.
Claims (4)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004032136A JP4088258B2 (en) | 2004-02-09 | 2004-02-09 | Rubber composition and tire using the same |
| EP04023793A EP1535959B1 (en) | 2003-11-28 | 2004-10-06 | Rubber composition for a tire 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 |
| 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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| JP2004032136A JP4088258B2 (en) | 2004-02-09 | 2004-02-09 | Rubber composition and tire using the same |
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| JP2005220313A JP2005220313A (en) | 2005-08-18 |
| JP4088258B2 true JP4088258B2 (en) | 2008-05-21 |
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Cited By (3)
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| EP3552840A1 (en) | 2018-04-09 | 2019-10-16 | Sumitomo Rubber Industries, Ltd. | Tire rubber composition and tire |
| WO2020162304A1 (en) | 2019-02-05 | 2020-08-13 | 住友ゴム工業株式会社 | Rubber composition and tire |
| EP4092077A2 (en) | 2021-05-21 | 2022-11-23 | Sumitomo Rubber Industries, Ltd. | Cap tread and passenger car tire |
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Cited By (3)
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| EP3552840A1 (en) | 2018-04-09 | 2019-10-16 | Sumitomo Rubber Industries, Ltd. | Tire rubber composition and tire |
| WO2020162304A1 (en) | 2019-02-05 | 2020-08-13 | 住友ゴム工業株式会社 | Rubber composition and tire |
| EP4092077A2 (en) | 2021-05-21 | 2022-11-23 | Sumitomo Rubber Industries, Ltd. | Cap tread and passenger car tire |
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